JP5384999B2 - Organic polymer with excellent heat resistance - Google Patents

Description

  The present invention relates to an organic polymer having a low degree of polymerization, excellent handleability, moldability / workability, and recyclability, and having a high glass transition point and excellent heat resistance despite its low degree of polymerization, and a method for producing the same. More specifically, the present invention provides a polycyclic structure at the end of a polymer chain of an organic polymer having a chain structure composed of a structural unit derived from an addition polymerizable monomer and having a number average polymerization degree of 10 to 200. The organic polymer which has an alicyclic hydrocarbon group which has, and its manufacturing method. The organic polymer of the present invention has an alicyclic hydrocarbon group having a polycyclic structure at the end of the polymer chain because of its low polymerization degree and excellent handleability, moldability / processability, recyclability, etc. Therefore, the glass transition temperature is high and the heat resistance is excellent despite the low degree of polymerization. By the production method of the present invention, the organic polymer can be produced easily and smoothly.

Among organic polymers having a linear structure, an organic polymer having a low degree of polymerization melts at a low temperature to form a low-viscosity melt that is rich in fluidity, and thus has excellent molding / workability and handling properties. However, it is often inferior in heat resistance, while organic polymers with a high degree of polymerization are excellent in rigidity, strength, heat resistance, etc., but poor in meltability and melt fluidity, inferior in handleability, moldability / workability, etc. In many cases, organic polymers having a chain structure do not always have physical properties such as heat resistance, rigidity, and strength, and handleability, moldability and processability.
In view of the above, there is a demand for an organic polymer that is excellent in heat resistance while being excellent in handleability, processing / moldability, and the like.
In addition, from the viewpoint of effective use of resources, it is required that an organic polymer be easily reused and excellent in recyclability.
The glass transition temperature (Tg) of the organic polymer is one of heat resistance indicators and corresponds to the temperature at which the translational motion of the chain segment starts. The glass transition temperature of an organic polymer basically depends on the molecular structure and does not depend much on the molecular weight, but an organic polymer having a low degree of polymerization is easily influenced by the terminal structure of the polymer chain.
In view of this, a glass-type silsesquioxane having a dimethylsiloxy group at the end of a low-polymerization degree polymethylmethacrylate having a molecular weight of 20,000 or less is introduced to increase the glass transition temperature (non-patented). Non-patent document 1 describes that the glass transition temperature is increased by 5 ° C. or more by the introduction of silsesquioxane.
However, the polymer material described in Non-Patent Document 1 is an organic-inorganic composite material in which polymethyl methacrylate and silsesquioxane are combined, and includes an inorganic component derived from silsesquioxane. It is inferior in reusability and has problems in terms of recyclability.

JP 2006-96988 A

“Macromolecules”, 2004, Vol. 37, no. 23, p. 8517-8522 J. et al. March, “Advanced Organic Chemistry”, 2001, 5th. Ed. p. 518 “Macromolecules”, 1992, 25, p. 4840-4847

The object of the present invention is to have a low degree of polymerization and excellent heat resistance, hardly deteriorate or decompose even when exposed to a high temperature, and because of the low degree of polymerization, it is easy to produce a low-viscosity melt. The present invention provides an organic polymer that can be formed in a wide range and is excellent in handleability and moldability / processability, and can be used effectively and smoothly for various purposes including the production of molded articles.
An object of the present invention is to provide an organic polymer excellent in recyclability, which can be easily reused after use by, for example, heat melting treatment.
Furthermore, an object of the present invention is to provide a method for easily and smoothly producing an organic polymer having the above-mentioned excellent characteristics without requiring complicated labor and time-consuming polymerization steps and treatment steps. That is.

Among organic polymers having a chain structure composed of structural units derived from addition polymerizable monomers, organic polymers with a low degree of polymerization are generally excellent in terms of handling properties, moldability and processability as described above. However, on the other hand, it is inferior in heat resistance due to its low degree of polymerization, and is often not suitable for applications requiring heat resistance.
The present inventor has conducted various studies to improve the physical properties, particularly heat resistance, of an organic polymer having a chain structure composed of structural units derived from an addition polymerizable monomer and having a low degree of polymerization. As a result, for an organic polymer having a chain structure with a number average degree of polymerization of 10 to 200 consisting of structural units derived from addition polymerizable monomers, at least one of the plurality of polymer chain ends When an alicyclic hydrocarbon group having a polycyclic structure is introduced into the glass, the glass transition temperature is 5 ° C. or higher while maintaining the characteristics such as good handleability and molding / workability of an organic polymer having a low polymerization degree. And the thermal decomposition temperature tends to increase, and the heat resistance is found to be improved.

Furthermore, the inventor of the present invention, as the alicyclic hydrocarbon group having the above-described polycyclic structure introduced into the polymer chain terminal of the organic polymer, includes an adamantyl group, a biadamantyl group, and other bridged alicyclic groups. It has been found that a hydrocarbon group is preferable in terms of the effect of increasing the glass transition temperature.
In addition, the present inventor can easily reuse the organic polymer introduced with an alicyclic hydrocarbon group having a polycyclic structure at the end of the polymer chain by melting after use, and has excellent recyclability. I found out.
Furthermore, the present inventor has produced an organic polymer having a chain structure using an addition polymerizable monomer, the organic polymer having an alicyclic hydrocarbon group having a polycyclic structure at the polymer chain end. In this case, while basically following the conventional polymerization method, an addition polymerizable monomer is polymerized using a polymerization initiator having an alicyclic hydrocarbon group having a polycyclic structure. And / or after the production of an organic polymer having a chain structure by polymerizing an addition polymerizable monomer, the polymerization is terminated by using a polymerization terminator having an alicyclic hydrocarbon group having a polycyclic structure. Or by capping the polymer chain end using a capping agent having an alicyclic hydrocarbon group having a polycyclic structure, and found that it can be produced easily and smoothly, and based on these various findings To complete the present invention.

That is, the present invention
(1) An organic polymer having a chain structure composed of a structural unit derived from an addition polymerizable monomer and having a number average degree of polymerization of 10 to 200, and a plurality of polymer chain ends in the organic polymer It is an organic polymer characterized by having an alicyclic hydrocarbon group having a polycyclic structure in at least one of the above.
And this invention,
(2) At least one of a plurality of polymer chain ends in the organic polymer has the following general formula (I):

［式中、Ｒ¹、Ｒ²およびＲ³は、それぞれ独立して、下記の一般式（II）；

[Wherein R ¹ , R ² and R ³ each independently represents the following general formula (II);

（式中、Ｒ⁴は多環構造を有する１価の脂環式炭化水素基、ｎは０または１を示す）
で表される基（II）、水素原子、炭素数１〜４のアルキル基または炭素数６〜１４のアリール基であって、Ｒ¹、Ｒ²およびＲ³のうちの少なくとも１つが上記の一般式（II）で表される基（II）である。］
で表される基（Ｉ）を有する上記（１）の有機重合体である。

(Wherein R ⁴ is a monovalent alicyclic hydrocarbon group having a polycyclic structure, and n is 0 or 1)
A hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 14 carbon atoms, wherein at least one of R ¹ , R ² and R ³ is It is group (II) represented by the formula (II). ]
The organic polymer of the above (1) having a group (I) represented by the formula:

Furthermore, the present invention provides
(3) The above (1) or (), wherein the alicyclic hydrocarbon group having a polycyclic structure at least one of a plurality of polymer chain ends in the organic polymer is a bridged alicyclic hydrocarbon group. 2) organic polymer;
(4) The organic polymer according to any one of (1) to (3), wherein the alicyclic hydrocarbon group having a polycyclic structure is an adamantyl group or a biadamantyl group;
(5) The organic polymer having a structural unit derived from one or more monomers selected from aromatic vinyl monomers and methacrylates in a proportion of 50 mol% or more (1) to (1) to (5) above. (4) any organic polymer;
It is.

And this invention,
(6) (i) Having a polymerization terminator having an alicyclic hydrocarbon group having a polycyclic structure or a polycyclic structure after polymerizing an addition polymerizable monomer to produce an organic polymer having a chain structure Use capping agent having alicyclic hydrocarbon group to stop polymerization or capping the end of polymer chain, or (ii) add using polymerization initiator having alicyclic hydrocarbon group having polycyclic structure Polymerize the polymerizable monomer in a chain form, or (iii) polymerize the addition polymerizable monomer in a chain form using a polymerization initiator having an alicyclic hydrocarbon group having a polycyclic structure. The polymerization is terminated using a polymerization terminator having an alicyclic hydrocarbon group having a ring structure or a capping agent having an alicyclic hydrocarbon group having a polycyclic structure, or the polymer chain end is capped. The organic polymer of (1) It is a manufacturing method.

Although the organic polymer of the present invention has an alicyclic hydrocarbon group having a polycyclic structure at at least one of a plurality of polymer chain ends, although the degree of polymerization is low, the glass transition temperature, It has a high thermal decomposition temperature, excellent heat resistance, hardly deteriorates or decomposes even when exposed to high temperatures, and has good mechanical and physical properties even at high temperatures.
The organic polymer of the present invention is excellent in moldability / workability, particularly melt moldability, and handleability due to its low degree of polymerization.
The organic polymer of the present invention can be easily reused by melting after use, and is excellent in recyclability.
By the production method of the present invention, the organic polymer of the present invention having the above-described excellent characteristics can be produced easily and smoothly.
The organic polymer of the present invention makes use of the above-mentioned properties for various uses, such as housings for home appliances, OA equipment, food containers, foams for packaging materials, food trays, automobile parts, electric / electronic parts, films. -It can be used effectively for sheets, medical materials, elastic members, etc.

