JP2010083979A - Cyclized polymer and hydrogenated product of the same - Google Patents

Abstract

【Task】
An optical material having characteristics such as high heat resistance, high transparency, low linear expansion coefficient, and low water absorption is provided.
[Solution]
Containing a structural unit derived from a styrene derivative and a structural unit derived from a conjugated diene derivative, and a molar content ratio of the structural unit derived from the styrene derivative and the structural unit derived from the conjugated diene derivative (the structural unit derived from the styrene derivative / derived from the conjugated diene derivative) A polymer cyclized product obtained by cyclizing a random copolymer having a structural unit of 50/50 to 95/5, having a cyclization rate of 95% or more and a glass transition temperature of 100 ° C to 170 ° C. A polymer cyclized product characterized by being.
[Selection figure] None

Description

The present invention relates to a novel polymer cyclized product excellent in heat resistance, transparency, linear expansion coefficient, and the like, a hydrogenated product thereof, and a resin composition containing them.

In recent years, the demand for optical resins has become higher, and not only transparency but also high optical stability under high temperature and high humidity environment is required. However, in the conventional optical resin, these required performances are not well-balanced at a high level, and there are cases where there is a problem as an optical resin.

For example, polymethyl methacrylate, polycarbonate and the like have been conventionally used as optical resins with high transparency.
Polymethyl methacrylate has high optical properties such as high transparency and low birefringence, but it has low heat resistance, and the dimensions of the molded product are likely to change under high-temperature environments, and contains polar groups. Therefore, the water absorption is large and the refractive index easily changes in a high humidity environment. For example, when a lens or the like is used, there is a problem of optical stability such as fluctuation of optical performance such as focal length.
Polycarbonate, on the other hand, has a high glass transition temperature (Tg) and excellent heat resistance, but has a drawback that it contains a polar group and therefore has a slightly high water absorption, and its refractive index is likely to change in a high humidity environment. .

As optical resins that have improved the above water absorption problem, conjugated diene polymer cyclized products and hydrogenated products thereof are known (Patent Document 1). However, these conjugated diene polymer cyclized products and hydrogenated products thereof have excellent transparency and low water absorption, but Tg is low and heat resistance is not sufficient, and because the linear expansion coefficient is high, In a high temperature environment, the size of the molded body changes greatly, so that when using a lens or the like, the optical performance such as focal length fluctuates.

In addition, as the resin having improved heat resistance, there is a method of improving heat resistance and adhesion by cyclizing a halide and / or a hydroxyl group of a copolymer containing a styrene derivative unit and a conjugated diene derivative unit. It has been reported (Patent Document 2). However, this method has a low cyclization rate of 76 to 80% and poor heat resistance. In addition, a long reaction step and an increase in environmental load due to halogenation are problems, and further, discoloration is likely due to liberation of halogen. Furthermore, there is a disadvantage that the water absorption is increased by introducing a hydroxyl group.

JP-A 64-1705 JP 2007-269961 A

Accordingly, an object of the present invention is to provide an optical resin having high transparency and high optical stability, that is, a heavy resin having characteristics such as high heat resistance, high transparency, low linear expansion coefficient, and low water absorption. An object of the present invention is to provide a combined cyclized product, a hydrogenated product thereof, and a resin composition using them.

  As a result of intensive studies to solve the above problems, the present inventors have cyclized a random copolymer having a specific composition containing a structural unit derived from a styrene derivative and a structural unit derived from a conjugated diene derivative to a high cyclization rate. The obtained polymer cyclized product and its hydrogenated product were found to have characteristics such as high heat resistance, high transparency, low linear expansion coefficient, and low water absorption, and the present invention was completed.

  The present invention includes a structural unit derived from a styrene derivative and a structural unit derived from a conjugated diene derivative, and a molar content ratio of the structural unit derived from the styrene derivative and the structural unit derived from the conjugated diene derivative (styrene derivative unit / conjugated diene derivative unit). ) Is a polymer cyclized product obtained by cyclizing a random copolymer of 50/50 to 95/5, having a cyclization rate of 95% or more and a glass transition temperature of 100 ° C to 170 ° C. A polymer cyclized product is provided.

In the present invention, the polymer cyclized product is hydrogenated, and has a glass transition temperature of 130 ° C. to 200 ° C. and a linear expansion coefficient of 50 × 10 ^{−5 to} 65 × 10 ⁻⁵ / ° C. A hydrogenated polymer cyclized product is provided.

  The present invention further provides a resin composition containing the polymer cyclized product or a hydrogenated product of the polymer cyclized product.

The polymer cyclized product and hydrogenated product thereof according to the present invention are resin materials with improved performance such as high transparency, high heat resistance, low water supply rate, and low linear expansion coefficient, which are required in recent optical fields. Then, by molding these, a molded body such as a lens having excellent optical stability is provided.

  The present invention contains a structural unit derived from a styrene derivative and a structural unit derived from a conjugated diene derivative, and a molar content ratio of the structural unit derived from the styrene derivative and the structural unit derived from the conjugated diene derivative (structural unit derived from styrene derivative / conjugated). A polymer cyclized product obtained by cyclizing a random copolymer having a diene derivative-derived structural unit) of 50/50 to 95/5, having a cyclization rate of 95% or more and a glass transition temperature of 100 ° C. It consists of a polymer cyclized product characterized by being -170 ° C.

1) Random copolymer The random copolymer used in the present invention is usually obtained by addition polymerization of a styrene derivative and a conjugated diene derivative, and contains a structural unit derived from a styrene derivative and a structural unit derived from a conjugated diene derivative. .

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

一般式[Ｉ]

Formula [I]

In general formula [I], 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, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or Represents 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.

Specific examples of the styrene derivative used in the present invention include styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-ethylstyrene, 4-t-butylstyrene, 1-vinylnaphthalene, 4-methoxy. Aromatic vinyl compounds such as styrene and divinylbenzene can be mentioned, and styrene, α-methylstyrene or 4-methylstyrene is preferable because it is inexpensive and easily available. Moreover, said styrene derivative may be used independently or may be used in combination of 2 or more type.

(Conjugated diene derivative)
The conjugated diene derivative used in the present invention is preferably a compound represented by the general formula [II].

一般式[ＩＩ]

Formula [II]

In the general formula [II], 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.

Specific examples of the conjugated diene derivative used in the present invention include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 2-phenyl-1,3-butadiene, 1,3- Mention may be made of conjugated diene compounds such as cyclohexadiene. Since there is a long chain alkyl in the side chain, Tg is lowered, and when the substituent is large, cyclization reactivity is lowered. Therefore, 1,3-butadiene or isoprene is preferable. The above conjugated diene derivatives may be used alone or in combination of two or more.

The random copolymer used in the present invention may be a copolymer obtained by polymerizing any combination of the above styrene derivatives and conjugated diene derivatives. Specific examples of the random copolymer include styrene-isoprene copolymer, styrene-1,3-butadiene copolymer, α-methylstyrene-isoprene copolymer, α-methylstyrene-1,3-butadiene copolymer. 3- (or 4-) methylstyrene-isoprene copolymer, 3- (or 4-) methylstyrene-1,3-butadiene copolymer, 4-ethylstyrene-isoprene copolymer, 4-ethylstyrene- 1,3-butadiene copolymer, 4-t-butylstyrene-isoprene copolymer, 4-t-butylstyrene-1,3-butadiene copolymer, 1-vinylnaphthalene-isoprene copolymer, 1-vinyl Naphthalene-1,3-butadiene copolymer, divinylbenzene-isoprene copolymer, divinylbenzene-1,3-butadiene copolymer, steel Len-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.

