JP4340128B2 - Method for producing lactone ring-containing polymer - Google Patents

Description

The present invention relates to the production how the lactone ring-containing polymer. For details, it relates to the production how of the lactone ring-containing polymer and a melt flow rate to a high molecular weight is within a predetermined range.

Conventionally, a (meth) acrylic resin is known as a resin having transparency. (Meth) acrylic resins are not only transparent, but also have excellent surface gloss and weather resistance, and are well-balanced in mechanical strength, moldability, and surface hardness. Widely used in applications. However, since the glass transition temperature (Tg) of the (meth) acrylic resin is around 110 ° C., it has been difficult to use in fields where heat resistance is required.
As a transparent heat-resistant resin that has both transparency and heat resistance, and also has various properties such as mechanical strength and moldability, a polymer having a hydroxyl group and an ester group in the molecular chain has recently been introduced. Several lactone ring-containing polymers obtained by a lactone cyclization condensation reaction have been proposed (see, for example, Patent Documents 1, 2, 3, and 4).

On the other hand, lactone ring-containing polymers are expected to be applied to various films, sheets and the like because they are excellent in surface gloss and surface hardness. However, conventional lactone ring-containing polymers have extremely poor moldability in film formation and sheet formation, and in films and sheets obtained by molding, cracks occur and the surface condition is poor, resulting in high mechanical strength. Was also inferior.
JP 2000-230016 A JP 2001-151814 A JP 2002-120326 A JP 2002-254544 A

The problem to be solved by the present invention has both high transparency and heat resistance, and is excellent in molding processability to a film and the like, and can give a molded product having high physical properties such as mechanical strength. is to provide a manufacturing how the molecular weight of the lactone ring-containing polymer.

The present inventor has intensively studied to solve the above problems.
As a result, a novel lactone ring-containing polymer having a high molecular weight of 180,000 to 500,000 and a melt flow rate within a specific range of 0.2 to 7.0 g / 10 min is obtained by using various films. The present invention was found to be a lactone ring-containing polymer suitable for applications such as sheet and sheet, and the lactone ring-containing polymer of the present invention was completed.
Furthermore, the method for producing the lactone ring-containing polymer of the present invention was also examined. In order to produce such a high molecular weight lactone ring-containing polymer, it is necessary to increase the concentration of the monomer component used for polymerization to increase the conversion rate. However, a polymer having a hydroxyl group and an ester group in a molecular chain and giving a lactone ring-containing polymer by a lactone cyclocondensation reaction has a very low solubility, so that a solvent is sufficiently present. If the polymerization reaction is not performed, the reaction solution gels, and the reaction cannot be controlled. Such gelation of the reaction solution is a big problem in operating the manufacturing process industrially. Furthermore, this gelation tendency is further increased by increasing the ratio of hydroxyl groups and ester groups in the molecular chain in order to increase the lactone ring content and improve heat resistance. The present inventor has paid attention to the above-mentioned problems, and has conducted intensive studies considering that the elimination of such problems leads to the completion of the method for easily producing the lactone ring-containing polymer of the present invention. As a result, the initial charge concentration of the monomer component to be subjected to polymerization is set to a high concentration of 55 to 95% by weight, and a specific solvent such as a ketone solvent and / or an ether solvent is selected as a polymerization solvent, and a polymerization reaction is performed. By performing polymerization by adding a polymerization solvent to the polymerization reaction mixture so that the concentration of the produced polymer in the mixture is 50% by weight or less, the gelation problem can be solved, and the lactone ring-containing polymer of the present invention can be eliminated. It has been found that the coalescence can be easily produced.

The method for producing a lactone ring-containing polymer according to the present invention comprises the steps of polymerizing a monomer component containing the monomer (1) represented by the following general formula and a (meth) acrylate ester , or simultaneously with the polymerization, the lactone ring. This is a process for producing a lactone ring-containing polymer having a weight average molecular weight of 180,000 to 500,000 and a melt flow rate of 0.2 to 7.0 g / 10 minutes by carrying out a polycondensation reaction, and a ketone as a polymerization solvent Using an organic solvent and / or an ether solvent, the initial charge concentration of the monomer component to be polymerized is 55 to 95% by weight, and the concentration of the produced polymer in the polymerization reaction mixture is 50% by weight or less. Polymerization is performed by adding a polymerization solvent to the polymerization reaction mixture.

(In the formula, R ¹ and R ² each independently represents a hydrogen atom or an organic residue having 1 to 20 carbon atoms.)
In the method for producing a lactone ring-containing polymer according to the present invention, preferably, the content ratio of the monomer (1) in all monomer components to be subjected to polymerization is 10 to 50% by weight , and the (meth) acrylic acid The proportion of ester is 90-50% by weight .

According to the present invention, a high molecular weight lactone ring that has both high transparency and heat resistance, is excellent in moldability into a film and the like, and can give a molded product having high physical properties such as mechanical strength. it is possible to provide a manufacturing how-containing polymer.

Hereinafter, the present invention will be described in detail. However, the scope of the present invention is not limited to these descriptions, and modifications other than the following examples can be made as appropriate without departing from the spirit of the present invention.
[Lactone ring-containing polymer]
The lactone ring-containing polymer obtained by the production method of the present invention (hereinafter sometimes referred to as “the lactone ring-containing polymer according to the present invention”) is a monomer (1) represented by the following general formula: A lactone ring-containing polymer obtained by polymerizing a monomer component containing or simultaneously with polymerizing, and having a lactone cyclization condensation reaction, having a weight average molecular weight of 180,000 to 500,000 and a melt flow rate of 0.2 to It is characterized by 7.0 g / 10 min.

(In the formula, R ¹ and R ² each independently represents a hydrogen atom or an organic residue having 1 to 20 carbon atoms.)
The lactone ring-containing polymer according to the present invention is a high molecular weight polymer having a weight average molecular weight of 180,000 to 500,000. The weight average molecular weight is preferably 190000-450,000, more preferably 200000-400000.
If the weight average molecular weight is lower than 180,000, a problem that the formed film or sheet is cracked easily occurs. If the weight average molecular weight is higher than 500,000, a problem that molding processability is poor tends to occur.

