JP2009275130A - Alicyclic polymer having silicon-containing group, and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a readily producible polymer having excellent heat stability, film-forming properties, and gas permeability. <P>SOLUTION: The polymer comprises a repeating unit represented by formula (1) (wherein, R<SP>1</SP>and R<SP>2</SP>are mutually independently a 1-12C alkyl group which may be substituted; a and b are each 0, 1, 2, 3, or a combination thereof), and has a 5,000-5,000,000 Mn (number-average molecular weight). <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to an alicyclic polymer, and more specifically, it has both the properties of an alicyclic polymer and a silicon-containing compound by having a specific silicon-containing group as a pendant, and has excellent heat resistance. The present invention relates to polymers and methods for producing them.

  A polymer obtained by subjecting a norbornene-based monomer having a functional group as a substituent to metathesis polymerization is attracting attention as a functional group-containing polymer excellent in heat resistance, electrical characteristics, low water absorption and the like. The polymer has excellent adhesion to inorganic materials such as metals and glass, and also has excellent compatibility with organic materials such as antioxidants, plasticizers, ultraviolet absorbers, colorants, curing agents, flame retardants, etc. It is expected to be used for various composite materials.

Several reports on the polymer have been made. For example, a polymer obtained by copolymerizing a norbornene derivative having a polar group and a cycloalkene having a reactive silyl group (Patent Documents 1 and 2), a polymer obtained by polymerizing a norbornene derivative having a silicon content (Patent Documents) 4) is known. However, there is a problem that these polymers are thermally unstable.

Further, there is known a polymer obtained by hydrosilylating a double bond of a polymer obtained by metascission polymerization of a norbornene-based monomer and further hydrogenating if desired (Patent Document 3). However, the silylation reaction for the polymer main chain has a remarkably low reaction rate, and it is difficult to introduce a large number of silicon-containing organic groups.
JP 52-52999 A Japanese Unexamined Patent Publication No. 1-294681 Japanese Patent Laid-Open No. 5-214079 JP 2007-291150 A

  Accordingly, an object of the present invention is to provide an alicyclic polymer capable of forming a thermally stable film and having a large number of silicon-containing groups and excellent oxygen permeation performance, and a method for producing the same. And

That is, this invention is a polymer which contains the repeating unit shown by following formula (1), and the number average molecular weight (Mn) of polystyrene conversion measured by GPC is 5,000-5,000,000. .

（式中、Ｒ^１及び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、aは０、１、２、３又はこれらの組合せであり、ｂは０、１、２、３又はこれらの組合せである）

(Wherein R ¹ and R ² are each independently an alkyl group having 1 to 12 carbon atoms, which may be substituted, a is 0, 1, 2, 3 or a combination thereof, and b is 0, 1, 2, 3 or a combination thereof)

  The polymer of the present invention is excellent in thermal stability as compared with conventional norbornene-based polymers. Moreover, in addition to the film-forming property and toughness which polycycloolefin has, it has the characteristics which silicone has, such as elasticity and gas permeability. Furthermore, since it is soluble in various organic solvents, it is useful as a raw material for gas separation membranes, cosmetic materials, adhesives, fiber treatment agents and the like.

  Moreover, according to the method of the present invention, an alicyclic polymer having a high silicon content can be obtained efficiently.

In the above formula (1), R ¹ and R ² are, for example, a methyl group, an ethyl group, an n-propyl group, a butyl group, a pentyl group, etc., and some or all of these hydrogen atoms are substituted with fluorine atoms, etc. May have been. Of these, a methyl group is preferred.

a is 0, 1, 2, or a combination thereof. For example, a may be a polymer in which a repeating unit of 0 and a repeating unit of 1 exist. From the viewpoint of gas permeability, a is preferably 0, 1 or a combination thereof, and most preferably 0. b is also 0, 1 or 2, or a combination thereof. In view of polymerizability, b is preferably 0, 1 or a combination thereof, and most preferably 0.

  The repeating unit (1) can be obtained by hydrogenating a polymer of the formula (4) obtained by metathesis polymerization of an organosilicon compound represented by the following formula (3).

ここで、Ｒ^１、Ｒ^２、a及びｂは上述の通りである。

Here, R ¹ , R ² , a and b are as described above.