(Other monomers)
The random copolymer used in the present invention may contain a structural unit derived from another monomer copolymerizable with a styrene derivative and a conjugated diene derivative. 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 acid monomers such as 2-hydroxyethyl acrylate and glycidyl (meth) acrylate; vinyl monomers containing nitrile groups such as acrylonitrile and methacrylonitrile; vinyl monomers containing amide groups such as acrylamide and methacrylamide; ethylene Olefins such as propylene and norbornene; vinyl esters such as vinyl acetate, vinyl pivalate and vinyl benzoate; maleic anhydride, maleic acid, fumaric acid, maleimide and the like; and styrene derivatives having a polar group. Moreover, these monomers may be used independently or may be used in combination of 2 or more types.

When the copolymerizable monomer is copolymerized with a styrene derivative and a conjugated diene derivative, the amount of copolymerization is preferably 20 mol% or less, more preferably 10 mol% or less, more preferably 5 mol% or less, based on all monomer units in the polymer. Is most preferred. If the amount of copolymerization is too large, the water absorption rate may increase.

(Addition polymerization)
The random copolymer used in the present invention is obtained by subjecting a monomer mixture composed of the styrene derivative monomer and a conjugated diene derivative monomer composed only of carbon and hydrogen to a known method such as a radical polymerization method, an anionic polymerization method, or a cationic polymerization method. It can be obtained by polymerization. From the viewpoint that it can be easily carried out industrially, a radical polymerization method or an anionic polymerization method is particularly preferable.

The composition of the monomer mixture comprising a styrene derivative and a conjugated diene derivative is usually 50/50 to 95/5, preferably 50/50 to 70/30, in terms of molar content ratio (styrene derivative unit / conjugated diene derivative unit). Preferably it is 50 / 50-60 / 40.

In the case of radical polymerization, methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization can be used in the presence of a radical polymerization initiator, usually at 0 ° C to 200 ° C, preferably 20 ° C to 150 ° C. However, especially when it is necessary to prevent impurities from being mixed into the resin, bulk polymerization and suspension polymerization are desirable. As radical polymerization initiators, organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butyl-peroxy-2-ethylhexanoate, azoisobutyronitrile, 4,4-azobis-4-cyanopentane Acids, azo compounds such as azodibenzoyl, water-soluble catalysts such as potassium persulfate and ammonium persulfate, redox initiators and the like can be used.

In the case of anionic polymerization, bulk polymerization, solution polymerization, slurry in the temperature range of usually 0 ° C. to 200 ° C., preferably 20 ° C. to 100 ° C., particularly preferably 20 ° C. to 80 ° C. in the presence of an anionic polymerization initiator. Although a method such as polymerization can be used, solution polymerization is preferable in consideration of removal of reaction heat. In this case, it is preferable to use an inert solvent capable of dissolving the polymer and its hydride. Examples of the inert solvent used in the solution reaction include aliphatic hydrocarbons such as n-butane, n-pentane, iso-pentane, n-hexane, n-heptane, and iso-octane; cyclopentane, cyclohexane, methylcyclopentane, Examples include alicyclic hydrocarbons such as methylcyclohexane and decalin; aromatic hydrocarbons such as benzene and toluene. Among them, when aliphatic hydrocarbons and alicyclic hydrocarbons are used, hydrogenation reaction is also performed. It can be used as it is as an inert solvent. These inert solvents can be used alone or in combination of two or more, and are usually used at a ratio of 200 to 10,000 parts by weight with respect to 100 parts by weight of all the monomers used.

Examples of the anionic polymerization initiator include monoorganolithium such as n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium and phenyllithium, dilithiomethane, 1,4-diobane, 1,4-dilithio-2. -Polyfunctional organolithium compounds such as ethylcyclohexane can be used.

In the polymerization reaction, it is preferable to use a randomizer (an additive having a function of preventing a certain one-component chain from becoming long). In the case of anionic polymerization, for example, a Lewis base compound can be used as a randomizer. Specific examples of the Lewis base compound include ether compounds such as dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, diphenyl ether, ethylene glycol diethyl ether, ethylene glycol methyl phenyl ether; tetramethylethylenediamine, trimethylamine, triethylamine, pyridine Tertiary amine compounds such as potassium; t-amyl oxide, alkali metal alkoxide compounds such as potassium t-butyl oxide; and phosphine compounds such as triphenylphosphine. These Lewis base compounds can be used alone or in combination of two or more.

The form of polymerizing the random copolymer used in the present invention is not particularly limited, but includes a batch polymerization method (batch method), a continuous monomer addition method (a method in which polymerization is continued by continuously adding monomers), and the like. In particular, the continuous monomer addition method is preferred because it has a more random chain structure.

The reactivity between the olefinic double bond of the structural unit derived from the conjugated diene derivative and the aromatic ring of the structural unit derived from the styrene derivative is higher than the reactivity between the olefinic double bonds of the structural unit derived from the conjugated diene derivative. The higher the randomness of the random copolymer, the higher the reaction rate of the cyclization reaction, which is preferable.

Further, according to the continuous monomer addition method, since the uniformly mixed monomer is sequentially added into the polymerization system, unlike the batch method, the polymerization selectivity of the monomer is increased in the growth process by polymer polymerization. Since it can be lowered, the resulting copolymer has a more random chain structure. In addition, since the accumulation of polymerization reaction heat in the polymerization system is small, the polymerization temperature can be kept low and stable.

The monomer addition time in the continuous monomer addition method is preferably 2 to 5 hours, more preferably 3 to 5 hours.
If the monomer addition time is too short, the randomness of the polymer is lowered, and the cyclization rate may be lowered. If the monomer addition time is too long, the catalyst may be deactivated and the molecular weight distribution may increase.

The molar content ratio of the structural unit derived from the styrene derivative and the structural unit derived from the conjugated diene derivative (the structural unit derived from the styrene derivative / the structural unit derived from the conjugated diene derivative) in the random copolymer is 50/50 to 95/5. , Preferably 50/50 to 70/30, more preferably 50/50 to 60/40.

When there are many structural units derived from a conjugated diene derivative, the glass transition temperature (Tg) of the polymer cyclized product after cyclization becomes low and the linear expansion coefficient becomes high.
Moreover, when there are few structural units derived from a conjugated diene derivative, it will become difficult to advance cyclization reaction, Tg of the polymer cyclization product after cyclization will fall, and a linear expansion coefficient will also become high.

  The polymerization average molecular weight (Mw) of the random copolymer used in the present invention is preferably in the range of 10,000 to 1,000,000, more preferably 50,000 to 500,000, and most preferably 50,000 to 250,000. If the Mw is low, the strength decreases, and if the Mw is high, the viscosity increases, and the cyclization reaction and / or the hydrogenation reaction may hardly proceed.

  The molecular weight distribution (Mw / Mn) of the random copolymer used in the present invention is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, and most preferably 1.0 to 1.5. is there. When Mw / Mn increases, the strength may decrease.

The structure derived from the conjugated diene derivative of the random copolymer used in the present invention is any of trans-1,4-structural units, cis-1,4-structural units, 1,2-structural units, and 3,4-structural units. These structural units may be constituted singly or in combination of two or more kinds.

2) Polymer cyclized product The polymer cyclized product of the present invention is obtained by cyclizing the random copolymer.

(Cyclization reaction)
The cyclization reaction indicates a reaction between olefinic double bonds of a structural unit derived from a conjugated diene derivative, a reaction between an olefinic double bond of a structural unit derived from a conjugated diene derivative and an aromatic ring of a structural unit derived from a styrene derivative. .