2 is a diagram showing a ¹ H-NMR spectrum and a ¹³ C-NMR spectrum of 1- (2-bromoethyl) adamantane obtained in Reference Example 1. FIG. 2 is a diagram showing a ¹ H-NMR spectrum and a ¹³ C-NMR spectrum of 1,1-bis [4- (1-adamantyl) phenyl] ethylene obtained in Reference Example 2. FIG. 4 is a diagram showing a ¹ H-NMR spectrum and a ¹³ C-NMR spectrum of 1- [4- (1-adamantyl) phenyl] -1-phenylethylene obtained in Reference Example 3. FIG. It is a figure which shows the ¹ H-NMR spectrum and ¹³ C-NMR spectrum of 1- [4- (3- (1,1′-biadamantyl) phenyl)]-1-phenylethylene obtained in Reference Example 4.

The present invention is described in detail below.
The organic polymer of the present invention is an organic polymer having a chain structure composed of structural units derived from an addition polymerizable monomer and having a number average degree of polymerization of 10 to 200, and a plurality of heavy polymers in the organic polymer. At least one of the chain ends has an alicyclic hydrocarbon group having a polycyclic structure.
The “alicyclic hydrocarbon group having a polycyclic structure” that the organic polymer of the present invention has at least one of a plurality of polymer chain ends means two or more aliphatic rings (aliphatic A hydrocarbon group having a ring).
In addition, the “polymer chain end” in the present invention is a general term for the ends of the polymer chains constituting the organic polymer having a chain structure, and includes the ends of the main chain (the polymer chain forming the trunk) and It includes the end of a branched chain (branched polymer chain).
The organic polymer of the present invention may be a linear organic polymer or a branched organic polymer as long as it is an organic polymer having a chain structure composed of a structural unit derived from an addition polymerizable monomer. It may be a chain polymer, and when it is a branched chain organic polymer, it may be an organic polymer having a graft structure or an organic polymer having a star structure. Good (hereinafter, “organic polymer” may be simply referred to as “polymer”).

When the polymer of the present invention is a linear polymer, alicyclic carbonization having a polycyclic structure only at one (one side) of two polymer chain ends in the linear polymer It may have a hydrogen group, or may have an alicyclic hydrocarbon group having a polycyclic structure at each (both) of two polymer chain ends. In a linear polymer, having an alicyclic hydrocarbon group having a polycyclic structure at each (both) of two polymer chain ends increases the degree of increase in glass transition temperature, Further, the thermal decomposition temperature tends to be high, which is preferable from the viewpoint of further improving the heat resistance.
In addition, when the polymer of the present invention is a polymer having a branched chain structure (graft structure, star structure, etc.), one polymer chain end among three or more polymer chain ends in the polymer May have an alicyclic hydrocarbon group having a polycyclic structure only, or may have an alicyclic hydrocarbon group having a polycyclic structure at two polymer chain ends, One or more polymer chain ends may have an alicyclic hydrocarbon group having a polycyclic structure, or a polymer having a branched chain structure may have a polycyclic structure at all polymer chain ends. It may have a cyclic hydrocarbon group. As the proportion of polymer chain ends having an alicyclic hydrocarbon group having a polycyclic structure increases, the degree of increase in the glass transition temperature tends to increase, and the thermal decomposition temperature tends to increase. Will be improved.
When the polymer of the present invention is a polymer having a branched chain structure, it has a polycyclic structure at 1/2 or more, particularly 2/3 or more, of 3 or more polymer chain ends in the polymer. Having an alicyclic hydrocarbon group is preferable from the viewpoint of heat resistance and the like.

  The “alicyclic hydrocarbon group having a polycyclic structure” that the polymer of the present invention has at least one of the polymer chain ends is a hydrocarbon group having two or more aliphatic rings (alicyclic rings). Any one is acceptable. Among them, the polymer of the present invention has the following general formula (I) at least one of a plurality of polymer chain ends in the polymer:

［式中、Ｒ¹、Ｒ²およびＲ³は、それぞれ独立して、下記の一般式（II）；

[Wherein R ¹ , R ² and R ³ each independently represents the following general formula (II);

（式中、Ｒ⁴は多環構造を有する１価の脂環式炭化水素基、ｎは０または１を示す）
で表される基（II）、水素原子、炭素数１〜４のアルキル基または炭素数６〜１４のアリール基であって、Ｒ¹、Ｒ²およびＲ³のうちの少なくとも１つが上記の一般式（II）で表される基（II）である。］
で表される基（Ｉ）を有する有機重合体であることが、製造の容易性、耐熱性などの点から好ましい。

(Wherein R ⁴ is a monovalent alicyclic hydrocarbon group having a polycyclic structure, and n is 0 or 1)
A hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 14 carbon atoms, wherein at least one of R ¹ , R ² and R ³ is It is group (II) represented by the formula (II). ]
The organic polymer having the group (I) represented by the formula is preferred from the viewpoint of ease of production, heat resistance and the like.

The “alicyclic hydrocarbon group having a polycyclic structure” (hereinafter sometimes referred to as “polyalicyclic hydrocarbon group”) possessed by the polymer chain terminal of the polymer of the present invention has a polycyclic structure. The degree of increase in the glass transition temperature of the polymer is a bridged alicyclic hydrocarbon group, that is, a polyalicyclic hydrocarbon group in which two adjacent alicyclic rings share two or more carbon atoms. The thermal decomposition temperature tends to increase and the heat resistance is further improved, which is preferable.
The polyalicyclic hydrocarbon group may have an aliphatic unsaturated bond in one or more of two or more alicyclic rings constituting the polyalicyclic hydrocarbon group depending on the case. Good. However, it is necessary that the aliphatic unsaturated bond present in the alicyclic ring does not participate in polymerization or has low polymerizability. Otherwise, the introduction of the polyalicyclic hydrocarbon group to the polymer chain end may not be smoothly performed.

Specific examples of the polyalicyclic hydrocarbon group [group R ⁴ in the above general formula (II)] possessed by the polymer of the present invention at the polymer chain end include an adamantyl group ( Tricyclo [3.3.1.1 ^3,7 ] decyl group) [the following chemical formula (a)], biadamantyl group [the following chemical formula (b)], norbornyl group [the following chemical formula (c)], isobornyl group [Chemical Formula (d ₁ ), (d ₂ ), (d ₃ )], Bicyclononyl Group [Chemical Formula (e ₁ ), (e ₂ )], Bicyclo [2.1.0] Pentyl Group [Following Chemical formula (f)], bicyclo [3.2.1] octyl group [following chemical formula (g ₁ ), (g ₂ )], tricyclo [2.2.1.0 ^2,6 ] heptyl group [following Chemical formula (h)] and the like. These polyalicyclic hydrocarbon groups may be optionally substituted with an alkyl group, a halogen, an alkoxyl group or the like.

When n is 0 in the group (II) represented by the general formula (II), the chemical formulas (a) to (c), (d ₁ ) to (d ₃ ), and (e ₁ ) to (e ₂ ) ), (F), (g ₁ ) to (g ₂ ), and (h), the polyalicyclic hydrocarbon group R ⁴ is the central carbon atom (R) in the above general formula (I). ¹ , carbon atoms to which R ² and R ³ are bonded).
In addition, as a specific example of the group (II) (a phenyl group substituted by a group R ⁴ which is a polyalicyclic hydrocarbon group) when n is 1 in the above general formula (II), the following chemical formula (A ′) to (c ′), (d ₁ ′) to (d ₃ ′), (e ₁ ′) to (e ₂ ′), (f ′), (g ₁ ′) to (g ₂ ′) And a phenyl group having a polyalicyclic hydrocarbon group R ⁴ as a substituent as shown in (h ′).
At that time, the bonding position of the polyalicyclic hydrocarbon group R ^{4 to} the benzene ring may be any of the ortho position, the meta position, and the para position with respect to the bonding site to the carbon atom at the end of the polymer chain. Of these, R ⁴ is preferably bonded to the para position from the viewpoint that a polyalicyclic hydrocarbon group (group R ⁴ ) can be introduced quantitatively at the end of the polymer chain.

When the polymer of the present invention is a polymer having the group (I) represented by the above general formula (I) at least one of a plurality of polymer chain ends, the group (I) In which at least one of R ¹ , R ² and R ³ is substituted with a group (II) represented by the above general formula (II) (polyalicyclic hydrocarbon group or polyalicyclic hydrocarbon group) Phenyl group).
From the viewpoint of increasing the degree of increase in the glass transition temperature of the polymer and increasing the thermal decomposition temperature to further improve the heat resistance, two or three of R ¹ , R ² and R ³ are: The group (II) represented by the general formula (II) is preferable.
In the group (I) represented by the above general formula (I), a plurality (two or three) of R ¹ , R ² and R ³ are groups represented by the above general formula (II) ( In the case of II), the plurality of groups (II) may be the same as or different from each other.

In the group (I) represented by the above general formula (I), when one or two of R ¹ , R ² and R ³ are groups other than the group (II), a hydrogen atom, carbon C 1-4 alkyl group (methyl group, ethyl group, propyl group or butyl group), C 6-14 aryl group (for example, phenyl group, naphthyl group, phenanthryl group, anthryl group, indenyl group, biphenylyl group, etc.) One of When one or two of R ¹ , R ² and R ³ are an aryl group having 6 to 14 carbon atoms, the aryl group has one or two substituents such as an alkyl group, a halogen, and an alkoxyl group. You may have more than one.
In the group (I) represented by the above general formula (I), when ^{two of} R ¹ , R ² and R ³ are groups other than the group (II), they are the same as each other Or may be different.
When one or two of R ¹ , R ² and R ³ are the aforementioned hydrogen atom other than the group (II), an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 14 carbon atoms, A hydrogen atom, a methyl group or a phenyl group is preferable from the viewpoint of ease of production.

