JP2005105122A - Polyketone - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyketone having excellent mechanical and thermal characteristics, and high thermal stability, and suitable for melt molding processing; and to provide a method for producing the polyketone. <P>SOLUTION: The polyketone comprising a copolymer of an ethylenically unsaturated compound and carbon monoxide contains a structure represented by chemical formula (1) [wherein, R<SP>1</SP>is an atomic group constituted of at least one element selected from hydrogen, a typical element, a halogen element, Si, P and S; X<SP>1</SP>is a reactive group or an atomic group having a reactive group and constituted of at least one element selected from hydrogen, a typical element, a halogen element, Si, P and S; and Y<SP>1</SP>is a silicon element-containing group such as a group represented by chemical formula (2)], and has &ge;0.01 and &le;20 dl/g intrinsic viscosity. <P>COPYRIGHT: (C)2005,JPO&amp;NCIPI

Description

  The present invention relates to a polyketone having a high strength, a high elastic modulus, a high melting point, a melt moldability excellent in thermal stability, and a method for producing the same.

It is known that a polyketone can be obtained by copolymerization of carbon monoxide (CO) with an ethylenically unsaturated compound such as ethylene and propylene. This polyketone is a material that has high wear resistance, chemical resistance, and gas barrier properties, has many properties, and is excellent in mechanical properties and thermal properties, and thus can be developed for various applications. Polyketone is an effective material as, for example, a high-strength, high-heat-resistant resin, fiber, or film. Particularly when a high-molecular-weight polyketone is used as a fiber, it has a high strength and high elasticity as a fiber, belt, hose. It is useful for building materials and industrial materials such as rubber reinforcing materials such as tire cords, concrete reinforcing materials, etc.
In order to use the polymer in various applications, it is necessary to form the polymer into a resin, fiber, film, or the like. Usually, molding in a molten state and dissolution and molding in a solvent such as an organic solvent are employed, and industrially inexpensive melt molding is important.

Conventionally, attempts have been made to melt mold polyketone (hereinafter abbreviated as ECO) mainly composed of repeating units composed of ethylene and carbon monoxide, but crystalline resin having a high melting point of ECO of 250 ° C. or higher. Therefore, a molding temperature of 280 ° C. to 300 ° C. is required. However, at this temperature, there is a problem that heat denaturation such as three-dimensional crosslinking occurs due to high temperature and long stay at the time of melt molding, impairing fluidity, and further deteriorating the mechanical and thermal performance of the molded body. Workability was considered difficult.
As an attempt to improve the moldability of ECO, improvement of the molding method itself and improvement of the resin for the purpose of controlling the melting point and crystallinity have been performed.

As an improvement of the molding method itself, as shown in many documents such as Non-Patent Document 1, a technique is known in which carbon dioxide is absorbed into a resin, thereby acting as a plasticizer for the resin and lowering the glass transition temperature. However, it is difficult to guess that the amount of carbon dioxide dissolved in ECO is large, and the actual situation is that it has not been put into practical use.
On the other hand, as an improvement of the resin, the ethylene unit in the alternating copolymer of ethylene and carbon monoxide is replaced by several mol% with an ethylenically unsaturated compound having a substituent such as propylene, and the melting point and crystallinity of the polymer are changed. A terpolymer polyketone (hereinafter abbreviated as “EPCO”, which was previously marketed as “Carillon” (registered trademark) by Shell Inc.) whose melt moldability is improved by lowering is known.

  EPCO has a melting point of 220 ° C. and a crystallinity of 30% (both are “Carillon” (registered trademark) catalog value of Shell) and can be molded at about 250 ° C. However, since hydrogen on tertiary carbon derived from an ethylenically unsaturated compound having a substituent (see chemical formula (10)) is extremely unstable, it becomes a source of radicals and has moldability but is thermally stable. However, the present situation is that the moldability of the polyketone has not been improved.

（式中、Ｒ^Ａは炭素数１以上の炭化水素構造）

(Wherein R ^A is a hydrocarbon structure having 1 or more carbon atoms)

  In addition to this, several techniques for improving thermal stability and enhancing the moldability of polyketone are known. For example, Patent Document 1 discloses phenolic dicarboxylates, phenolic dicarboxyamines or phenolic phosphates. A technique of adding 0.03 to 5% by weight of fights is disclosed. Patent Document 2 describes a technique of adding 0.03 to 3% by weight of a hindered phenol stabilizer. According to these techniques, although the strength reduction at high temperature can be suppressed, the additive used is expensive and must be used in a large amount in order to obtain a sufficient effect. In addition, these techniques are improvements in stability at a temperature less than the melting point, and the stability at the time of melt molding has not been obtained.

As a technique for increasing the thermal stability of polyketone at the time of melt molding, Patent Document 3 discloses a technique that uses hydroxyapatite to increase the stability at the time of melting. According to this technique, the fluidity lost due to thermal deterioration during melting can be suppressed to some extent. However, in order to obtain a sufficient effect, a large amount of hydroxyapatite must be used, which is difficult to adopt industrially.
As described above, ECO itself is difficult to mold, and EPCO has moldability, but there is a problem that the thermal stability is lowered and its improvement method is insufficient. Development was desired.

J. et al. S. Chiou, et al. Appl. Polym. Sci. , Vol. 30, 2633 (1985) European Patent Application No. 289077 European Patent Application No. 326223 US Pat. No. 5,066,701

  An object of the present invention is to provide a polyketone having excellent mechanical and thermal characteristics, high thermal stability, and suitable for melt molding and a method for producing the same. Specifically, polyketone is a technique different from EPCO (that is, a technique that does not generate a large amount of tertiary hydrogen that causes degradation such as thermal crosslinking inherent in EPCO). It is to provide a polyketone having a lowered melting point and a method for producing the same.

  In order to achieve the above-mentioned problems, the present inventors have intensively studied on improvement of thermal stability and molding processability by controlling the structure of polyketone. As a result, a polyketone having improved melt moldability was found by copolymerizing a very small amount of silicon compound in the polyketone structure without impairing the original mechanical and thermal properties of the polyketone. It came to complete.

That is, the present invention is as follows.
(1) A polyketone comprising a copolymer of an ethylenically unsaturated compound and carbon monoxide, including a structure represented by the chemical formula (1) in the molecule and having an intrinsic viscosity of 0.01 dl / g or more and 20 dl / g A polyketone that is:

(Wherein R ¹ is an atomic group composed of an element selected from hydrogen, a typical element, a halogen element, Si, P, and S, X ¹ is a reactive group, or hydrogen having a reactive group, a typical element, An atomic group composed of an element selected from a halogen element, Si, P, and S, Y ¹ is a compound represented by chemical formulas (2) to (5), and four repeating units represented by chemical formula (2) 0.01 to 100 mol %, A chemical formula (3) 0 to 99.99 mol%, a chemical formula (4) 0 to 50 mol%, and a chemical formula (5) in the range of 0 to 33 mol%, 1 to 10,000 silicon element-containing groups connected, R ¹ , X ¹ and Y ¹ may be the same or different when a plurality of R ¹ , X ¹ and Y ¹ are present. M is 0 to 3, n is 0 to 3, p is 0 to 3, and m + n + p = 3.

（式中、Ｒ^２〜Ｒ^６は同じでも異なってもよく、水素、典型元素、ハロゲン元素、Ｓｉ、Ｐ、およびＳから選ばれる元素により構成される原子団、Ｘ^２は反応性基、または反応性基を有する水素、典型元素、ハロゲン元素、Ｓｉ、Ｐ、およびＳから選ばれる元素により構成される原子団、ｉは０〜３、ｊは０〜３、ｋは０〜３、ｉ＋ｊ＋ｋ＝３である。）

(Wherein R ^{2 to} R ⁶ may be the same or different, and an atomic group composed of an element selected from hydrogen, a typical element, a halogen element, Si, P, and S, X ² is a reactive group, or An atomic group composed of hydrogen having a reactive group, typical element, halogen element, Si, P, and S, i is 0 to 3, j is 0 to 3, k is 0 to 3, i + j + k = 3)

(2) The polyketone according to (1) having a structure represented by the chemical formula (1) at a polymer terminal.
(3) The polyketone according to (1), wherein 90% by weight or more of the repeating units have at least one chemical structure selected from chemical formulas (6) to (8).

（式中、R^ａは水素、典型元素、ハロゲン元素、Ｓｉ、Ｐ、およびＳから選ばれる元素により構成される原子団を表す。）

(Wherein, R ^a represents hydrogen, typical elements, halogen elements, Si, P, and atomic group composed of element selected from S.)

（式中、化学式（７）のR^ｂ、R^ｃは水素、典型元素、ハロゲン元素、Ｓｉ、Ｐ、およびＳから選ばれる元素により構成される原子団を表し、同じであっても異なってもよい。化学式（７）、（８）のＭとＮは、いずれか一方または両方が、化学式（１）で示される珪素元素含有基であり、化学式（１）で示される珪素元素含有基でないときは、水素、典型元素、ハロゲン元素、Ｓｉ、Ｐ、およびＳから選ばれる元素により構成される原子団を表す。ＭとＮは同じであっても異なってもよい。

(In the formula, R ^b and R ^c in the chemical formula (7) represent atomic groups composed of an element selected from hydrogen, a typical element, a halogen element, Si, P, and S, which may be the same or different. When either or both of M and N in the chemical formulas (7) and (8) are a silicon element-containing group represented by the chemical formula (1) and not a silicon element-containing group represented by the chemical formula (1) Represents an atomic group composed of an element selected from hydrogen, a typical element, a halogen element, Si, P, and S. M and N may be the same or different.

(Wherein R ¹ is an atomic group composed of an element selected from hydrogen, a typical element, a halogen element, Si, P, and S, X ¹ is a reactive group, or hydrogen having a reactive group, a typical element, An atomic group composed of an element selected from a halogen element, Si, P, and S, Y ¹ is a compound represented by chemical formulas (2) to (5), and four repeating units represented by chemical formula (2) 0.01 to 100 mol %, A chemical formula (3) 0 to 99.99 mol%, a chemical formula (4) 0 to 50 mol%, and a chemical formula (5) in the range of 0 to 33 mol%, 1 to 10,000 silicon element-containing groups connected, R ¹ , X ¹ and Y ¹ may be the same or different when a plurality of R ¹ , X ¹ and Y ¹ are present. M is 0 to 3, n is 0 to 3, p is 0 to 3, and m + n + p = 3.

