JP2007269961A - Transparent heat resisting resin, hydrogenated product thereof, method for producing the resin and the product, and optical material comprising transparent heat resisting resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin economically producible by using a low cost easily available monomer, excellent in heat resistance and adhesion and having high transparency, and to provide a method for producing the resin. <P>SOLUTION: The polymer cyclization products or hydrogenated products thereof are produced by cyclization of a copolymer (B) produced by halogenation and/or hydroxylation of olefinic double bond of a copolymer (A) containing styrene derivative unit and conjugated diene unit, and have 105-200°C glass transition temperature. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention is a novel polymer cyclized product that can be manufactured at low cost using inexpensive and easily available monomers and is excellent in heat resistance, adhesiveness, transparency, and the like, a hydrogenated product thereof, a method for producing the same, and a polymer The present invention relates to an optical material containing a cyclized product or a hydrogenated product thereof.

  In recent years, the demand for optical resins has become more and more sophisticated, and it can be manufactured at low cost using inexpensive and readily available monomers. Resins with excellent heat resistance and adhesion, low water absorption, and high transparency It has been demanded. However, conventional optical resins do not have these required performances in a well-balanced manner and have various drawbacks as optical resins.

  For example, polymethyl methacrylate, polycarbonate and the like have been conventionally used as optical resins with high transparency. Polymethylmethacrylate is excellent in optical properties such as high transparency and low birefringence, but has the disadvantages that its dimensions are easily changed due to its large water absorption, and its heat resistance is also low. Polycarbonate, on the other hand, has a high glass transition temperature (Tg) and excellent heat resistance, but has a disadvantage that it has a slightly high water absorption and is easily hydrolyzed by alkali.

  As an optical resin having high heat resistance, low water absorption, and excellent transparency, a ring-opening polymer hydrogenated product of a norbornene monomer and an addition copolymer of a norbornene monomer and ethylene are known. (Patent Documents 1 to 4). However, tetracyclododecene polycyclic monomers used as norbornene-based monomers are not always easy to produce. Moreover, when using as a film or a sheet form, since it does not contain a polar group, the adhesiveness with another base material was inadequate.

  A conjugated diene polymer cyclized product and a hydrogenated product thereof are known as optical resins that have improved the above problems (Patent Document 5). However, these conjugated diene polymer cyclized products and hydrogenated products thereof are obtained from inexpensive and easily available monomers, have excellent transparency and low water absorption, but have low Tg and are not sufficiently heat resistant. .

  As examples of improving the heat resistance of polymer cyclized products, cyclized products of phenyl-norbornene ring-opening polymers are known (Patent Documents 6 to 7). However, phenyl-norbornene monomers are not always easy to produce.

Moreover, the cyclization copolymer (nonpatent literature 1) which cyclized adjacent isoprenes by processing the copolymer of styrene and isoprene under acidic conditions is reported. However, the above document shows only the cyclization structure between adjacent conjugated dienes, does not show the cyclization structure by styrene derivatives and conjugated diene derivatives, and only shows the conditions for synthesizing the copolymer of styrene and isoprene. The ratio of styrene units and isoprene units in the copolymer produced in is not shown. Furthermore, this cyclized copolymer is used as a photoresist and has not been studied at all from the viewpoint of heat resistance.
JP-A 64-24826 JP 60-168708 A Japanese Patent Laid-Open No. 61-115912 JP 61-120816 A JP-A 64-1705 JP 50-154399 A Japanese Patent No. 3259465 Journal of Photopolymer Science and Technology, vol. 6, No. 1, (1993), pp 7-14

  Accordingly, an object of the present invention is to produce a polymer cyclized product or a hydrogenated product thereof, which can be produced at low cost using an inexpensive and easily available monomer, has excellent heat resistance, adhesiveness, etc., and has high transparency, and an optical system using the polymer It is to provide materials for use.

  As a result of intensive studies to solve the above problems, the present inventors have found that heat resistance is remarkably improved by cyclizing the halide and / or hydroxylate of a copolymer containing a styrene derivative unit and a conjugated diene derivative unit. It has been found that not only the improvement but also the adhesion with other substrates is improved, and the present invention has been completed.

  That is, the present invention relates to a polymer obtained by cyclizing a copolymer (B) obtained by halogenating and / or hydroxylating an olefinic double bond of a copolymer (A) containing a styrene derivative unit and a conjugated diene derivative unit. The polymer cyclized product or a hydrogenated product thereof, wherein the polymer cyclized product or the hydrogenated product thereof has a glass transition temperature of 105 ° C to 200 ° C.

  Further, the present invention provides the above heavy polymer, wherein the molar content ratio (styrene derivative / conjugated diene derivative) of the styrene derivative and the conjugated diene derivative in the copolymer (A) before cyclization is 15/85 to 90/10. The present invention relates to a combined cyclized product or a hydrogenated product thereof.

  Furthermore, the present invention relates to the above heavy polymer, wherein the molar content ratio (styrene derivative / conjugated diene derivative) of the styrene derivative and the conjugated diene derivative in the copolymer (A) before cyclization is 30/70 to 80/20. The present invention relates to a combined cyclized product or a hydrogenated product thereof.

  The present invention also relates to the polymer cyclized product or a hydrogenated product thereof, wherein the cyclization rate is 70% or more.

  Furthermore, the present invention relates to the polymer cyclized product or a hydrogenated product thereof, wherein the styrene derivative is at least one of styrene, α-methylstyrene and 4-methylstyrene.

  The present invention also relates to the polymer cyclized product or a hydrogenated product thereof, wherein the conjugated diene derivative is at least one of butadiene and isoprene.

  Furthermore, this invention relates to the said polymer cyclization thing or its hydrogenation thing whose number average molecular weight is 10,000-1 million.

  Moreover, this invention contains 0.1 weight%-10 weight% of halogen atoms and / or oxygen atoms with respect to the weight of a polymer cyclization thing or its hydrogenated product, In any one of Claims 1-7. The present invention relates to a polymer cyclized product or a hydrogenated product thereof.

  Furthermore, this invention relates to the hydrogenated product of the said polymer cyclization thing whose olefinic double bond is 10 mol% or less with respect to the conjugated diene derivative in a copolymer (A).

  The present invention also relates to the polymer cyclized product or a hydrogenated product thereof containing a cyclized structure formed by a styrene derivative and a conjugated diene derivative.

一般式［Ｉ］〜［IＶ］中、Ｒ_１は水素原子またはメチル基を示し、Ｒ_２、Ｒ_３、Ｒ_４およびＲ_５はそれぞれ独立して水素原子、炭素原子数１〜６のアルキル基またはビニル基を示し、Ｒ_２、Ｒ_３、Ｒ_４およびＲ_５のうち隣接する２つの基が互いに結合してベンゼン環を形成していてもよく、Ｘ_１、Ｘ_２、Ｘ_３およびＸ_４はそれぞれ独立して水素原子、炭素原子数１〜１０のアルキル基、フェニル基、水酸基またはハロゲン原子を示す、で表される構造の少なくとも１つを含む、前記重合体環化物またはその水素添加物に関する。 Furthermore, the present invention provides the following general formulas [I] to [IV]:

In the general formulas [I] to [IV], R ₁ represents a hydrogen atom or a methyl group, and R ₂ , R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Or a vinyl group, and two adjacent groups out of R ₂ , R ₃ , R ₄ and R ₅ may be bonded to each other to form a benzene ring, and X ₁ , X ₂ , X ₃ and X ₄ Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group, a hydroxyl group or a halogen atom, wherein the polymer cyclized product or hydrogenated product thereof About.