ここで、Ｒ^１、Ｒ^２、a及びｂは上述の通りである。

Here, R ¹ , R ² , a and b are as described above.

  Examples of the organosilicon compound of the formula (3) include the following, where Me represents a methyl group. Moreover, you may use these mixtures.

  The organosilicon compound can be easily prepared by subjecting the following vinyl group-containing polysiloxane and cyclopentadiene to a Diels-Alder reaction. The details of the preparation method will be described in Examples below.

  In the metathesis polymerization for obtaining the polymer of the formula (4), a monomer is dissolved in an aromatic hydrocarbon solvent such as toluene or xylene according to a conventional method, and the temperature is 40 to 60 ° C. under normal pressure in the presence of a polymerization catalyst. And stirring under a nitrogen atmosphere. As the polymerization catalyst, tungsten, molybdenum or ruthenium complex called carbene complex can be used, and preferably, Grubbs first generation catalyst, Grubbs second generation catalyst, Hoveyda-Grubbs catalyst or the like is used. A ruthenium carbene complex catalyst such as benzylidene-bis (tricyclohexylphosphine) dichlororuthenium is particularly preferable because it can be used as a hydrogenation catalyst described later. The usage-amount of a catalyst is 1-1000 ppm with respect to the monomer of a raw material, Preferably it is 5-500 ppm. If it is less than 5 ppm, the polymerization rate is slow and the practicality is poor. Usually, 500 ppm is sufficient for metathesis polymerization, but if it is used continuously in the hydrogenation step described later, there is no problem even if it is more.

  In addition to the organosilicon compound of formula (3), other olefin compounds may be used as comonomers and subjected to metathesis polymerization. As the olefin compound, a norbornene-based alicyclic organic compound can be used. Preferably, an alicyclic organic compound represented by the formula (5) is used. Thereby, the polymer which also has a repeating unit of Formula (6) is obtained, and the polymer which also has a repeating unit of Formula (2) is obtained by further hydrogenating them. The repeating unit (2) may be combined with the repeating unit (1) in a block shape or a random shape.

式（２）、（５）、（６）において、Ｒ^３及びＲ^４は、互いに独立に、水素原子または一価の有機基である。該一価の基としては、アルキル基、アリール基、アルカリール基、アルコキシ基、アルコキシシリル基、ポリグリセリル基、ヒドロキシポリ（オキシアルキル）基、ポリシロキシシリル基、及びこれらの水素原子の一部もしくは全部がフッ素原子に置換された基を挙げることができ、好ましくは、炭素数１〜７のアルキル基、パーフルオロアルキル基、アルコキシシリル基、ポリグリセリル基、ヒドロキシポリ（オキシアルキル）基、ポリシロキシシリル基から選ばれる。造膜性の点で、水素原子またはメチル基がより好ましい。ｃは０、１、２又はこれらの組合せであり、重合性の点で、０、１又はこれらの組合せが好ましく、最も好ましくは０である。

In the formulas (2), (5) and (6), R ³ and R ⁴ are each independently a hydrogen atom or a monovalent organic group. Examples of the monovalent group include an alkyl group, an aryl group, an alkaryl group, an alkoxy group, an alkoxysilyl group, a polyglyceryl group, a hydroxypoly (oxyalkyl) group, a polysiloxysilyl group, and a part of these hydrogen atoms or A group in which all of them are substituted with fluorine atoms can be mentioned, and preferably, an alkyl group having 1 to 7 carbon atoms, a perfluoroalkyl group, an alkoxysilyl group, a polyglyceryl group, a hydroxypoly (oxyalkyl) group, a polysiloxysilyl group. Selected from the group. From the viewpoint of film forming property, a hydrogen atom or a methyl group is more preferable. c is 0, 1, 2 or a combination thereof, and 0, 1 or a combination thereof is preferable, and 0 is most preferable from the viewpoint of polymerizability.

As the alicyclic organic compound represented by the formula (5), the following compounds can be exemplified.

（これらの式中、Ｒは、互いに独立に、炭素数１〜１２の、水素原子の一部もしくは全部がフッ素原子で置換されていてよいアルキル基である。）

(In these formulas, R is independently an alkyl group having 1 to 12 carbon atoms, in which some or all of the hydrogen atoms may be substituted with fluorine atoms.)