(Wherein R ^{2 to} R ⁶ may be the same or different, and an atomic group composed of an element selected from hydrogen, a typical element, a halogen element, Si, P, and S, X ² is a reactive group, or An atomic group composed of an element selected from hydrogen having a reactive group, typical element, halogen element, Si, P, and S, i is 0 to 3, j is 0 to 3, k is 0 to 3, i + j + k = 3.)
(4) The method for producing a polyketone according to (1), wherein carbon monoxide and an ethylenically unsaturated compound are polymerized in the presence of a silicon compound having a structure represented by the chemical formula (9).

（式中、R^１は水素、典型元素、ハロゲン元素、Ｓｉ、Ｐ、およびＳから選ばれる元素により構成される原子団、Ｘ^１は反応性基、または反応性基を有する水素、典型元素、ハロゲン元素、Ｓｉ、Ｐ、およびＳから選ばれる元素により構成される原子団、Ｙ^１は化学式（２）〜（５）示される４種の繰返し単位が、化学式（２）０.０１〜１００モル％と、化学式（３）０〜９９.９９モル％と、化学式（４）０〜５０モル％と、化学式（５）０〜３３モル％の範囲で、１〜１００００つながった珪素元素含有基を示す。Ｒ^１、Ｘ^１、Ｙ^１はそれぞれが複数個存在する時、同一でも異なってもよい。ｍは０〜４、ｎは０〜４、ｐは０〜４、ｍ＋ｎ＋ｐ＝４である。）

(Wherein R ¹ is an atomic group composed of an element selected from hydrogen, a typical element, a halogen element, Si, P, and S, X ¹ is a reactive group, or hydrogen having a reactive group, a typical element, An atomic group composed of an element selected from a halogen element, Si, P, and S, Y ¹ is a compound represented by chemical formulas (2) to (5), and four repeating units represented by chemical formula (2) 0.01 to 100 mol %, Chemical formula (3) 0 to 99.99 mol%, chemical formula (4) 0 to 50 mol%, and chemical formula (5) in the range of 0 to 33 mol%. R ¹ , X ¹ , and Y ¹ may be the same or different when a plurality of R ¹ , X ¹ , and Y ¹ are present, m is 0 to 4, n is 0 to 4, p is 0 to 4, and m + n + p = 4. )

（式中、Ｒ^２〜Ｒ^６は同じでも異なってもよく、水素、典型元素、ハロゲン元素、Ｓｉ、Ｐ、およびＳから選ばれる元素により構成される原子団、Ｘ^２は反応性基、または反応性基を有する水素、典型元素、ハロゲン元素、Ｓｉ、Ｐ、およびＳから選ばれる元素により構成される原子団、ｉは０〜３、ｊは０〜３、ｋは０〜３、ｉ＋ｊ＋ｋ＝３である。）

(Wherein R ^{2 to} R ⁶ may be the same or different, and an atomic group composed of an element selected from hydrogen, a typical element, a halogen element, Si, P, and S, X ² is a reactive group, or An atomic group composed of hydrogen having a reactive group, typical element, halogen element, Si, P, and S, i is 0 to 3, j is 0 to 3, k is 0 to 3, i + j + k = 3)

(5) In a method for producing a polyketone by copolymerizing carbon monoxide and an ethylenically unsaturated compound, (a) a Group 9, 10 or 11 transition metal compound and (b) a Group 15 element. The polyketone according to (4), wherein a silicon compound represented by the chemical formula (9), carbon monoxide, and ethylenically unsaturated carbon are reacted in the presence of a metal complex catalyst composed of a ligand having an atom. Manufacturing method.

(Wherein R ¹ is an atomic group composed of an element selected from hydrogen, a typical element, a halogen element, Si, P, and S, X ¹ is a reactive group, or hydrogen having a reactive group, a typical element, An atomic group composed of an element selected from a halogen element, Si, P, and S, Y ¹ is a compound represented by chemical formulas (2) to (5), and four repeating units represented by chemical formula (2) 0.01 to 100 mol %, Chemical formula (3) 0 to 99.99 mol%, chemical formula (4) 0 to 50 mol%, and chemical formula (5) in the range of 0 to 33 mol%. R ¹ , X ¹ , and Y ¹ may be the same or different when a plurality of R ¹ , X ¹ , and Y ¹ are present, m is 0 to 4, n is 0 to 4, p is 0 to 4, and m + n + p = 4. )

(Wherein R ^{2 to} R ⁶ may be the same or different, and an atomic group composed of an element selected from hydrogen, a typical element, a halogen element, Si, P, and S, X ² is a reactive group or a reaction Atomic group composed of hydrogen having a functional group, typical element, halogen element, Si, P, and S, i is 0 to 3, j is 0 to 3, k is 0 to 3, i + j + k = 3 .)
(6) A molded article comprising the polyketone according to (1).

  The polyketone of the present invention has high thermal stability. Therefore, it can be processed by a melt molding method, is excellent in productivity, and has a low molding cost. Specific applications can be expanded to various applications such as gears, gasoline tanks, high-strength films, concrete reinforcements, and electronic material bases due to their high gas barrier properties and mechanical and thermal characteristics.

Hereinafter, the present invention will be described in detail.
The polyketone in the present invention refers to a ketone polymer having a structure in which an ethylenically unsaturated compound and carbon monoxide are bonded side by side.
The polyketone of the present invention has at least one molecule including a silicon-containing structure represented by the chemical formula (1) in the polymer molecule. The polyketone of the present invention has a low melting point and low crystallinity as compared with conventional ECO. These features are the effects of the contained silicon compound, but the theoretical interpretation has not been made sufficiently. In general, when lowering the melting point of a polymer, polymers having different melting points are mixed (melting point drop), but even when a very small amount of silicon compound used in the present invention (one molecule / one molecular chain) is present, a surprising melting point drop Is recognized. Originally, in order to reduce the crystallinity of the polyketone, means such as changing the molecular structure, that is, copolymerizing the amorphous component or randomizing the regularity in the molecule are taken. This silicon compound-containing polyketone retains the complete alternation of carbon monoxide and ethylene.

Thus, the theoretical interpretation of lowering the melting point and lowering the crystallization of a polymer by containing a small amount of a silicon compound cannot be imagined by conventional techniques.
According to the present invention, the molding temperature of the polyketone can be lowered by lowering the melting point while maintaining the polyketone structure. So far, polyketone cannot be melt-molded because its melting point is close to the thermal degradation temperature at which decomposition, thermal crosslinking, etc. occur. Therefore, in order to mold, solvents such as hexafluoroisopropanol, cresol, zinc chloride concentrated aqueous solution, etc. It was necessary to dissolve using
Since the polyketone of the present invention has a silicon element-containing group in the polyketone structure, the melting point of the polyketone is lowered. Therefore, the melting temperature can be lowered, and stabilization during molding can be obtained. As a result, EPCO achieves only a decrease in melting point without causing thermal degradation due to the large amount of tertiary hydrogen inherent in EPCO. Therefore, thermal stability at the time of melting is increased, and molding without using a solvent or the like is possible. Became.

This lowering of the melting point is obtained by a very small amount of silicon-containing group. Surprisingly, even if one atom of silicon element is bonded per one polyketone polymer molecular chain, the effect is exhibited. Since the amount of the silicon element-containing group in the molecule is extremely small, it is possible to retain the characteristics inherent to the polyketone, such as thermal and mechanical properties and chemical resistance, and to impart only melt stability. This is completely unimaginable from conventional knowledge.
The polyketone of the present invention is a polyketone composed of a copolymer of an ethylenically unsaturated compound and carbon monoxide, and includes a structure represented by the chemical formula (1) in the molecule.

(Wherein R ¹ is an atomic group composed of an element selected from hydrogen, a typical element, a halogen element, Si, P, and S, X ¹ is a reactive group, or hydrogen having a reactive group, a typical element, An atomic group composed of an element selected from a halogen element, Si, P, and S, Y ¹ is a compound represented by chemical formulas (2) to (5), and four repeating units represented by chemical formula (2) 0.01 to 100 mol %, Chemical formula (3) 0 to 99.99 mol%, chemical formula (4) 0 to 50 mol%, and chemical formula (5) in the range of 0 to 33 mol%. When a plurality of R ¹ , X ¹ and Y ¹ are present, they may be the same or different, m is 0 to 3, n is 0 to 3, p is 0 to 3, and m + n + p = 3. )

(Wherein R ^{2 to} R ⁶ may be the same or different, and an atomic group composed of an element selected from hydrogen, a typical element, a halogen element, Si, P, and S, X ² is a reactive group, or An atomic group composed of hydrogen having a reactive group, typical element, halogen element, Si, P, and S, i is 0 to 3, j is 0 to 3, k is 0 to 3, i + j + k = 3)
90% by weight or more of the polyketone of the present invention preferably has at least one chemical structure selected from chemical formulas (6) to (8).

（式中、R^ａは水素、典型元素、ハロゲン元素、Ｓｉ、Ｐ、およびＳから選ばれる元素により構成される原子団を表す。）

(Wherein, R ^a represents hydrogen, typical elements, halogen elements, Si, P, and atomic group composed of element selected from S.)

(In the formula, R ^b and R ^c in the chemical formula (7) represent atomic groups composed of an element selected from hydrogen, a typical element, a halogen element, Si, P, and S, which may be the same or different. When either or both of M and N in the chemical formulas (7) and (8) are a silicon element-containing group represented by the chemical formula (1) and not a silicon element-containing group represented by the chemical formula (1) Represents an atomic group composed of an element selected from hydrogen, a typical element, a halogen element, Si, P, and S. M and N may be the same or different.