The polymer of the present invention comprises a structural unit derived from an addition polymerizable monomer, and the addition polymerizable monomer used to form the polymer of the present invention is a single monomer having an unsaturated double bond. And ring-opening addition polymerizable monomers.
Examples of the monomer having an unsaturated double bond include aromatic vinyl compounds, conjugated diene compounds, (meth) acrylic acid esters, (meth) acrylamide compounds, olefins, vinyl esters, vinyl halides, and vinylidene halides. , Acrylonitrile and the like, and one or more of these can be used.

  More specifically, examples of the aromatic vinyl compound include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-ethylstyrene, 4-isopropylstyrene, and 4-n. -Propyl styrene, 4-isopropyl styrene, 4-n-butyl styrene, 4-isobutyl styrene, 4-t-butyl styrene, 4-n-octyl styrene, 1- (4-vinylphenyl) adamantane, 2,4-dimethyl Styrene, 2,5-dimethylstyrene, 3,5-dimethylstyrene, 2,4,6-trimethylstyrene, α-methyl-4-methylstyrene, α-methyl-4-t-butylstyrene, 2-methoxystyrene, 3-methoxystyrene, 4-methoxystyrene, 1,1-diphenylethylene, vinylnaphthalene, Cycloalkenyl anthracene, 2-vinyl pyridine, etc. can be mentioned 4-vinyl pyridine, may be used alone or two or more thereof. Of these, styrene, α-methylstyrene, 4-methylstyrene, 4-t-butylstyrene, and 1- (4-vinylphenyl) adamantane are preferably used.

  Examples of the conjugated diene compound include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 3,4-dimethyl-1,3-pentadiene, 1,3-cyclohexadiene, and chloroprene. One or two or more of these can be used.

  Examples of the methacrylic acid ester include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-pentyl methacrylate, and methacrylic acid. Methacrylic acid such as n-hexyl, cyclohexyl methacrylate, n-heptyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate, stearyl methacrylate, isobornyl methacrylate Alkyl ester, alicyclic alkyl ester of methacrylic acid; aromatic hydrocarbon ester of methacrylic acid such as phenyl methacrylate, toluyl methacrylate, benzyl methacrylate Alkoxyalkyl esters of methacrylic acid such as 2-methoxyethyl methacrylate and 3-methoxybutyl methacrylate; Hydroxyalkyl esters of methacrylic acid such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; Methacrylic acid Glycidyl; aminoalkyl esters of methacrylic acid such as methacrylic acid-2-aminoethyl; silanes having a methacryloyloxyalkyl group such as γ- (methacryloyloxypropyl) trimethoxysilane, γ- (methacryloyloxypropyl) dimethoxymethylsilane; Alkylene oxide adducts of methacrylic acid, such as ethylene oxide adducts of acids; trifluoromethyl methyl methacrylate, 2-trifluoromethyl ethyl methacrylate, 2-perfluoroethylethyl tacrylate, 2-perfluoroethyl-2-perfluorobutylethyl methacrylate, 2-perfluoroethyl methacrylate, perfluoromethyl methacrylate, diperfluoromethyl methyl methacrylate, methacryl 2-Perfluoromethyl-2-perfluoroethyl methyl acid, 2-perfluorohexyl ethyl methacrylate, 2-perfluorodecyl ethyl methacrylate, 2-perfluorohexadecyl ethyl methacrylate, fluoro of methacrylic acid An alkyl ester etc. can be mentioned, These 1 type (s) or 2 or more types can be used. Of these, methyl methacrylate, ethyl methacrylate, tert-butyl methacrylate, isobornyl methacrylate and benzyl methacrylate are preferably used.

  Examples of the acrylate ester include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-pentyl acrylate, and acrylic acid. Acrylic acid such as n-hexyl, cyclohexyl acrylate, n-heptyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, stearyl acrylate, isobornyl acrylate Alkyl esters and alkyl alicyclic alkyl esters; aromatic hydrocarbon esters of acrylic acid such as phenyl acrylate, toluyl acrylate, and benzyl acrylate; 2-methoxyethyl acrylate, 3-methyl acrylate Alkoxyalkyl esters of acrylic acid such as xylbutyl; hydroxyalkyl esters of alkoxyalkyl such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; glycidyl acrylate; acrylic acid such as 2-aminoethyl acrylate Aminoalkyl esters; silanes having an acryloyloxyalkyl group such as γ- (acryloyloxypropyl) trimethoxysilane, γ- (acryloyloxypropyl) dimethoxymethylsilane; alkylene oxides of acrylic acid such as ethylene oxide adducts of acrylic acid Adducts: trifluoromethyl methyl acrylate, 2-trifluoromethyl ethyl acrylate, 2-perfluoroethyl ethyl acrylate, 2-perfluoroethyl acrylate 2-perfluorobutylethyl, 2-perfluoroethyl acrylate, perfluoromethyl acrylate, diperfluoromethyl methyl acrylate, 2-perfluoromethyl-2-perfluoroethyl methyl acrylate, acrylic acid Fluoroalkyl esters of acrylic acid such as 2-perfluorohexylethyl, 2-perfluorodecylethyl acrylate, 2-perfluorohexadecylethyl acrylate, and the like, and one or more of these Can be used.

  Examples of (meth) acrylamide compounds include acrylamide, N-methylacrylamide, N, N-dimethylacrylamide, N-isopropylacrylamide, N, N-diisopropylacrylamide, methacrylamide, N-methylmethacrylamide, N, N- Examples thereof include dimethylmethacrylamide, N-isopropylmethacrylamide, N, N-diisopropylmethacrylamide, and one or more of these can be used.

Examples of the olefin include ethylene, propylene, butene-1, 4-methylpentene-1, cyclopentene, cyclohexene, and the like, and one or more of these can be used.
Examples of the vinyl ester include vinyl acetate, and examples of the vinyl halide and vinylidene halide include vinyl chloride, vinyl fluoride, vinylidene chloride, and vinylidene fluoride.

  Examples of the ring-opening addition polymerizable monomer include lactones such as ε-caprolactone, lactams such as ε-caprolactam and ω-laurolactam, ethylene oxide, ethylene oxide, propylene oxide, and tetrahydroether. Examples thereof include cyclic ethers and silicon-containing heterocyclic compounds.

Among them, the polymer of the present invention includes aromatic vinyl compounds such as styrene, α-methylstyrene, 4-methylstyrene, 4-t-butylstyrene, 1- (4-vinylphenyl) adamantane, particularly styrene and / or Structural units derived from α-methylstyrene, and methacrylic esters such as methyl methacrylate, ethyl methacrylate, tert-butyl methacrylate, isobornyl methacrylate, benzyl methacrylate, especially methyl methacrylate and / or tert-butyl methacrylate It is preferable that it is mainly composed of one or two or more of the structural units derived from the viewpoint of a large effect of improving the heat resistance of the polymer and ease of production.
The polymer of the present invention is derived from one or more aromatic vinyl compounds such as styrene, α-methylstyrene, 4-methylstyrene, 4-t-butylstyrene, and 1- (4-vinylphenyl) adamantane. In the case of mainly comprising structural units, the proportion of structural units derived from the aromatic vinyl compound is preferably 50 mol% or more based on the total number of moles of all structural units constituting the polymer, More preferably, it is more than mol%, and still more preferably 70-100 mol%.
In the case where the polymer of the present invention mainly comprises a structural unit derived from one or more of methyl methacrylate, tert-butyl methacrylate and the above-mentioned other methacrylic acid esters, a structure derived from the methacrylic acid ester The proportion of units is preferably 50 mol% or more, more preferably 60 mol% or more, and preferably 70 to 100 mol% based on the total number of moles of all structural units constituting the polymer. Is more preferable.

The polymer of the present invention exhibits the effect of increasing the glass transition temperature, the effect of increasing the thermal decomposition temperature, and the effect of improving the heat resistance by introducing a polyalicyclic hydrocarbon group at the end of the polymer chain. In addition, the number average degree of polymerization needs to be 10 to 200, preferably 10 to 100.
When the number average degree of polymerization of the polymer exceeds 200, it is difficult to sufficiently exhibit the effect of increasing the glass transition point due to the introduction of the polyalicyclic hydrocarbon group at the end of the polymer chain and the effect of improving the heat resistance. Become. On the other hand, when the number average degree of polymerization of the polymer is less than 10, it becomes difficult to exhibit the characteristics as a polymer.
The number average degree of polymerization of the polymer in the present specification indicates a value obtained by dividing the number average degree of polymerization of the polymer by the molecular weight of the addition polymerizable monomer used for forming the polymer, and its detailed measurement. The (calculation) method is as described in the following examples. When the polymer of the present invention is formed from a plurality of addition polymerizable monomers, the sum of the products of the molar fraction of each monomer forming the polymer and its molecular weight is expressed as “polymer The value obtained by dividing the number average molecular weight of the polymer by the molecular weight (M) is regarded as the “number average degree of polymerization”. For example, when the polymer A having a number average molecular weight of 2000 is formed from 80 mol% of the addition polymerizable monomer a having a molecular weight of 100 and 20 mol% of the addition polymerizable monomer b having a molecular weight of 120 , (100 × 0.80) + (120 × 0.20) = 80 + 24 = 104 is the molecular weight of the addition polymerizable monomer forming the polymer A, and the molecular weight of the polymer A is 2000 ÷ 104 = 19. .2≈19 is the number average degree of polymerization of the polymer A.
Further, the molecular weight of the polyalicyclic hydrocarbon group is preferably larger than the molecular weight (M) of the addition polymerizable monomer in order to satisfactorily exert the effects of the present invention, and is 1.3 times or more. More preferably, it is more preferably 2 times or more.