(Cyclization reaction solvent)
The cyclization reaction is performed, for example, by adding or contacting a cyclization catalyst in an inert organic solvent or in a molten state of the copolymer. The inert organic solvent can be used without particular limitation as long as the copolymer is dissolved and the organic solvent is inert to the cyclization catalyst. 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 is not particularly limited, but is usually 100 to 10,000 parts by weight, preferably 150 to 5000 parts by weight with respect to 100 parts by weight of the random copolymer. More preferably, it is 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 the reaction becomes non-uniform, and there is a possibility that a uniform resin cannot be obtained or the control of the reaction becomes difficult. If it is too much, productivity may be reduced.

(Cyclization catalyst)
An acidic compound can be used as the 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 Examples thereof include zirconia, zirconia tungstate, zeolite exchanged with H + or rare earth elements, activated clay, acidic clay, solid acid such as solid phosphoric acid in which γ-Al ₂ O ₃ , P ₂ O ₅ is supported on diatomaceous earth. These acidic compounds may be used alone or in combination, and other compounds that can further improve the activity of the acidic compound may be added.
Examples of compounds that improve the activity of 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 SnCl, and other metal alkyl compounds; 2-methoxy-2-phenylpropane, t-butanol, 1,4-bis (2- Examples include methoxy-2-propyl) benzene and 2-phenyl-2-propanol.

  The amount of cyclization catalyst used varies depending on the type of cyclization catalyst, so it is difficult to define the amount used in general, but in the case of a homogeneous catalyst, the amount used is 100 parts by weight of a random copolymer. On the other hand, the amount 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. When a heterogeneous catalyst such as a solid acid or ion exchange resin is used as the cyclization catalyst, the amount used is preferably 0.1 to 10,000 parts by weight, and 1-1000 parts by weight with respect to 100 parts by weight of the random copolymer. More preferred. If the amount of catalyst is small, the cyclization reaction proceeds slowly, and if it is large, side reactions tend to occur, and removal of the catalyst tends to be difficult.

(Cyclization reaction temperature)
In the present invention, when the cyclization reaction is carried out in an inert organic solvent, the reaction temperature is usually preferably −40 ° C. to 200 ° C., more preferably 0 ° C. to 150 ° C., and most preferably 20 ° C. to 130 ° C. If it is too low, the progress of the reaction is slow, and if it is too high, it is difficult to control the reaction, it is difficult to obtain reproducibility, and it is difficult to suppress the side reaction.

(Cyclization reaction pressure)
Although the reaction pressure at the time of performing cyclization reaction is not specifically limited, 0.5-50 atmospheres is preferable and 0.7-10 atmospheres is more preferable. Usually, the cyclization reaction is performed at around 1 atm.

(Cyclization reaction time)
The reaction time for performing the cyclization reaction is not particularly limited, and a resin having a 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.

(Reaction treatment)
After completion of the cyclization, after adding the cyclization catalyst inactive agent and adsorbent, the cyclization catalyst and the like are filtered off from the reaction solution, and by removing volatile components such as a solvent from the reaction solution after the filtration, The intended polymer cyclized product of the present invention can be obtained. Examples of the inert agent used include alcohols such as ethyl alcohol, n-propyl alcohol, and isopropyl alcohol. Examples of the adsorbent used include activated clay, acid clay, activated carbon, talc, and alumina.

  As a method for removing volatile components such as a solvent, a known method such as a coagulation method or a direct drying method can be employed.

  The coagulation method is a method in which a polymer is precipitated by mixing a polymer solution with a poor solvent for the polymer. Examples of the poor solvent to be used include polar solvents such as alcohols such as ethyl alcohol, n-propyl alcohol and isopropyl alcohol; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate and butyl acetate;

  The particulate component obtained by solidification is dried by heating in vacuum, nitrogen or air, for example, or extruded from a melt extruder as necessary to form a pellet. Can do.

  The direct drying method is a method in which the polymer solution is heated under reduced pressure to remove the solvent. This method can be carried out using a known apparatus such as a centrifugal thin film continuous evaporation dryer, a scratched heat exchange type continuous reactor type dryer, a high viscosity reactor device or the like. The degree of vacuum and temperature are appropriately selected depending on the device and are not limited.

(Cyclization rate)
The cyclization rate of the polymer cyclized product of the present invention is 95% or more, preferably 97% or more, more preferably 99% or more. If the cyclization rate is low, the heat resistance of the resulting polymer cyclized product will decrease.

In the present invention, the cyclization rate means cyclization based on the ratio of olefinic double bond protons (4 to 6 ppm) / total protons determined from the integral value of ¹ H-NMR spectrum of the random copolymer. It means the reduction rate (%) of the ratio of olefinic double bond protons / total protons determined from the ¹ H-NMR spectrum of the polymer cyclized product after the reaction.

(Structure of cyclized product)
The polymer cyclized product of the present invention has a structure (III) obtained by a cyclization reaction between olefinic double bonds of structural units derived from adjacent conjugated diene derivatives, and an olefinic compound of structural units derived from conjugated diene derivatives. It contains a structure (IV) obtained by a cyclization reaction between a heavy bond and an aromatic ring of a structural unit derived from a styrene derivative.

The structure of polymer cyclized product of random copolymer of isoprene and styrene is shown.
Chemical formula 3 is an example of the structure (III) obtained by cyclization of olefinic double bonds derived from isoprene.

Chemical formula 4 is an example of the structure (IV) obtained by a cyclization reaction between an olefinic double bond derived from isoprene and an aromatic ring derived from styrene. The cyclized skeleton is considered to form a stable 6-membered ring, but other structures such as a 5-membered ring structure containing the 1st and 2nd carbon atoms of the benzene ring, and the 1st position of the benzene ring You may form the ring structure containing the carbon atom of 3rd-position, and the 1st-position and 4th-position carbon atom of a benzene ring.

A part of ¹³ C-NMR chart of isoprene homopolymer and polymer cyclized product obtained by cyclization of this is shown in FIG. 1, random copolymer of isoprene and styrene, and cyclization reaction thereof. A part of the ¹³ C-NMR chart of the polymer cyclized product is shown in FIG. 2. 2 is for the styrene / isoprene polymer (e1) of Production Example 13 and the cyclized product of styrene / isoprene polymer (e3) of Production Example 15.
In the polymer cyclized product obtained by cyclization of a random copolymer of isoprene and styrene, a peak appears at around 140 ppm, which is not found in the polymer cyclized product of isoprene monopolymer. Not only the structure (III) obtained by cyclization of the bonds but also the structure (IV) obtained by the cyclization reaction between the olefinic double bond derived from soprene and the aromatic ring derived from styrene is formed.

The structure of the cyclized product in the polymer cyclized product was calculated by measuring a ¹³ C-NMR spectrum at 25 ° C. using deuterated chloroform as a solvent with an NMR spectrometer (JMN-GSX400, manufactured by JEOL).

(Molecular weight)
The polymerization average molecular weight (Mw) of the polymer cyclized product of the present invention is preferably 10,000 to 1,000,000, more preferably 50,000 to 500,000, and most preferably 50,000 to 250,000. If the Mw is low, the strength is lowered, and if the Mw is high, the viscosity is high and molding becomes difficult. In addition, it is difficult for the hydrogenation reaction to proceed.

  The molecular weight distribution (Mw / Mn) of the polymer cyclized product in the present invention is preferably in the range of Mw / Mn = 1.00 to 6.00, more preferably 1.00 to 4.00, most preferably 1.00. ~ 2.00. When Mw / Mn is increased, the strength is decreased and the viscosity is increased, so that molding becomes difficult and the hydrogenation reaction does not proceed easily.