(Wherein R ¹ is an atomic group composed of an element selected from hydrogen, a typical element, a halogen element, Si, P, and S, X ¹ is a reactive group, or hydrogen having a reactive group, a typical element, An atomic group composed of an element selected from a halogen element, Si, P, and S, Y ¹ is a compound represented by chemical formulas (2) to (5), and four repeating units represented by chemical formula (2) 0.01 to 100 mol %, Chemical formula (3) 0 to 99.99 mol%, chemical formula (4) 0 to 50 mol%, and chemical formula (5) in the range of 0 to 33 mol%. When a plurality of R ¹ , X ¹ and Y ¹ are present, they may be the same or different, m is 0 to 3, n is 0 to 3, p is 0 to 3, and m + n + p = 3. )

(Wherein R ^{2 to} R ⁶ may be the same or different, and an atomic group composed of an element selected from hydrogen, a typical element, a halogen element, Si, P, and S, X ² is a reactive group, or An atomic group composed of hydrogen having a reactive group, typical element, halogen element, Si, P, and S, i is 0 to 3, j is 0 to 3, k is 0 to 3, i + j + k = 3)
Chemical formulas (6) to (8) are repeating units, but only one unit may be present in the polymer chain. Further, chemical formulas (6) to (8) may be combined in any manner. Chemical formulas (7) and (8) which are silicon element-containing repeating units may be in the chain of the polymer chain or at the end. It may be an alternating copolymer composed of two arbitrary types, or a random copolymer or a block copolymer. Furthermore, from the viewpoint of maintaining the original characteristics of the polyketone, it is preferable that the chemical formulas (7) and (8) exist at the terminal. Here, when the repeating units of the chemical formulas (6) to (8) do not have adjacent units bonded, the adjacent bonds are H, a hydroxyl group, a hydrocarbon structure having 1 to 20 carbon atoms, an alkoxyl group (-OR : R is an organic group having 1 to 20 carbon atoms), COOH or the like.

The silicon element-containing structure represented by the chemical formulas (1) to (5) contained in the polyketone of the present invention can be selected from various structures. In the above formula, R ^{1 to} R ⁶ are an atomic group composed of an element selected from hydrogen, a typical element, a halogen element, Si, P, and S. Here, the typical element is a chemical dictionary This means seven elements of Li, Be, B, C, N, O and F according to the edition No. 32 (Kyoritsu Shuppan 1989).
Specific examples of R ^{1 to} R ⁶ include hydrocarbon groups such as H, hydroxy, methyl, methoxy, ethyl, ethoxy, propyl, propoxy, butyl, cyclohexyl, hexyl, octyl, phenyl, benzyl, naphthyl, and alkoxy hydrocarbons. Groups, and substituted hydrocarbon groups and substituted alkoxy hydrocarbon groups in which any part thereof is substituted with a functional group containing a typical element or a halogen element.

These structures may be branched or linear. From the viewpoint of thermal stability of the resulting polyketone polymer, methyl, ethyl, methoxy and ethoxy structures are preferable, hydroxy and methoxy are preferable from the viewpoint of yield, and methoxy group and ethoxy group are preferable from the viewpoint of production cost. . Most preferred is methoxy.
Examples of X ¹ and X ² include methyl acrylate group, acrylate group, epoxy group (glycidyl group), amino group, hydroxyamino group, vinyl group, acetylene group, carbonyl group, dicarbonyl group, acid anhydride group, aldehyde group Reactive groups such as isocyanate groups, mercapto groups, alkyl mercapto groups, chloro groups, bromo groups, fluoro groups, iodo groups, formamide groups, acetamide groups, cyano groups, amide groups, imide groups, hydroxyl groups, oxazoline groups, and the like And substituted alkyl, substituted alkenyl groups and the like in which the above group is substituted with a hydrocarbon group.

  Specific silicon element-containing groups include, for example, trimethylsilane group, trimethoxysilane group, triethylsilane group, trifluoromethyldimethylsilane group, triethoxysilane group, methoxydimethylsilane group, tetramethyldisiloxane group, pentamethyl Diryloxane group, phenylmethylsilane group, trimethylsiloxydimethylcarbinol group, methylbis (trimethylsiloxy) silane group, vinyltetramethyldisiloxane group, vinyltetramethyldisilane group, allyldimethylsilane group, allyldimethoxysilane group, allyltrimethyl Silane group, allyltrimethoxysilane group, triethylsilanol group, t-butyldimethylsilanol group, triphenylsilanol group, tris (trimethylsiloxy) silanol group, polysiloxane, etc. Group or a hydroxyl group, a carboxyl group, a methacryloxy group, various silicon compounds containing a structure of an aryl group.

Y ¹ has four repeating units represented by chemical formulas (2) to (5), chemical formula (2) 0.01 to 100 mol%, chemical formula (3) 0 to 99.99 mol%, chemical formula (4) It is a silicon element-containing group connected in an amount of 1 to 10000 in a range of 0 to 50 mol% and chemical formula (5) from 0 to 33 mol%. The four repeating units can be arbitrarily connected to the —O—Si—O— bond basis. That is, when chemical formula (3) is connected, a straight structure is formed with -O-Si-O-Si-O-, and when chemical formulas (4) and (5) are connected, a branched structure is obtained. Chemical formula (2) is a terminal structure.
In the polyketone of the present invention, the amount of the silicon element-containing group is not limited, but the molar ratio of (silicon element-containing group) / (ethylenically unsaturated compound) is preferably 0.00001 or more and 10 or less. The effect of the present invention appears when a very small amount of silicon compound reacts, but if it is less than 0.00001, a sufficient effect cannot be obtained. If the silicon compound reacts too much, the polyketone may not fully exhibit the mechanical and thermal properties inherently possessed, and is preferably 10 or less. More preferably, it is 0.0001 or more and 1 or less, and most preferably 0.0005 or more and 0.1 or less.

The content of elemental silicon is not limited, but the weight percent of (silicon weight) / (total polyketone weight) × 100 is preferably 50 wt% or less, more preferably 20 wt%, still more preferably 5 wt%. Most preferably, it is 1% by weight or less.
The intrinsic viscosity of the polyketone of the present invention is 0.1 or more and 20 dl / g or less. When the intrinsic viscosity is less than 0.1 dl / g, the characteristics of the polyketone are not exhibited. Moreover, when it exceeds 20 dl / g, workability and productivity will fall and cost will increase. From the physical properties of the polyketone and the process passability, it is more preferably 0.5 to 15 dl / g.
There is no restriction | limiting in the property of the polyketone of this invention, What kind of form may be sufficient. It may be liquid at normal temperature and pressure.

When the polyketone of the present invention has a melting point, the melting point can be designed depending on the degree of polymerization of the polyketone and the content of silicon element. Although there is no restriction | limiting in melting | fusing point, it is preferable that it exists in the range of 150 to 260 degreeC. In order to use it as a high-performance engineering resin also in a heat-resistant region, it is more preferable that the melting point is in the range of 180 ° C to 245 ° C. From the viewpoint of stability at the time of melting, the melting point is most preferably in the range of 200 ° C to 240 ° C.
When the polyketone of the present invention is crystalline, the degree of crystallinity is not limited, but is preferably 15% or more, more preferably 30% or more from the viewpoint of excellent heat resistance, chemical resistance and mechanical properties. Most preferred is 40% or more.

  As the repeating unit of the polyketone of the present invention, various ethylenically unsaturated compounds can be used as shown in the chemical formula (6), but it is preferable that the repeating unit is substantially only ethylene.

(Wherein, R ^a represents hydrogen, typical elements, halogen elements, Si, P, and atomic group composed of element selected from S.)
That is, it is preferably a complete alternating copolymer structure (1-oxotrimethylene structure) of ethylene and carbon monoxide represented by chemical formula (11).

An ethylenically unsaturated compound having a substituent such as propylene may generate tertiary hydrogen in the polyketone and impair the thermal stability. It also tends to disrupt the crystal system and reduce mechanical, thermal and heat resistance. Therefore, the 1-oxotrimethylene structure in the polyketone is preferably 90 mol% or more, more preferably 95 mol% or more, and most preferably substantially 100%.
There is no restriction | limiting in repeating units other than 1-oxo trimethylene, For example, ethylenically unsaturated compounds other than carbon monoxide and ethylene can be used.
Examples of the ethylenically unsaturated compound include α-olefins such as propylene, 1-butene, 1-hexene, 1-octene and 1-decene, alkenyl aromatic compounds such as styrene and α-methylstyrene, cyclopentene, norbornene, 5- Mention may be made of cyclic olefins such as methylnorbornene, tetracyclododecene, tricyclodecene, pentacyclopentadecene and pentacyclohexadecene, vinyl halides such as vinyl chloride; acrylic esters such as ethyl acrylate and methyl methacrylate. These repeating units derived from carbon monoxide and the ethylenically unsaturated compound may be a single type or a mixture of plural types.

  Moreover, you may have structures other than a repeating unit in the range below 10 weight%. For example, alkoxy structure such as hydroxy group, methoxy group, ethoxy group, propoxy group and isopropoxy group, vinyl structure such as ethylene group and propylene group, furan ring structure, polyolefin structure such as polyethylene, and polyalkyl ether structure such as polyethylene glycol , Polyacrylonitrile structure, polyamide structure such as polyamide 6, polyester structure such as polyethylene terephthalate, polysulfone structure, polysulfide structure, polycarbonate structure, polymethacrylate, polyacetal, polyvinyl alcohol, polyvinyl chloride, polyvinyl chloride, polyvinyl acetate, etc. polar vinyl structure, cellulose And saccharides, and the like. These may be a single species or a plurality of species may be present.

The production method of the polyketone of the present invention is not limited, but it is desired that the polyketone reacts with a silicon compound more efficiently with high polymerization activity from the viewpoint of industrially efficient production with a simple process. A preferable production method will be described below.
The polyketone of the present invention is obtained by reacting carbon monoxide with an ethylenically unsaturated compound in the presence of a specific silicon compound. The most important point in the present invention is to add a silicon compound into the polymerization system.
The silicon compound added to the system may be any substance as long as the structure of the chemical formula (1) shown above can be included in the polyketone, and is preferably a compound represented by the chemical formula (9). is there.