In the present invention, the ratio of the integral value of protons of 0 to 3 ppm and the integral value of protons of 6 to 8 ppm (integral value of protons of 0 to 3 ppm / 6 integral values of protons of 6 to 8 ppm) of the ¹ H-NMR spectrum is The polymer cyclized product or a hydrogenated product thereof is 0.7 to 20.

Further, in the present invention, the ratio of the integral value of 0 to ¹ ppm proton and the integral value of 6 to 8 ppm proton in the ¹ H-NMR spectrum (0 to 1 ppm proton integral value / 6 to 8 ppm proton integral value) is It relates to the polymer cyclized product or hydrogenated product thereof, which is 0.1 to 5.0.

  In the present invention, the copolymer (A) containing a styrene derivative unit and a conjugated diene derivative unit is halogenated and / or hydroxylated, further cyclized with a cyclization catalyst, and further hydrogenated as necessary. The present invention relates to a method for producing a polymer cyclized product or a hydrogenated product thereof, which performs a reaction.

  Furthermore, the present invention relates to a method for producing the polymer cyclized product or a hydrogenated product thereof, wherein the cyclization catalyst is a Bronsted acid or a Lewis acid.

  The present invention also relates to an optical material comprising the polymer cyclized product or a hydrogenated product thereof as a constituent component.

  The polymer cyclized product of the present invention further comprises a copolymer (B) obtained by halogenating and / or hydroxylating an olefinic double bond of a copolymer (A) containing a styrene derivative unit and a conjugated diene derivative unit. It becomes. The hydrogenated product of the polymer cyclized product is obtained by further hydrogenating the polymer cyclized product. Since the polymer cyclized product or hydrogenated product thereof has a glass transition temperature (Tg) of 105 ° C. or higher, the heat resistance is remarkably improved as compared with the conventional polymer cyclized product. The upper limit of Tg is about 200 ° C., although it varies depending on the type of styrene derivative or conjugated diene. On the other hand, Patent Document 5 discloses a polymer cyclized product obtained by cyclizing polybutadiene or polyisoprene as a conjugated diene. Despite a high cyclization rate of 72 to 96%, Tg is 102 ° C. It is as follows. Thus, the present invention provides an unprecedented heat resistant resin having excellent heat resistance and transparency by cyclizing a copolymer containing a styrene derivative unit and a conjugated diene derivative unit, and having a Tg of 105 ° C. or higher. Is realized.

  The polymer cyclized product or hydrogenated product thereof according to the present invention is halogenated and / or hydroxylated in addition to the above-mentioned heat resistance effect, so that these polar groups provide adhesion to other substrates. It has excellent properties as an optical material.

  The Tg of the polymer cyclized product can be improved more effectively by adjusting the ratio (molar content ratio) of the styrene derivative and the conjugated diene derivative and appropriately selecting the cyclization conditions. Since the Tg of styrene is about 100 ° C., the present inventors have found that the improvement of Tg in the present invention is not simply due to the addition effect of styrene, and the ring between conjugated diene derivatives as shown in Patent Document 5. Since the Tg does not increase significantly only by crystallization (at 102 ° C. or lower), the increase in Tg of the polymer cyclized product of the present invention is not obtained only by cyclization of the conjugated diene derivatives of the constituent components. As shown in the formulas [I] to [IV], it is considered to be due to the formation of a cyclized structure by a styrene derivative and a conjugated diene derivative.

  That is, the cyclized structure of the polymer cyclized product of the present invention includes a cyclized structure of a styrene derivative and a conjugated diene derivative, in addition to the cyclized structure of adjacent conjugated dienes represented by the following general formula [V]. included. For example, the cyclized structure of the styrene derivative and the conjugated diene derivative is such that the olefinic double bond derived from the conjugated diene derivative contained in the halide and / or hydroxyl group (B) of the copolymer (A) is caused by the cyclization catalyst. Bicyclic or polycyclic structures that are cationized and alkylated by Friedel-Crafts reaction with other olefinic double bonds in halides and / or hydroxylates (B) and aromatic rings of styrene derivatives Specifically, from the following general formula [I ′] to general formula [I], from general formula [II ′] to general formula [II], and from general formula [III ′] to general formula [III] And / or a structure cyclized by the reaction from the general formula [IV ′] to the general formula [IV]. Furthermore, the halogen and hydroxyl group of the copolymer (B) that has been halogenated and / or hydroxylated are cationized by a cyclization catalyst, and free from the olefinic double bond in the copolymer (B) or the aromatic ring of the styrene derivative. Also included are bicyclic or polycyclic structures alkylated by the Dell-Crafts reaction. Specifically, for example, in the copolymer (B) represented by the following general formula [VI] or general formula [VII], from the general formula [VI] to the general formula [I], from the general formula [VII] to the general formula Includes structures cyclized by reaction to Formula [II]. The structures represented by these general formulas [I] to [IV] are bulky and are considered to contribute greatly to the improvement of heat resistance.

  In addition, since the cyclized structure containing the 1st and 2nd carbon atoms of the benzene ring represented by the general formulas [I] to [IV] is a stable 6-membered ring, it can be easily formed. Other structures such as a 5-membered ring structure containing the 1st and 2nd carbon atoms of the benzene ring, a ring structure containing the 1st and 3rd carbon atoms of the benzene ring and the 1st and 4th carbon atoms of the benzene ring May be formed.

一般式［ＶＩ］ 一般式［ＶＩＩ］
一般式［ＶＩ］および一般式［ＶＩＩ］中、Ｙ_１はハロゲン原子または水酸基を表し、Ｙ_２は水素、ハロゲン原子または水酸基を表す。また、Ｘ_１〜Ｘ_４は上記一般式［Ｉ］〜［IＶ］におけるＸ_１〜Ｘ_４の意味と同じであり、Ｒ_１およびＲ_２〜Ｒ_５は、それぞれ上記一般式［Ｉ］〜［IＶ］におけるＲ_１およびＲ_２〜Ｒ_５の意味と同じである。

General formula [VI] General formula [VII]
In General Formula [VI] and General Formula [VII], Y ₁ represents a halogen atom or a hydroxyl group, and Y ₂ represents hydrogen, a halogen atom or a hydroxyl group. _Further, X 1 to X ₄ is the same meaning of _X 1 to X ₄ in the general formula [I] ~ [IV], R 1 and _R 2 to R ₅ are each the general formula [I] ~ [ IV] has the same meaning as R ₁ and R _{2 to} R ₅ .

  The polymer cyclized product of the present invention increases the cyclization rate by appropriately selecting the ratio of the styrene derivative and the conjugated diene derivative, the halogenation rate, the hydroxylation rate, and the cyclization conditions. Accordingly, heat resistance is improved by increasing Tg. It is considered that the formation of a cyclized structure by a styrene derivative and a conjugated diene derivative is promoted by an increase in the cyclization rate. The molar content ratio of the styrene derivative to the conjugated diene derivative (styrene derivative / conjugated diene derivative) is preferably 15/85 to 90/10, more preferably 20/80 to 90/10, and further preferably 30/70 to 80/20. Preferably, it exceeds 40/60 and is particularly preferably 80/20 or less. The cyclization rate is preferably 70% or more, more preferably 80% or more. The Tg of the polymer cyclized product or its hydrogenated product may vary depending on the copolymer component, cyclization rate, hydrogenation rate, etc., but usually depends on the molar content ratio and the cyclization rate range described above. A polymer cyclized product having a Tg of 105 ° C to 200 ° C can be obtained.