(Glass-transition temperature)
The glass transition temperature (Tg) of the polymer cyclized product of the present invention is 100 to 170 ° C, preferably 115 to 170 ° C.

The linear expansion coefficient of the polymer cyclized product of the present invention is preferably 55 × 10 ⁻⁵ to 70 × 10 ⁻⁵ / ° C., more preferably 55 × 10 ^{−5 to} 65 × 10 ⁻⁵ / ° C.

  The refractive index of the polymer cyclized product of the present invention is preferably 1.55 to 1.60.

  The polymer cyclized product of the present invention is characterized by an increase in Tg and a decrease in linear expansion coefficient compared to before the cyclization reaction, and has excellent transparency, high heat resistance and low linear expansion coefficient. It is characterized by.

3) Hydrogenated product of polymer cyclized product The hydrogenated product of the polymer cyclized product of the present invention is obtained by hydrogenating the carbon-carbon unsaturated bond of the main chain and unsaturated ring of the polymer cyclized product. It is done.

Hydrogenation catalyst and hydrogenation reaction The hydrogenation reaction of a polymer cyclized product is performed by adding a hydrogenation catalyst to an inert solvent solution of the polymer cyclized product and supplying hydrogen into the reaction system.

(Inert solvent)
The inert solvent is not particularly limited as long as it is an organic solvent that dissolves the resin and is inert to the hydrogenation catalyst. 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.

(Hydrogenation catalyst)
The hydrogenation catalyst to be used is not particularly limited, and those generally used for hydrogenation of olefin compounds can be used. For example, homogeneous catalysts such as Wilkinson complex, cobalt acetate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, diatomaceous earth, magnesia, alumina, silica, alumina-magnesia, silica-magnesia, silica-alumina, synthetic zeolite, etc. A known method using a heterogeneous catalyst in which a catalytic metal such as nickel, palladium or platinum is supported on the body can be used. Considering the removal of residual metal in the hydrogenated product of the polymer cyclized product obtained, a heterogeneous catalyst is preferred.

The amount of the hydrogenation catalyst used is usually 5 to 20 parts by weight with respect to 100 parts by weight of the polymer cyclized product.

(Reaction temperature)
The reaction temperature of the hydrogenation reaction depends on the hydrogenation catalyst used and the hydrogen pressure, but is preferably, for example, 20 ° C to 250 ° C, more preferably 25 ° C to 200 ° C, and most preferably 40 ° C to 170 ° 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.

(Reaction hydrogen pressure)
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.

(Reaction concentration)
The concentration of the polymer cyclized product in the hydrogenation reaction system is usually 2% to 40% by weight, preferably 5% to 30% by weight, more preferably 10% to 25% by weight. If the concentration of the polymer cyclized product is low, the productivity tends to be lowered. Moreover, when the density | concentration of a polymer cyclization thing is too high, the hydrogenated polymer may precipitate, the viscosity of a reaction mixture may become high, and the case where stirring cannot be performed arises.

(Reaction time)
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.

(Reaction treatment)
After completion of the hydrogenation reaction, the hydrogenation catalyst and the like are filtered off from the reaction solution, and volatile components such as a solvent are removed from the polymer solution after the filtration to remove hydrogen from the target polymer cyclized product of the present invention. Additives can be obtained.

  As a method for removing volatile components such as a solvent, a known method such as a coagulation method or a direct drying method can be employed.

  The coagulation method is a method in which a polymer is precipitated by mixing a polymer solution with a poor solvent for the polymer. Examples of the poor solvent to be used include polar solvents such as alcohols such as ethyl alcohol, n-propyl alcohol and isopropyl alcohol; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate and butyl acetate;

  The particulate component obtained by solidification is dried by heating in vacuum, nitrogen or air, for example, or extruded from a melt extruder as necessary to form a pellet. Can do.

  The direct drying method is a method in which the polymer solution is heated under reduced pressure to remove the solvent. This method can be carried out using a known apparatus such as a centrifugal thin film continuous evaporation dryer, a scratched heat exchange type continuous reactor type dryer, a high viscosity reactor device or the like. The degree of vacuum and temperature are appropriately selected depending on the device and are not limited.

(Hydrogen addition rate)
The hydrogenated product of the polymer cyclized product of the present invention has a hydrogenation rate of carbon-carbon unsaturated bonds of the main chain and unsaturated ring of usually 80% or more, preferably 90% or more, more preferably 95% or more, Preferably it is 99% or more, Most preferably, it is 99.9% or more. When the hydrogenation rate is high, the heat resistance is excellent.

The hydrogenation rate of the polymer cyclized product of the present invention is determined by the ratio of the integral value of 6 to 9 ppm protons to the total protons in the ¹ H-NMR spectrum (tetramethylsilane (TMS) proton is 0 ppm) (6 -9 ppm proton integral value / total protons).

(Molecular weight)
The polymerization average molecular weight (Mw) of the hydrogenated product of the polymer cyclized product of the present invention is preferably 10,000 to 1,000,000, more preferably 50,000 to 500,000, and most preferably 50,000 to 250,000. If the Mw is low, the strength is lowered, and if the Mw is high, the viscosity is high and molding becomes difficult.

  The molecular weight distribution (Mw / Mn) of the hydrogenated product of the polymer cyclized product of the present invention is preferably 1.00 to 6.00, more preferably 1.00 to 4.00, and most preferably 1.00 to 2. .00. When Mw / Mn is increased, the strength is decreased and the viscosity is increased, so that molding becomes difficult.

(Glass-transition temperature)
The glass transition temperature (Tg) of the hydrogenated product of the polymer cyclized product of the present invention is usually 130 to 200 ° C, preferably 140 to 180 ° C.

(Linear expansion coefficient)
The linear expansion coefficient of the hydrogenated product of the polymer cyclized product of the present invention is preferably 50 × 10 ^{−5 to} 65 × 10 ⁻⁵ / ° C., more preferably 50 × 10 ^{−5 to} 60 × 10 ⁻⁵ / ° C. is there.

4) Resin composition The resin composition of the present invention contains the polymer cyclized product of the present invention or a hydrogenated product of the polymer cyclized product.

The resin composition of the present invention preferably contains an antioxidant.
The antioxidant to be used is not particularly limited, but those having a molecular weight of 700 or more are preferable. If the molecular weight of the antioxidant is too low, the antioxidant may be eluted from the molded product.

  Specific examples of the antioxidant used include octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, tetrakis [methylene-3- (3 ′, 5′-di-t-butyl). -4'-hydroxyphenyl) propionate] methane, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and other phenolic antioxidants; triphenyl phosphite, Phosphorous antioxidants such as tris (cyclohexylphenyl) phosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene; dimyristyl 3,3′-thiodipropionate, distearyl-3,3′-thio Dipropionate, lauryl stearyl-3,3′-thiodipropionate, pentaerythritol - tetrakis - sulfur-based antioxidants such as (beta-laurylthiopropionate); and the like. These antioxidants can be used alone or in combination of two or more. Among these, a phenolic antioxidant is preferable.

  The blending amount of the antioxidant is usually 0.01 to 1 part by weight, preferably 0.05 to 0.5 part by weight based on 100 parts by weight of the polymer cyclized product or the hydrogenated product of the polymer cyclized product of the present invention. Part. If the amount of antioxidant added is too small, the molded product may be burned. On the other hand, when there is too much addition amount, there exists a possibility that a molded article may become cloudy or antioxidant may elute from a molded article.