(Wherein R ¹ is an atomic group composed of an element selected from hydrogen, a typical element, a halogen element, Si, P, and S, X ¹ is a reactive group, or hydrogen having a reactive group, a typical element, An atomic group composed of an element selected from a halogen element, Si, P, and S, Y ¹ is a compound represented by chemical formulas (2) to (5), and four repeating units represented by chemical formula (2) 0.01 to 100 mol %, Chemical formula (3) 0 to 99.99 mol%, chemical formula (4) 0 to 50 mol%, and chemical formula (5) in the range of 0 to 33 mol%. R ¹ , X ¹ , and Y ¹ may be the same or different when a plurality of R ¹ , X ¹ , and Y ¹ are present, m is 0 to 4, n is 0 to 4, p is 0 to 4, and m + n + p = 4. )

（式中、Ｒ^２〜Ｒ^６は同じでも異なってもよく、水素、典型元素、ハロゲン元素、Ｓｉ、Ｐ、およびＳから選ばれる元素により構成される原子団を示す。）

(In the formula, R ^{2 to} R ⁶ may be the same or different and represent an atomic group composed of an element selected from hydrogen, a typical element, a halogen element, Si, P, and S.)

R ^{1 to} R ⁶ are atomic groups composed of an element selected from hydrogen, a typical element, a halogen element, Si, P, and S. Here, the typical element means seven elements of Li, Be, B, C, N, O, and F according to the Chemical Dictionary, the 32nd edition (Kyoritsu Shuppan 1989).
Specific examples of R ^{1 to} R ⁶ include hydrocarbon groups such as H, hydroxy, methyl, methoxy, ethyl, ethoxy, propyl, propoxy, butyl, cyclohexyl, hexyl, octyl, phenyl, benzyl, naphthyl, and alkoxy hydrocarbons. Groups, and substituted hydrocarbon groups and substituted alkoxy hydrocarbon groups in which any part thereof is substituted with a functional group containing a typical element or a halogen element.

These structures may be branched or linear. From the viewpoint of thermal stability of the resulting polyketone polymer, methyl, ethyl, methoxy and ethoxy structures are preferable, hydroxy and methoxy are preferable from the viewpoint of yield, and methoxy group and ethoxy group are preferable from the viewpoint of production cost. . Most preferred is methoxy.
Examples of X ¹ and X ² include methyl acrylate group, acrylate group, epoxy group (glycidyl group), amino group, hydroxyamino group, vinyl group, acetylene group, carbonyl group, dicarbonyl group, acid anhydride group, aldehyde group Reactive groups such as isocyanate groups, mercapto groups, alkyl mercapto groups, chloro groups, bromo groups, fluoro groups, iodo groups, formamide groups, acetamide groups, cyano groups, amide groups, imide groups, hydroxyl groups, oxazoline groups, and the like And substituted alkyl, substituted alkenyl groups and the like in which the above group is substituted with a hydrocarbon group.

  Specific silicon compounds include, for example, trimethylvinylsilane, trimethoxyvinylsilane, triethylvinylsilane, vinyl (trifluoromethyl) dimethylsilane, triethoxyvinylsilane, methoxydimethylvinylsilane, vinyltetramethyldisiloxane, vinylpentamethyldisiloxane, Vinylphenylmethylsilane, trimethylsiloxyvinyldimethylcarbinol, vinylmethylbis (trimethylsiloxy) silane, 1,3-divinyltetramethyldisiloxane, divinyltetramethyldisilane, allyldimethylsilane, allyldimethoxysilane, allyltrimethylsilane, allyltri Methoxysilane, triethylsilanol, t-butyldimethylsilanol, triphenylsilanol, tris (trimethylsiloxy) Other silane compounds such as silanol, modified silicone polysiloxane can also be used.

The polysiloxane modified silicone is specifically a polysiloxane modified compound represented by the following chemical formula.
(R ^p R ^q SiO _2/2 ) _D · (R ^r R ^S R ^t SiO _1/2 ) _M · (R ^u SiO _3/2 ) _T · (SiO _4/2 ) _Q
In the formula, D / (M + D + T + Q) = 0.1-1, M / (M + D + T + Q) = 0-0.5, T / (M + D + T + Q) = 0-0.8, Q / (M + D + T + Q) = 0-0.5 It is. More preferably, D / (M + D + T + Q) = 0.5-1, M / (M + D + T + Q) = 0-0.1, T / (M + D + T + Q) = 0-0.4, Q / (M + D + T + Q) = 0-0.1. It is. The preferred viscosity of these polysiloxanes is 0.1 to 10,000,000 cSt at 25 ° C.

R ^{p to} R ^q may be the same or different and are selected from the following. These selection methods are based on the same unit, for example, (R ^p R ^q SiO _2/2 ) _D structural unit, for example, when R ^p is a methyl group, R ^q has no effect on the structure of R ^p. Various things can be selected. That is, it does not preclude the simultaneous selection of three groups of methyl, phenyl and hydrogen. Further, the structure for connecting the units may be different from each unit structure.
Examples of R ^{p to} R ^q are linear or branched alkyl groups having 1 to 20 carbon atoms, alkenyl groups and halogen substituted products thereof, cycloalkyl groups having 5 to 25 carbon atoms or cycloalkenyl groups and halogen substituted substituents thereof. , Aralkyl group or aryl group having 6 to 25 carbon atoms and halogen-substituted product thereof, hydrogen, hydroxyl group, alkoxy group, halogen group, acyloxy group, ketoximate group, amino group, amide group, aminoxy group, mercapto group, alkenyloxy A group, an acid anhydride group, a carbonyl group, a saccharide, a cyano group, an oxazoline group, an isocyanato group, etc. and / or a hydrocarbon substituent of these groups.

  Preferable examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tertiary butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, isohexyl group, heptyl group, isoheptyl group. Straight chain or branched alkyl groups such as octyl group, isooctyl group, nonyl group, decyl group and the like, and halogen substituted products thereof, alkenyl groups such as vinyl group, allyl group, homoallyl group, cyclopentyl group, cyclohexyl group, cyclohex A cycloalkyl group such as a butyl group, a cyclooctyl group, a dicyclopentyl group, a decahydronaphthyl group, and a halogen substituent thereof, a cyclopentenyl group (1- and 2-, 3-), a cyclohexenyl group (1- and 2-, 3-) cycloalkenyl group, phenyl group, naphthyl group Aralkyl groups and aryl groups such as tetrahydronaphthyl group, tolyl group, ethylphenyl group and their halogen substitution products, hydrogen, hydroxyl group, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, tertiary Butoxy, hexyloxy, isohexyloxy, 2-hexyloxy, octyloxy, isooctyloxy, 2-octyloxy, fluoro, chloro, bromo, iodo, acetoxy, dimethylketoxime, methylethylketoxime, amino Group, hydroxyamino group, dimethylamino group, diethylamino group, formamide group, acetamide group, aminooxy group, mercapto group, methyl mercapto group, ethyl mercapto group, glycidyl group, etc. .

The polysiloxane of the present invention can be produced by a known method in the industry as found in a silicone handbook (Nikkan Kogyo Shimbun, 1990).
The modified silicone is obtained by substituting an arbitrary part of the polysiloxane with various functional groups.
Examples of functional groups include vinyl groups, hydroxyl groups, ether groups, polyether groups, carboxyl groups, methacryloxy groups, polymethacryloxy groups, and aryl groups. Among these, a polyether group is preferable. Examples of the polyether group include an oxyethylene group (—CH ₂ CH ₂ —O—), an oxypropylene group (—O—CH (CH ₃ ) CH ₂ —), and the like. Specific examples include ethylene glycoloxy group, diethyleneglycoxy group, polyethyleneglycoxy group, propyleneglycoxy group, dipropyleneglycoxy group, polypropyleneglycoxy group, polyoxyethylene-polyoxypropylene copolymer group, methoxyethyleneglycoxy Group, ethoxyethyleneglycoxy group, methoxydiethyleneglycoxy group, ethoxydiethyleneglycoxy group, methoxypropyleneglycoxy group, methoxydipropyleneglycoxy group, ethoxydipropyleneglycoxy group, and the like. Among these, a polyethyleneglycoxy group, a polypropyleneglycoxy group, and a polyoxyethylene-polyoxypropylene copolymer group are preferable.

In the present invention, various silicon compounds can be used as described above. However, a compound having a chlorosilane structure may easily react in the polymerization system to generate HCl, resulting in a decrease in polymerization activity.
A silicon compound may be used independently and may mix and use 2 or more types of compounds simultaneously. There is no restriction | limiting in the usage-amount of a silicon compound. Moreover, compounds other than silicon compounds may be added to the reaction system. Examples of compounds other than silicon compounds include water, hydroxyl group-containing compounds having 1 to 10 carbon atoms, and specifically, methanol, ethanol, propanol, butanol, hexafluoroisopropanol, ethylene glycol. Examples of the alcohols include phenols such as m-cresol.

Examples of aprotic compounds include hydrocarbons having 3 to 20 carbon atoms, ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether, tetrahydrofuran and diglyme; nitriles such as acetonitrile; esters such as methyl acetate; Examples include butyrolactone and N-methylpyrrolidone.
From the viewpoint of polymerization activity, a protic compound is preferable, and water, methanol, ethanol, propanol, and isopropanol are preferable. From the viewpoint that the molecular weight of the resulting polyketone can be increased, aprotic compounds are preferred, and hexane and acetone are used. From the viewpoint of efficiently reacting the silicon compound, toluene, hexane, octane and the like are preferable. Although there is no restriction | limiting in these quantities, The quantity mixed with a silicon compound uniformly is preferable.

Protic and aprotic compounds may be used alone, but two or more compounds selected from these compounds may be used simultaneously.
In producing the polyketone of the present invention, a silicon compound is polymerized in a reaction vessel such as an autoclave in the presence of an ethylenically unsaturated compound and carbon monoxide under the following conditions.
The polymerization temperature is preferably 50 to 300 ° C, more preferably 70 to 200 ° C. When the polymerization temperature is less than 50 ° C., the reaction with the silicon compound may be difficult. When the polymerization temperature exceeds 300 ° C., the polymerization activity is high and the productivity is high, but the molecular weight of the resulting polyketone is low, and the mechanical / thermal properties may not be exhibited.