The lactone ring-containing polymer according to the present invention has a melt flow rate of 0.2 to 7.0 g / 10 min. As will be described later, the melt flow rate is measured at a test temperature of 240 ° C. and a load of 10 kg based on JIS-K6874. The melt flow rate is preferably 0.2 to 0.5 g / 10 minutes, more preferably 0.3 to 4.0 g / 10 minutes.
If the melt flow rate is lower than 0.2 g / 10 min, there is a problem that the molding processability is poor, and if it is higher than 7.0 g / 10 min, the molded film or sheet is cracked. Prone to occur.
The lactone ring-containing polymer according to the present invention preferably has a weight loss rate of 150% to 300 ° C. in dynamic TG measurement of 1% or less, more preferably 0.5% or less, and still more preferably 0. .3% or less.

Since the lactone ring-containing polymer according to the present invention has a high cyclization condensation reaction rate, it is possible to avoid the disadvantage that bubbles and silver streaks enter the molded product after molding. Furthermore, since the lactone ring structure is sufficiently introduced into the polymer due to a high cyclization condensation reaction rate, the obtained lactone ring-containing polymer has sufficiently high heat resistance and solvent resistance.
The lactone ring-containing polymer according to the present invention preferably has a coloring degree (YI) in a 15% by weight chloroform solution of 6 or less, more preferably 3 or less, still more preferably 2 or less, and most preferably 1 It is as follows. If the coloring degree (YI) exceeds 6, transparency may be impaired due to coloring, and it may not be used for the intended purpose.

The proportion of the lactone ring structure in the lactone ring-containing polymer according to the present invention is preferably 5 to 90% by weight, more preferably 10 to 80% by weight, and still more preferably 15 to 70% by weight. % By weight.
The lactone ring-containing polymer according to the present invention preferably has a 5% weight loss temperature in thermogravimetric analysis (TG) of 280 ° C. or higher, more preferably 300 ° C. or higher, and further preferably 320 ° C. or higher. The 5% weight loss temperature in thermogravimetric analysis (TG) is an index of thermal stability, and if it is less than 280 ° C., sufficient thermal stability may not be exhibited.

The lactone ring-containing polymer according to the present invention has a glass transition temperature (Tg) of preferably 115 ° C. or higher, more preferably 125 ° C. or higher, further preferably 130 ° C. or higher, more preferably 135 ° C. or higher, and most preferably 140 ° C. It is above ℃.
The total amount of residual volatile components contained in the lactone ring-containing polymer according to the present invention is preferably 1500 ppm or less, more preferably 1000 ppm or less. If the total amount of residual volatile components is more than 1500 ppm, it may cause molding defects such as coloration, foaming, or silver streak due to alteration during molding.
The lactone ring-containing polymer according to the present invention preferably has a total light transmittance of 85% or more, more preferably 88%, of a molded product obtained by injection molding, as measured by a method according to ASTM-D-1003. More preferably, it is 90% or more. The total light transmittance is a measure of transparency, and if it is less than 85%, the transparency is lowered and there is a possibility that it cannot be used for the intended purpose.

The lactone ring-containing polymer according to the present invention has a haze measured by a method according to ASTM-D-1003 of a molded product obtained by injection molding, preferably 5% or less, more preferably 3% or less, More preferably, it is 1% or less. The haze value is a measure of transparency, and if it exceeds 5%, the transparency is lowered and cannot be used for the intended purpose.
Although the shape of the lactone ring containing polymer concerning this invention is not specifically limited, The form of the resin material of a pellet form or a powder form is preferable.
The method for producing the lactone ring-containing polymer of the present invention is not particularly limited, but according to the production method according to the present invention described below, the lactone ring-containing polymer of the present invention can be easily produced. .

[Polymerization process]
In the method for producing a lactone ring-containing polymer according to the present invention, first, a polymerization reaction of a monomer component including the monomer (1) represented by the following general formula in the polymerization step is performed, so that A polymer having a hydroxyl group and an ester group is obtained.

(In the formula, R ¹ and R ² each independently represents a hydrogen atom or an organic residue having 1 to 20 carbon atoms.)
Examples of the monomer (1) include, for example, methyl 2- (hydroxymethyl) acrylate, ethyl 2- (hydroxymethyl) acrylate, isopropyl 2- (hydroxymethyl) acrylate, and normal 2- (hydroxymethyl) acrylate. Examples thereof include butyl and tertiary butyl 2- (hydroxymethyl) acrylate. Among these, methyl 2- (hydroxymethyl) acrylate and 2- (hydroxymethyl) ethyl acrylate are preferable, and methyl 2- (hydroxymethyl) acrylate is particularly preferable in that the effect of improving heat resistance is high. These monomers (1) may be used alone or in combination of two or more.

The content ratio of the monomer (1) in the monomer component to be subjected to polymerization is preferably 10 to 50% by weight, more preferably 10 to 40% by weight, and further preferably 15 to 35% by weight. When the content ratio of the monomer (1) is less than 10% by weight, the heat resistance, solvent resistance and surface hardness of the finally obtained lactone ring-containing polymer may be lowered. When the content ratio of the monomer (1) is more than 50% by weight, gelation tends to occur at the time of polymerization / lactonization, and the resulting lactone ring-containing polymer may be inferior in molding processability. .
The monomer component used for polymerization preferably contains a monomer other than the monomer (1). Such a monomer is not particularly limited as long as it does not impair the effects of the present invention. For example, (meth) acrylic acid ester, hydroxyl group-containing monomer, unsaturated carboxylic acid, Preferred is the monomer (2) represented. Only one type of monomer other than the monomer (1) may be used, or two or more types may be used in combination.

(Wherein R ³ represents a hydrogen atom or a methyl group, X represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, an —OAc group, a —CN group, a —CO—R ⁴ group, or —C It represents ^{-O-R 5} group, Ac group represents an acetyl group, ^{R 4} and ^{R 5} represents a hydrogen atom or an organic residue having 1 to 20 carbon atoms.)
The (meth) acrylic acid ester is not particularly limited as long as it is a (meth) acrylic acid ester other than the monomer (1). For example, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate Acrylates such as t-butyl acrylate, cyclohexyl acrylate, benzyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, methacrylic acid And methacrylic acid esters such as cyclohexyl and benzyl methacrylate. These may be used alone or in combination of two or more. Among these, methyl methacrylate is particularly preferable from the viewpoint of heat resistance and transparency.