  The amount of these comonomers used can be variously adjusted depending on the use of the polymer and the desired degree of film strength. For the gas permeable membrane, it is preferable to use about 0 to 2.0 by weight with respect to the compound of the formula (3). Further, the polymerization catalyst, polymerization conditions, and the like may be the same as in the case where the comonomer is not used.

  The polymer of the present invention has a number average molecular weight (Mn) in terms of styrene measured by GPC of 5,000 to 5,000,000, preferably 50,000 to 500,000. A polymer whose Mn is less than the lower limit value has insufficient film strength, and a polymer whose Mn exceeds the upper limit value may be inferior in film-forming properties.

  In the polymer of the present invention, the ratio of hydrogenated main chain carbon-carbon double bonds (hydrogenation rate) is 50% or more, and preferably 80% or more from the viewpoint of thermal stability, 90 % Or more is more preferable. As shown in the examples described later, about 99.5% can be hydrogenated. Therefore, in the polymer of the present invention, the repeating unit represented by the following formula (4) and / or (6) is 50% or less of the total number of repeating units, preferably 20% or less, more preferably 10% or less, Preferably it is contained at 0.5% or less.

（式中、Ｒ^１、Ｒ^２、a、及びｂは上述のとおりである。）

(Wherein R ¹ , R ² , a, and b are as described above.)

（式中、Ｒ^３、Ｒ^４及びｃは上述の通りである。）

(Wherein R ³ , R ⁴ and c are as described above.)

The hydrogenation rate is, for example, the peak intensity derived from the main chain carbon-carbon double bond in the ¹ H-NMR spectrum of the siloxane-containing polycycloolefin and the main chain carbon-carbon double bond in the ¹ H-NMR spectrum of the hydride. It can obtain | require by comparing with the peak intensity derived from.

  The hydrogenation reaction can be performed, for example, by adding hydrogen to the main chain carbon-carbon double bond of the siloxane-containing polycycloolefin using hydrogen gas in the presence of a hydrogenation catalyst.

  The hydrogenation catalyst to be used is not particularly limited, such as a homogeneous catalyst and a heterogeneous catalyst, and those generally used for hydrogenation of olefin compounds can be appropriately used.

  Examples of the homogeneous catalyst include dichlorotris (triphenylphosphine) rhodium known as Wilkinson complex, ruthenium carbene complex catalyst described in the above metasis polymerization catalyst, JP-A-7-2929, JP-A-11-109460, JP-A-11-158256. And transition metal complex catalysts composed of ruthenium compounds described in JP-A-11-193323 and the like.

  Examples of the heterogeneous catalyst include a hydrogenation catalyst in which a metal such as nickel, palladium, platinum, rhodium, and ruthenium is supported on a carrier such as carbon, silica, celite, alumina, and titanium oxide, such as nickel-alumina and palladium. -Carbon or the like can be used. These hydrogenation catalysts can be used alone or in combination of two or more.

  Among these, rhodium, ruthenium, and the like can be selectively hydrogenated from the main chain carbon-carbon double bond of the polymer without causing side reactions such as functional groups contained in the siloxane-containing polycycloolefin. The use of a noble metal complex catalyst and a palladium-supported catalyst such as palladium-carbon is preferred, and a ruthenium carbene complex catalyst is particularly preferred.

  The ruthenium carbene complex catalyst can be used as a ring-opening metathesis reaction catalyst and a hydrogenation catalyst. In this case, the ring-opening metathesis reaction and the hydrogenation reaction can be performed continuously.

  In addition, when a metathesis reaction and a hydrogenation reaction are continuously performed using a ruthenium carbene complex catalyst, a catalyst modifier such as ethyl vinyl ether or a vinyl compound or α-olefin is added to activate the catalyst. A method for starting the hydrogenation reaction is also preferably employed.

  The hydrogenation reaction is usually performed in an organic solvent. As an organic solvent, it can select conveniently by the solubility of the hydride to produce | generate, The organic solvent similar to the above-mentioned polymerization solvent can be used. Therefore, the reaction can be carried out as it is or after adding a hydrogenation catalyst without replacing the solvent after the polymerization reaction.