Various ethylenically unsaturated compounds can be used simultaneously with carbon monoxide. For example, α-olefin such as ethylene, propylene, 1-butene, 1-hexene, 1-octene and 1-decene, alkenyl aromatic compounds such as styrene and α-methylstyrene, cyclopentene, norbornene, 5-methylnorbornene, tetra Examples thereof include cyclic olefins such as cyclododecene, tricyclodecene, pentacyclopentadecene and pentacyclohexadecene, vinyl halides such as vinyl chloride; acrylic acid esters such as ethyl acrylate and methyl methacrylate, and vinyl acetate.
These repeating units derived from carbon monoxide and the ethylenically unsaturated compound may be a single type or a mixture of plural types. Of these, ethylene is preferred because of the characteristics of the polyketone obtained.

The ratio of carbon monoxide and ethylenically unsaturated compound in the reaction vessel is preferably such that the molar ratio of (carbon monoxide / ethylenically unsaturated compound) is 10/1 to 1/10, more preferably 5 / 1 to 1/5. There is no restriction | limiting in the addition method of carbon monoxide and an ethylenically unsaturated compound, You may add after mixing both beforehand, and may add from a separate supply line, respectively.
The polyketone of the present invention may be reacted in the presence of a catalyst under the above conditions. As the catalyst, an organometallic complex catalyst or a radical initiator is used.
The organometallic complex catalyst has (a) a Group 9, 10 or 11 transition metal compound of the periodic table (IUPAC Inorganic Chemical Nomenclature Revised Edition, 1989), and (b) a Group 15 atom. It consists of a ligand. Furthermore, an anion of (c) acid may be added thereto as a third component.

Examples of Group 9 transition metal compounds in component (a) include cobalt or ruthenium complexes, carboxylates, phosphates, carbamates, sulfonates, and the like. Examples thereof include cobalt acetate, cobalt acetyl acetate, ruthenium acetate, ruthenium trifluoroacetate, ruthenium acetyl acetate, and ruthenium trifluoromethanesulfonate.
Examples of Group 10 transition metal compounds include nickel or palladium complexes, carboxylates, phosphates, carbamates, sulfonates, etc., and specific examples thereof include nickel acetate, nickel acetylacetate. Nate, palladium acetate, palladium trifluoroacetate, palladium acetylacetonate, palladium chloride, bis (N, N-diethylcarbamate) bis (diethylamino) palladium, palladium sulfate and the like.

Examples of Group 11 transition metal compounds include copper or silver complexes, carboxylates, phosphates, carbamates, sulfonates, etc., and specific examples thereof include copper acetate, trifluoro Examples thereof include copper acetate, copper acetylacetonate, silver acetate, silver trifluoroacetate, silver acetylacetonate, and silver trifluoromethanesulfonate.
Among these, inexpensive and economically preferable transition metal compounds (a) are nickel and copper compounds, and transition metal compounds (a) preferable in terms of the yield and molecular weight of the polyketone are palladium compounds. These may be used alone or in combination of several kinds.

  Ligand is the 7th edition of the Chemical Dictionary 7th edition (1974) Kyoritsu Shuppan p. As defined in 4, it is an atomic group containing an atom directly bonded to a central atom in a complex. In the present invention, a ligand having an atom of Group 15 of the periodic table is used. Examples include monodentate ligands of nitrogen such as pyridine; phosphorus monodentate ligands such as triphenylphosphine and trinaphthylphosphine; arsenic monodentate ligands such as triphenylarsine; antimony monodentate coordination such as triphenylantimony Nitrogen bidentate ligands such as 2,2′-bipyridyl, 4,4′-dimethyl-2,2′-bipyridyl, 2,2′-bi-4-picoline, 2,2′-biquinoline; 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,3-bis {di (2-methyl) phosphino} Propane, 1,3-bis {di (2-isopropyl) phosphino} propane, 1,3-bis {di (2-methoxyphenyl) phosphino} propane, 1,3-bis {di (2-meth) Sodium cis-4-sulfonate-phenyl) phosphino} propane, 1,2-bis (diphenylphosphino) cyclohexane, 1,2-bis (diphenylphosphino) benzene, 1,2-bis {(diphenylphosphino) methyl } Benzene, 1,2-bis [{di (2-methoxyphenyl) phosphino} methyl] benzene, 1,2-bis [{sodium di (2-methoxy-4-sulfonate) -phenyl) phosphino} methyl] benzene, 1,1′-bis (diphenylphosphino) ferrocene, 2-hydroxy-1,3-bis {di (2-methoxyphenyl) phosphino} propane, 2,2-dimethyl-1,3-bis {di (2- And phosphorous bidentate ligands such as methoxyphenyl) phosphino} propane. These may be used alone or in combination of two or more.

  Among these, preferred ligands are phosphorus bidentate ligands. In particular, from the viewpoint of reactivity with silicon compounds and yield of polyketone, preferred phosphorus ligands are 1,3-bis (diphenylphosphino) propane and 1,3-bis {di (2-methoxyphenyl) phosphino}. Propane, and 1,2-bis [{di (2-methoxyphenyl) phosphino} methyl] benzene. From the aspect of improving the molecular weight of the polyketone, 2-hydroxy-1,3-bis {di (2-methoxyphenyl) phosphino} propane and 2,2-dimethyl-1,3-bis {di (2-methoxy) Phenyl) phosphino} propane. In terms of safety without the need for organic solvents, water-soluble 1,3-bis {di (sodium 2-methoxy-4-sulfonate) -phosphino} propane, and 1,2-bis [{di (2-Methoxy-4-sulfonic acid sodium-phenyl) phosphino} methyl] benzene is preferred. 1,3-bis (diphenylphosphino) propane and 1,4-bis (diphenylphosphino) butane are preferred because they are easy to synthesize and available in large quantities and are economically preferable.

As a catalyst for the polyketone of the present invention, in addition to the above (a) and (b), (c) an anion of an acid may be added. Examples include anions of organic acids having a pKa of 4 or less, such as trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid; perchloric acid, sulfuric acid, nitric acid, phosphoric acid, heteropolyacid, Anions of inorganic acids having a pKa of 4 or less, such as tetrofluoroboric acid, hexafluorophosphoric acid, fluorosuccinic acid; trispentafluorophenylborane, trisphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilium Mention may be made of anions of boron compounds such as tetrakis (pentafluorophenyl) borate. These can be used alone or in combination. Among these, preferred acid anions are sulfuric acid, methanesulfonic acid, and trifluoromethanesulfonic acid from the viewpoints of both polymer yield and molecular weight. pKa is a numerical value defined by pKa = −log ₁₀ Ka where the acid dissociation constant is Ka, and the smaller the value, the stronger the acid.

The amount of the transition metal compound (a) used as a catalyst varies depending on the type of the ethylenically unsaturated compound or silicon compound selected and the other polymerization conditions, and therefore the range cannot be generally defined. Preferably, it is 0.01-10000 micromol per liter of reaction zone volume, more preferably 0.1-1000 micromol. The capacity of the reaction zone refers to the volume of the liquid phase of the reactor.
Although the usage-amount of a ligand (b) is not restrict | limited, Preferably it is 0.1-10 mol with respect to 1 mol of transition metal compounds, More preferably, it is 1-5 mol.
The amount of the acid anion (c) used is preferably 0.1 to 1000 mol, more preferably 1 to 100 mol, and most preferably 3 to 10 mol per mol of the palladium compound.

The catalyst is formed by mixing a transition metal compound and a ligand having atoms of Group 15 elements of the periodic table, more preferably an anion of an acid.
Although there is no restriction | limiting about the usage method of a catalyst composition, It is preferable to prepare in the reaction container after preparing the catalyst composition which consists of a mixture of each component previously. When preparing the catalyst composition, it is preferable to first mix the transition metal compound and the ligand, and then mix the acid.
The solvent used for the preparation of the catalyst composition may be an aprotic organic solvent such as alcohol, acetone, methyl ethyl ketone and the like. Moreover, you may add oxidizing agents, such as a benzoquinone and a naphthoquinone, to the catalyst which consists of said 3 component of (a) (b) and (c). The addition amount of these quinones is preferably 1 to 1000 mol, more preferably 10 to 200 mol, per 1 mol of the transition metal compound. Addition of quinones may be either a method of adding to the catalyst composition and then adding to the reaction vessel, or a method of adding to the polymerization solvent, and if necessary, continuously into the reaction vessel during the reaction. It may be added.

On the other hand, when a radical initiator is used as a catalyst, a peroxydicarbonate, peroxyester, diacyl peroxide, or azo initiator can be used. Here, each system includes a monoradical initiator containing one —O—O— bond or —N═N— bond in one molecule, —O—O— bond or —N═N in one molecule. -A bi-radical initiator containing two bonds, and a polymer initiator containing three or more -O-O- bonds or -N = N- bonds in one molecule are included.
Examples of the monoradical type initiator include di-2-ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, bis- (4-tert-butylcyclohexyl) peroxydicarbonate, and t-butylperoxyisobutyrate. , T-butylperoxypivalate, t-hexylperoxyneohexanoate, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauryl peroxide, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2 ′ -Azobisisobutylnitrile, 2,2'-aozobis (2-cyclopropylpropionitrile), 2,2'-azobis (4-methoxy-2,4'-dimethylvaleronitrile) as biradical initiators Is, for example, (α, α′-bis- Neodecanoylperoxy) diisopropylbenzene, 2,5-dimethyl-2,5-bis (2-ethylhexylperoxy) hexane, 2,5-dimethyl-2,5-bis (neodecanoylperoxy) hexane can be used. As the polymer type initiator, for example, polyperoxydicarbonate represented by the chemical formula (12) can be used.

In the formula, n is a natural number of 3 to 200, preferably 3 to 200, more preferably 3 to 100. When n is less than 3, a polymer having a high degree of polymerization cannot be obtained, and when it exceeds 200, the solubility in a solvent decreases. R ^C is an atomic group composed of an element selected from hydrogen, a typical element, a halogen element, Si, P, and S, and may include an ether group, a carbonate group, an ester bond, a saturated carbocycle, or an aromatic ring. Represents a hydrocarbon group or the like in which both ends having 3 to 50 carbon atoms are primary, secondary or tertiary carbons.
When a radical initiator is used as a catalyst, the diluent includes hydrocarbons such as cyclohexane, hexane, pentane, octane and benzene, carbonates such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate and dibutyl carbonate, tetrahydrofuran, tetrahydropyran, 1 , 4-dioxane, 1,3-dioxane, cyclic ethers such as 1,3-dioxolane, and one or more ethers such as diethyl ether, dipropyl ether, and dibutyl ether can be used. Among these, preferred polymerization diluents are dimethyl carbonate, diethyl carbonate, and 1,4-dioxane.