When (meth) acrylic acid ester other than monomer (1) is used, the content ratio in the monomer component to be used for polymerization is 90 to 50% by weight in order to sufficiently exhibit the effects of the present invention. More preferably, it is 90-60 weight%, More preferably, it is 85-65 weight%.
The hydroxyl group-containing monomer is not particularly limited as long as it is a hydroxyl group-containing monomer other than the monomer (1). For example, α-hydroxymethylstyrene, α-hydroxyethylstyrene, 2- (hydroxyethyl) acrylic 2- (hydroxyalkyl) acrylic acid esters such as methyl acid; 2- (hydroxyalkyl) acrylic acid such as 2- (hydroxyethyl) acrylic acid; and the like. More than one species may be used in combination.

In the case of using a hydroxyl group-containing monomer other than the monomer (1), the content ratio in the monomer component to be subjected to polymerization is preferably 0 to 30% by weight in order to sufficiently exhibit the effects of the present invention. More preferably, it is 0-20 weight%, More preferably, it is 0-10 weight%.
Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-substituted acrylic acid, α-substituted methacrylic acid and the like. These may be used alone or in combination of two or more. You may do it. Among these, acrylic acid and methacrylic acid are preferable in that the effects of the present invention are sufficiently exhibited.
When using an unsaturated carboxylic acid, the content ratio in the monomer component to be subjected to polymerization is preferably 0 to 30% by weight, more preferably 0 to 20% by weight, in order to sufficiently exhibit the effects of the present invention. More preferably, it is 0 to 10% by weight.

Examples of the monomer (2) include styrene, vinyl toluene, α-methyl styrene, acrylonitrile, methyl vinyl ketone, ethylene, propylene, vinyl acetate and the like. More than one species may be used in combination. Among these, styrene and α-methylstyrene are particularly preferable in that the effects of the present invention are sufficiently exhibited.
In the case of using the monomer (2), the content ratio in the monomer component to be subjected to polymerization is preferably 90 to 50% by weight, more preferably 90 to 60%, in order to sufficiently exhibit the effects of the present invention. % By weight, more preferably 85-65% by weight.
As a form of the polymerization reaction for polymerizing the monomer component to obtain a polymer having a hydroxyl group and an ester group in the molecular chain, it is necessary to be a polymerization form using a solvent, particularly solution polymerization. Is preferred.

The polymerization temperature and polymerization time vary depending on the type of monomer used, the ratio of use, etc., but are preferably a polymerization temperature of 0 to 150 ° C. and a polymerization time of 0.5 to 20 hours, more preferably a polymerization temperature of 60 ˜140 ° C., polymerization time 1-10 hours, more preferably polymerization temperature 80-120 ° C., polymerization time 4-8 hours.
In the present invention, it is important that the initial charge concentration of the monomer component used for polymerization is 55 to 95% by weight, preferably 55 to 90% by weight, more preferably 60 to 80% by weight, still more preferably. 65 to 75% by weight. If the initial charge concentration of the monomer component to be subjected to polymerization is lower than 55% by weight, the effects of the present invention cannot be sufficiently exhibited, and in particular, the finally obtained lactone ring-containing polymer may not have a high molecular weight. is there. If the initial charge concentration of the monomer component used for polymerization is higher than 95% by weight, gelation may occur in the initial stage of the polymerization reaction.

In the present invention, it is important to use a ketone solvent and / or an ether solvent as a polymerization solvent. By using a ketone solvent and / or an ether solvent, the effect of the present invention can be exerted. In particular, the initial charge concentration of the monomer component to be subjected to polymerization is as high as 55 to 100% by weight. Can also suppress gelation of the polymerization reaction solution.
Examples of the ketone solvent include acetone, diethyl ketone, cyclohexanone, methyl ethyl ketone, and methyl isobutyl ketone, and only one of them may be used, or two or more may be used in combination.
Examples of the ether solvent include tetrahydrofuran, dioxane, diethylene glycol dialkyl ether, dipropylene glycol dialkyl ether, and the like, and only one of them may be used, or two or more may be used in combination.

When the boiling point of the solvent to be used is too high, the residual volatile component of the finally obtained lactone ring-containing polymer is increased, and therefore, those having a boiling point of 50 to 200 ° C. are preferable.
During the polymerization reaction, a polymerization initiator may be added as necessary. Although it does not specifically limit as a polymerization initiator, For example, cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, t-amyl Organic peroxides such as peroxy-2-ethylhexanoate and t-amylperoxy-3,5,5-trimethylhexanoate; 2,2′-azobis (isobutyronitrile), 1,1 ′ -Azo compounds such as azobis (cyclohexanecarbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl-2,2'-azobisisobutyrate; May be used alone, or two or more of them may be used in combination. The amount of the polymerization initiator used is not particularly limited as long as it is appropriately set according to the combination of the monomers used and the reaction conditions.

  In the present invention, it is important to perform polymerization by adding a polymerization solvent to the polymerization reaction mixture so that the concentration of the produced polymer in the polymerization reaction mixture is 50% by weight or less. By controlling the concentration of the produced polymer in the polymerization reaction mixture in this way, the gelation of the reaction solution can be more sufficiently suppressed, and in particular, to increase the lactone ring content and improve the heat resistance. Even when the ratio of the hydroxyl group to the ester group in the molecular chain is increased, gelation can be sufficiently suppressed. The concentration of the produced polymer in the polymerization reaction mixture is more preferably 45% by weight or less, still more preferably 40% by weight or less. Note that if the concentration of the polymer in the polymerization reaction mixture is too low, the productivity is lowered. Therefore, the lower limit of the concentration of the polymer in the polymerization reaction mixture is preferably 10% by weight or more, and more preferably 20% by weight or more. It is more preferable that

The form of adding the polymerization solvent to the polymerization reaction mixture so that the concentration of the produced polymer in the polymerization reaction mixture is 50% by weight or less is not particularly limited, and the polymerization solvent may be added continuously. The polymerization solvent may be added intermittently.
The polymerization solvent to be added is preferably the ketone solvent and / or the ether solvent described above, but it may be the same type of solvent as the solvent used at the initial stage of the polymerization reaction or a different type of solvent. May be. More preferably, the same type of solvent as that used in the initial charge of the polymerization reaction is used. Moreover, the polymerization solvent to add may be only 1 type of solvent, and 2 or more types of mixed solvents may be sufficient as it.