The production method of the polymer of the present invention is not particularly limited, and any method can be used as long as it is a method capable of producing a polymer having a polyalicyclic hydrocarbon group at least one of a plurality of polymer chain ends. You may employ | adopt and the polymer of this invention can be manufactured by performing anionic polymerization, radical polymerization, cationic polymerization, coordination polymerization, etc.
Among them, from the viewpoint of quantitatively introducing a polyalicyclic hydrocarbon group at the polymer chain end, it is preferable to perform living polymerization such as living anion polymerization, living cation polymerization, and living radical polymerization. More preferably.

As a method for producing the polymer of the present invention by living polymerization such as living anionic polymerization,
(I) A polymerization terminator having a polyalicyclic hydrocarbon group after producing a terminal-growth type organic polymer having a chain structure by polymerizing an addition polymerizable monomer using a living polymerization initiator Alternatively, a method of stopping or capping polymerization at the living end using a capping agent having an alicyclic hydrocarbon group having a polycyclic structure [hereinafter referred to as “production method (i)”];
(Ii) a method of polymerizing an addition polymerizable monomer in a chain using a living polymerization initiator having a polyalicyclic hydrocarbon group [hereinafter referred to as “production method (ii)”];
(Iii) A polymerization terminator having a polyalicyclic hydrocarbon group or a polyalicyclic group after polymerizing an addition polymerizable monomer in a chain using a living polymerization initiator having a polyalicyclic hydrocarbon group A method of stopping or capping polymerization at a living end using a capping agent having a hydrocarbon group [hereinafter referred to as “production method (iii)”];
And so on.

In the production method (i), when a living polymerization initiator that forms a both-end-grown polymer is used, a polyalicyclic hydrocarbon group is attached to two polymer chain ends (both ends of the polymer chain). The polymer which has can be obtained. In addition, when a living polymerization initiator that forms a one-end growth type polymer is used in the production method (i), a polymer having a polyalicyclic hydrocarbon group at one end of the polymer chain is obtained. .
Further, in the case of production method (ii), a polymer having a polyalicyclic hydrocarbon group is obtained at the polymerization start end, and in the case of production method (iii), a polyfatty acid is present at both the polymerization start end and the polymerization stop end. A polymer having a cyclic hydrocarbon group can be obtained.

When the polymer of the present invention is produced by living anion polymerization based on the production method (i), for example, living anion polymerization is started in an organic solvent in an inert gas atmosphere such as nitrogen or argon or under vacuum. After adding an agent and polymerizing the addition polymerizable monomer at a temperature of −100 ° C. to 100 ° C., particularly −90 ° C. to 80 ° C. under normal pressure or pressurized conditions, the following general formula ( The method of introducing a polyalicyclic hydrocarbon group at the end of a polymer chain by adding a polymerization terminator represented by III) or a capping agent represented by the following general formula (IV) is used to quantify the reaction. It is preferably employed from the viewpoint of sex.
When a capping agent represented by the following general formula (IV) is used, a polymerization terminator such as methanol, ethanol or various alkyl halides is added after capping, or the polymerization mixture is polymerized with methanol as described above. Polymerization can be stopped by charging it into a stopper.

［式中、Ｒ⁴は多脂環式炭化水素基、Ｒ⁵は炭素数１〜４のアルキレン基または直接結合（結合手：−）、Ｘはハロゲン原子、Ｒ⁶は水素原子、炭素数１〜４のアルキル基または炭素数６〜１４のアリール基、ｎは０または１、ｐは１または２、ｑは０または１であって、ｐ＋ｑ＝２である。］

[Wherein, R ⁴ is a polyalicyclic hydrocarbon group, R ⁵ is an alkylene group having 1 to 4 carbon atoms or a direct bond (bond:-), X is a halogen atom, R ⁶ is a hydrogen atom, 1 carbon atom. -4 alkyl group or C6-C14 aryl group, n is 0 or 1, p is 1 or 2, q is 0 or 1, and p + q = 2. ]

In the polymerization terminator represented by the general formula (III) and the capping agent represented by the general formula (IV), R ⁴ is represented by a polyalicyclic hydrocarbon group, that is, the general formula (II). And a polyalicyclic hydrocarbon group similar to R ⁴ in the group (II), and specific examples thereof include the above chemical formulas (a) to (c), (d ₁ ) to (d ₃ ), (e ₁ ) To (e ₂ ), (f), (g ₁ ) to (g ₂ ), and (h) polyalicyclic hydrocarbon groups.

In the polymerization terminator represented by the general formula (III), R ⁵ is an alkylene group having 1 to 4 carbon atoms, that is, a methylene group, an ethylene group, a propylene group or a butylene group, or a direct bond (bonding bond). :-), and among them, R ⁵ is preferably an ethylene group, a propylene group, a direct bond (-), or a methylene group from the viewpoint of the quantitativeness of the reaction.
In the polymerization terminator represented by the above general formula (III), X is a halogen atom such as bromine, chlorine or iodine, and among them, bromine and chlorine are preferable from the viewpoint of quantitativeness of the reaction.

In the capping agent represented by the general formula (IV), R ⁶ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms (methyl group, ethyl group, propyl group, or butyl group), or aryl having 6 to 14 carbon atoms. Group (for example, phenyl group, naphthyl group, phenanthryl group, anthryl group, indenyl group, biphenylyl group, etc.). When R ⁶ is an aryl group having 6 to 14 carbon atoms, the aryl group may have one or more substituents such as an alkyl group, a halogen, and an alkoxyl group.

  Specific examples of the polymerization terminator represented by the general formula (III) that are not limited include 1- (2-bromoethyl) adamantane [also known as: 1-adamantyl-2-bromoethane], 1- (3- Bromopropyl) adamantane [also known as: 1-adamantyl-3-bromopropane], 1- (4-bromobutyl) adamantane [also known as: 1-adamantyl-4-bromobutane], 1- (4-bromophenyl) adamantane [also known as: 1 -Adamantyl-4-bromobenzene], 1- (2-bromoethyl) biadamantane [also known as: 1-biadamantyl-2-bromoethane], 1- (4-bromophenyl) biadamantane [also known as: 1-biadamantyl-4] -Bromobenzene] and the like.

  Although not limited, specific examples of the capping agent represented by the general formula (IV) include 1,1-bis [4- (1-adamantyl) phenyl] ethylene, 1- [4- ( 1-adamantyl) phenyl] -1-phenylethylene, 1- [4- (3- (1,1′-biadamantyl) phenyl) -1-phenylethylene, and the like can be given.

The polymerization terminator represented by the above general formula (III) can be produced by a conventional method (such as the method described in Non-Patent Document 2) in which an alcoholic hydroxyl group is converted to a bromo group.
For example, taking 1- (2-bromoethyl) adamantane as an example, as shown in the following reaction formula (1), it is produced by reacting 1-adamantyl-2-ethanol and phosphorus tribromide in dichloromethane. be able to.

The capping agent represented by the above general formula (IV) can also be produced by a conventionally known method (for example, the method described in Non-Patent Document 3).
For example, symmetrical 1,1-bis (4-adamantylphenyl) ethylene is obtained by reacting 1-phenyladamantane with bromine as shown in the following reaction formula (2). ) It can be produced by reacting 2 equivalents or more of 4-adamantyl-phenylmagnesium bromide (Grignard reagent) obtained by reacting adamantane with magnesium and 1 equivalent of ethyl acetate, and dehydrating the produced alcohol.

  Further, for example, asymmetric 1- (4-adamantylphenyl) -1-phenylethylene is obtained by reacting magnesium with 1- (4-bromophenyl) adamanan as shown in the following reaction formula (3). It can be produced by reacting 1 equivalent or more of the obtained 4-adamantyl-phenyl magnesium bromide (Grignard reagent) with 1 equivalent of acetophenone and dehydrating the produced alcohol.

  Further, for example, asymmetric 1- [4- (3- (1,1′-biadamantyl) phenyl)]-1-phenylethylene is represented by 3- (4 as shown in the following reaction formula (4). More than 1 equivalent of 4- (3-1,1′-biadamantyl) -phenylmagnesium bromide (Grignard reagent) obtained by reacting magnesium with -bromophenyl) -1,1′-biadamantane and 1 equivalent of acetophenone. It can be produced by reacting and dehydrating the produced alcohol.

In producing the polymer of the present invention by living anionic polymerization based on the above production method (i), as an anionic polymerization initiator, alkyl such as n-butyllithium, sec-butyllithium, ethyllithium and methyllithium is used. Conventionally known anionic polymerization initiators such as alkali metal naphthalene such as lithium, potassium naphthalene, sodium naphthalene and lithium naphthalene can be used, and these anionic polymerization initiators can be used alone or 2 More than one species may be used in combination. Among these, n-butyllithium, sec-butyllithium, potassium naphthalene, and lithium naphthalene are preferably used from the viewpoints of polymer yield, polymerization initiation rate, and the like.
The amount of anionic polymerization initiator used is generally the number average specified in the present invention to be 0.5 to 10 mol%, particularly 1 to 10 mol%, based on the total mass of the addition polymerizable monomer. A polymer having a degree of polymerization is preferred from the viewpoint of obtaining smoothly.

Examples of the organic solvent that can be used during the living anionic polymerization include hydrocarbon solvents such as cyclohexane, toluene, and benzene, tetrahydrofuran, and the like. These organic solvents may be used alone or in combination of two or more. May be.
The amount of the organic solvent used is preferably about 0.1 to 30 mL, particularly about 1 to 20 mL, with respect to 1 g of the addition polymerizable monomer, from the viewpoint of easiness of stirring, production cost, and the like.