It is possible to increase the content of elemental silicon in the polyketone of the present invention. Similar to the generally known silicone production method, the content of elemental silicon can be increased by introducing an organopolysiloxane structure into the polyketone by the hydrolysis reaction of an already synthesized polyketone and an organohalogen silane or organoalkoxysilane. it can.
Examples of the organohalogen silane used in the hydrolysis reaction include trialkylmonohalogen silane compounds such as trimethylmonochlorosilane, trimethylmonobromosilane, triethylmonochlorosilane, tripropylmonochlorosilane, dimethyldichlorosilane, dimethyldibromosilane, and diethyl. Examples thereof include dialkyldihalogen silane compounds such as dichlorosilane, and alkyltrihalogen silane compounds such as methyltrichlorosilane, methyltribromosilane, and ethyltrichlorosilane.

Examples of the organoalkoxysilane include trialkylmonoalkoxysilane compounds such as trimethylmonohydroxysilane, trimethylmonomethoxysilane, trimethylmonoethoxysilane, triethylmonomethoxysilane, and tripropylmonomethoxysilane, dimethyldihydroxysilane, and dimethyldimethoxysilane. And dialkyldialkoxysilane compounds such as dimethyldiethoxysilane and diethyldimethoxysilane, and alkyltrialkoxysilane compounds such as methyltrihydroxysilane, methyltrimethoxysilane, methyltriethoxysilane, and ethyltrimethoxysilane.
This reaction proceeds with moisture in the air at room temperature, but a small amount of water, acid or alkali may be added. Moreover, you may heat and may use tin catalysts, such as di-n-lauryl dibutyl tin.

  The polymerization time for producing the polyketone is preferably 1 to 24 hours, more preferably 1.5 to 10 hours, and most preferably 2 to 6 hours. When the polymerization time is less than 1 hour, the amount of residual catalyst increases, and a special catalyst removal step may be required. On the other hand, when the polymerization time exceeds 24 hours, the molecular weight dispersion of the resulting polyketone is widened, and it may be impossible to exhibit excellent mechanical and thermal characteristics. In the present invention, the polymerization time refers to the time when carbon monoxide and an ethylenically unsaturated compound are introduced into a reaction vessel in which the catalyst composition, the additive, and the polymerization solvent are present, and the polymerization conditions are as described above. It means the time until a point at which a polymerization reaction does not substantially occur such as lowering the temperature or releasing the internal pressure. In the continuous polymerization method in which carbon monoxide and the ethylenically unsaturated compound are continuously charged into the reaction vessel and the polymerization product is continuously extracted, the average residence time from the addition to the extraction is defined as the polymerization time.

The production method of the polyketone of the present invention desirably has high polymerization activity from the viewpoint of producing the polyketone at an industrial cost. The polymerization activity is a numerical value calculated by the following formula when a transition metal compound is used, and the larger the value, the more polyketone obtained per unit metal amount and unit polymerization time, that is, the same amount. This means that the amount of catalyst required to obtain the polyketone is small and the time required for polymerization is short.
Polymerization activity (kg / g-M · hr) =
Polyketone yield (kg) / [M amount (g) × polymerization time (hr)] (M is metal)
Even if the polymerization activity is low, the amount of residual catalyst in the polyketone can be reduced by increasing the polymerization time. However, if the polymerization time is increased, a large amount of oxidant is required to suppress catalyst deactivation. And the resulting polyketone has an increased molecular weight dispersibility. Therefore, the polymerization activity is preferably 5 kg / g-M · hr or more. From the viewpoint of productivity and the cost of the catalyst used for the obtained raw material, the polymerization activity is more preferably 10 kg / g-M · hr or more, and most preferably 20 kg / g-M · hr or more.

It is preferable to produce a polyketone with a small amount of residual catalyst only through the polymerization step without passing through the steps of washing and removing the catalyst. In this case, the polymerization activity (kg / g-M · hr) and the polymerization time (hr) The catalyst efficiency (kg / g-M) expressed by the product of is preferably 20 kg / g-M or more. The higher the catalyst efficiency, the smaller the amount of residual catalyst in the polyketone, so the catalyst efficiency is more preferably 40 or more, and most preferably 50 or more.
There is no restriction | limiting in the polymerization system of the polyketone of this invention, A well-known polymerization system and a manufacturing process can be used. For example, as a polymerization method, a suspension polymerization method using a liquid medium, a gas phase polymerization method in which a small amount of polymer is impregnated with a high concentration catalyst solution, a solid phase polymerization method, or the like is used. Any of continuous processes may be used.

Carbon monoxide and ethylene may be supplied to either the gas phase portion or the liquid phase portion of the reaction vessel, but they may be supplied into the liquid phase from the viewpoint of uniformity of polymerization and solubility in the polymerization solvent. preferable.
The reaction vessel may be an autoclave type, a tubular type, or the like. The inner wall of the reaction vessel is preferably subjected to a surface treatment such as glass lining, Teflon (registered trademark) lining, or electrolytic polishing. When using an autoclave type reaction vessel, a plurality of reaction vessels may be connected in series to carry out polymerization in two or more stages.
The catalyst composition is prepared in advance in a catalyst preparation device and continuously fed into the reaction vessel at the start of polymerization or during the polymerization time.

In the polyketone, the transition metal compound, phosphorus compound, acid and the like used for the polymerization catalyst remain. When the residual amount of these compounds is large, problems such as deterioration and coloring during storage of the polyketone occur, and also there arises problems such as reduction in heat resistance and coloring during molding and molding. For this reason, the amount of transition metal in the polyketone is preferably 20 ppm or less, more preferably 10 ppm or less, and most preferably 0 ppm or less.
The amount of phosphorus element is preferably 20 ppm or less, more preferably 10 ppm, still more preferably 5 ppm or less, and most preferably 0 ppm. When the acid contains a sulfur element such as sulfuric acid, methanesulfonic acid, or trifluoromethanesulfonic acid, the amount of the sulfur element in the polyketone is preferably 20 ppm or less, more preferably 10 ppm or less, still more preferably 5 ppm or less, and most preferably. Is 0 ppm.

The shape of the polyketone according to the present invention is such that when a crystalline polymer is obtained, a polymer having an average particle size of 0.01 to 2 mm is obtained in normal liquid phase polymerization, and a larger particle size is obtained in gas phase or solid phase polymerization. A polymer can be obtained. The bulk density of the polyketone of the present invention is usually in the range of 0.05 to 0.30 g / cm ³ and can be controlled by changing the reaction conditions and the like depending on the application. Although the specific surface area of the polyketone of the present invention varies depending on the solvent used, it is generally in the range of 10 to 30 m ² / g.
For the polyketone of the present invention, various additives, for example, heat stabilizer, antifoaming agent, color adjuster, flame retardant, antioxidant, ultraviolet absorber, infrared absorber, crystal nucleating agent, A surfactant or the like may be contained.

  The polyketone of the present invention is excellent in thermal stability during processing and use, and can be developed in various fields as a molded body. In the present invention, the molded product means a useful artificial product formed by pressure, heat, solvent, or the like. Specific examples include films, pellets, bars, blocks, spheres, cylinders, pans, and multilayer laminates molded by injection molding, melting, solvent dissolution, and the like.

The present invention will be specifically described by way of examples, but they are not intended to limit the scope of the present invention.
The organic solvent used in the examples is a completely dry solvent obtained by further dehydrating what was dehydrated for organic synthesis with magnesium sulfate under a stream of dry nitrogen before polymerization. Distilled water containing no impurities such as metals was used as water. As sulfuric acid, reagent special grade 96 mass% sulfuric acid was used.
The measuring method of each measured value used in the present invention is as follows.

式中、ｔおよびＴは、純度９８％以上のヘキサフルオロイソプロパノールおよびヘキサフルオロイソプロパノールに溶解したポリケトンの希釈溶液の２５℃での粘度管の流下時間、Ｃは上記溶液１００ｍｌ中のグラム単位による溶質質量値である。 (1) Intrinsic viscosity ([η])
Intrinsic viscosity [η] is a value determined by Equation (1).

In the formula, t and T are the flow time of a viscosity tube at 25 ° C. of hexafluoroisopropanol having a purity of 98% or more and a polyketone diluted solution in hexafluoroisopropanol, and C is the solute mass in grams in 100 ml of the above solution. Value.

(2) Element amount in polyketone Each element such as Pd, P and Si is measured by high-frequency plasma emission spectroscopic analysis using a known method.
(3) Melting point (Tm) and crystallinity 5 mg of a sample is sealed in an aluminum pan under a nitrogen atmosphere, and measurement is performed under the following conditions using a differential heat measuring device Pyris 1 (trademark) manufactured by PerkinElmer.
Sample mass: 5mg
Atmosphere: Nitrogen, flow rate = 200 mL / min
Temperature conditions: (a) Hold at 20 ° C. for 1 minute
(B) 20 ° C. → 300 ° C. (Temperature increase rate = 20 ° C./min)
In the endothermic curve observed under the temperature condition (b), the peak top point of the maximum endothermic peak observed in the range of 200 ° C. to 300 ° C. is defined as the melting point (Tm).
In the endothermic curve observed in (b), the calorific value ΔH (J / g) calculated from the area of the maximum endothermic peak observed in the range of 200 ° C. to 300 ° C. is calculated by the following formula.
Crystallinity = ΔH / 225 × 100 (%)

(4) Heat resistance evaluation 5 mg of a sample is sealed in an aluminum pan in a nitrogen atmosphere, and measurement is performed under the following conditions using a differential heat measuring device Pyris 1 (trade name) manufactured by PerkinElmer.
Sample weight: 5mg
Atmosphere: Nitrogen, flow rate = 200 mL / min
Temperature conditions: (I) Hold at 20 ° C for 1 minute
(B) 20 ° C. → Tm + 20 ° C. (Temperature increase rate = 20 ° C./min)
(C) Tm + 20 ° C. → 20 ° C. (Cooling rate = 20 ° C./min)
(D) 20 ° C. → Tm + 20 ° C. (Temperature increase rate = 20 ° C./min)
(E) Hold at Tm + 20 ° C. for 10 minutes
(F) Tm + 20 ° C. → 20 ° C. (Cooling rate = 20 ° C./min)
(G) 20 ° C. → Tm + 20 ° C. (Temperature increase rate = 20 ° C./min)
Measuring the maximum peak top temperature T ₃ of an endothermic peak observed at the end of the heating process of (g). T ₃ and more less heat denaturation of polyketone temperature difference is small in the Tm, excellent heat resistance.
Tm-T ₃ ≦ 10 ° C .: good heat resistance Tm-T ₃ ≦ 20 ° C .: poor heat resistance Tm-T ₃ ≦ 30 ° C .: extremely poor heat resistance