In the polymerization reaction mixture obtained when the above polymerization reaction is completed, a solvent is contained in addition to the obtained polymer. In the present invention, the solvent is completely removed to remove the polymer in a solid state. It is not necessary to take out, and it is preferable to introduce into the subsequent lactone cyclization condensation step in a state containing a solvent. If necessary, after taking out in a solid state, a solvent suitable for the subsequent lactone cyclization condensation step may be added again.
The concentration of the polymer in the polymerization reaction mixture obtained when the polymerization reaction is completed is 50% by weight or less, preferably 10 to 50% by weight, more preferably 20 to 50% by weight, and still more preferably 25%. ~ 45 wt%.

The polymer obtained in the polymerization step is a polymer (a) having a hydroxyl group and an ester group in the molecular chain, and becomes a lactone ring-containing polymer by being subjected to the subsequent lactone cyclization condensation step.
The weight average molecular weight of the polymer (a) obtained in the polymerization step is preferably 150,000 to 500,000, more preferably 160000 to 450,000, and still more preferably 180000 to 400,000.
[Lactone cyclization condensation step]
In the method for producing a lactone ring-containing polymer according to the present invention, the polymer (a) obtained in the polymerization step is heated to introduce a lactone ring structure into the polymer to obtain a lactone ring-containing polymer. The method for the heat treatment is not particularly limited.

The reaction for introducing the lactone ring structure into the polymer (a) is a reaction in which a hydroxyl group and an ester group present in the molecular chain of the polymer (a) are cyclized and condensed to form a lactone ring structure by heating. The cyclized condensation produces alcohol as a by-product. By forming the lactone ring structure in the molecular chain of the polymer (in the main skeleton of the polymer), high heat resistance is imparted. If the reaction rate of the cyclization condensation reaction leading to the lactone ring structure is insufficient, the heat resistance will not be improved sufficiently, or the condensation reaction will occur during the molding process due to the heat treatment during molding, and the resulting alcohol will be contained in the molded product. It is not preferable because it is present as bubbles or silver streaks.
The method for heat-treating the polymer (a) is not particularly limited, and a known method can be used. For example, you may heat-process the polymerization reaction mixture containing the solvent obtained by the superposition | polymerization process as it is. Moreover, you may heat-process using a ring-closing catalyst as needed in presence of a solvent. Further, the heat treatment can be performed using a heating furnace or reaction apparatus having a vacuum apparatus or a devolatilizing apparatus for removing volatile components, an extruder having a devolatilizing apparatus, or the like.

In carrying out the cyclization condensation reaction, in addition to the polymer (a), another thermoplastic resin may coexist. When performing the cyclization condensation reaction, if necessary, an esterification catalyst or a transesterification catalyst such as p-toluenesulfonic acid generally used as a catalyst for the cyclization condensation reaction may be used. Basic compounds, organic carboxylates, carbonates and the like may be used as disclosed in JP-A-61-254608 and JP-A-61-261303.
In the present invention, it is preferable to use an organic phosphorus compound as a catalyst when performing the cyclization condensation reaction. By using an organophosphorus compound as a catalyst, the cyclization condensation reaction rate can be improved, and coloring of the resulting lactone ring-containing polymer can be greatly reduced. Furthermore, by using an organophosphorus compound as a catalyst, it is possible to suppress a decrease in molecular weight that can occur when a devolatilization step described later is used in combination, and to impart excellent mechanical strength.

  Examples of the organic phosphorus compound that can be used as a catalyst in the cyclocondensation reaction include alkyl (aryl) phosphonous acids such as methylphosphonous acid, ethylphosphonous acid, and phenylphosphonous acid (however, Tautomers (which may be alkyl (aryl) phosphinic acid) and diesters or monoesters thereof; dimethylphosphinic acid, diethylphosphinic acid, diphenylphosphinic acid, phenylmethylphosphinic acid, phenylethylphosphinic acid, etc. Dialkyl (aryl) phosphinic acids and esters thereof; alkyl (aryl) phosphonic acids such as methyl phosphonic acid, ethyl phosphonic acid, trifluoromethyl phosphonic acid, phenyl phosphonic acid, and their diesters or monoesters; Alkyl (aryl) phosphinic acids such as phosphoric acid, ethylphosphinic acid, phenylphosphinic acid and their esters; methyl phosphite, ethyl phosphite, phenyl phosphite, dimethyl phosphite, phosphorous acid Phosphorous acid diester or monoester or triester such as diethyl, diphenyl phosphite, trimethyl phosphite, triethyl phosphite, triphenyl phosphite; methyl phosphate, ethyl phosphate, 2-ethylhexyl phosphate, phosphorus Isodecyl phosphate, lauryl phosphate, stearyl phosphate, isostearyl phosphate, phenyl phosphate, dimethyl phosphate, diethyl phosphate, di-2-ethylhexyl phosphate, diisodecyl phosphate, dilauryl phosphate, distearyl phosphate, phosphorus Diisostearyl acid, diphenyl phosphate, trimethyl phosphate , Phosphoric diesters or monoesters or triesters such as triethyl phosphate, triisodecyl phosphate, trilauryl phosphate, tristearyl phosphate, triisostearyl phosphate, triphenyl phosphate; methylphosphine, ethylphosphine, phenylphosphine, dimethyl Mono- or di- or trialkyl (aryl) phosphine such as phosphine, diethylphosphine, diphenylphosphine, trimethylphosphine, triethylphosphine, triphenylphosphine; methyldichlorophosphine, ethyldichlorophosphine, phenyldichlorophosphine, dimethylchlorophosphine, diethylchlorophosphine, Alkyl (aryl) halogen phosphines such as diphenylchlorophosphine; Mono- or di- or trialkyl (aryl) phosphine oxides such as tilphosphine, phenylphosphine oxide, dimethylphosphine oxide, diethylphosphine oxide, diphenylphosphine oxide, trimethylphosphine oxide, triethylphosphine oxide, triphenylphosphine oxide; tetramethylphosphonium chloride, And halogenated tetraalkyl (aryl) phosphonium such as tetraethylphosphonium chloride and tetraphenylphosphonium chloride. Among these, alkyl (aryl) phosphonous acid, phosphorous acid diester or monoester, phosphoric acid diester or monoester, and alkyl (aryl) phosphonic acid are preferable because of high catalytic activity and low colorability. ) Phosphorous acid, phosphorous acid diester or monoester, phosphoric acid diester or monoester are more preferred, and alkyl (aryl) phosphonous acid, phosphoric acid diester or monoester is particularly preferred. These organic phosphorus compounds may be used alone or in combination of two or more.