  The conditions for the hydrogenation reaction may be appropriately selected according to the type of hydrogenation catalyst used. The usage-amount of a hydrogenation catalyst is 100-10,000 ppm normally with respect to 100 weight part of polymers obtained by metathesis polymerization, Preferably it is 500-5,000 ppm. As described above, this amount of catalyst may be used also in the metathesis polymerization step, or 5 to 500 ppm may be used in the polymerization step and added in the hydrogenation step. The reaction temperature is 100 ° C. to 200 ° C. If the temperature exceeds 200 ° C., side reactions tend to occur. The reaction pressure of hydrogen is usually 0.01 to 10.0 MPa, preferably 0.1 to 5.0 MPa. When the hydrogen pressure is 0.01 MPa or less, the hydrogenation reaction rate decreases. High breakdown voltage device is required at 5.0MPa or more

  The hydrogenation reaction performed as described above can hydrogenate 50% or more, preferably 80% or more, and most preferably 90% or more of the main chain carbon-carbon double bonds in the polymer.

  Further, for hydrogenation of 95% or more, reductive hydrogenation of the main chain carbon-carbon double bond with diimide is effective. When a diimide generator such as hydrazine or tosyl hydrazide is reacted with a polymer under reflux of an organic solvent, a polymer in which the main chain carbon-carbon double bond is further hydrogenated can be obtained in high yield.

  What is necessary is just to select the conditions of reductive hydrogenation suitably according to the kind of diimide generator to be used. The usage-amount of a diimide generator is 0.01-50 weight part normally with respect to 100 weight part of polymers, Preferably it is 0.05-10 weight part. The solvent should just be a thing which does not contain an unsaturated group, for example, a saturated hydrocarbon solvent, and is 0.01-50 weight part normally, Preferably it is 0.05-10 weight part. The reaction temperature is usually 50 ° C. to 200 ° C., preferably at the reflux temperature of the solvent used.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited to the following Example. In addition, unless otherwise indicated, the part and% in an Example are weight%.

Example of monomer synthesis: Synthesis of tris (trimethylsiloxy) silylnorbornene 307 g of dicyclopentadiene and 750 g of tristrimethylsiloxyvinylsilane were charged into a 2 L reactor and reacted at 160 to 170 ° C. for 8 hours under a nitrogen seal. When the reaction solution was distilled under reduced pressure, 757 g of a fraction having a boiling point of 118 to 120 ° C./5 mmHg was obtained. ^The structure was confirmed by ¹ H-NMR analysis (measuring device LAMBDA LA-300W manufactured by JEOL) and infrared spectroscopic analysis (measuring device Perkin Elmer FT-IR Spectrometer Spectrum One), and the compound represented by the following structural formula It was confirmed that there was. This is monomer A.

Synthesis of prepolymer: metathesis polymerization of tris (trimethylsiloxy) silylnorbornene 50 g of monomer A synthesized in the monomer synthesis example was placed in a 5 L four-necked flask equipped with a stirrer and dissolved in 2 L of toluene. Ar (or N ₂ ) substitution. The mixture was heated with stirring so that the monomer diffused uniformly and kept at 40 ° C. A catalyst solution prepared by dissolving Grubbs first generation catalyst [benzylidene-bis (tricyclohexylphosphine) dichlororuthenium] in 0.105 g of toluene (110 ml) was quickly added thereto. After 20 minutes, 1 ml of ethyl vinyl ether was added to stop the polymerization and stirred for 5 minutes to obtain a polymer solution (hereinafter referred to as “prepolymer solution”). A part of the polymer solution was collected, and its molecular weight was examined by gel permeation chromatography (HLC-8220 manufactured by Tosoh Corporation) using polystyrene as a standard. Mn = 163,000, Mw / Mn = 1.75. The ¹ H-NMR spectrum of this prepolymer is shown in FIG.

Example 1
The whole amount of the prepolymer solution is put into an autoclave with stirring, and the inside of the autoclave is purged with nitrogen. A hydrogenation catalyst solution dissolved in 10 ml was added, and hydrogenation was performed at 0.8 MPa hydrogen and 160 ° C. for 8 hours. Thereafter, the solution was added dropwise to a large amount of methanol while stirring, and the precipitated polymer (hereinafter referred to as “polymer 1”) was collected by filtration and dried. The weight was 49 g, and the yield was 98%. ^{From 1} H-NMR, it was confirmed that 93% of the main chain carbon-carbon double bonds were hydrogenated.