(6) Polymer melt flow stability Polymer flow test: The melt flow index (MI) is measured based on JIS-K-7210 (with a load of 2160 g at 250 ° C.) (first time: MI ₁ ).
After the extruded polymer has cooled to room temperature, the measurement is performed again (second time: MI ₂ ). The smaller the change ratio between the MI ₁ and MI ₂ values, the less heat denaturation during melting of the polyketone and the better the moldability.
MI ₂ / MI ₁ ≦ 0.8: Poor formability (lower fluidity)
0.8 <MI ₂ / MI ₁ <1.05: Good moldability MI ₂ / MI ₁ ≧ 1.05: Poor moldability (thermal decomposition)

[Example 1]
2.5 micromolar palladium acetate, 3.0 micromolar 1,3-bis (diphenylphosphino) propane, 12.5 micromolar sulfuric acid, 25 micromolar 1,4-benzoquinone, 225 ml n-hexane, and trimethoxy 25 ml of vinylsilane was charged into a 500 ml autoclave made of stainless steel with a stirrer purged with nitrogen. After sealing the autoclave, nitrogen substitution was performed three times at 25 ° C. and 2.0 MPa.
The contents were heated with stirring, and when the internal temperature reached 100 ° C., an equimolar mixed gas of carbon monoxide and ethylene was added to 8.0 MPa. Thereafter, an equimolar mixed gas of ethylene and carbon monoxide was continuously supplied, and stirring was continued for 2 hours while maintaining the internal pressure and the internal temperature. After cooling, the gas in the autoclave was purged and the contents were taken out. The reaction solution was filtered, washed 3 times with water and 3 times with isopropanol, and then dried under reduced pressure to obtain 3.5 g of a ketone polymer.
The polymerization activity was 6.6 kg / g-Pd · hr, and [η] was 3.9 dl / g. As a result of analysis of this ketone polymer, the silicon content was 0.05% by weight, the crystallinity was 42%, Tm was 246 ° C., and T3 was 236 ° C., showing good heat resistance.

[Example 2]
The same operation as in Example 1 was carried out except that 225 ml of n-hexane in Example 1 was changed to 225 ml of toluene to obtain 2.8 g of a ketone polymer.
The polymerization activity was 5.3 kg / g-Pd · hr, and [η] was 2.3 dl / g. As a result of analyzing the ketone polymer, the silicon content was 0.06% by weight, the crystallinity was 44%, the Tm was 239 ° C., and the T3 was 230 ° C., showing good heat resistance.

[Example 3]
The same operation as in Example 1 was carried out except that 225 ml of n-hexane in Example 1 was changed to 225 ml of isopropanol to obtain 3.8 g of a ketone polymer.
The polymerization activity was 7.2 kg / g-Pd · hr, and [η] was 1.2 dl / g. As a result of analyzing the ketone polymer, the silicon content was 0.2% by weight, the crystallinity was 33%, Tm was 222 ° C., and T3 was 213 ° C., which showed good heat resistance.

[Example 4]
In Example 1, 225 ml of n-hexane and 25 ml of trimethoxyvinylsilane were changed to 75 ml of n-hexane, 75 ml of isopropanol, and 100 ml of trimethoxyvinylsilane. 4.2 g of ketone polymer was obtained.
The polymerization activity was 7.9 kg / g-Pd · hr, and [η] was 1.6 dl / g. As a result of analyzing the ketone polymer, the silicon content was 0.3% by weight, the crystallinity was 46%, Tm was 226 ° C., and T3 was 218 ° C., which showed good heat resistance.

[Comparative Example 1]
The same operation as in Example 1 was performed except that 225 ml of n-hexane and 25 ml of trimethoxyvinylsilane in Example 1 were changed to 250 ml of n-hexane alone, whereby 0.8 g of a ketone polymer was obtained. It was.
The polymerization activity was 1.5 kg / g-Pd · hr, and [η] was 3.3 dl / g. As a result of analyzing the ketone polymer, the silicon content was 0% by weight, the crystallinity was 54%, Tm was 259 ° C., and T3 was 221 ° C.

[Comparative Example 2]
An operation similar to that of Example 1 was performed except that 225 ml of n-hexane and 25 ml of trimethoxyvinylsilane in Example 1 were changed to 250 ml of methanol alone, whereby 8.6 g of a ketone polymer was obtained.
The polymerization activity was 16.2 kg / g-Pd · hr, and [η] was 1.3 dl / g. As a result of analyzing the ketone polymer, the silicon content was 0% by weight, the crystallinity was 58%, Tm was 260 ° C., and T3 was 229 ° C.

[Comparative Example 3]
In Example 1, 225 ml of n-hexane, 25 ml of trimethoxyvinylsilane were changed to 225 ml of methanol and 25 ml of liquid propylene, and the reaction temperature was 80 ° C. 0.6 g of ketone polymer was obtained.
The polymerization activity was 6.7 kg / g-Pd · hr, and [η] was 1.7 dl / g. As a result of analyzing the ketone polymer, the silicon content was 0% by weight, the crystallinity was 38%, Tm was 225 ° C., and T3 was 214 ° C.

[Example 5]
In Example 1, an equimolar mixture of carbon monoxide and ethylene was added to 8.0 MPa, and a 4: 1 (molar ratio) mixture of carbon monoxide and ethylene was added to 8.0 MPa. Except for the above, the same operation as in Example 1 was carried out to obtain 3.2 g of a ketone polymer.
The polymerization activity was 6.0 kg / g-Pd · hr, and [η] was 2.8 dl / g. As a result of analyzing the ketone polymer, the silicon content was 0.1% by weight, the crystallinity was 38%, the Tm was 236 ° C., and the T3 was 227 ° C., and the heat resistance was good.

[Example 6]
The same operation as in Example 1 was carried out except that 225 ml of n-hexane and 25 ml of trimethoxyvinylsilane in Example 1 were changed to 200 ml of n-hexane and 50 ml of trimethoxyvinylsilane. A ketone polymer was obtained.
The polymerization activity was 5.4 kg / g-Pd · hr, and [η] was 2.8 dl / g. As a result of analysis of this ketone polymer, the silicon content was 0.1% by weight, the crystallinity was 40%, Tm was 240 ° C., and T3 was 231 ° C., indicating good heat resistance.

[Example 7]
The same operation as in Example 1 was carried out except that 225 ml of n-hexane and 25 ml of trimethoxyvinylsilane in Example 1 were changed to 250 ml of trimethoxyvinylsilane alone to obtain 2.7 g of a ketone polymer. It was.
The polymerization activity was 5.1 kg / g-Pd · hr, and [η] was 2.7 dl / g. As a result of analysis of this ketone polymer, the silicon content was 0.5% by weight, the crystallinity was 35%, Tm was 230 ° C., and T3 was 222 ° C., showing good heat resistance.

[Example 8]
The same operation as in Example 1 was carried out except that 25 ml of trimethoxyvinylsilane in Example 1 was changed to 25 ml of trimethylvinylsilane to obtain 1.9 g of a ketone polymer.
The polymerization activity was 2.6 kg / g-Pd · hr, and [η] was 1.3 dl / g. As a result of analyzing the ketone polymer, the silicon content was 0.08% by weight, the degree of crystallinity was 40%, Tm was 240 ° C., and T3 was 230 ° C., showing good heat resistance.

[Example 9]
As a radical initiator, 800 ml of n-hexane and 0.98 g of di-2-ethylhexyl peroxydicarbonate (trade name Parroyl (registered trademark) OPP, 70 wt% hydrocarbon solution manufactured by NOF Corporation) were substituted with nitrogen. Into a stainless steel autoclave equipped with a stirrer. After sealing the autoclave, nitrogen substitution was performed three times at 25 ° C. and 2.0 MPa.
The contents were heated with stirring, and when the internal temperature reached 70 ° C., an equimolar mixed gas of carbon monoxide and ethylene was added to 8.0 MPa. Thereafter, an equimolar mixed gas of ethylene and carbon monoxide was continuously supplied, and stirring was continued for 2 hours while maintaining the internal pressure and the internal temperature. After cooling, the gas in the autoclave was purged and the contents were taken out. The reaction solution was filtered, washed 3 times with water and 3 times with isopropanol, and then dried under reduced pressure to obtain 14.1 g of a ketone polymer.
[Η] was 1.4 dl / g. As a result of analysis of this ketone polymer, the silicon content was 0.2% by weight, the crystallinity was 42%, Tm was 240 ° C., and T3 was 232 ° C., indicating good heat resistance.

[Example 10]
When the same operation as in Example 1 was performed except that an equimolar mixed gas of carbon monoxide and ethylene in Example 1 was added to 8.0 MPa, and 15.0 MPa was obtained, 8.2 g of ketone polymer was obtained.
The polymerization activity was 15.5 kg / g-Pd · hr, and [η] was 7.3 dl / g. As a result of analysis of this ketone polymer, the silicon content was 0.04% by weight, the crystallinity was 49%, Tm was 248 ° C., and T3 was 238 ° C., showing good heat resistance.

[Example 11]
Except that the polymerization reaction temperature at 100 ° C. in Example 1 was changed to 110 ° C., the same operation as in Example 1 was performed to obtain 3.9 g of a ketone polymer.
The polymerization activity was 7.4 kg / g-Pd · hr, and [η] was 2.0 dl / g. As a result of analysis of the ketone polymer, the silicon content was 0.12% by weight, the crystallinity was 39%, Tm was 236 ° C., and T3 was 226 ° C., indicating good heat resistance.