Although the usage-amount of the catalyst used in the case of the said cyclization condensation reaction is not specifically limited, Preferably, it is 0.001 to 5 weight% with respect to a polymer (a), More preferably, it is 0.01 to 2.5. % By weight, more preferably 0.01 to 1% by weight, particularly preferably 0.05 to 0.5% by weight. If the amount of the catalyst used is less than 0.001% by weight, the reaction rate of the cyclization condensation reaction may not be sufficiently improved. On the other hand, if the amount exceeds 5% by weight, coloring may occur, This is not preferable because it is difficult to melt and form by cross-linking of the coalescence.
The addition timing of the catalyst is not particularly limited, and it may be added at the beginning of the reaction, during the reaction, or both.

In the present invention, it is preferable to carry out the cyclization condensation reaction in the presence of a solvent and to use a devolatilization step in combination with the cyclization condensation reaction. In this case, a mode in which the devolatilization step is used throughout the cyclization condensation reaction and a mode in which the devolatilization step is not used over the entire cyclization condensation reaction but only in a part of the process. In the method using the devolatilization step in combination, the alcohol produced as a by-product in the condensation cyclization reaction is forcibly devolatilized and removed, so that the equilibrium of the reaction is advantageous for the production side.
The devolatilization step refers to a step of removing volatile components such as a solvent and residual monomers and alcohol produced as a by-product by a cyclocondensation reaction leading to a lactone ring structure, if necessary under reduced pressure heating conditions. If this removal treatment is insufficient, the residual volatile components in the produced resin increase, resulting in problems such as coloration due to alteration during molding, or molding defects such as bubbles or silver streaks.

In the case of a form in which a devolatilization step is used throughout the cyclization condensation reaction, the apparatus to be used is not particularly limited, but a devolatilization apparatus comprising a heat exchanger and a devolatilization tank in order to perform the present invention more effectively. It is preferable to use an extruder equipped with a vent, or a device in which the devolatilizer and the extruder are arranged in series, and it is more preferable to use a devolatilizer comprising a heat exchanger and a devolatilization tank or an extruder equipped with a vent. preferable.
In the case of using a devolatilizer comprising the heat exchanger and a devolatilizer, the reaction treatment temperature is preferably in the range of 150 to 350 ° C, more preferably in the range of 200 to 300 ° C. If the reaction treatment temperature is lower than 150 ° C., the cyclization condensation reaction may be insufficient and the residual volatile matter may increase, and if it is higher than 350 ° C., coloring or decomposition may occur.

When using a devolatilizer comprising the heat exchanger and the devolatilization tank, the pressure during the reaction treatment is preferably in the range of 931 to 1.33 hPa (700 to 1 mmHg), and 798 to 66.5 hPa (600 to 50 mmHg). The range of is more preferable. When the pressure is higher than 931 hPa, there is a problem that volatile components including alcohol easily remain, and when the pressure is lower than 1.33 hPa, there is a problem that industrial implementation becomes difficult.
When using the extruder with a vent, one or a plurality of vents may be used, but it is preferable to have a plurality of vents.
The reaction processing temperature in the case of using the vented extruder is preferably in the range of 150 to 350 ° C, more preferably in the range of 200 to 300 ° C. If the temperature is lower than 150 ° C., the cyclization condensation reaction may be insufficient and the residual volatile content may increase. If the temperature is higher than 350 ° C., coloring or decomposition may occur.

When using the extruder with a vent, the pressure during the reaction treatment is preferably in the range of 931 to 1.33 hPa (700 to 1 mmHg), and more preferably in the range of 798 to 13.3 hPa (600 to 10 mmHg). When the pressure is higher than 931 hPa, there is a problem that volatile components including alcohol easily remain, and when the pressure is lower than 1.33 hPa, there is a problem that industrial implementation becomes difficult.
In the case of using the devolatilization step throughout the cyclization condensation reaction, as described later, the physical properties of the lactone ring-containing polymer obtained may be deteriorated under severe heat treatment conditions. It is preferable to use a catalyst for a dealcoholization reaction and under a mild condition as much as possible using an extruder with a vent.

In the case of using the devolatilization step throughout the entire cyclization condensation reaction, preferably, the polymer (a) obtained in the polymerization step is introduced into the cyclization condensation reactor system together with the solvent. If necessary, it may be passed through the reactor system such as a vented extruder once again.
In the present invention, the devolatilization step may not be used over the entire process of the cyclization condensation reaction, but may be used only in a part of the process. For example, the apparatus for producing the polymer (a) is further heated, and if necessary, a part of the devolatilization step is used together to advance the cyclization condensation reaction to some extent in advance, followed by the devolatilization step. Is a form in which a cyclization condensation reaction is simultaneously used to complete the reaction.