Example 2
2.7 g of the polymer 1 obtained in Example 1 was dissolved in 20 ml of methylcyclohexane, then 2.0 g of tosyl hydrazide was added, and the mixture was refluxed at 100 ° C. for 8 hours. Thereafter, the solution was added dropwise to a large amount of methanol while stirring, and the precipitated polymer (hereinafter referred to as “polymer 2”) was collected by filtration and dried. The number average molecular weight (Mn) of the polymer 2 is 173,000, Mw / Mn = 2.14, and 99.5% of the main chain carbon-carbon double bond is hydrogenated from ¹ H-NMR. confirmed. The ¹ H-NMR spectrum of polymer 2 is shown in FIG.

TGA measurements <br/> prepolymer, polymer 1, and the thermal decomposition resistance of the TGA measurements of the polymer 2 were compared in (sample 1 mg, _{N 2} gas under a heating up 500 ℃ 10 ℃ / min). The results are shown in FIG. As can be seen from FIG. 3, the onset temperature of weight reduction due to thermal decomposition of polymer 1 and polymer 2 was significantly higher than that of the prepolymer, and it was confirmed that the thermal stability of the polymer was improved.

Heat resistance Prepolymer and polymer 2 were dissolved in toluene, cast on a plate made of polytetrafluoroethylene, and dried at 60C for 6 hours to prepare a film having a thickness of 100 m. These films were aged at 150 ° C. for a predetermined time. The photograph of the film after progress of each time is shown in FIG. The prepolymer film (upper) was colored with heat over time, whereas the polymer 2 (lower) film was not colored.

Oxygen permeability <br/> heat resistance test similar method where, to create a cast film of the polymer 2 was measured oxygen permeability coefficient (PO ₂₎ using Rika Seiki Kogyo Co., Ltd. gas permeability measuring device 250 × 10 ⁻¹⁰ cm ³ (STP) · cm / cm ² · s · cmHg.

As described above, the polymer of the present invention is excellent in film-forming properties, and since the film is transparent and excellent in heat stability, gas permeability, etc., gas separation membranes, cosmetic materials, adhesives, fiber treatment agents, various kinds of Applications are expected as raw materials for optical materials.

^{1 is} a ¹ H-NMR spectrum of a prepolymer. 2 is a ¹ H-NMR spectrum of polymer 2 prepared in Example 2. 2 is a TGA chart of polymer 1, polymer 2 and prepolymer. It is the photograph after aging of the polymer 2 and a prepolymer film.

Claims (8)

The polymer which contains the repeating unit shown by following formula (1), and the number average molecular weight (Mn) of polystyrene conversion measured by GPC is 5,000-5,000,000.

(In the formula, R ¹ and R ² are each independently an alkyl group having 1 to 12 carbon atoms which may be substituted with a fluorine atom, and a is 0, 1, 2, 3 or a combination thereof. , B is 0, 1, 2, 3, or a combination thereof) The polymer according to claim 1, further comprising a repeating unit represented by the following formula (2).

(Wherein R ³ and R ⁴ are each independently a hydrogen atom or a monovalent organic group, and c is 0, 1, 2, or a combination thereof) The polymer of Claim 1 or 2 which contains the repeating unit shown by following formula (4) and / or (6) in 50% or less of the total number of repeating units.

(In the formula, R ¹ , R ² , a, and b are as described above.)

(Wherein R ³ , R ⁴ and c are as described above.) The polymer according to any one of claims 1 to 3, wherein R ¹ and R ² are a methyl group, and a is 1. The polymer according to any one of claims 1 to 3, wherein R ¹ and R ² are a methyl group, and a is 0. The R ³ and R ⁴ are selected from the group consisting of an alkyl group, a perfluoroalkyl group, an alkoxysilyl group, a polyglyceryl group, a hydroxypolyoxyalkyl group, and a polysiloxysilyl group. Polymer. (1) A step of subjecting a silyl group-containing norbornene derivative monomer to metathesis polymerization,
(2) a step of hydrogenating the main chain double bond of the polymer obtained in step (1),
The manufacturing method of the polymer of any one of Claims 1-6 containing these. The production method according to claim 7, wherein a ruthenium carbene complex catalyst is used as the metasis polymerization reaction and the hydrogenation catalyst.

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