  In addition to the polymer cyclized product of the present invention or the hydrogenated product of the polymer cyclized product and the antioxidant, the resin composition of the present invention generally includes synthetic resins as long as the object of the present invention is not impaired. Various compounding agents used may be added.

  Such compounding agents include rubbery polymers, other resins, ultraviolet absorbers, antistatic agents, slip agents, antifogging agents, dyes, pigments, colorants, natural oils, synthetic oils, plasticizers, organic or inorganic Examples include fillers, antibacterial agents, deodorants, and deodorizers.

  The rubbery polymer is a polymer having a glass transition temperature of 40 ° C. or lower. Rubbery polymers include rubber and thermoplastic elastomers. When there are two or more glass transition temperatures as in the block copolymer, the glass transition temperature can be used as a rubbery polymer if the lowest glass transition temperature is 40 ° C. or lower. The Mooney viscosity (ML1 + 4, 100 ° C.) of the rubbery polymer is appropriately selected according to the purpose of use, but is usually 5 to 300.

  Examples of rubber polymers include ethylene-α-olefin rubbers; ethylene-α-olefin-polyene copolymer rubbers; copolymers of ethylene and unsaturated carboxylic acid esters such as ethylene-methyl methacrylate and ethylene-butyl acrylate. Polymer: Copolymer of ethylene and fatty acid vinyl such as ethylene-vinyl acetate copolymer; alkyl acrylate such as ethyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, etc. Polymer: Polybutadiene, polyisoprene, random copolymer of styrene and butadiene or isoprene, acrylonitrile-butadiene copolymer, butadiene-isoprene copolymer, butadiene- (meth) acrylic acid alkyl ester copolymer, butadiene- ( Meta) Diene rubbers such as alkyl acrylate-acrylonitrile copolymer and butadiene- (meth) acrylic acid alkyl ester-acrylonitrile-styrene copolymer; butylene-isoprene copolymer; styrene-butadiene block copolymer, hydrogenated styrene -Aromatic vinyl-conjugated diene block copolymers such as butadiene block copolymer, hydrogenated styrene-butadiene random copolymer, styrene-isoprene block copolymer, hydrogenated styrene-isoprene block copolymer, low crystal And polybutadiene resins, ethylene-propylene elastomers, styrene-grafted ethylene-propylene elastomers, thermoplastic polyester elastomers, and ethylene ionomer resins.

  The amount of the rubbery polymer is appropriately selected according to the purpose of use. When impact resistance and flexibility are required, the amount of the rubbery polymer is usually 0.01 to 100 with respect to 100 parts by weight of the polymer cyclized product or the hydrogenated product of the polymer cyclized product of the present invention. Parts by weight, preferably 0.1 to 70 parts by weight, more preferably 1 to 50 parts by weight.

  Examples of other resins include amorphous norbornene-based ring-opening polymers, amorphous norbornene-based ring-opening polymers hydrides, amorphous norbornene-based addition polymers, crystalline norbornene-based ring-opening polymers, crystals Norbornene-based ring-opening polymer hydride, crystalline norbornene-attached polymer, low-density polyethylene, high-density polyethylene, linear low-density polyethylene, ultra-low-density polyethylene, ethylene-ethyl acrylate copolymer, ethylene-acetic acid Vinyl copolymer, polypropylene, polystyrene, hydrogenated polystyrene, polymethyl methacrylate, polyvinyl chloride, polyvinylidene chloride, polyphenylene sulfide, polyphenylene ether, polyamide, polyester, polycarbonate, cellulose triacetate, polyether imide, polyimide, poly Relate, polysulfone, polyether sulfone, and the like.

  These other resins can be used alone or in combination of two or more, and the blending ratio can be appropriately selected within a range not impairing the object of the present invention.

Examples of the ultraviolet absorber and the weathering stabilizer include 2,2,6,6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, and bis (1 , 2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate, 4- [3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -1- {2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl} -2, Hindered amine compounds such as 2,6,6-tetramethylpiperidine; 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (3-t-butyl-2-hydroxy-5-methylpheny ) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) ) Benzotriazole compounds such as benzotriazole; 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-t-butyl-4- Examples thereof include bezoate compounds such as hydroxybenzoate.
These ultraviolet absorbers and weathering stabilizers can be used alone or in combination of two or more.

  The amount of the ultraviolet absorber and the weathering stabilizer is usually 0.001 to 5 parts by weight, preferably 0.01 to 2 parts by weight, with respect to 100 parts by weight of the polymer cyclized product or hydrogenated polymer cyclized product of the present invention. Part range.

  Antistatic agents include: long-chain alkyl alcohols such as stearyl alcohol and behenyl alcohol; alkylsulfonic acid sodium salts and / or alkylsulfonic acid phosphonium salts; fatty acid esters such as glycerin ester of stearic acid; hydroxyamine compounds; amorphous carbon; Examples thereof include tin oxide powder and antimony-containing tin oxide powder. The amount of the antistatic agent is usually in the range of 0.001 to 5 parts by weight with respect to 100 parts by weight of the polymer cyclized product or the hydrogenated product of the polymer cyclized product of the present invention.

  As a method for preparing the resin composition of the present invention, for example, a hydrogenated product of a polymer cyclized product is mixed with an antioxidant and other compounding agents as necessary, for example, by a twin-screw kneader or the like, 200 to 400. Examples thereof include a method of forming a pellet, granule, or powder after melt-kneading at a temperature of about ° C.

The resin composition of the present invention is excellent in transparency and heat resistance, has a low coefficient of linear expansion, and is suitable for various optical materials.

(Molded body)

The resin composition of the present invention can be molded by a known molding method to produce various molded products.

The molding method is not particularly limited, but a general thermoplastic resin molding method, for example,
Injection molding, blow molding, injection blow molding, rotational molding, vacuum molding, extrusion molding, calendar molding, solution casting, and the like are possible.

The molded body made of the resin composition of the present invention is excellent in transparency and heat resistance, and has a low water absorption and linear expansion coefficient, so it is suitable for optical applications requiring heat resistance, high transparency and high dimensional stability. is there.
Optical applications include, for example, lenses, aspherical lenses, Fresnel lenses, silver salt camera lenses, digital electronic camera lenses, video camera lenses, projector lenses, copier lenses, mobile phone camera lenses, and glasses lenses. , 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) 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 vane 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.

Especially when used as an optical application, it exhibits excellent characteristics.For example, when used as a lens, it has a low water absorption and linear expansion coefficient, so there is little change in lens shape and refractive index even under high temperature and high humidity conditions. Low focal length variation and excellent optical stability.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. Parts and% in these examples are based on weight unless otherwise specified. However, the present invention is not limited only to these examples.

Various physical properties were measured according to the following methods. When there were not enough samples to measure physical properties, the sample was obtained by repeatedly reacting under the same conditions.
(1) Molecular weight The number average molecular weight (Mn), the weight average molecular weight (Mw) and the molecular weight distribution (MW / MN) were measured as standard polystyrene conversion values by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent. As standard polystyrene, a total of 8 points of standard polyisoprene manufactured by Tosoh Corporation, Mw = 500, 2630, 10200, 37900, 96400, 427000, 1090000, and 5780000 were used.
For measurement, Tosoh HLC8120GPC was used, and Tosoh TSKgel SuperH5000, TSKgel SuperH4000 and TSKgel SuperH2000 were connected in series as a column, flow rate 0.6 ml / min, sample injection amount 20 μml, column temperature 40 ° C. Performed under conditions.
(2) Cyclization rate The cyclization rate in the polymer cyclized product was calculated by measuring ¹ H-NMR spectrum at 25 ° C using deuterated chloroform as a solvent with an NMR spectrometer (JMN-GSX400, manufactured by JEOL). .
The cyclization rate was determined from the 1H-NMR spectrum of the polymer cyclized product after the cyclization reaction based on the ratio of olefinic double bond protons (4 to 6 ppm) / total protons of the random copolymer. It means the reduction rate (%) of the ratio of olefinic double bond protons / total protons.
Hereinafter, description (3) Hydrogenation rate A ¹ H-NMR spectrum was measured and calculated at 25 ° C. using heavy chloroform as a solvent with an NMR spectrometer (JMN-GSX400, manufactured by JEOL) of a polymer cyclized product.
The hydrogenation rate is obtained from the ratio of the integral value of 6-9 ppm protons to the total protons (6-9 ppm proton integral value / total protons) when the tetramethylsilane (TMS) proton is 0 ppm.