  In the form in which the devolatilization step is used throughout the cyclization condensation reaction described above, for example, when the polymer (a) is heat-treated at a high temperature close to 250 ° C. or higher using a twin-screw extruder. Depending on the difference in thermal history, partial decomposition or the like may occur before the cyclization condensation reaction occurs, and the physical properties of the resulting lactone ring-containing polymer may be deteriorated. Therefore, if the condensation cyclization reaction is allowed to proceed to some extent before the cyclization condensation reaction using the devolatilization process at the same time, the reaction conditions in the latter half can be relaxed and the physical properties of the resulting lactone ring-containing polymer deteriorated. Is preferable. As a particularly preferred embodiment, the devolatilization step is started after a lapse of time from the start of the cyclization condensation reaction, that is, the hydroxyl group and the ester group present in the molecular chain of the polymer (a) obtained in the polymerization step. A form in which a cyclization condensation reaction is performed in advance to increase the cyclization condensation reaction rate to some extent and then a cyclization condensation reaction using a devolatilization step in combination is performed. Specifically, for example, a cyclization condensation reaction is allowed to proceed to a certain reaction rate in the presence of a solvent in advance using a kettle-type reactor, and then a reactor equipped with a devolatilizer, for example, a heat Preferred is a mode in which the cyclization condensation reaction is completed with a devolatilizer comprising an exchanger and a devolatilization tank, an extruder with a vent, or the like. Particularly in this form, it is more preferable that a catalyst for the cyclization condensation reaction is present.

  As described above, the hydroxyl group and ester group present in the molecular chain of the polymer (a) obtained in the polymerization step are preliminarily subjected to a cyclization condensation reaction to increase the cyclization condensation reaction rate to some extent. The method of carrying out the cyclization condensation reaction using the steps at the same time is a preferred form in obtaining a lactone ring-containing polymer in the present invention. With this form, a lactone ring-containing polymer having a higher glass transition temperature, a higher cyclization condensation reaction rate, and excellent heat resistance can be obtained. In this case, as a measure of the cyclization condensation reaction rate, the weight loss rate between 150 and 300 ° C. in the dynamic TG measurement shown in the examples is preferably 2% or less, more preferably 1.5% or less. More preferably, it is 1% or less.

  The reactor that can be employed in the cyclization condensation reaction that is performed in advance before the cyclization condensation reaction using the devolatilization process at the same time is not particularly limited, but preferably an autoclave, a kettle reactor, a heat exchanger, and a devolatilization tank A vented extruder suitable for a cyclocondensation reaction in which a devolatilization step is simultaneously used can also be used. More preferred are autoclaves and kettle reactors. However, even when using a reactor such as an extruder with a vent, by adjusting the temperature condition, barrel condition, screw shape, screw operating condition, etc. It is possible to carry out the cyclization condensation reaction in the same state as the reaction state in the kettle reactor.

In the case of the cyclization condensation reaction performed in advance before the cyclization condensation reaction using the devolatilization step at the same time, preferably, a mixture containing the polymer (a) obtained in the polymerization step and the solvent is used as (i). Examples thereof include a method in which a catalyst is added and subjected to a heat reaction, (ii) a method in which a heat reaction is performed without a catalyst, and a method in which the above (i) or (ii) is performed under pressure.
The “mixture containing the polymer (a) and the solvent” introduced into the cyclization condensation reaction in the lactone cyclization condensation step may be the polymerization reaction mixture obtained in the polymerization step as it is, or once It means that a solvent suitable for the cyclocondensation reaction may be added again after removing the solvent.

The solvent that can be re-added in the cyclization condensation reaction that is carried out in advance before the cyclization condensation reaction simultaneously used in the devolatilization step is not particularly limited, and examples thereof include aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; Ketones such as methyl ethyl ketone and methyl isobutyl ketone; chloroform, DMSO, tetrahydrofuran and the like may be used, but preferably the same solvent as that which can be used in the polymerization step, that is, a ketone solvent and / or an ether solvent. Although it is not necessary to use the same type of ketone solvent and / or ether solvent as the solvent actually used in the polymerization step, it is preferable to use the same type.
Examples of the catalyst added in the above method (i) include esterification catalysts such as p-toluenesulfonic acid or transesterification catalysts, basic compounds, organic carboxylates, carbonates and the like that are generally used. Is preferably the above-described organophosphorus compound. The addition timing of the catalyst is not particularly limited, and it may be added at the beginning of the reaction, during the reaction, or both. The amount of the catalyst to be added is not particularly limited, but is preferably 0.001 to 5% by weight, more preferably 0.01 to 2.5% by weight, and still more preferably 0.01 to the weight of the polymer (a). -0.1 wt%, particularly preferably 0.05-0.5 wt%. The heating temperature and heating time of method (i) are not particularly limited, but the heating temperature is preferably room temperature or higher, more preferably 50 ° C. or higher, and the heating time is preferably 1 to 20 hours, more preferably 2 to 10 hours. If the heating temperature is low or the heating time is short, the cyclization condensation reaction rate is lowered, which is not preferable. Further, if the heating time is too long, the resin may be colored or decomposed, which is not preferable.

In addition, if a monomer having an acid group is an essential component as a monomer component for performing the polymerization reaction, the monomer having an acid group and / or the resulting polymer acts as a catalyst for lactone cyclization. Therefore, lactone cyclization can be performed simultaneously with the polymerization reaction of the monomer component without using a separate catalyst for lactone cyclization.
Examples of the method (ii) include a method of heating the polymerization reaction mixture obtained in the polymerization step as it is using a pressure-resistant kettle or the like. The heating temperature is preferably 100 ° C. or higher, more preferably 150 ° C. or higher. The heating time is preferably 1 to 20 hours, more preferably 2 to 10 hours. If the heating temperature is low or the heating time is short, the cyclization condensation reaction rate is lowered, which is not preferable. Further, if the heating time is too long, the resin may be colored or decomposed, which is not preferable.