  The polymer cyclized product or hydrogenated product thereof according to the present invention is particularly suitable for optical applications because it is excellent in heat resistance and adhesiveness and has high transparency.

[I] Polymer cyclized product The polymer cyclized product of the present invention is a polymer cyclized product obtained by cyclizing the halogenated and / or hydroxylated product (B) of the copolymer (A). The copolymer (A) is obtained by copolymerizing a monomer containing a styrene derivative and a conjugated diene derivative.

(1) Styrene derivative The styrene derivative used in the present invention is a compound represented by the general formula [VIII].

In general formula [VIII], R ₁ represents a hydrogen atom or a methyl group, and R ₂ , R ₃ , R ₄ and R ₅ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a vinyl group. 2 groups adjacent to each other among R ₂ , R ₃ , R ₄ and R ₅ may be bonded to each other to form a benzene ring.

  Preferable specific examples of the compound represented by the general formula [VIII] include styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-ethylstyrene, 4-t-butylstyrene, 1-vinylnaphthalene. Styrene, α-methylstyrene or 4-methylstyrene is more preferable from the viewpoints of being inexpensive and easily available. These styrene derivatives may be used alone or in combination of two or more.

(2) Conjugated Diene Derivative The conjugated diene derivative used in the present invention is a compound represented by the general formula [IX].

In general formula [IX], X ′ ₁ , X ′ ₂ , X ′ ₃ and X ′ ₄ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group. Here, for example, when X ′ ₂ or X ′ ₃ is a hydrogen atom, the polymer of the monomer represented by the general formula [IX] can form a cyclized structure represented by the general formula [V].

  Specific examples of the compound represented by the general formula [IX] include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 2-phenyl-1,3-butadiene, 1,3- Conjugated diene compounds such as cyclohexadiene can be mentioned, and 1,3-butadiene or isoprene is more preferable from the viewpoint of being inexpensive and easily available. These conjugated diene derivatives may be used alone or in combination of two or more.

  The copolymer (A) used in the present invention may be a copolymer obtained by polymerizing any combination of the above styrene derivatives and conjugated dienes. Specific examples of the copolymer (A) include styrene-isoprene copolymer, styrene-1,3-butadiene copolymer, α-methylstyrene-isoprene copolymer, α-methylstyrene-1,3-butadiene copolymer. Polymer, 3- (or 4-) methylstyrene-isoprene copolymer, 3- (or 4-) methylstyrene-1,3-butadiene copolymer, 4-ethylstyrene-isoprene copolymer, 4-ethyl Styrene-1,3-butadiene copolymer, 4-t-butylstyrene-isoprene copolymer, 4-t-butylstyrene-1,3-butadiene copolymer, 1-vinylnaphthalene-isoprene copolymer, 1 -Vinylnaphthalene-1,3-butadiene copolymer, divinylbenzene-isoprene copolymer, divinylbenzene-1,3-butadiene copolymer, styrene 1,3-pentadiene copolymer, α-methylstyrene-1,3-pentadiene copolymer, styrene-2,3-dimethylbutadiene copolymer, α-methylstyrene-2,3-dimethylbutadiene copolymer Polymer, styrene-2-phenyl-1,3-butadiene copolymer, α-methylstyrene-2-phenyl-1,3-butadiene copolymer, styrene-1,3-cyclohexadiene copolymer, α-methyl Examples include styrene-cyclohexadiene copolymer.

  The structure of the copolymer (A) is not particularly limited, and for example, any of random, block, and tapered copolymers may be used. The copolymer (A) is particularly preferably a random copolymer from the viewpoint of heat resistance. When the conjugated diene is isoprene, it is composed of any structural unit of trans-1,4-structural unit, cis-1,4-structural unit, 1,2-structural unit, and 3,4-structural unit. In addition, these structural units may be constituted singly or in combination of two or more.

  From the viewpoint of the heat resistance of the polymer cyclized product obtained after the cyclization reaction, the molar content ratio (styrene derivative / conjugated diene derivative) of the styrene derivative and the conjugated diene derivative in the copolymer (A) used in the present invention is: The range of 15/85 to 90/10 is preferable, the range of 20/80 to 90/10 is more preferable, the range of 30/70 to 80/20 is further preferable, the range is more than 40/60, and particularly 80/20 or less. preferable.

The molar content ratio of styrene derivative and conjugated diene derivative in the polymer cyclized product varies depending on the type of styrene derivative and conjugated diene derivative, so it is generally difficult to analyze accurately, but those types are specified within a predetermined range. By doing so, an approximate molar content ratio can be obtained. For example, when the styrene derivative is at least one of styrene, α-methylstyrene and 4-methylstyrene, and the conjugated diene derivative is at least one of 1,3-butadiene and isoprene, the ¹ H-NMR spectrum Thus, the approximate molar content ratio of the styrene derivative and the conjugated diene derivative can be determined. That is, the ratio of the integral value of the proton of 0-3 ppm and the integral value of the proton of 6-8 ppm (integral value of the proton of 0-3 ppm) of the ¹ H-NMR spectrum (the proton of tetramethylsilane (TMS) is 0 ppm). (Integral value of proton of / 6 to 8 ppm) is about 0.7 to 20, the molar content ratio of styrene derivative and conjugated diene derivative of the polymer cyclized product is in the range of about 15/85 to 90/10, If the ratio of the integral value of protons of 0 to 3 ppm and the integral value of protons of 6 to 8 ppm is about 1.0 to 12, it is approximately in the range of 30/70 to 80/20.

(3) Other Copolymerized Monomer The polymer cyclized product of the present invention may contain another monomer copolymerizable with a styrene derivative and a conjugated diene derivative as a constituent component. The copolymerizable monomer is not particularly limited as long as it is a vinyl monomer. Specific examples include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth ) (Meth) acrylic monomers such as 2-hydroxyethyl acrylate and glycidyl (meth) acrylate; maleic anhydride, maleic acid, fumaric acid, maleimide; nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; acrylamide Amide group-containing vinyl monomers such as methacrylamide; olefins such as ethylene, propylene and norbornene; vinyl esters such as vinyl acetate, vinyl pivalate and vinyl benzoate; and styrene derivatives having a polar group. These may be used alone or in combination of two or more.

  When the copolymerizable monomer is copolymerized with a styrene derivative and a conjugated diene derivative, the amount of copolymerization is preferably 0.001 to 50 mol% and more preferably 0.01 to 20 mol% per all monomer units in the polymer. Preferably, 0.05 to 10 mol% is most preferable. If the amount of copolymerization is too large, the cyclization reaction may not proceed easily.

(4) Number average molecular weight The number average molecular weight of the polymer containing a styrene derivative and a conjugated diene derivative used in the present invention is not particularly limited, but from the viewpoint of mechanical properties and processability of the polymer cyclized product obtained, 10,000 to 1,000,000 g / mol is preferable. If the number average molecular weight is too small, the mechanical strength is insufficient, and if it is too large, molding becomes difficult. Here, the number average molecular weight means a molecular weight in terms of polystyrene by gel permeation chromatography.