(4) Glass transition temperature (Tg)
Tg was measured by using a differential scanning calorimeter (DSC 6220, manufactured by SII Nanotechnology) based on JIS K 7121. After heating the sample to 30 ° C. or higher from Tg, the sample was cooled to room temperature, and then the rate of temperature increase was 10 ° C. / Measured in minutes.
(5) Total light transmittance The total light transmittance is obtained by filling a 3 mm-thick mold with a resin, melting the resin at Tg + 60 ° C. under a vacuum, and maintaining it at 20 MPa for 5 minutes. Based on ASTM D1003, a spectrophotometer (V-570, manufactured by JASCO Corporation) was used for measurement.
(6) Water absorption rate The water absorption rate was measured based on JIS7209.
(7) Refractive index Refractive index is 90% by filling a 3mm thick mold with resin, melting the resin at Tg + 60 ° C under vacuum and vacuum conditions, maintaining at 20MPa for 5 minutes, cutting and polishing. A test piece having a measurement surface having ± 0.5 ° C. was measured using a Kalnew refractometer (KPR-200, manufactured by Kalnew Optical Co., Ltd.) in accordance with ASTM D542.
(8) Linear expansion coefficient The linear expansion coefficient is obtained by filling a mold having a thickness of 5 mm with resin, melting the resin at Tg + 60 ° C. under vacuum vacuum conditions, and maintaining the molded condition by maintaining at 20 MPa for 5 minutes. A test piece of 5 mm × 5 mm × 10 mm was prepared. The sample is fixed with a load of 2.2 g, and the expansion rate in the 10 mm direction is measured using a thermomechanical analyzer (TMA / SS6100, manufactured by SII Nanotechnology) from 30 ° C. to Tg + 10 ° C. at a rate of temperature increase of 3 ° C./min. The coefficient of linear expansion was from 40 ° C to 80 ° C.
(9) 0.1 parts by weight of an antioxidant (IRGANOX1010 manufactured by Ciba Japan) is kneaded with a small kneader (DSM XPplore 5 & 15, manufactured by DSM Xplore) with respect to 100 parts by weight of the focal length variation resin, and the resin composition is Obtained. The obtained resin composition was injected with an injection molding machine (Micro Injection Molding Machine 10 cc, manufactured by DSM Xplore), the resin temperature was 260 ° C., the mold temperature was Tg-7 ° C., the holding pressure was 600 Kg / cm ³ , the cooling time. Was molded in 230 seconds to obtain a lens having the cross-sectional shape of FIG.
After measuring the focal length of the obtained lens, the test was allowed to stand for 15 hours in an environment of 85 ° C., the focal length was measured again, and the difference in focal length before and after the test was defined as the focal length variation. As shown in FIG. 4, the focal length is measured by passing a 670 nm, 3 mmφ light beam at 25 ° C. using a flange back measuring device (made by Pearl Optics Co., Ltd.) and scanning the detector to minimize the spot diameter. The distance to the point was measured.

(Production Example 1) Polymer (a1)
A stainless steel autoclave equipped with a magnetic stirrer, thoroughly dried and purged with nitrogen, was charged with 900 parts of dehydrated cyclohexane and 0.6 part of dibutyl ether, and stirred at 50 ° C. with an n-butyllithium solution (containing 15%). 1 part of a hexane solution) was added, and 300 parts of styrene as a monomer was continuously added over 4 hours to carry out polymerization. The reaction was carried out 30 minutes after completion of the addition, and then 0.3 part of isopropyl alcohol was added to stop the reaction to obtain a polymer. The polymerization conversion rate of the obtained polymer was 100%, the weight average molecular weight (Mw) was 159000, and the molecular weight distribution (Mw / Mn) was 1.10.
After adding 1200 parts of cyclohexane to the above reaction solution, the mixture was poured into 10 liters of isopropanol to precipitate a styrene polymer (a1). The polymer (a1) was separated by filtration and then dried using a vacuum dryer.

(Production Example 2) Hydrogenated product (a2) of polymer (a1)
Subsequently, 240 parts of cyclohexane and 9 parts of a stabilized nickel hydrogenation catalyst E19Z (manufactured by JGC Chemical Industry Co., Ltd.) are added to and mixed with 60 parts of the polymer (a1), and an electric heating apparatus and electromagnetic stirring for adjusting the hydrogenation reaction temperature. A stainless steel autoclave equipped with the equipment was charged. After completion of the preparation, the inside of the autoclave was replaced with hydrogen gas, and a hydrogenation reaction was carried out for 6 hours at 160 ° C. with stirring while supplying hydrogen so that the pressure inside the autoclave was maintained at 45 kg / cm ² .
After completion of the reaction, this solution was filtered under pressure at a pressure of 0.25 MPa using a radiofilter # 500 (manufactured by Showa Chemical Co., Ltd.) and a pressure filter (Hunda filter, manufactured by Ishikawajima-Harima Heavy Industries Co., Ltd.). A colorless and transparent solution of the polymer hydrogenated product (a2) was obtained. The hydrogenation rate of the resulting hydrogenated polymer was 99.4%, the weight average molecular weight (Mw) was 159000, and the molecular weight distribution (Mw / Mn) was 1.10.
After adding 1200 parts of cyclohexane to the above reaction solution, it was poured into 10 liters of isopropanol to precipitate a hydrogenated product (a2) of the polymer. The polymer hydrogenated product (a2) was separated by filtration and then dried in a vacuum dryer.

(Production Example 3) Polymer (b1)
The polymerization was carried out in the same manner as in Production Example 1 except that the monomer composition was (styrene (St) / isoprene (IP)) = (70/30) in terms of weight ratio and the monomer sequential addition time was 30 minutes. ) The polymerization conversion rate of the obtained polymer was 100%, the weight average molecular weight (Mw) was 165000, and the molecular weight distribution (Mw / Mn) was 1.15.
After adding 1200 parts of cyclohexane to the above reaction solution, the mixture was poured into 10 liters of isopropanol to precipitate a styrene polymer (b1). The polymer (b1) was separated by filtration and then dried using a vacuum dryer.