Both the above methods (i) and (ii) have no problem even under pressure depending on conditions.
In the case of the cyclization condensation reaction performed in advance before the condensation cyclization reaction using the devolatilization step at the same time, there is no problem even if a part of the solvent volatilizes spontaneously during the reaction.
The weight loss rate between 150 and 300 ° C. in dynamic TG measurement at the end of the cyclization condensation reaction performed in advance before the cyclization condensation reaction simultaneously using the devolatilization step, that is, immediately before the start of the devolatilization step is 2% or less is preferable, More preferably, it is 1.5% or less, More preferably, it is 1% or less. When the weight reduction rate is higher than 2%, the cyclization condensation reaction rate does not rise to a sufficiently high level even if the cyclization condensation reaction is performed simultaneously with the devolatilization step, and the physical properties of the resulting lactone ring-containing polymer. May decrease. In addition, when performing said cyclization condensation reaction, in addition to a polymer (a), you may coexist other thermoplastic resins.

  The hydroxyl group and ester group present in the molecular chain of the polymer (a) obtained in the polymerization step were subjected to a cyclization condensation reaction in advance to increase the cyclization condensation reaction rate to some extent, and then the devolatilization step was simultaneously used in combination. In the case of a form in which a cyclization condensation reaction is performed, a polymer obtained by a cyclization condensation reaction performed in advance (a polymer in which at least a part of hydroxyl groups and ester groups present in the molecular chain are subjected to cyclization condensation reaction) and a solvent The devolatilization step may be used as it is, and may be introduced into the cyclization condensation reaction. If necessary, the polymer (a polymer obtained by cyclization condensation reaction of at least a part of hydroxyl groups and ester groups present in the molecular chain) may be used. You may introduce | transduce into the cyclocondensation reaction which used the devolatilization process together after passing through other processes, such as adding a solvent again after isolating a compound.

In the present invention, the devolatilization step is not necessarily completed at the same time as the cyclization condensation reaction, and may be completed after a lapse of time from the completion of the cyclization condensation reaction.
According to the production method according to the present invention described above, the lactone ring-containing polymer of the present invention can be easily produced.
[Use of lactone ring-containing polymer]
Since the lactone ring-containing polymer according to the present invention has excellent physical properties as described above, an antioxidant, a stabilizer, a reinforcing material such as glass fiber, an ultraviolet absorber, a flame retardant, and an antistatic agent, as necessary. An additive, a coloring agent, and the like may be blended to form a transparent heat-resistant resin molding material, or the molding material may be molded into a molded product. Since these transparent heat-resistant resin molding materials and molded articles comprise the lactone ring-containing polymer of the present invention, they have excellent physical properties.

The lactone ring-containing polymer according to the present invention has both high transparency and heat resistance, and is excellent in molding processability to a film and the like, and can give a molded product having high physical properties such as mechanical strength. Since it is a high molecular weight lactone ring-containing polymer, in particular, a molded body (film) obtained by forming the lactone ring-containing polymer of the present invention into a film, a laminate having the lactone ring-containing polymer of the present invention as a surface layer, and the present invention The coating resin solution containing the lactone ring-containing polymer has extremely excellent physical properties.
Since the film of the present invention is composed of the lactone ring-containing polymer of the present invention, it is a molded product exhibiting high physical properties such as transparency, heat resistance, mechanical strength, etc., and cracks are not generated during film formation. The film surface is smooth and fish eyes are hardly generated.

When forming the lactone ring-containing polymer of the present invention into a film, the molding method is not particularly limited, and examples thereof include injection molding, extrusion molding, inflation molding, and blow molding. The molding temperature is not particularly limited, but is preferably 150 to 350 ° C, more preferably 200 to 300 ° C. As for the thickness of a film, 10-1000 micrometers is preferable, More preferably, it is 20-800 micrometers, More preferably, it is 50-500 micrometers.
Since the multilayer laminate of the present invention has the lactone ring-containing polymer of the present invention in the surface layer, it is a molded product exhibiting high physical properties such as transparency, heat resistance, mechanical strength, etc. Since the moldability of the containing polymer is good, it is possible to suppress deterioration of the surface layer when the laminate is molded by coextrusion, for example.

The multilayer laminate having the lactone ring-containing polymer of the present invention in the surface layer may be of any other layer as long as the surface layer has a layer made of the lactone ring-containing polymer. A surface layer can be manufactured by the same method as the case where the above-mentioned film is manufactured, for example.
As other layers, for example, PMMA resin, impact PMMA resin, polycarbonate resin, rubber-reinforced styrene resin, vinyl chloride resin, styrene resin, AS (acrylonitrile-styrene) resin, polyester resin, polyolefin resin, polyamide Based resins, and only one of these may be used, or two or more may be used. Examples of the rubber-reinforced styrene resin include ABS (acrylonitrile-butadiene rubber-styrene) resin, AES (acrylonitrile-ethylene / propylene rubber-styrene) resin, and ACS (acrylonitrile-chlorinated polyethylene-styrene) resin. , ASA (acrylonitrile-acrylic rubber-styrene) resin, and the like, and only one of these may be used, or two or more may be used.

Since the coating resin liquid of the present invention contains the lactone ring-containing polymer of the present invention, the effect of protecting the base material layer from the solvent and heat by coating the surface of the base material layer with respect to the formed film, The effect of adding scratch resistance and heat resistance can be exhibited. In addition, weather resistance can be imparted, and when an ultraviolet absorber is contained as described later, or when an ultraviolet absorbing monomer or an ultraviolet stable monomer is copolymerized, the effect is more effective. Become prominent.
The coating resin solution of the present invention may contain the organic solvent used for the polymerization as it is, or may contain another solvent after once removing the solvent.
The concentration of the lactone ring-containing polymer of the present invention in the coating resin solution of the present invention is preferably 1 to 90% by weight, more preferably 3 to 80% by weight, and still more preferably 5 to 70% by weight.

A film comprising the lactone ring-containing polymer of the present invention, a multilayer laminate having a lactone ring-containing polymer in the surface layer, and a coating resin solution containing the lactone ring-containing polymer, if necessary, an ultraviolet absorber, Other additives may be included. Further, a lactone ring-containing polymer produced using a monomer component containing an ultraviolet-absorbing monomer or an ultraviolet-stable monomer may be used as the film, multilayer laminate, or coating resin liquid of the present invention. .
Examples of the ultraviolet absorber include benzophenone compounds, salicinate compounds, benzoate compounds, and triazole compounds. Examples of the benzophenone compounds include 2,4-dihydroxybenzophenone and 4-n-octyloxy-2-hydroxybenzophenone. Examples of the silicate compound include pt-butylphenyl silicate. Furthermore, examples of the benzoate compound include 2,4-di-t-butylphenyl-3 ′, 5′-di-t-butyl-4′-hydroxybenzoate. Further, as triazole compounds, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H— Examples include benzotriazole. These may be used alone or in combination of two or more.