  When the polymer of the present invention is produced by living anionic polymerization based on the above production method (ii), the polyalicyclic ring in an organic solvent under an inert gas atmosphere such as nitrogen or argon or under vacuum. By adding a living anionic polymerization initiator having a hydrocarbon group and at −100 ° C. to 100 ° C., particularly at a temperature of −90 ° C. to 80 ° C. under normal pressure or pressurized conditions. A method in which polymerization is performed and a polyalicyclic hydrocarbon group is introduced at the initiation terminal of the polymerization is preferably employed.

  As the living anionic polymerization initiator having a polyalicyclic hydrocarbon group used in that case, for example, a lithium catalyst having a polyalicyclic hydrocarbon group represented by the following general formula (V) is preferably used. .

［式中、Ｒ⁴は多脂環式炭化水素基、Ｒ⁶は炭素数１〜４のアルキレン基または直接結合（結合手：−）、ｎは０または１である。］

[Wherein, R ⁴ is a polyalicyclic hydrocarbon group, R ⁶ is an alkylene group having 1 to 4 carbon atoms or a direct bond (bond:-), and n is 0 or 1. ]

In the general formula (V), R ⁴ is a polyalicyclic hydrocarbon group, that is, a polyalicyclic hydrocarbon group similar to R ⁴ in the group (II) represented by the general formula (II). Specific examples include the above chemical formulas (a) to (c), (d ₁ ) to (d ₃ ), (e ₁ ) to (e ₂ ), (f), (g ₁ ) to (g ₂ ). And polyalicyclic hydrocarbon groups represented by (h).
In the above general formula (V), R ⁶ is an alkylene group having 1 to 4 carbon atoms, that is, a methylene group, an ethylene group, a propylene group or a butylene group, or a direct bond (bond:-), and among these, R ⁶ is An ethylene group, a propylene group, and a butylene group are preferable from the viewpoints of ease of production of an anionic polymerization initiator having a polyalicyclic hydrocarbon group, stability, polymerization initiation rate, and the like.
Specific examples of the lithium catalyst represented by the general formula (V) include, but are not limited to, 2-adamantyl-ethyllithium, 3-adamantyl-propyllithium, 4-adamantyl-butyllithium, and the like. it can.

  The amount of the living anionic polymerization initiator having a polyalicyclic hydrocarbon group is generally 0.5 to 10 mol%, particularly 0.5 to 1 mol%, based on the total mass of the addition polymerizable monomer. It is preferable from the point that the polymer which has the number average degree of polymerization prescribed | regulated by this invention is obtained smoothly.

Examples of the organic solvent that can be used in producing the polymer of the present invention by the production method (ii) include hydrocarbon solvents such as cyclohexane, toluene, and benzene, tetrahydrofuran, and the like. These organic solvents are used alone. Alternatively, two or more kinds may be used in combination.
The amount of the organic solvent used is preferably about 0.1 to 30 mL, particularly about 1 to 20 mL, with respect to 1 g of the addition polymerizable monomer, from the viewpoint of easiness of stirring, production cost, and the like.

  When the polymer of the present invention is produced according to the production method (iii) described above, the polymerization is initiated using a living polymerization initiator having a polyalicyclic hydrocarbon group according to the production method (ii) described above. A polymer in which a polyalicyclic hydrocarbon group is introduced at the end is produced, and then a polymerization terminator having a polyalicyclic hydrocarbon group according to the production method (i) described above [for example, the above general formula (III) Or a capping agent [for example, a capping agent represented by the above general formula (IV)] may be used to introduce a polyalicyclic hydrocarbon group into the terminal portion of the polymerization.

  The polymer of the present invention may be used alone, or may be used by blending with other thermoplastic resin, thermosetting resin, rubber, thermoplastic elastomer or the like as required. At that time, an antioxidant, a softening agent, a plasticizer, an antistatic agent, a lubricant, an ultraviolet absorber, a flame retardant, a pigment, an inorganic filler, and the like may be further blended within a range that does not impair the spirit of the present invention. .

Hereinafter, the present invention will be described more specifically with reference to Examples, Comparative Examples, and Reference Examples, but the present invention is not limited to the following examples. In addition, the chemical | medical agent (compound etc.) used in the following examples used the thing of the highest purity as long as it can obtain. The solvent used was sufficiently degassed.
In the following examples, confirmation of the structures of the products (intermediate compounds, final compounds, polymers) obtained in Reference Examples 1 to 4, Examples 1 to 6 and Comparative Examples 1 to 5, and in each Example and Comparative Example The number average molecular weight, molecular weight distribution, number average polymerization degree, and glass transition temperature of the obtained polymer were measured as follows.

(1) Confirmation of product structure:
Each of the products (intermediate compounds and final compounds) synthesized in the following Reference Examples 1 to 4 and the polymers obtained in Examples 1 to 6 and Comparative Examples 1 to 5 were dissolved in deuterated chloroform, and a nuclear magnetic resonance apparatus (Bruker's “BRUCKER DPX300”) was used to measure the proton nucleus ( ¹ H) and carbon nucleus ( ¹³ C) at 27 ° C. to confirm the structure.
Further, gas chromatography (“GC-14B” manufactured by Shimadzu Corporation) was used for tracing the reaction of the Grignard reagent, and the measurement was performed at a column temperature of 150 to 230 ° C.

(2) Number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the polymer:
Using standard polystyrene with a known peak molecular weight, gel permeation chromatography (GPC) calibrated with the standard (“HLC-8020” manufactured by Tosoh Corporation), the number average molecular weight (Mn) and weight average molecular weight of the polymer (Mw) was measured (solvent: tetrahydrofuran, temperature: 40 ° C.). Molecular weight distribution was calculated | required as ratio (Mw / Mn) of a weight average molecular weight (Mw) and a number average molecular weight (Mn).

(3) Number average degree of polymerization of the polymer:
The number average molecular weight (Mn) of the polymer obtained in the above (2) is the molecular weight of the addition polymerizable monomer used in the production of the polymer (molecular weight of styrene = 104, molecular weight of α-methylstyrene = 118, The value divided by the molecular weight of methyl methacrylate = 100) was taken as the number average degree of polymerization.

(4) Glass transition temperature (Tg) of polymer:
It measured using the DSC apparatus ("DSC6220" by Seiko Instruments).
Specifically, in the measurement of polystyrene and methyl methacrylate, the sample was once heated from room temperature to 130 ° C. at a temperature rising rate of 20 ° C. per minute, and then rapidly cooled to room temperature. Thereafter, the temperature was raised at a rate of temperature rise of 10 ° C. per minute, and the glass transition temperature (Tg) was measured.
In the measurement of poly (α-methylstyrene), the sample was heated from room temperature to 180 ° C. at a rate of temperature increase of 20 ° C. per minute, and then rapidly cooled to room temperature. Thereafter, similarly to polystyrene, the temperature was raised at a rate of 10 ° C. per minute, and the glass transition temperature (Tg) was measured.

(5) Thermal decomposition temperature of polymer (T ₁₀ ):
Using a pyrolysis measurement device (“TG / DTA6200” manufactured by Seiko Instruments), the sample was heated from room temperature to 130 ° C. at 20 ° C./min in a nitrogen stream, then rapidly cooled to room temperature, and then 600 ° C. at 10 ° C./min. The sample was measured for mass loss and the temperature at which the sample was reduced by 10% (T ₁₀ ) was used as an indicator of the thermal decomposition temperature.

<< Reference Example 1 >> [Synthesis of 1- (2-bromoethyl) adamantane]
1- (2-Bromoethyl) adamantane was synthesized according to the above reaction formula (1).
Specifically, 1.00 g (5.56 mmol) of 1-adamantane ethanol and 10 mL of dehydrated methylene chloride are placed in a 100 mL two-neck flask purged with nitrogen, and 1 mol of phosphorus tribromide is dissolved in 20 mL of methylene chloride. The solution was added dropwise at 0 ° C. Then, after standing overnight at room temperature, since consumption of the raw material was confirmed by NMR measurement, 30 mL of water was added dropwise to stop the reaction. Next, the aqueous layer was extracted three times with methylene chloride, the methylene chloride solution used for extraction and the organic layer (methylene chloride layer) were combined, washed with water, and dried over anhydrous magnesium sulfate. When the solvent was distilled off under reduced pressure and purification was performed by silica gel column chromatography using hexane as a developing solvent, 0.27 g (1.11 mmol, 20% yield) of the target 1- (2-bromoethyl) adamantane was obtained. It was.
The ¹ H-NMR spectrum and ¹³ C-NMR spectrum of 1- (2-bromoethyl) adamantane thus obtained are as shown in (a) and (b) of FIG. 1, and the respective peaks are as follows. there were.
¹ H-NMR (300 MHz, CDCl 3): δ = 1.51 (s, 6H, C (2) H ₂ ), 1.64 (m, 8H, C (4) H ₂ and CH ₂ C), 1.95 ((br, 3H, C (3) H), 3.41 (t, J = 9 Hz, 2H, CH ₂ Br).
^{· 13 C-NMR (75MHZ,} CDCl 3): δ = 28.9,29.5,34.4,37.4,42.5,48.5.

Reference Example 2 [Synthesis of 1,1-bis [4- (1-adamantyl) phenyl] ethylene]
According to the above reaction formula (2), 1,1-bis [4- (1-adamantyl) phenyl] ethylene was synthesized.
(1) Synthesis of 1- (4-bromophenyl) adamantane:
Under a nitrogen atmosphere, 6.41 g (30.2 mmol) of 1-phenyladamantane and 40 mL of carbon tetrachloride were added to a 500 mL two-necked flask, and then 30 mL (582 mmol, about 20 equivalents) of bromine was added and stirred at room temperature. . After 20 minutes, the consumption of the raw material was confirmed by gas chromatography. After 1 hour and a half, the reaction solution was poured into an ice bath, and the excess bromine was treated with sodium bisulfite, followed by extraction with methylene chloride three times. The methylene chloride solution used for extraction and the organic layer were combined and washed with water, then dried over magnesium sulfate, the organic solvent was distilled off under reduced pressure, and silica gel column chromatography was performed using hexane as a developing solvent. As a result, 6.61 g (22.7 mmol, yield 75%) of 1- (4-bromophenyl) adamantane was obtained. NMR measurement confirmed that the product was 1- (4-bromophenyl) adamantane.