(Production Example 4) Polymer cyclized product (b2) of polymer (b1)
Next, 20 parts of the polymer (b1) was placed in a stainless steel autoclave equipped with an electromagnetic stirrer and sufficiently purged with nitrogen, and then 380 parts of dehydrated cyclohexane was added under a nitrogen stream and stirred to dissolve uniformly. While stirring at 50 ° C., 1.4 parts of WCl ₆ was added as a catalyst and stirred for 30 minutes. While stirring, 2.5 parts of isopropanol was added to complete the reaction. After adding 4 parts of activated clay (Galleon Earth, manufactured by Mizusawa Chemical Co., Ltd.) to this solution and stirring for 1 hour at 40 ° C., a pressure filter (Hunda filter) using Radiolite # 500 (manufactured by Showa Chemical Co., Ltd.) as a filter bed. , Manufactured by Ishikawajima-Harima Heavy Industries, Ltd.) and filtered under pressure at a pressure of 0.25 MPa to obtain a colorless and transparent solution of the polymer cyclized product (b2). The cyclization rate of the obtained polymer cyclized product was 78%, the molecular weight was Mw = 154000, and Mw / Mn = 1.28.
After adding 1200 parts of cyclohexane to the above reaction solution, it was poured into 10 liters of isopropanol to precipitate a polymer cyclized product (b2). The polymer cyclized product (b2) was separated by filtration and then dried with a vacuum dryer.

(Production Example 5) Polymer (c1)
A polymer (c1) was obtained in the same manner as in Production Example 1 except that the monomer composition was (styrene (St) / isoprene (IP)) = (96.4 / 3.6) in terms of weight ratio. The polymerization conversion rate of the obtained polymer was 100%, the weight average molecular weight (Mw) was 171000, and the molecular weight distribution (Mw / Mn) was 1.12.

(Production Example 6) Hydrogenated product (c2) of polymer (c1)
Subsequently, it implemented similarly to manufacture example 2 except having used the polymer (c1), and obtained the hydrogenated product (c2) of the polymer. The hydrogenation rate of the resulting hydrogenated polymer was 99.5%, the weight average molecular weight (Mw) was 135,000, and the molecular weight distribution (Mw / Mn) was 1.24.

(Production Example 7) Polymer cyclized product (c3) of polymer (c1)
Subsequently, it implemented similarly to manufacture example 4 except having used the polymer (c1), and obtained the polymer cyclization thing (d3). The cyclization rate of the obtained polymer cyclized product was 100%, the molecular weight was Mw = 154000, and Mw / Mn = 1.56.

(Production Example 8) Hydrogenated product (c4) of polymer cyclized product (c3)
Subsequently, it implemented similarly to manufacture example 2 except having used the polymer cyclization thing (c3), and obtained the hydrogenated product (c4) of the polymer cyclization thing. The hydrogenation rate of the resulting polymer cyclized product was 99.5%, the weight average molecular weight (Mw) was 126000, and the molecular weight distribution (Mw / Mn) was 1.61.

(Production Example 9) Polymer (d1)
The same procedure as in Production Example 1 was carried out, except that the composition of the monomer was (styrene (St) / isoprene (IP)) = (90/10) by weight ratio to obtain a polymer (d1). The polymerization conversion rate of the obtained polymer was 100%, the weight average molecular weight (Mw) was 168,000, and the molecular weight distribution (Mw / Mn) was 1.15.

(Production Example 10) Hydrogenated product (d2) of polymer (d1)
Subsequently, it implemented similarly to manufacture example 2 except having used the polymer (d1), and obtained the hydrogenated product (d2) of the polymer. The hydrogenation rate of the resulting hydrogenated polymer was 99.5%, the weight average molecular weight (Mw) was 133,000, and the molecular weight distribution (Mw / Mn) was 1.21.

(Production Example 11) Polymer cyclized product (d3) of polymer (d1)
Subsequently, it implemented similarly to manufacture example 4 except having used the polymer (d1), and obtained the polymer cyclization thing (d3). The cyclization rate of the obtained polymer cyclized product was 100%, the weight average molecular weight (Mw) was 149000, and the molecular weight distribution (Mw / Mn) was 1.51.

(Production Example 12) Hydrogenated product (d4) of polymer cyclized product (d3)
Subsequently, it implemented similarly to manufacture example 2 except having used the polymer cyclization thing (d3), and obtained the hydrogenated product (d4) of the polymer cyclization thing. The hydrogenation rate of the resulting polymer cyclized product was 99.4%, the weight average molecular weight (Mw) was 138000, and the molecular weight distribution (Mw / Mn) was 1.58.

(Production Example 13) Polymer (e1)
A polymer (e1) was obtained in the same manner as in Production Example 1 except that the monomer composition was (styrene (St) / isoprene (IP)) = (70/30) in terms of weight ratio. The polymerization conversion rate of the obtained polymer was 100%, the weight average molecular weight (Mw) was 179000, and the molecular weight distribution (Mw / Mn) was 1.14.

(Production Example 14) Hydrogenated product (e2) of polymer (e1)
Subsequently, it implemented similarly to manufacture example 2 except having used the polymer (e1), and obtained the hydrogenated product (e2) of the polymer. The hydrogenation rate of the obtained hydrogenated polymer was 99.5%, the weight average molecular weight (Mw) was 142000, and the molecular weight distribution (Mw / Mn) was 1.27.

(Production Example 15) Polymer cyclized product (e3) of polymer (e1)
Subsequently, it implemented similarly to manufacture example 4 except having used the polymer (d1), and obtained the polymer cyclization thing (e3). The obtained polymer cyclized product had a cyclization rate of 100%, a weight average molecular weight (Mw) of 143,000, and a molecular weight distribution (Mw / Mn) of 1.59.

(Production Example 16) Hydrogenated product (e4) of polymer cyclized product (e3)
Subsequently, it implemented similarly to manufacture example 2 except having used the polymer cyclization thing (e3), and obtained the hydrogenated product (e4) of the polymer cyclization thing. The hydrogenation rate of the resulting polymer cyclized product was 99.4%, the weight average molecular weight (Mw) was 157,000, and the molecular weight distribution (Mw / Mn) was 1.54.

(Production Example 17) Polymer (f1)
A polymer (f1) was obtained in the same manner as in Production Example 1 except that the monomer composition was (styrene (St) / isoprene (IP)) = (60/40) in terms of weight ratio. The polymerization conversion rate of the obtained polymer was 100%, the weight average molecular weight (Mw) was 175000, and the molecular weight distribution (Mw / Mn) was 1.16.

(Production Example 18) Cyclized product (f3) of polymer (f1)
Subsequently, it implemented similarly to manufacture example 4 except having used the polymer (f1), and obtained the polymer cyclization thing (f3). The resulting polymer cyclized product had a cyclization rate of 100%, a weight average molecular weight (Mw) of 155000, and a molecular weight distribution (Mw / Mn) of 1.54.

(Production Example 19) Hydrogenated product (f3) of polymer cyclized product (f3)
Subsequently, it implemented similarly to manufacture example 2 except having used the polymer cyclization thing (f3), and obtained the hydrogenated product (f4) of the polymer cyclization thing. The hydrogenation rate of the resulting polymer cyclized product was 99.4%, the weight average molecular weight (Mw) was 146000, and the molecular weight distribution (Mw / Mn) was 1.65.

The cyclization rate and hydrogenation rate of the resins obtained in Production Examples 1 to 19 are shown in Table 1.

Example 1
Various test pieces were prepared from the polymer cyclized product (d3) obtained in Production Example 11, and the glass transition temperature (Tg), refractive index, water absorption, total light transmittance, linear expansion coefficient, and focal length variation were measured. The results are shown in Table 2.

(Example 2)
Various test pieces were prepared from the hydrogenated product (d4) of the polymer cyclized product obtained in Production Example 12, glass transition temperature (Tg), refractive index, water absorption, total light transmittance, linear expansion coefficient, focal length. Variations were measured and are shown in Table 2.

(Example 3)
Various test pieces were prepared from the polymer cyclized product (e3) obtained in Production Example 13, and the glass transition temperature (Tg), refractive index, water absorption, total light transmittance, linear expansion coefficient, and focal length variation were measured. The results are shown in Table 2.