(5) Halide The halide of the copolymer (A) is obtained by introducing halogen from chlorine, bromine, iodine or the like or a combination thereof into the olefinic double bond of the copolymer (A). In this specification, a halogenation rate means the ratio (%) of the olefinic double bond in which the halogen was introduced with respect to the total olefinic double bond amount of the copolymer (A). The olefinic double bond of the copolymer (A) is preferably from 0.1% to 99%, more preferably from 0.1% to 50%, and most preferably from 0.1% to the total amount of olefinic double bonds. 1% to 30% is halogenated. If the halogenation rate is too high, the weather resistance of the resulting polymer cyclized product or its hydrogenated product is lowered, and if the halogenation rate is too low, the adhesion or flame retardancy is insufficient.

(6) Hydroxide The hydroxyl group of the copolymer (A) is obtained by introducing a hydroxyl group into the olefinic double bond of the copolymer (A). In this specification, a hydroxylation rate means the ratio (%) of the olefinic double bond into which the hydroxyl group was introduce | transduced with respect to the total olefinic double bond amount of a copolymer (A). The olefinic double bond of the copolymer (A) is preferably from 0.1% to 60%, more preferably from 0.1% to 30%, most preferably from 0.1% to the total amount of olefinic double bonds. 1% to 10% are hydroxylated. If the hydroxylation rate is too high, the solvent becomes insoluble in a solvent that can be used for the cyclization reaction, and the cyclization reaction does not proceed easily.

(7) Cyclization rate The cyclization rate of the polymer cyclized product of the present invention is preferably 70% or more, more preferably 80% or more. When the cyclization rate is low, the heat resistance of the resulting polymer cyclized product is lowered.

Here, in this specification, the cyclization rate means the weight when the ratio of olefinic double bond protons / total protons obtained from the integral value of the ¹ H-NMR spectrum of the copolymer (A) is used as a reference. It means the reduction rate (%) of the ratio of olefinic double bond protons / total protons determined from the ¹ H-NMR spectrum of the combined cyclized product.

The polymer cyclized product of the present invention is characterized in that the ratio of the integral value of the proton of 0 to 1 ppm in the ¹ H-NMR spectrum (the proton of tetramethylsilane (TMS) is 0 ppm) is large. The ratio of the integral value of 0 to 1 ppm proton and the integral value of 6 to 8 ppm proton (integral value of 0 to 1 ppm proton / 6 to 8 ppm proton) is 0.1 to 5.0. Preferably, 0.1 to 3.0 is more preferable, and 0.15 to 2.0 is more preferable. If the ratio of the integral value of protons of 0 to 1 ppm and the integral value of protons of 6 to 8 ppm is too small, the content of the conjugated diene derivative is low (the content of the styrene derivative is high) or the cyclization rate is low. , Heat resistance is lowered. On the other hand, if the ratio of the integral value of protons of 0 to 1 ppm and the integral value of protons of 6 to 8 ppm is too large, the content of the styrene derivative is low, so that the heat resistance is also lowered.

(8) Hydrogenated product In the hydrogenated product of the polymer cyclized product of the present invention, the olefinic double bond other than aromatic is preferably in the copolymer (A) in order to prevent deterioration due to oxygen in the air. It is 10 mol% or less, more preferably 5 mol% or less, and most preferably 1 mol% or less with respect to the conjugated diene derivative unit. The hydrogenated product of the polymer cyclized product of the present invention has a ratio of the integral value of 4 to 6 ppm protons in the ¹ H-NMR spectrum (tetramethylsilane (TMS) proton is 0 ppm) and the total protons (4 (Integral value of protons of ˜6 ppm / total protons) is preferably 0.05 or less, and more preferably 0.01 or less. When the said ratio is large, the quantity of an olefin double bond may increase and it may be easy to deteriorate.

(9) Glass transition temperature (Tg)
The polymer cyclized product or hydrogenated product thereof according to the present invention is characterized in that Tg is remarkably increased as compared with that before the cyclization reaction. The increase in Tg is caused not only by the cyclization reaction between adjacent conjugated diene derivative units in the copolymer (A) but also by the cyclization reaction between adjacent styrene derivative units and conjugated diene derivative units.

  Tg can be measured by differential scanning calorimetry (DSC). First, the sample is heated from 25 ° C. to 10 ° C. at a rate of 10 ° C./min under a nitrogen stream to obtain a DSC curve. Next, the intersection of the parallel line 7 passing through the intersection of the central tangent line 4 of the DSC curve shown in FIG. 1 and the base line 5 before transition and parallel to the temperature axis 2, and the intersection of the central tangent line 4 and the baseline 6 after transition are shown. A parallel line 8 parallel to the temperature axis 2 is drawn. In this specification, the temperature 3 at the intersection of the parallel line 9 that bisects the two parallel lines 7 and 8 and the DSC curve is defined as Tg.

  Tg can be adjusted to a desired temperature depending on the resin used, the type and amount of the cyclization catalyst, the reaction temperature, the reaction pressure, the reaction time, etc., but from the viewpoint of the heat resistance and strength of the polymer cyclized product. To 105 ° C to 200 ° C, preferably 105 ° C to 190 ° C, more preferably 108 ° C to 180 ° C, and further preferably 110 ° C to 150 ° C. When Tg is low, the heat resistance is insufficient, and when it is too high, the polymer cyclized product becomes brittle.

(10) Total light transmittance The polymer cyclized product or hydrogenated product thereof of the present invention preferably has a high total light transmittance particularly when used in an optical material. The total light transmittance of the polymer cyclized product or its hydrogenated product is preferably 80% or more, and more preferably 85% or more.

(11) Specific gravity When the polymer cyclized product or the hydrogenated product thereof according to the present invention has a large specific gravity, the polymer cyclized product or the hydrogenated product increases in weight when applied to a material such as an optical material, and narrows its application range. Therefore, the specific gravity of the polymer cyclized product or its hydrogenated product is preferably 1.10 or less, and more preferably 1.05 or less.

[II] Production method of polymer cyclized product (1) Polymerization reaction Copolymer (A) containing a styrene derivative and a conjugated diene derivative as a structural unit is a known polymer such as a radical polymerization method, an anionic polymerization method, and a cationic polymerization method. It can be obtained by a method. From the viewpoint that it can be easily carried out industrially, a radical polymerization method or an anionic polymerization method is particularly preferable.

(2) Halogenation reaction The halogenation method of the copolymer (A) is not particularly limited. For example, a method of adding a hydrogen halide such as hydrogen chloride or hydrogen bromide, or a halogen such as chlorine, bromine or iodine is added. Publicly known methods such as a method of adding iodine monochloride, a method of adding iodine monobromide, a method of using thionyl chloride, and the like can be used.

  By halogenating the copolymer (A), since the halogen is present in the finally obtained polymer cyclized product or its hydrogenated product, flame retardancy and adhesion are improved.

  The amount of halogen atoms contained in the polymer cyclized product or hydrogenated product thereof is preferably 0.1 to 10% by weight, more preferably 0.1 to 5% by weight, based on the weight of the polymer cyclized product or hydrogenated product thereof. It is.