(2) Synthesis of 1,1-bis [4- (1-adamantyl) phenyl] ethylene:
(I) Under a nitrogen atmosphere, add 0.74 g (30.5 mmol) of magnesium and 10 mL of tetrahydrofuran (hereinafter referred to as “THF”) to a 200 mL two-necked flask, add a few drops of 1,2-dibromoethane, The surface was activated. A solution prepared by dissolving 6.59 g (22.6 mmol) of 1- (4-bromophenyl) adamantane obtained in (1) above in 20 mL of THF was added dropwise in an ice bath, and the mixture was stirred at 85 to 90 ° C. for 2.5 hours. The mixture was refluxed, and consumption of the raw material was confirmed by gas chromatography. Subsequently, after the system was cooled to 0 ° C., a solution in which 0.95 g (10.8 mmol) of ethyl acetate was dissolved in 5 mL of THF was dropped into the system. After stirring at room temperature overnight, the system was refluxed at 90 ° C. for 3 hours. After cooling the system to room temperature, the reaction was stopped with 2N-HCl, THF was distilled off under reduced pressure, and the aqueous layer was extracted three times with methylene chloride. The organic layer (methylene chloride layer) was mixed and then washed with water. The organic layer was dried over anhydrous magnesium sulfate and the organic solvent was distilled off under reduced pressure to obtain 4.65 g of a white solid.
(Ii) Next, about 20 mg (0.1 mmol) of a catalytic amount of p-toluenesulfonic acid was added to a solution in which the total amount of the white solid obtained in (i) was dissolved in 60 mL of toluene, and the mixture was refluxed at 130 ° C. for 2 hours. did. The system was cooled to room temperature, the reaction was stopped with 50 mL of saturated aqueous sodium hydrogen carbonate solution, and then the toluene layer was separated. Thereafter, the aqueous layer was extracted three times with methylene chloride, and the organic layer (mixed solution of toluene layer and methylene chloride used for extraction) was washed with a saturated aqueous sodium hydrogen carbonate solution and water. The organic layer was dried using anhydrous magnesium sulfate, and the organic solvent was distilled off under reduced pressure to obtain 4.73 g (10.6 mmol, 98%) of crude 1,1-bis [4- (1-adamantyl) phenyl] ethylene. It was.

(Iii) The crude product obtained in (ii) above was dispersed in hexane, and hexane soluble components were removed by suction filtration. As a result, almost pure 1,1-bis [4- (1-adamantyl) phenyl] was obtained. 1.79 g (4.00 mmol) of ethylene was obtained. This was purified using silica gel column chromatography using a cyclohexane solvent to obtain 1.76 g (3.93 mmol) of the target 1,1-bis [4- (1-adamantyl) phenyl] ethylene. Furthermore, by recrystallization using a cyclohexane solvent, 1.15 g (2.57 mmol, yield 24%, melting point 242-243 ° C.) of 1,1-bis [4- (1-adamantyl) phenyl] ethylene as a pure white solid )
The ¹ H-NMR spectrum and ¹³ C-NMR spectrum of 1,1-bis [4- (1-adamantyl) phenyl] ethylene thus obtained are as shown in (a) and (b) of FIG. Each peak was as follows.
^{· 1 H-NMR (300MHz,} CDCL 3): δ = 1.78 (s, 12H, C (4) H 2), 1.94 (s, 12H, C (2) H 2), 2.10 (br, 6H, C ( 3) H), 5.40 (s, 2H, CH ₂ =), 7.31 (s, 8H, aromatic).
^{· 13 C-NMR (75MHz,} CDCL 3): δ = 29.3,36.4,37.2,43.5,113.5,124.9,128.3,139.0,150.0,151.2.

<< Reference Example 3 >> [Synthesis of 1- [4- (1-adamantyl) phenyl] -1-phenylethylene]
1- [4- (1-adamantyl) phenyl] ethylene was synthesized according to the above reaction formula (3).
(1) Under a nitrogen atmosphere, after adding 3.60 g (143 mmol) of magnesium and 20 mL of dehydrated THF to a 200 mL two-necked flask, the surface of magnesium to which several drops of 1,2-dibromoethane were added was activated. . A solution prepared by dissolving 10.6 g (36.5 mmol) of 1- (4-bromophenyl) adamantane prepared in the same manner as (1) of Reference Example 2 in 40 mL of dehydrated THF was added dropwise at room temperature and refluxed. After the completion of the reaction was confirmed by gas chromatography, the system was cooled to 0 ° C., and 4.8 g (40 mmol) of acetophenone purified by distillation was added dropwise. After stirring for 1 hour at room temperature, the reaction was stopped by pouring carefully into water. 2N-HCl was added for neutralization, THF was removed under reduced pressure, the aqueous layer was extracted three times with ether, the organic layer (ether layer) was washed with water, and then dried over anhydrous magnesium sulfate. The organic solvent was distilled off under reduced pressure to obtain a pale yellow solid crude product. The crude product was purified by silica gel column chromatography using hexane as a developing solvent, and then recrystallized in hexane to obtain white crystals.

(2) To a 200 mL two-necked eggplant flask, 11.0 g of white crystals obtained in (1) above, 100 mL of toluene and a catalytic amount (about 20 mg) of p-toluenesulfonic acid were added, and the mixture was heated to reflux for 6 hours. . The system was washed twice with 5% NaOH aqueous solution and then dried over anhydrous magnesium sulfate. After distilling off the organic solvent under reduced pressure, separation and purification were performed by silica gel column chromatography using hexane as a developing solvent. This was further purified by repeating recrystallization from hexane, and 4.95 g (15.8 mmol, 43% yield) of the desired white solid 1- [4- (1-adamantyl) phenyl] -1-phenylethylene was obtained. , Melting point 78-81 ° C.).
The ¹ H-NMR spectrum and ¹³ C-NMR spectrum of 1- [4- (1-adamantyl) phenyl] -1-phenylethylene thus obtained are as shown in (a) and (b) of FIG. The respective peaks were as follows.
^{· 1 H-NMR (300MHz,} CDCl 3): δ = 1.79 (s, 6H, C (4) H 2), 1.94 (s, 6H, C (2) H 2), 2.11 (br, 3H, C ( 3) H), 5.41 and 5.47 (2s, 2H, CH ₂ =), 7.31 (m, 9H, aromatic).
^{· 13 C-NMR (75MHz,} CDCl 3): δ = 29.3,36.4,37.1,43.5,114.1,125.0,127.9,128.2,128.4,128.7,138.8,142.1,150.2,151.3.

<< Reference Example 4 >> [Synthesis of 1- [4- (3- (1,1′-biadamantyl) phenyl)]-1-phenylethylene]
1- [4- (3- (1,1′-biadamantyl) phenyl)]-1-phenylethylene was synthesized according to the above reaction formula (4).
(1) Synthesis of 1- [4- (3- (1,1′-biadamantyl) phenyl)]-1-phenylethanol:
After adding 15 mL of dehydrated THF to 1.50 g (61.7 mmol) of magnesium in a 200 mL two-necked flask under nitrogen atmosphere, several drops of 1,2-dibromoethane were added to activate the surface of magnesium. 120 mL of dehydrated THF solution of 6.00 g (14.1 mmol) of 3- (4-bromophenyl) -1,1′-biadamantane synthesized by the method described in Patent Document 1 was added dropwise thereto at room temperature. After completion of the reaction was confirmed by gas chromatography, the system was cooled to 0 ° C. and 2.67 g (22.2 mmol) of acetophenone purified by distillation was added dropwise. After stirring for 1 hour at room temperature, the reaction was stopped by pouring carefully into water. 2N-HCl was added for neutralization, the aqueous layer was extracted three times with chloroform, and the combined organic layer was washed with water. After the organic phase was dried over anhydrous magnesium sulfate, the organic solvent was distilled off under reduced pressure to obtain a pale yellow solid [1- [4- (3- (1,1′-biadamantyl) phenyl)]-1-phenylethanol]. (8.83 g) was obtained. The crude product was used for the next reaction without purification.

(2) Synthesis of 1- [4- (3- (1,1′-biadamantyl) phenyl)]-1-phenylethylene:
In a 200 mL two-necked flask, 8.83 g of pale yellow solid [1- [4- (3- (1,1′-biadamantyl) phenyl)]-1-phenylethanol] obtained in (1) above, toluene 80 mL and a catalyst amount (about 20 mg) of p-toluenesulfonic acid were added, and the mixture was heated to reflux for 6 hours. The system was washed twice with 5% NaOH aqueous solution and then dried over anhydrous magnesium sulfate. After distilling off the organic solvent under reduced pressure, the obtained brown crude product was separated and purified by silica gel chromatography using hexane as a developing solvent, and the target 1- [4- (3- (1 , 1′-biadamantyl) phenyl)]-1-phenylethylene (1.81 mmol, yield 13%, melting point 183-186 ° C.).
The ¹ H-NMR spectrum and ¹³ C-NMR spectrum of 1- [4- (3- (1,1′-biadamantyl) phenyl)]-1-phenylethylene thus obtained are shown in FIG. Shown in (b).