[Example 12]
In Example 1, 225 ml of n-hexane and 25 ml of trimethoxyvinylsilane were changed to Example 1 except that 200 ml of n-hexane and 50 ml of ether-modified silicone (trade name IM11 manufactured by Asahi Kasei Silicone Co., Ltd.) were used. When a similar operation was performed, 2.2 g of a ketone polymer was obtained.
The polymerization activity was 4.1 kg / g-Pd · hr, and [η] was 1.0 dl / g. As a result of analysis of this ketone polymer, the silicon content was 4.5% by weight, the crystallinity was 50%, Tm was 240 ° C., and T3 was 231 ° C., indicating good heat resistance.
^From the measurement results of ¹³ C-NMR and IR, the ketone polymers obtained in Examples 1 to 7, 10 and 11 are —CO— (C ₂ H ₄ ) — and —CO— (C ₂ H ₃ Si). It has been confirmed that it has repeating units of the structure (OCH ₃ ) ₃ ) — and these are randomly distributed in the polymer.
The ketone polymer obtained in Example 8 has repeating units having a structure of —CO— (C ₂ H ₄ ) — and —CO— (C ₂ H ₃ Si (CH ₃ ) ₃ ) — It was confirmed that it was randomly distributed in the polymer.

Furthermore, it was confirmed that the ketone polymers obtained in Comparative Examples 1 and 2 were substantially polyketones composed of carbon monoxide and ethylene-derived repeating units. The polymer obtained in Comparative Example _{3, -CO- (C 2 H 4)} - in _{other, -CO- (C 3 H 6)} - has a repeating unit of the structure of these units in the polymer It was confirmed that it was randomly distributed.
The ketone polymer obtained in Example 8 was confirmed to be a copolymer having an ethylene: carbon monoxide molar ratio of 67:33.
The ketone polymer obtained in Example 12 was confirmed to have a structure in which a polysiloxane structure was substantially connected in a block manner via a trimene group and a polyketone portion composed of carbon monoxide and ethylene-derived repeating units. It was.

[Example 13]
Using the polyketone obtained by the operation of Example 4, a flow test was conducted based on JIS-K-7210. In the test, extrusion was performed at 250 ° C. with a load of 2160 g.
The value of MI ₁ was 5.8 g / 10 min and MI ₂ was 5.0 g / 10 min. The change ratio of MI ₂ / MI ₁ was a good result of 0.86.

[Example 14]
A flow test was conducted on the polyketone obtained by the operation of Example 7 in the same manner as in Example 13.
The value of MI ₁ was 4.2 g / 10 min and MI ₂ was 3.5 g / 10 min. The change ratio of MI ₂ / MI ₁ was 0.83, which was a good result.

[Comparative Example 4]
The polyketone obtained by the operation of Comparative Example 3 was subjected to a flow test in the same manner as in Example 13.
The value of MI ₁ was 6.2 g / 10 min and MI ₂ was 4.9 g / 10 min. The change ratio of MI ₂ / MI ₁ was 0.79, indicating a decrease in fluidity.
Test results for various silicon compounds are shown in Examples 15-20. That is, in the same operation as in Example 1, the following silicon compound was used instead of trimethoxyvinylsilane.

  [Example 15] Triethoxyvinylsilane

  [Example 16] Methoxydimethylvinylsilane

  [Example 17] Dimethoxymethylvinylsilane

  [Example 18] Vinylpentamethyldisiloxane

  [Example 19] Allyldimethylsilane

Example 20 Triethylsilanol Examples 1-12 and Comparative Examples 1-3 are shown in Table 1. Examples 15 to 20 are shown in Table 2. Examples 13 and 14 and Comparative Example 4 are shown in Table 3.

  The polyketone of the present invention can be applied to various fields. It can be used for industrial materials, packaging, containers, electrical / electronics, automobiles, gears, sliding parts, thermosetting resin composites, blends, and adhesives.

Claims (6)

A polyketone comprising a copolymer of an ethylenically unsaturated compound and carbon monoxide, including a structure represented by the chemical formula (1) in the molecule and having an intrinsic viscosity of 0.01 dl / g or more and 20 dl / g or less. Polyketone.

(Wherein R ¹ is an atomic group composed of an element selected from hydrogen, a typical element, a halogen element, Si, P, and S, X ¹ is a reactive group, or hydrogen having a reactive group, a typical element, An atomic group composed of an element selected from a halogen element, Si, P, and S, Y ¹ is a compound represented by chemical formulas (2) to (5), and four repeating units represented by chemical formula (2) 0.01 to 100 mol %, A chemical formula (3) 0 to 99.99 mol%, a chemical formula (4) 0 to 50 mol%, and a chemical formula (5) in the range of 0 to 33 mol%, 1 to 10,000 silicon element-containing groups connected, R ¹ , X ¹ and Y ¹ may be the same or different when a plurality of R ¹ , X ¹ and Y ¹ are present. M is 0 to 3, n is 0 to 3, p is 0 to 3, and m + n + p = 3.

(Wherein R ^{2 to} R ⁶ may be the same or different, and an atomic group composed of an element selected from hydrogen, a typical element, a halogen element, Si, P, and S, X ² is a reactive group, or An atomic group composed of hydrogen having a reactive group, typical element, halogen element, Si, P, and S, i is 0 to 3, j is 0 to 3, k is 0 to 3, i + j + k = 3)   The polyketone according to claim 1, which has a structure represented by the chemical formula (1) at a polymer terminal. The polyketone according to claim 1, wherein 90% by weight or more of the repeating units have at least one chemical structure selected from chemical formulas (6) to (8).

(Wherein, R ^a represents hydrogen, typical elements, halogen elements, Si, P, and atomic group composed of element selected from S.)

(In the formula, R ^b and R ^c in the chemical formula (7) represent atomic groups composed of an element selected from hydrogen, a typical element, a halogen element, Si, P, and S, which may be the same or different. When either or both of M and N in the chemical formulas (7) and (8) are a silicon element-containing group represented by the chemical formula (1) and not a silicon element-containing group represented by the chemical formula (1) Represents an atomic group composed of an element selected from hydrogen, a typical element, a halogen element, Si, P, and S. M and N may be the same or different.

(Wherein R ¹ is an atomic group composed of an element selected from hydrogen, a typical element, a halogen element, Si, P, and S, X ¹ is a reactive group, or hydrogen having a reactive group, a typical element, An atomic group composed of an element selected from a halogen element, Si, P, and S, Y ¹ is a compound represented by chemical formulas (2) to (5), and four repeating units represented by chemical formula (2) 0.01 to 100 mol %, A chemical formula (3) 0 to 99.99 mol%, a chemical formula (4) 0 to 50 mol%, and a chemical formula (5) in the range of 0 to 33 mol%, 1 to 10,000 silicon element-containing groups connected, R ¹ , X ¹ and Y ¹ may be the same or different when a plurality of R ¹ , X ¹ and Y ¹ are present. M is 0 to 3, n is 0 to 3, p is 0 to 3, and m + n + p = 3.

(Wherein R ^{2 to} R ⁶ may be the same or different, and an atomic group composed of an element selected from hydrogen, a typical element, a halogen element, Si, P, and S, X ² is a reactive group, or An atomic group composed of an element selected from hydrogen having a reactive group, typical element, halogen element, Si, P, and S, i is 0 to 3, j is 0 to 3, k is 0 to 3, i + j + k = 3.) The method for producing a polyketone according to claim 1, wherein carbon monoxide and an ethylenically unsaturated compound are polymerized in the presence of a silicon compound having a structure represented by the chemical formula (9).

(Wherein R ¹ is an atomic group composed of an element selected from hydrogen, a typical element, a halogen element, Si, P, and S, X ¹ is a reactive group, or hydrogen having a reactive group, a typical element, An atomic group composed of an element selected from a halogen element, Si, P, and S, Y ¹ is a compound represented by chemical formulas (2) to (5), and four repeating units represented by chemical formula (2) 0.01 to 100 mol %, Chemical formula (3) 0 to 99.99 mol%, chemical formula (4) 0 to 50 mol%, and chemical formula (5) in the range of 0 to 33 mol%. R ¹ , X ¹ , and Y ¹ may be the same or different when a plurality of R ¹ , X ¹ , and Y ¹ are present, m is 0 to 4, n is 0 to 4, p is 0 to 4, and m + n + p = 4. )

(Wherein R ^{2 to} R ⁶ may be the same or different, and an atomic group composed of an element selected from hydrogen, a typical element, a halogen element, Si, P, and S, X ² is a reactive group, or An atomic group composed of hydrogen having a reactive group, typical element, halogen element, Si, P, and S, i is 0 to 3, j is 0 to 3, k is 0 to 3, i + j + k = 3) In a method for producing a polyketone by copolymerizing carbon monoxide and an ethylenically unsaturated compound, (a) a group 9, 10 or 11 transition metal compound and (b) a group 15 element atom. The method for producing a polyketone according to claim 4, wherein the silicon compound represented by the chemical formula (9), carbon monoxide and ethylenically unsaturated carbon are reacted in the presence of a metal complex catalyst comprising a ligand.

(Wherein R ¹ is an atomic group composed of an element selected from hydrogen, a typical element, a halogen element, Si, P, and S, X ¹ is a reactive group, or hydrogen having a reactive group, a typical element, An atomic group composed of an element selected from a halogen element, Si, P, and S, Y ¹ is a compound represented by chemical formulas (2) to (5), and four repeating units represented by chemical formula (2) 0.01 to 100 mol %, Chemical formula (3) 0 to 99.99 mol%, chemical formula (4) 0 to 50 mol%, and chemical formula (5) in the range of 0 to 33 mol%. R ¹ , X ¹ , and Y ¹ may be the same or different when a plurality of R ¹ , X ¹ , and Y ¹ are present, m is 0 to 4, n is 0 to 4, p is 0 to 4, and m + n + p = 4. )

(Wherein R ^{2 to} R ⁶ may be the same or different, and an atomic group composed of an element selected from hydrogen, a typical element, a halogen element, Si, P, and S, X ² is a reactive group or a reaction Atomic group composed of hydrogen having a functional group, typical element, halogen element, Si, P, and S, i is 0 to 3, j is 0 to 3, k is 0 to 3, i + j + k = 3 .)   A molded article comprising the polyketone according to claim 1.