(3) Hydroxylation reaction The method of hydroxylation of the copolymer (A) is not particularly limited. For example, a hydroxyl group is bonded to the carbon-carbon double bond of the copolymer (A) by hydrometallation reaction and subsequent oxidation reaction. Can be introduced. Examples of the hydrometallation reaction include hydroboration, hydrosilylation, hydrozirconation, and hydroalumination. Among these, hydroboration is most widely used, and hydroboration can be preferably used in the production method of the present invention. In addition, hydrometallation reaction itself is well-known and the manufacturing method of this invention can be implemented according to a well-known method.

  Examples of the oxidation reaction subsequent to the hydrometallation reaction include oxidation with air or oxygen, oxidation with hydrogen peroxide, oxyamine, etc., but oxidation with hydrogen peroxide is particularly preferable from the viewpoint of ease of implementation and reaction rate. preferable.

  The hydroxylation of the copolymer (A) makes the cyclization reaction difficult to proceed, and the water absorption of the finally obtained polymer cyclized product or its hydrogenated product is somewhat increased. Since hydroxyl groups are present in the cyclized product or hydrogenated product thereof, the adhesion and solvent resistance are improved.

  The amount of oxygen atoms contained in the polymer cyclized product or hydrogenated product thereof is preferably 0.1 to 10% by weight, more preferably 0.1 to 5% by weight, based on the weight of the polymer cyclized product or hydrogenated product thereof. It is.

(4) Cyclization reaction The cyclization reaction can be controlled by the type of catalyst, amount of catalyst, reaction temperature, reaction pressure, reaction time, and the like. The polymer cyclized product of the present invention is preferably selected in advance by appropriately selecting the type of catalyst, amount of catalyst, reaction temperature, reaction pressure, reaction time, etc. according to the types of styrene derivatives and conjugated diene derivatives, their composition ratios, etc. The conditions are such that the Tg of coalescence is 105 ° C to 200 ° C.

(5) Cyclization solvent The cyclization reaction used for this invention can be performed by the well-known method as described in patent 3170937. Specifically, it is carried out, for example, by adding or contacting a cyclization catalyst in an inert organic solvent or in a molten state of a copolymer (resin). The inert organic solvent can be used without particular limitation as long as it is an organic solvent that dissolves the resin and is inert to the cyclization catalyst. Specifically, aromatic hydrocarbon solvents such as benzene, toluene, xylene; aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, cyclopentane, cyclohexane, methylcyclohexane, decalin; methyl chloride, methylene chloride Halogenated hydrocarbon solvents such as 1,2-dichloroethane, 1,1,2-trichloroethylene; oxygen-containing solvents such as esters and ethers. In view of reactivity, aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, halogenated hydrocarbon solvents and the like are preferable. These solvents may be used alone or in combination of two or more.

  When an inert organic solvent is used in the cyclization reaction, the amount of the inert organic solvent used is not particularly limited, but is usually 100 to 10,000 parts by weight, preferably 150 to 5000 parts per 100 parts by weight of the copolymer (A). Part by weight, more preferably 200 to 3000 parts by weight. If the amount of the inert solvent is small, it becomes difficult to uniformly mix the cyclization catalyst, so that the reaction becomes non-uniform and a uniform resin cannot be obtained or the control of the reaction becomes difficult. When the amount of the inert solvent is large, productivity is lowered.

  When the cyclization reaction is carried out in a molten state, a small amount of an inert organic solvent may be added for the purpose of lowering the melt viscosity. The inert organic solvent used in this case is not particularly limited, and for example, the above-described inert organic solvent can be used. The amount of the inert organic solvent used is usually 0.001 to 30 parts by weight, preferably 0.005 to 10 parts by weight, more preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the copolymer (A). is there. If the amount of the inert solvent is small, the melt viscosity may not be sufficiently lowered. When there are many inert solvents, solvent viscosity is too low and reaction in a molten state becomes difficult.

(6) Cyclization catalyst The manufacturing method of this invention can use an acidic compound as a cyclization catalyst. The acidic compound is not particularly limited, and examples thereof include Lewis acid or Bronsted acid. _BF 3 in _{particular, BF 3 OEt 2, BBr 3} , BBr 3 OEt 2, AlCl 3, AlBr 3, AlI 3, TiCl 4, TiBr 4, TiI 4, FeCl 3, FeCl 2, SnCl 2, SnCl 4, Metal halides from Group IIIA to Group VIII of the periodic table such as WCl ₆ , MoCl ₅ , SbCl ₅ , TeCl ₂ ; Hydrogen acids such as HF, HCl, HBr; H ₂ SO ₄ , H ₃ BO ₃ , HClO ₄ , Oxonic acids such as CH ₃ COOH, CH ₂ ClCOOH, CHCl ₂ COOH, CCl ₃ COOH, CF ₃ COOH, p-toluenesulfonic acid, CF ₃ SO ₃ H, H ₃ PO ₄ , P ₂ O ₅ , and these groups Polymer compounds such as ion exchange resins having heteropolyacids such as phosphomolybdic acid and phosphotungstic acid _{; SiO 2, Al 2 O 3} , SiO 2 -Al 2 O 3, MgO-SiO 2, B 2 O 3 -Al 2 O 3, WO 3 -Al 2 O 3, Zr 2 O 3 -SiO 2, sulphated include zirconia, tungsten acid zirconia, H ⁺ or zeolites exchanged with rare earth, activated clay, acid _{clay, γ-Al 2 O 3,} P 2 O 5 and the like solid acid solid phosphoric acid or the like is diatomaceous earth and carrying the . These acidic compounds may be used in combination, or other compounds may be added. Other compounds etc. are compounds etc. which can improve the activity of an acidic compound, for example by adding it. Examples of compounds that improve the activity of metal halide compounds as acidic compounds include MeLi, EtLi, BuLi, Et ₂ Mg, EtMgBr, Et ₃ Al, Et ₂ AlCl, EtAlCl ₂ , Et ₃ Al ₂ Cl ₃ , (i _{-Bu) 3 Al, Et 2 Al} (OEt), Me 4 Sn, Et 4 Sn, Bu 4 Sn, Bu 3 metal alkyl compound such as SnCl; 2-methoxy-2-phenylpropane, t-butanol, 1,4 Examples include compounds used as polymerization initiators in living cationic polymerization, such as -bis (2-methoxy-2-propyl) benzene and 2-phenyl-2-propanol.

  The amount of the cyclization catalyst used in the cyclization reaction of the present invention is difficult to define in general because the catalytic ability varies depending on the type of cyclization catalyst, but in the case of a homogeneous catalyst, the amount used Is preferably 0.001 to 1000 parts by weight, more preferably 0.01 to 100 parts by weight, and most preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the copolymer (A). When a heterogeneous catalyst such as a solid acid or an ion exchange resin is used as the cyclization catalyst, the amount used is preferably 0.1 to 10,000 parts by weight, preferably 1-1000 parts by weight based on 100 parts by weight of the copolymer (A). Part is more preferred. If the amount of catalyst is small, the cyclization reaction proceeds slowly, and if it is large, it is uneconomical.

  In the present invention, when the cyclization reaction is performed in an inert organic solvent, the reaction temperature is usually preferably from -40 ° C to 200 ° C, more preferably from 0 ° C to 150 ° C, and most preferably from 20 ° C to 130 ° C. When the cyclization reaction is performed in a molten state, the temperature may be any temperature at which the resin is not thermally decomposed, and is usually 350 ° C. or lower, preferably 300 ° C. or lower. If the reaction temperature is too low, the progress of the reaction is slow, and if it is too high, the reaction is difficult to control and reproducibility is difficult to obtain.