<< Example 1 >> [Production of polystyrene having 2,2-bis (4-adamantylphenyl) ethyl groups at both ends]
(1) A high-vacuum solution in which 129 mg (0.775 mmol) of potassium naphthalene was dissolved in 5 mL of THF in a glass container and 549 mg (5.28 mmol) of styrene in 8 mL of THF was vigorously stirred at -78 ° C. It was added with stirring to synthesize both-end growth type living polystyrene. The reaction solution had a deep red color. Ten minutes later, a solution prepared by dissolving 218 mg (0.486 mmol) of 1,1-bis (4-adamantylphenyl) ethylene synthesized in Reference Example 2 in 37 mL of THF was added at −78 ° C. and reacted for 10 minutes. The reaction system changed from dark red to slightly bright red. After stopping the reaction with methanol, the polymer was precipitated by pouring the polymerization solution into a large excess of methanol.
(2) The structure of the polymer obtained in the above (1) was examined by ¹ H-NMR measurement and confirmed to be polystyrene having 2,2-bis (4-adamantylphenyl) ethyl groups at both ends. It was done.
When the molecular weight, molecular weight distribution, polymerization degree, and glass transition temperature of this polymer were measured by the methods described above, the number average molecular weight (Mn) was 4000, the weight average molecular weight was 4480, and the molecular weight distribution as shown in Table 1 below. (Mw / Mn) was 1.12, the number average degree of polymerization was 30, the glass transition temperature was 113 ° C., and the thermal decomposition temperature (T ₁₀ ) was 415 ° C.

<< Example 2 >> [Production of polystyrene having 2- (4-adamantylphenyl) -2-phenylethyl groups at both ends]
(1) A high-vacuum solution in which potassium naphthalene (64.0 mg, 0.386 mmol) was dissolved in THF (4 mL) and styrene (493 mg, 4.74 mmol) in THF (8 mL) was dissolved at −78 ° C. in a glass container. The both-end growth type living polystyrene was synthesized with vigorous stirring. The reaction solution had a deep red color. Ten minutes later, a solution prepared by dissolving 122 mg (0.390 mmol) of 1- (4-adamantylphenyl) -1-phenylethylene synthesized in Reference Example 3 in 3 mL of THF solution was added at −78 ° C. and reacted for 10 minutes. The reaction system changed from dark red to slightly bright red. After stopping the reaction with methanol, the polymer was precipitated by pouring the polymerization solution into a large excess of methanol.
(2) When the structure of the polymer obtained in the above (1) was examined by ¹ H-NMR measurement, it was a polystyrene having 2- (4-adamantylphenyl) -2-phenylethyl groups at both ends. confirmed.
When the molecular weight, molecular weight distribution, polymerization degree, and glass transition temperature of this polymer were measured by the methods described above, the number average molecular weight (Mn) was 3200, the weight average molecular weight was 3500, and the molecular weight distribution as shown in Table 1 below. (Mw / Mn) was 1.10, the number average degree of polymerization was 31, the glass transition temperature was 100 ° C., and the thermal decomposition temperature (T ₁₀ ) was 413 ° C.

<< Example 3 >> [Production of polystyrene having 2- (1-adamantyl) ethyl groups at both ends]
(1) A high-vacuum solution of 69.4 mg (0.418 mmol) of potassium naphthalene dissolved in 3 mL of THF in a glass container and a solution of 518 mg (4.98 mmol) of styrene dissolved in 8 mL of THF at −78 ° C. The both-end growth type living polystyrene was synthesized with vigorous stirring. The reaction solution had a deep red color. A solution prepared by dissolving 112 mg (0.460 mmol) of 1- (2-bromoethyl) adamantane synthesized in Reference Example 1 in 2 mL of a THF solution was added to the reaction solution at −78 ° C. and reacted for 10 minutes. The dark red color of the reaction system turned dark purple immediately after the addition of 1- (2-bromoethyl) adamantane. After opening the glass container, the polymer was precipitated by pouring the polymerization solution into a large excess of methanol.
(2) When the structure of the polymer obtained in the above (1) was examined by ¹ H-NMR measurement, it was confirmed to be polystyrene having 2- (1-adamantyl) ethyl groups at both ends.
When the molecular weight, molecular weight distribution, polymerization degree, and glass transition temperature of this polymer were measured by the methods described above, as shown in Table 1 below, the number average molecular weight (Mn) was 2700, the weight average molecular weight was 3000, and the molecular weight distribution. (Mw / Mn) was 1.11, the number average degree of polymerization was 26, and the glass transition temperature was 87 ° C.

Example 4 [Production of polystyrene having 2- [4- (3- (1,1′-biadamantyl) phenyl)]-2-phenylethyl group at both ends]
(1) A high-vacuum solution in which 38.0 mg (0.228 mmol) of potassium naphthalene was dissolved in 2 mL of THF in a glass container, and a solution of 355 mg (3.41 mmol) of styrene in 5 mL of THF was −78 ° C. The both-end growth type living polystyrene was synthesized with vigorous stirring. The reaction solution had a deep red color. A solution obtained by dissolving 154 mg (0.343 mmol) of 1- [4- (3- (1,1′-biadamantyl) phenyl)]-1-phenylethylene synthesized in Reference Example 4 in 18 mL of THF was added to the reaction solution. The mixture was added at 78 ° C. and allowed to react for 10 minutes. The deep red color of the reaction system turned dark purple immediately after the addition of 1- [4- (3- (1,1′-biadamantyl) phenyl)]-1-phenylethylene. After opening the glass container, the polymer was precipitated by pouring the polymerization solution into a large excess of methanol.
(2) The structure of the polymer obtained in the above (1) was examined by ¹ H-NMR measurement. As a result, 2- [4- (3- (1,1′-biadamantyl) phenyl)]- It was confirmed to be polystyrene having a 2-phenylethyl group.
When the molecular weight, molecular weight distribution, polymerization degree, and glass transition temperature of this polymer were measured by the methods described above, the number average molecular weight (Mn) was 3900, the weight average molecular weight was 4200, and the molecular weight distribution as shown in Table 1 below. (Mw / Mn) was 1.08, the number average degree of polymerization was 29, the glass transition temperature was 103 ° C., and the thermal decomposition temperature (T ₁₀ ) was 412 ° C.

<< Comparative Example 1 >> [Production of polystyrene having no polyalicyclic hydrocarbon group at its terminal]
(1) As in (1) of Example 2, 493 mg (4 mg of styrene) was dissolved in a solution obtained by dissolving 64.0 mg (0.386 mmol) of potassium naphthalene in 2.5 mL of THF in a glass container under high vacuum. .74 mmol) in 7 mL of THF was added with vigorous stirring at −78 ° C. to synthesize both-end growth type living polystyrene. After stopping the reaction with methanol, the polymer (polystyrene having a structural unit derived from styrene at both ends and having no polyalicyclic hydrocarbon group at the ends) is precipitated by pouring the polymerization solution into a large excess of methanol. It was.
(2) When the molecular weight, molecular weight distribution, polymerization degree, and glass transition temperature of the polymer obtained in (1) above were measured by the methods described above, the number average molecular weight (Mn) was as shown in Table 1 below. The weight average molecular weight was 3000, the molecular weight distribution (Mw / Mn) was 1.11, the number average degree of polymerization was 26, the glass transition temperature was 75 ° C., and the thermal decomposition temperature (T ₁₀ ) was 400 ° C.

<< Comparative Example 2 >> [Production of polystyrene having no polyalicyclic hydrocarbon group at its terminal]
(1) Under a high vacuum, in a glass container, a solution obtained by dissolving 30.0 mg (0.224 mmol) of lithium naphthalene in 3 mL of THF, and a solution of 376 mg (3.62 mmol) of styrene in 5 mL of THF at −78 ° C. The both-end growth type living polystyrene was synthesized with vigorous stirring. The reaction solution had a bright red color. After 10 minutes, the reaction was stopped with methanol, and the polymer solution was poured into a large excess of methanol to give a polymer (polystyrene having structural units derived from styrene at both ends and having no polyalicyclic hydrocarbon groups at the ends). Precipitated.
(2) When the molecular weight, molecular weight distribution, polymerization degree, and glass transition temperature of the polymer obtained in (1) above were measured by the methods described above, the number average molecular weight (Mn) was as shown in Table 1 below. 3400, a weight average molecular weight of 3770, a molecular weight distribution (Mw / Mn) of 1.11, a number average degree of polymerization of 33, a glass transition temperature of 77 ° C., and a thermal decomposition temperature (T ₁₀ ) of 400 ° C.

<< Comparative Example 3 >> [Production of polystyrene having sec-butyl group at one end]
(1) Under a high vacuum, in a glass container, a solution of 12.4 mg (0.193 mmol) of sec-butyllithium dissolved in 3 mL of heptane and a solution of 498 mg (4.79 mmol) of styrene dissolved in 7 mL of THF, One-end growth type living polystyrene was synthesized by vigorously stirring at −78 ° C. The reaction solution was orange-red. After 10 minutes, the reaction was stopped with methanol, and the polymer solution was poured into a large excess of methanol to give a polymer (polystyrene having a sec-butyl group at one end and a styrene-derived structural unit at the other end). Precipitated.
(2) When the molecular weight, molecular weight distribution, polymerization degree, and glass transition temperature of the polymer obtained in (1) above were measured by the methods described above, the number average molecular weight (Mn) was as shown in Table 1 below. 2600, the weight average molecular weight was 2730, the molecular weight distribution (Mw / Mn) was 1.05, the number average degree of polymerization was 25, and the glass transition temperature was 65 ° C.

As seen in Table 1 above, the polymers of Examples 1 to 4 (polystyrene) have a polyalicyclic hydrocarbon group at the polymer chain end, so that the polyalicyclic ring at the polymer chain end. Compared to the polymers (polystyrene) of Comparative Examples 1 to 3 having no formula hydrocarbon group, the glass transition temperature is as high as 10 ° C. or more, and the heat resistance is excellent.
In particular, the polymers of Examples 1 to 4 having a polyalicyclic hydrocarbon group at the polymer chain end have a sec-butyl group at one end and a structural unit derived from styrene at the other end. Compared with the polymer of Comparative Example 3 having no polyalicyclic hydrocarbon group, the glass transition temperature is as high as 22 ° C. or higher.