Example 4
Various test pieces were prepared from the polymer cyclized product hydrogenated product (e4) obtained in Production Example 14, glass transition temperature (Tg), refractive index, water absorption, total light transmittance, linear expansion coefficient, focal length. Variations were measured and are shown in Table 2.

(Example 3)
Various test pieces were prepared from the polymer cyclized product (f3) obtained in Production Example 15, and the glass transition temperature (Tg), refractive index, water absorption, total light transmittance, linear expansion coefficient, and focal length variation were measured. The results are shown in Table 2.

(Example 6)
Various test pieces were prepared from the hydrogenated product (f4) of the polymer cyclized product obtained in Production Example 16, glass transition temperature (Tg), refractive index, water absorption, total light transmittance, linear expansion coefficient, focal length. Variations were measured and are shown in Table 2.

(Comparative Example 1)
Various test pieces were prepared from the polymer (a1) obtained in Production Example 1, and the glass transition temperature (Tg), refractive index, water absorption, total light transmittance, linear expansion coefficient, and focal length variation were measured. It was shown in 2.

(Comparative Example 2)
Various test pieces are prepared from the hydrogenated polymer (a2) obtained in Production Example 2, and the glass transition temperature (Tg), refractive index, water absorption, total light transmittance, linear expansion coefficient, and focal length variation are measured. Measured and shown in Table 2.
(Comparative Example 3)
Various test pieces were prepared from the polymer cyclized product (b2) obtained in Production Example 4, and the glass transition temperature (Tg), refractive index, water absorption, total light transmittance, and linear expansion coefficient were measured. Indicated. In addition, since Tg was low, the lens after the standing test was deformed, so that the focal length variation could not be measured.

(Comparative Example 4)
Various test pieces were prepared from the polymer (c1) obtained in Production Example 5, and the glass transition temperature (Tg), refractive index, water absorption, total light transmittance, and linear expansion coefficient were measured. . In addition, since Tg was low, the lens after the standing test was deformed, so that the focal length variation could not be measured.

(Comparative Example 5)
Various test pieces were prepared from the polymer hydrogenated product (c2) obtained in Production Example 6, and the glass transition temperature (Tg), refractive index, water absorption, total light transmittance, linear expansion coefficient, and focal length variation were determined. Measured and shown in Table 2.

(Comparative Example 6)
Various test pieces were prepared from the polymer cyclized product (c3) obtained in Production Example 7, and the glass transition temperature (Tg), refractive index, water absorption, total light transmittance, linear expansion coefficient, and focal length variation were measured. The results are shown in Table 2.

(Comparative Example 7)
Various test pieces were prepared from the hydrogenated product (c4) of the polymer cyclized product obtained in Production Example 8, glass transition temperature (Tg), refractive index, water absorption, total light transmittance, linear expansion coefficient, focal length. Variations were measured and are shown in Table 2.

(Comparative Example 8)
Various test pieces were prepared from the polymer (d1) obtained in Production Example 9, and the glass transition temperature (Tg), refractive index, water absorption, total light transmittance, linear expansion coefficient, and focal length variation were measured. It was shown in 2.

(Comparative Example 9)
Various test pieces were prepared from the polymer hydrogenated product (d2) obtained in Production Example 10, and the glass transition temperature (Tg), refractive index, water absorption, total light transmittance, linear expansion coefficient, and focal length variation were determined. Measured and shown in Table 2.

(Comparative Example 10)
Various test pieces were prepared from the polymer (e1) obtained in Production Example 13, and the glass transition temperature (Tg), refractive index, water absorption, and total light transmittance were measured. Since Tg was low, the linear expansion coefficient and focal length variation could not be measured.

(Comparative Example 11)
Various test pieces were prepared from the hydrogenated polymer (e2) obtained in Production Example 14, and the glass transition temperature (Tg), refractive index, water absorption, and total light transmittance were measured. . Since Tg was low, the linear expansion coefficient and focal length variation could not be measured.

(Comparative Example 12)
Various test pieces were prepared from the polymer (f1) obtained in Production Example 17, and the glass transition temperature (Tg), refractive index, water absorption, and total light transmittance were measured. Since Tg was low, the linear expansion coefficient and focal length variation could not be measured.

<Discussion>
Non-cyclized polymers have low heat resistance, a large linear expansion coefficient, and large focal length fluctuations (Comparative Examples 1, 4, 8, 10, 12).
Although the polymer hydride is excellent in heat resistance, it has a large linear expansion coefficient and a large focal length variation (Comparative Examples 2, 5, 9, and 11).
The polymer cyclized product (b3) having a low cyclization rate has low heat resistance, a large linear expansion coefficient, and a large focal length variation (Comparative Example 3).
The polymer cyclized product (c3) having a small amount of isoprene and the hydrogenated product (c4) of the polymer cyclized product have a large linear expansion coefficient and a large focal length variation (Comparative Examples 6 and 7).
A polymer cyclized product having a suitable isoprene amount range and a high cyclization rate has excellent heat resistance, excellent refractive index, moderate water absorption, low linear expansion coefficient, and small focal length variation (Example 1) 3, 5)
A polymer cyclized hydride with a suitable range of isoprene amount and high cyclization rate has excellent heat resistance, moderate refractive index, excellent water absorption, low linear expansion coefficient, and small focal length variation ( Examples 2, 4, 6)

A part of ¹³ C-NMR chart of an isoprene homopolymer and a polymer cyclized product obtained by cyclization of the isoprene homopolymer. A part of ¹³ C-NMR chart of a random copolymer of isoprene and styrene and a polymer cyclized product obtained by cyclization reaction of the random copolymer. It is explanatory drawing regarding the shape of the lens used in the measuring method of a focal distance fluctuation | variation. It is explanatory drawing regarding the measuring method of a focal distance fluctuation | variation.

Claims (8)

  Containing a structural unit derived from a styrene derivative and a structural unit derived from a conjugated diene derivative, and a molar content ratio of the structural unit derived from the styrene derivative and the structural unit derived from the conjugated diene derivative (the structural unit derived from the styrene derivative / derived from the conjugated diene derivative) A polymer cyclized product obtained by cyclizing a random copolymer having a structural unit of 50/50 to 95/5, having a cyclization rate of 95% or more and a glass transition temperature of 100 ° C to 170 ° C. A polymer cyclized product characterized by being. The polymer cyclized product according to claim 1, wherein the linear expansion coefficient is in the range of 55 × 10 ⁻⁵ to 70 × 10 ⁻⁵ / ° C. The polymer cyclized product according to claim 1 or 2, wherein the refractive index is in the range of 1.55 to 1.60.   4. The polymer cyclized product according to claim 1, wherein a random copolymer is obtained by continuous addition polymerization of a styrene derivative and a conjugated diene derivative.   The polymer cyclized product according to any one of claims 1 to 4, comprising a cyclized structure obtained by a cyclization reaction of an olefinic double bond of a structural unit derived from a conjugated diene derivative and an aromatic ring of a structural unit derived from a styrene derivative. A glass transition temperature obtained by hydrogenating the polymer cyclized product according to any one of claims 1 to 5 and a linear expansion coefficient of 50 x ^{10-5 to} 65 x ^10-5 / ° C. A hydrogenated product of a polymer cyclized product, The hydrogenated product of a polymer cyclized product according to claim 6, wherein the refractive index is in the range of 1.50 to 1.55. A resin composition comprising the polymer cyclized product according to any one of claims 1 to 5 or the hydrogenated product of the polymer cyclized product according to claim 6 or 7.

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