  The reaction pressure for carrying out the cyclization reaction is not particularly limited, but is preferably 0.5 to 50 atm, and more preferably 0.7 to 10 atm. Usually, the cyclization reaction is performed at around 1 atm.

  The reaction time for carrying out the cyclization reaction is not particularly limited, and the resin having the desired performance after the cyclization reaction may be selected depending on the resin used, the amount thereof, the type and amount of the cyclization catalyst, the reaction temperature, the reaction pressure, and the like. What is necessary is just to determine reaction time suitably so that it may be obtained. Usually, it is 0.01 hours to 24 hours, preferably 0.2 hours to 10 hours.

  The polymer after the cyclization reaction is used for isolating the polymer from a solution such as reprecipitation, solvent removal under heating, solvent removal under reduced pressure, or removal of the solvent with steam (steam stripping). These can be separated and obtained from the reaction mixture by the usual operation.

(7) Hydrogenation The polymer cyclized product of the present invention may be hydrogenated for the purpose of preventing deterioration due to oxygen in the air. The method of hydrogenation is not particularly limited. For example, a homogeneous catalyst such as Wilkinson complex, cobalt acetate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, diatomaceous earth, magnesia, alumina, silica, alumina-magnesia, silica-magnesia. A known method using a heterogeneous catalyst in which a catalyst metal such as nickel, palladium or platinum is supported on a support such as silica-alumina or synthetic zeolite can be used.

  As a solvent that can be used for hydrogenation, any organic solvent that dissolves the resin and is inert to the hydrogenation catalyst can be used. Specifically, aromatic hydrocarbon solvents such as benzene, toluene and xylene; aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, cyclopentane, cyclohexane, methylcyclohexane and decalin can be used. . These may be used alone or in combination of two or more.

The reaction temperature of the hydrogenation reaction depends on the hydrogenation catalyst used and the hydrogen pressure, but is preferably 20 ° C to 250 ° C, more preferably 25 ° C to 150 ° C, and most preferably 40 ° C to 100 ° C. If the reaction temperature is too low, the reaction does not proceed smoothly, and if the reaction temperature is too high, side reactions and molecular weight reduction tend to occur. The hydrogen pressure is preferably normal pressure to 200 kgf / cm ² , more preferably 5 to 100 kgf / cm ² . If the hydrogen pressure is too low, the reaction does not proceed smoothly, and if the hydrogen pressure is too high, there are restrictions on the apparatus.

  The concentration of the polymer cyclized product in the hydrogenation reaction system is usually 2 to 40% by weight, preferably 3 to 30% by weight, more preferably 5 to 20% by weight. If the concentration of the polymer cyclized product is low, the productivity is liable to decrease, which is not preferable. On the other hand, when the concentration of the polymer cyclized product is too high, the hydrogenated polymer is precipitated, the viscosity of the reaction mixture is increased, and stirring may not be performed smoothly.

  The reaction time of the hydrogenation reaction depends on the hydrogenation catalyst used, the hydrogen pressure, and the reaction temperature, but is usually 0.1 hours to 50 hours, preferably 0.2 hours to 20 hours, more preferably 0.5 hours. For 10 hours.

  The polymer after the hydrogenation reaction is used for isolating the polymer from a solution, for example, by reprecipitation, solvent removal under heating, solvent removal under reduced pressure, or removal of the solvent with steam (steam stripping). These can be separated and obtained from the reaction mixture by the usual operation.

[III] Optical Material The polymer cyclized product or hydrogenated product thereof according to the present invention can be used for various optical materials, and the range thereof is not particularly limited, but is excellent in heat resistance and is required to have high transparency. Suitable for material. Examples of optical materials include lenses, aspheric lenses, Fresnel lenses, lenses for silver salt cameras, lenses for digital electronic cameras, lenses for video cameras, lenses for projectors, lenses for copying machines, camera lenses for mobile phones, and lenses for glasses. , Contact lenses, aspherical pickup lenses for digital optical disc devices using blue light emitting diodes, rod lenses, rod lens arrays, microlenses, microlens arrays, the above various lenses used in a relatively high temperature thermal environment, various lenses Array, step index type, gradient index type, single mode type, multi-core type, polarization plane preserving type, side emission type optical fiber, optical fiber connector, optical fiber adhesive, digital optical disc (compact disc, magneto-optical disc) Various disk substrates such as optical discs, digital discs, video discs, computer discs, blue light emitting diodes, etc.), polarizing films for liquid crystals, light guide plates for liquid crystals for backlights or front lights, light diffusion plates for liquid crystals, having different refractive indexes Light diffusing plate for liquid crystal with dispersed fine particles, glass substrate substitute film for liquid crystal, retardation film, retardation plate for liquid crystal, liquid crystal guiding plate for mobile phone, retardation plate for organic electroluminescence, color filter for liquid crystal, flat Anti-reflection film for panel display, touch panel substrate, transparent conductive film, anti-reflection film, anti-glare film, substrate for electronic paper, organic electroluminescence substrate, front protective plate for plasma display, anti-electromagnetic wave plate for plasma display, field emission Di Front protection plate for play, light guide plate that diffuses the light of a specific part using piezoelectric elements, prisms that constitute polarizers, analyzers, diffraction gratings, endoscopes, endoscopes that guide high-energy lasers , Camera mirrors or half mirrors typified by Dach mirrors, automotive headlight lenses, automotive headlight reflectors, solar cell front protection plates, residential window glass, moving objects (automobiles, trains, ships, aircraft, space) Ships, space bases, artificial satellites, etc.) window glass, anti-reflection film for window glass, dust-proof film during semiconductor exposure, protective film for electrophotographic photosensitive material, semiconductor (EPROM etc.) that can be written or rewritten by ultraviolet light Material, light emitting diode encapsulant, ultraviolet light emitting diode encapsulant, white light emitting diode encapsulant, SAW filter, optical band Pass filter, second harmonic generator, Kerr effect generator, optical switch, optical interconnection, optical isolator, optical waveguide, surface light emitter using organic electroluminescence, surface light emitter with dispersed semiconductor fine particles, fluorescence Examples thereof include phosphors in which substances are dissolved or dispersed.

  The polymer cyclized product or hydrogenated product thereof of the present invention can be used alone, or polyamide, polyurethane, polyester, polycarbonate, polyoxymethylene resin, acrylic resin, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, It can also be used as a composition blended with other polymers such as polyolefin, polystyrene, styrene block copolymers. When used as a composition, stabilizers, lubricants, pigments, impact resistance improvers, processing aids, reinforcing agents, colorants, flame retardants, weather resistance improvers, UV absorbers, antioxidants, fungicides, Various additives such as antibacterial agents, light stabilizers, antistatic agents, silicone oils, antiblocking agents, mold release agents, foaming agents, fragrances; various fibers such as glass fibers and polyester fibers; talc, mica, montmorillonite, smectite, Fillers such as silica and wood powder; optional components such as various coupling agents can be blended as required.

  As mentioned above, although embodiment of this invention was described, this invention is not limited to said specific example. Further, the exemplified materials may be used alone or in combination unless otherwise specified.

  EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Reference example 1
Styrene-isoprene copolymer (a1)
640 g of cyclohexane, 0.48 g of tetrahydrofuran, and 1.20 ml of sec-butyllithium (1.3 M cyclohexane solution) were added to a pressure vessel equipped with a stirrer purged with nitrogen, and heated to 40 ° C. A mixed monomer solution consisting of 92.8 g of styrene and 67.2 g of isoprene was sequentially added thereto at a rate of 2.0 ml / min. After completion of the addition, the mixture was reacted at 40 ° C. for 60 minutes, and 1 ml of methanol was added to complete the polymerization. I let you. The obtained polymerization solution was reprecipitated in 10 L of a mixed solvent of methanol / acetone (50/50 vol) and then sufficiently dried to obtain 148 g of a styrene-isoprene copolymer (a1). The number average molecular weight (GPC measurement, polystyrene conversion) was 127,000, the styrene content determined from ¹ H-NMR was 48 mol% (58 wt%), and the degree of vinylation was 28%.

Here, the degree of vinylation is the integral value (ii) of protons of 3.8 to 4.8 ppm in ¹ H-NMR of the styrene-isoprene copolymer, 3,4-structural units, and 4.8 to 5.8 ppm. The integral value (b) of the proton was determined from the following formula using 1,4-structural units.
Degree of vinylation = ((A) / 2) × 100 / [((A) / 2) + (B)]

Reference example 2
Chlorinated product of styrene-isoprene copolymer (b1)
30 g of the styrene-isoprene copolymer (a1) obtained in Reference Example 1 was placed in a glass flask equipped with a cock and sufficiently purged with nitrogen. Then, 720 g of dehydrated methylene chloride was added under a nitrogen stream, and stirred uniformly. Dissolved. Further, 10 g of alumina was added as an adsorbent and cooled to 0 ° C. While stirring, 43 g of thionyl chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was gradually added dropwise under a nitrogen stream. After reacting with stirring for 30 minutes, the reaction was performed with stirring at room temperature for 2 hours. Further, 10 ml of an aqueous sodium hydroxide solution (1N) was gradually added dropwise to decompose unreacted thionyl chloride. Distilled water was added to the obtained polymer solution to wash it until the aqueous layer became neutral, and then it was reprecipitated in 10 L of methanol and sufficiently dried to obtain 25 g of chlorinated styrene-isoprene copolymer (b1). As a result of ¹ H-NMR (400 MHz) measurement, it was found that 18% of the double bond derived from isoprene was halogenated from the decrease in the peak corresponding to the carbon-carbon double bond.

Reference example 3
Hydroxide of styrene-isoprene copolymer (b2)
30 g of the styrene-isoprene copolymer (a1) obtained in Reference Example 1 was placed in a glass flask with a cock and sufficiently purged with nitrogen. Then, 120 g of dehydrated tetrahydrofuran was added under a nitrogen stream and stirred to dissolve uniformly. . After cooling to 0 ° C., 50 ml of 9-borabicyclo (3,3,1) nonane (0.5M tetrahydrofuran solution, manufactured by Aldrich) was added with stirring. After stirring for 30 minutes, the mixture was stirred at room temperature for 10 hours, and further stirred at 40 ° C. for 2 hours for reaction. After cooling to 5 ° C., an aqueous sodium hydroxide solution in which 3 g of sodium hydroxide was dissolved in 7 g of water was added, and 20 g of 30% hydrogen peroxide was gradually added dropwise over 1 hour. Distilled water was added to the resulting solution, washed sufficiently, then reprecipitated in 3 L of methanol, and sufficiently dried to obtain 20 g of a hydroxylated styrene-isoprene copolymer (b2). As a result of ¹ H-NMR (400 MHz) measurement, it was found that 10% of the isoprene-derived double bonds were hydroxylated from the decrease in the peak corresponding to the carbon-carbon double bond.

Example 1
20 g of the styrene-isoprene copolymer chlorinated product (b1) obtained in Reference Example 2 was placed in a glass flask equipped with a cock and sufficiently purged with nitrogen. Then, 480 g of dehydrated cyclohexane was added in a nitrogen stream, and stirred uniformly. Dissolved. Further, while stirring at 25 ° C., 0.8 g of trifluoromethanesulfonic acid (manufactured by Wako Pure Chemical Industries, Ltd.) was added as a catalyst under a nitrogen stream and stirred for 30 minutes. Next, 50 g of an aqueous sodium hydroxide solution (0.3 wt%) was added with stirring to complete the reaction. The sodium hydroxide aqueous solution layer was extracted, distilled water was added and washed until the aqueous layer became neutral, and the catalyst was removed. The obtained cyclohexane layer was reprecipitated in 6 L of a mixed solvent of methanol / acetone (50/50 vol%) and then sufficiently dried to obtain 18 g of a polymer cyclized product (A1). The obtained polymer cyclized product (A1) was press-molded at 180 ° C. to prepare a plate having a thickness of 0.8 mm. Table 1 shows the evaluation results of the polymer cyclized product (A1) obtained in this example.

The measuring method of each parameter of the polymer cyclization product in an Example is shown below.
It is the number average molecular weight determined in terms of polystyrene by molecular weight gel permeation chromatography (GPC). Here, the Tosoh Co., Ltd. product and HLC-8020 (product number) are used as the GPC device, and the Tosoh Co., Ltd. product, two TSKgel GMH-M and one G2000H are connected in series as the column.
Cyclization rate
Styrene from ^{1 H-NMR} spectrum - isoprene copolymer ratio when based on the olefinic double bond protons / total proton, polymer cyclized ^{1 H-NMR} olefinic double bond protons obtained from the spectrum of the product / The reduction rate (%) of the total proton ratio was defined as the cyclization rate.
Here, deuterated chloroform was used as a solvent, tetramethylsilane (TMS) was set to 0 ppm, and ¹ H-NMR spectrum was obtained using JNM-LA-400 (product number) manufactured by JEOL Ltd. The measurement was performed at room temperature.
Glass transition temperature (Tg)
It measured by the differential scanning calorimetry (DSC) using the sample which fully dried and removed the solvent. The sample was heated from 25 ° C. to 10 ° C./min under an air flow of 100 ml / min to obtain a DSC curve. Next, the intersection of the parallel line 7 passing through the intersection of the central tangent line 4 of the DSC curve shown in FIG. 1 and the base line 5 before transition and parallel to the temperature axis 2, and the intersection of the central tangent line 4 and the baseline 6 after transition are shown. A parallel line 8 parallel to the temperature axis 2 was drawn. In this specification, the temperature 3 at the intersection of the parallel line 9 that bisects the two parallel lines 7 and 8 and the DSC curve is Tg.
Here, DSC30 (product number) manufactured by METTLER TOLEDO was used as a measuring apparatus.
The total light transmittance Murakami Color Research Laboratory Co., Ltd., was measured using the HR-100 (number).
Contact angle automatic contact angle measuring device SCA20 (dataphysics
Measurements were made using Instruments GmbH. In general, the smaller the contact angle, the higher the adhesion with a coating agent or the like.
Elemental analysis The chlorine atom content was quantified as chloride ions by ion chromatography (ion chromatography analyzer DX-120, manufactured by Dionex) after pretreatment by an oxygen flask combustion method.
The oxygen atom content was measured with an organic element analyzer (elemental analyzer 2400II manufactured by PerkinElmer).
0-3ppm / 6-8ppm, 0-1ppm / 6-8ppm
Ratio of integral value of proton of 0-3 ppm and integral value of proton of 6-8 ppm (integral value of proton of 0-3 ppm / 6) of ¹ H-NMR spectrum (with proton of tetramethylsilane (TMS) being 0 ppm) -8 ppm proton integral value) and the ratio of 0-1 ppm proton integral value to 6-8 ppm proton integral value (0-1 ppm proton integral value / 6-8 ppm proton integral value). .