<< Example 5 >> [Production method of poly (α-methylstyrene) having 2- (4-adamantylphenyl) -2-phenylethyl groups at both ends]
(1) Under a high vacuum, in a glass container, a solution of 20.4 mg (0.123 mmol) of potassium naphthalene dissolved in 2 mL of THF, a solution of 559 mg (4.74 mmol) of α-methylstyrene in 3 mL of THF, The mixture was added with vigorous stirring at −78 ° C. to synthesize both-end growth type living poly (α-methylstyrene). The reaction solution had a deep red color. After 20 hours, a solution prepared by dissolving 52.9 mg (0.169 mmol) of 1- (4-adamantylphenyl) -1-phenylethylene synthesized in Reference Example 3 in 4 mL of THF was added at −78 ° C., and the reaction was further continued for 10 minutes. I let you. The reaction system changed from dark red to slightly bright red. After stopping the reaction with methanol, the polymer was precipitated by pouring the polymerization solution into a large excess of methanol.
(2) When the structure of the polymer obtained in (1) was examined by ¹ H-NMR measurement, poly (α-methyl) having 2- (4-adamantylphenyl) -2-phenylethyl groups at both ends Styrene) was confirmed.
When the molecular weight, molecular weight distribution, polymerization degree, and glass transition temperature of this polymer were measured by the methods described above, the number average molecular weight (Mn) was 3100, the weight average molecular weight was 3300, and the molecular weight distribution as shown in Table 2 below. (Mw / Mn) was 1.05, the number average degree of polymerization was 26, and the glass transition temperature was 160 ° C.

Comparative Example 4 [Poly (α-methylstyrene) having no polyalicyclic hydrocarbon group at the terminal]
(1) Under a high vacuum, in a glass container, in a solution obtained by dissolving 21.6 mg (0.130 mmol) of potassium naphthalene in 2 mL of THF, 244 mg (2.07 mmol) of α-methylstyrene in 3 mL of THF at −78 ° C. The dissolved solution was added with vigorous stirring to synthesize both-end growth type living poly (α-methylstyrene). The reaction solution had a deep red color. After 20 hours, the polymerization reaction was stopped with methanol, and the reaction solution was poured into a large excess of methanol to give a polymer [having structural units derived from α-methylstyrene at both ends, and polyalicyclic hydrocarbon groups at the ends. Poly (α-methylstyrene) without] was precipitated.
(2) When the molecular weight, molecular weight distribution, polymerization degree, and glass transition temperature of the polymer obtained in (1) above were measured by the methods described above, the number average molecular weight (Mn) was as shown in Table 2 below. 3300, the weight average molecular weight was 3,500, the molecular weight distribution (Mw / Mn) was 1.06, the number average degree of polymerization was 28, and the glass transition temperature was 140 ° C.

  As seen in Table 2 above, the polymer [poly (α-methylstyrene)] of Example 5 has a polyalicyclic hydrocarbon group at the end of the polymer chain. Compared with the polymer [poly (α-methylstyrene)] of Comparative Example 4 having no polyalicyclic hydrocarbon group, the glass transition temperature is as high as 20 ° C. and the heat resistance is excellent.

Example 6 [Production of polymethyl methacrylate having a 5,5-bis (4-adamantylphenyl) -3-methylpentyl group at one end]
(1) 1,1-synthesized in Reference Example 2 at −78 ° C. in a solution obtained by dissolving 4.48 mg (0.0700 mmol) of sec-butyllithium in 2 mL of heptane in a glass container under high vacuum. A solution prepared by dissolving 62.7 mg (0.140 mmol) of bis (4-adamantylphenyl) ethylene in 10 mL of THF was added and reacted for 10 minutes. A solution in which 14.9 mg (0.350 mmol) of lithium chloride was dissolved in 2 mL of THF was added to the system exhibiting red color at −78 ° C., and then allowed to stand for 10 minutes. Subsequently, a solution prepared by dissolving 392 mg (3.92 mmol) of methyl methacrylate in 5 mL of THF was added with vigorous stirring at −78 ° C. to synthesize one-end growth type living polymethyl methacrylate. The reaction solution was colorless and transparent. After 1 hour, the reaction was stopped with methanol, and the polymer was precipitated by pouring the polymerization solution into a large excess of hexane.
(2) When the structure of the polymer obtained in (1) above was examined by ¹ H-NMR measurement, polymethacryl having a 5,5-bis (4-adamantylphenyl) -3-methylpentyl group at one end. It was confirmed to be methyl acid.
When the molecular weight, molecular weight distribution, polymerization degree, and glass transition temperature of this polymer were measured by the methods described above, as shown in Table 3 below, the number average molecular weight (Mn) was 6800, the weight average molecular weight was 7070, and the molecular weight distribution. (Mw / Mn) was 1.04, the number average degree of polymerization was 62, and the glass transition temperature was 113 ° C.

<< Comparative Example 5 >> [Production of polymethyl methacrylate having no polyalicyclic hydrocarbon group at its terminal]
(1) Under a high vacuum, in a glass container, a solution of 3.58 mg (0.056 mmol) of sec-butyllithium dissolved in 2 mL of heptane was added to 20.2 mg of 1,1-diphenylethylene at −78 ° C. 0.112 mmol) in 2 mL of THF was added and allowed to react for 10 minutes. A solution in which 11.9 mg (0.280 mmol) of lithium chloride was dissolved in 2 mL of THF was added to the red-colored system at −78 ° C., and then allowed to stand for 10 minutes. Subsequently, a solution of 345 mg (3.45 mmol) of methyl methacrylate dissolved in 5 mL of THF was added with vigorous stirring at −78 ° C. to synthesize one-end growth type living polymethyl methacrylate. The reaction solution was colorless and transparent. After 1 hour, the reaction was stopped with methanol, and the polymer was precipitated by pouring the polymerization solution into a large excess of hexane.
(2) When the molecular weight, molecular weight distribution, polymerization degree, and glass transition temperature of the polymer obtained in (1) above were measured by the methods described above, the number average molecular weight (Mn) was as shown in Table 3 below. 6300, the weight average molecular weight was 6740, the molecular weight distribution (Mw / Mn) was 1.07, the number average degree of polymerization was 60, and the glass transition temperature was 89 ° C.

  As seen in Table 3 above, the polymer [polymethyl methacrylate] of Example 6 has a polyaliphatic hydrocarbon group at the end of the polymer chain, so Compared to the polymer of Comparative Example 5 [polymethyl methacrylate] having no cyclic hydrocarbon group, the glass transition temperature is as high as 24 ° C., and the heat resistance is excellent.

  The organic polymer of the present invention has an alicyclic hydrocarbon group having a polycyclic structure at the end of the polymer chain because of its low polymerization degree and excellent handleability, moldability / processability, recyclability, etc. In spite of its low polymerization degree, it has a high glass transition temperature and excellent heat resistance. Taking advantage of these properties, it can be used to make housings for home appliances, OA equipment, food containers, and packaging materials. , Food trays, foams, automobile parts, electrical / electronic parts, films, sheets, medical materials, elastic members, and the like.

Claims (2)

A chain structure derived from an addition-polymerizable monomer having a structural unit derived from one or more monomers selected from an aromatic vinyl monomer and a methacrylic acid ester in a proportion of 50 mol% or more An organic polymer having a number average degree of polymerization of 10 to 200 ;
At least one of a plurality of polymer chain ends in the organic polymer has the following general formula (I):

[Wherein R ¹ , R ² and R ³ each independently represents the following general formula (II);

(In the formula, R ⁴ represents an adamantyl group or a biadamantyl group , and n represents 0 or 1)
A hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 14 carbon atoms, wherein at least one of R ¹ , R ² and R ³ is It is group (II) represented by the formula (II). ]
An organic polymer having the group (I) represented by the formula: (I) A chain structure is obtained by polymerizing an addition polymerizable monomer containing one or more monomers selected from aromatic vinyl monomers and methacrylates in a proportion of 50 mol% or more. has after producing the organic polymer, the following formula polymerization terminator represented by the general formula (III) or the general formula of polymerization using a capping agent represented by (IV) of the stop or the polymer chain ends, Do capping ;

[Wherein R ⁴ is an adamantyl group or biadamantyl group , R ⁵ is an alkylene group having 1 to 4 carbon atoms or a direct bond (bond:-), X is a halogen atom, R ⁶ is a hydrogen atom, 1 to C 1 4 alkyl group or aryl group having 6 to 14 carbon atoms, n is 0 or 1, p is 1 or 2, q is 0 or 1, and p + q = 2. ]
(Ii) Using a polymerization initiator represented by the following general formula (V), 50 mol% or more of one or more monomers selected from an aromatic vinyl monomer and a methacrylic ester are used . Whether the addition-polymerizable monomer contained in a proportion is polymerized in a chain form ;

[Wherein, R ⁴ is an adamantyl group or biadamantyl group , R ⁶ is an alkylene group having 1 to 4 carbon atoms or a direct bond (bond:-), and n is 0 or 1. ]
Or,
(Iii) Using the polymerization initiator represented by the general formula (V), one or more monomers selected from an aromatic vinyl monomer and a methacrylic acid ester are added in an amount of 50 mol% or more. Polymerization is carried out using a polymerization terminator represented by the above general formula (III) or a capping agent represented by the above general formula (IV) after polymerizing the addition polymerizable monomer contained in a chain form. Termination or capping of polymer chain ends ;
The method for producing an organic polymer according to claim 1.

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