Example 2
After 15 g of the styrene-isoprene copolymer hydroxylated product (b2) obtained in Reference Example 3 was placed in a glass flask equipped with a cock and sufficiently purged with nitrogen, 360 g of dehydrated cyclohexane was added under a nitrogen stream and stirred uniformly. Dissolved. While stirring at 25 ° C., a solution in which 0.15 g of trifluoromethanesulfonic acid (manufactured by Wako Pure Chemical Industries, Ltd.) as a catalyst was mixed with 10 mL of methylene chloride (manufactured by Wako Pure Chemical Industries, Ltd.) in advance. Added and stirred for 30 minutes. Next, 50 g of an aqueous sodium hydroxide solution (0.3 wt%) was added with stirring to complete the reaction. The sodium hydroxide aqueous solution layer was extracted, distilled water was added and washed until the aqueous layer became neutral, and the catalyst was removed. The obtained cyclohexane layer was reprecipitated in 6 L of a mixed solvent of methanol / acetone (50/50 vol%) and then sufficiently dried to obtain 14 g of a polymer cyclized product (A2). The obtained polymer cyclized product (A2) was press-molded at 180 ° C. to produce a plate having a thickness of 0.8 mm. Table 1 shows the evaluation results of the polymer cyclized product (A2) obtained in this example.

Comparative Example 1
It was press-molded in the same manner as in Example 1 except that the styrene-isoprene copolymer (a1) obtained in Reference Example 1 was used. Since the styrene-isoprene copolymer (a1) had a Tg of not more than room temperature and was rubbery, a press-molded product that retained its shape could not be obtained. Moreover, since it is rubbery, accurate measurement of the contact angle is difficult.

Comparative Example 2
Toyostyrene G-32 (manufactured by Toyo Styrene Co., Ltd.) as polystyrene (hereinafter referred to as PSt) was press-molded at 220 ° C. to produce a plate having a thickness of 0.8 mm. Table 1 shows the evaluation results of PSt obtained by this comparative example.

Comparative Example 3
Apel 5014DP (manufactured by Mitsui Chemicals) was press-molded at 220 ° C. to produce a plate having a thickness of 0.8 mm. Table 1 shows the evaluation results of the apels obtained in this comparative example.

  From the results of the examples, it can be seen that Tg is 105 ° C. or higher, the specific gravity is low, and the total light transmittance is high. PSt has a small contact angle and good adhesiveness but low heat resistance, and APEL has high heat resistance but a large contact angle and insufficient adhesion. It can be seen that the polymer cyclized product of the examples has high heat resistance and a small contact angle, and thus has high adhesion.

It is a figure which shows the glass transition temperature (Tg) measured by the differential scanning calorimetry (DSC).

Explanation of symbols

1 ... Heat generation direction 2 ... Temperature (temperature axis)
3 ... Glass transition temperature (Tg)
4 ... Center tangent 5 ... Base line before transition 6 ... Base line after transition 7 ... Parallel line passing through the intersection of the center tangent and baseline before transition 8 ... Center tangent and baseline after transition Parallel lines 9 passing through the intersection of the parallel lines 7 ... parallel lines that bisect the parallel lines 7 and 9

Claims (16)

  Polymer cyclized product obtained by cyclizing copolymer (B) in which olefinic double bond of copolymer (A) containing styrene derivative unit and conjugated diene derivative unit is halogenated and / or hydroxylated, or hydrogen thereof The polymer cyclized product or a hydrogenated product thereof, which is an additive having a glass transition temperature of 105 ° C to 200 ° C.   The heavy content according to claim 1, wherein the molar content ratio (styrene derivative / conjugated diene derivative) of the styrene derivative and the conjugated diene derivative in the copolymer (A) before cyclization is 15/85 to 90/10. Combined cyclized product or hydrogenated product thereof.   The heavy content according to claim 1, wherein the molar content ratio (styrene derivative / conjugated diene derivative) of the styrene derivative and the conjugated diene derivative in the copolymer (A) before cyclization is 30/70 to 80/20. Combined cyclized product or hydrogenated product thereof.   The polymer cyclized product or hydrogenated product thereof according to any one of claims 1 to 3, wherein the cyclization rate is 70% or more.   The polymer cyclized product or hydrogenated product thereof according to any one of claims 1 to 4, wherein the styrene derivative is at least one of styrene, α-methylstyrene, and 4-methylstyrene.   The polymer cyclized product or hydrogenated product thereof according to any one of claims 1 to 5, wherein the conjugated diene derivative is at least one of butadiene and isoprene.   The polymer cyclized product or hydrogenated product thereof according to any one of claims 1 to 6, having a number average molecular weight of 10,000 to 1,000,000.   The polymer cyclized product according to any one of claims 1 to 7, which contains a halogen atom and / or an oxygen atom in an amount of 0.1 to 10% by weight based on the weight of the polymer cyclized product or a hydrogenated product thereof. Its hydrogenated product.   The hydrogenated product of a polymer cyclized product according to any one of claims 1 to 8, wherein the olefinic double bond is 10 mol% or less based on the conjugated diene derivative in the copolymer (A).   The polymer cyclized product or hydrogenated product thereof according to any one of claims 1 to 9, which contains a cyclized structure formed by a styrene derivative and a conjugated diene derivative. The following general formulas [I] to [IV]:

In the general formulas [I] to [IV], R ₁ represents a hydrogen atom or a methyl group, and R ₂ , R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Or a vinyl group, and two adjacent groups out of R ₂ , R ₃ , R ₄ and R ₅ may be bonded to each other to form a benzene ring, and X ₁ , X ₂ , X ₃ and X ₄ The polymer cyclized product according to claim 10, comprising at least one of the structures represented by each independently representing a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group, a hydroxyl group or a halogen atom. Or its hydrogenated product. The ratio of the integral value of protons of 0 to 3 ppm and the integral value of protons of 6 to 8 ppm (integral value of protons of 0 to 3 ppm / 6 integral value of protons of 6 to 8 ppm) of the ¹ H-NMR spectrum is 0.7 to 20 The polymer cyclized product according to any one of claims 1 to 11 or a hydrogenated product thereof. The ratio of the integral value of protons of 0 to 1 ppm and the integral value of protons of 6 to 8 ppm in the ¹ H-NMR spectrum (integral value of protons of 0 to 1 ppm / 6 integral values of protons of 8 to 8 ppm) is 0.1 to 5 The polymer cyclized product or hydrogenated product thereof according to any one of claims 1 to 12, which is 0.0.   The copolymer (A) containing a styrene derivative unit and a conjugated diene derivative unit is halogenated and / or hydroxylated, further cyclized with a cyclization catalyst, and further subjected to a hydrogenation reaction as necessary. A method for producing a combined cyclized product or a hydrogenated product thereof.   The method for producing a polymer cyclized product or a hydrogenated product thereof according to claim 14, wherein the cyclization catalyst is a Bronsted acid or a Lewis acid.   An optical material comprising the polymer cyclized product according to claim 1 or a hydrogenated product thereof as a constituent component.

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