The blending amount of the ultraviolet absorber is not particularly limited, but 0.01% in a film made of a lactone ring-containing polymer, a surface layer having a lactone ring-containing polymer, and a coating resin solution containing a lactone ring-containing polymer. It is preferably ˜25% by weight, more preferably 0.05 to 10% by weight. If the amount added is too small, the contribution to improving the weather resistance is low, and if it is too large, the mechanical strength may be lowered or yellowing may be caused.
Other additives include, but are not limited to, the ultraviolet absorbers exemplified above, for example, hindered phenol-based, phosphorous-based, sulfur-based antioxidants; reinforcing materials such as glass fibers; Flame retardants such as (dibromopropyl) phosphate, ethylene tetrabromide, antimony oxide, zinc borate; antistatic agents such as anionic, cationic, nonionic and amphoteric surfactants; inorganic pigments, organic pigments, Colorants such as dyes; and the like. What is necessary is just to set suitably the addition time and addition amount of these additives in the range which does not impair the effect of this invention.

  Examples of the ultraviolet absorbing monomer include benzotriazole compounds, benzophenone compounds, triazine compounds, and acrylic monomers having a polymerizable unsaturated group. Examples of the benzotriazole compounds include 2- [2′-hydroxy-5 ′-(meth) acryloyloxymethylphenyl] -2H-benzotriazole, 2- [2′-hydroxy-5 ′-(meth) acryloyloxy. Ethylphenyl] -2H-benzotriazole, 2- [2′-hydroxy-5 ′-(meth) acryloyloxypropylphenyl] -2H-benzotriazole, 2- [2′-hydroxy-5 ′-(meth) acryloyloxy Hexylphenyl] -2H-benzotriazole, 2- [2′-hydroxy-3′-tert-butyl-5 ′-(meth) acryloyloxyethylphenyl] -2H-benzotriazole, 2- [2′-hydroxy-5 '-(Β- (Meth) acryloyloxyethoxy) -3'-tert-butylphenyl Or the like can be used -5-tert-butyl -2H- benzotriazole. Examples of the benzophenone compounds include 2-hydroxy-4- [2- (meth) acryloyloxy] ethoxybenzophenone, 2-hydroxy-4- [2- (meth) acryloyloxy] butoxybenzophenone, and 2,2′-dihydroxy. -4- [2- (meth) acryloyloxy] ethoxybenzophenone, 2-hydroxy-4- [2- (meth) acryloyloxy] ethoxy-4 '-(2-hydroxyethoxy) benzophenone, and the like can be used. Examples of triazine compounds include 4-diphenyl-6- [2-hydroxy-4- (2-acryloyloxyethoxy)]-s-triazine, 2,4-bis (2-methylphenyl) -6- [2-hydroxy-4- (2-acryloyloxyethoxy)]-s-triazine, 2,4-bis (2-methoxyphenyl) -6- [2-hydroxy-4- (2-acryloyloxyethoxy)]- An s-triazine or the like can be used. These may be used alone or in combination of two or more.

Although the compounding quantity of the said ultraviolet-absorbing monomer is not specifically limited, 0.1 to 25 weight% of all the monomer components is preferable, More preferably, it is 1 to 15 weight%. If the content is small, the contribution to improving weather resistance is low, and if the content is too large, the hot water resistance and solvent resistance may be reduced, or yellowing may occur.
As the ultraviolet-stable monomer, for example, one in which a polymerizable unsaturated group is bonded to a hindered amine compound can be used, and specific examples include 4- (meth) acryloyloxy-2,2,6. , 6-tetramethylpiperidine, 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4 -(Meth) acryloylamino-1,2,2,6,6-pentamethylpiperidine, 4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy -2,2,6,6-tetramethylpiperidine, 4-crotonoylamino-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl- -(Meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, Examples include 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidine. These may be used alone or in combination of two or more.

  Although the compounding quantity of the said ultraviolet stable monomer is not specifically limited, 0.1 to 25 weight% of all the monomer components is preferable, More preferably, it is 1 to 15 weight%. If the content is small, the contribution to improving weather resistance is low, and if the content is too large, the hot water resistance and solvent resistance may be reduced, or yellowing may occur.

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these. Hereinafter, for the sake of convenience, “liter” may be simply referred to as “L”.
<Polymerization reaction rate, polymer composition analysis>
The reaction rate during the polymerization reaction and the content of the specific monomer unit in the polymer were determined by gas chromatography (manufactured by Shimadzu Corp., apparatus name: GC17A). ) And measured.
<Dynamic TG>
The polymer (or polymer solution or pellet) is once dissolved or diluted in tetrahydrofuran, poured into excess hexane or methanol for reprecipitation, and the taken out precipitate is vacuum dried (1 mmHg (1.33 hPa), 80 ° C. Volatile components and the like were removed by conducting the reaction for 3 hours or more, and the obtained white solid resin was analyzed by the following method (dynamic TG method).

Measuring apparatus: Thermo Plus2 TG-8120 Dynamic TG (manufactured by Rigaku Corporation)
Measurement conditions: Sample amount 5 to 10 mg
Temperature increase rate: 10 ° C / min
Atmosphere: Nitrogen flow 200ml / min
Method: Step-like isothermal control method (controlled at a weight reduction rate value of 0.005% / sec or less between 60 ° C and 500 ° C)
<Dealcoholization reaction rate and proportion of lactone ring structure>
The dealcoholization reaction rate was determined based on the weight loss that occurred when all hydroxyl groups were dealcoholated as methanol from the polymer composition obtained by polymerization. From the 150 ° C. before the weight reduction began in dynamic TG measurement, It calculated | required from the weight reduction by the dealcoholization reaction to 300 degreeC before decomposition | disassembly started.

That is, in the dynamic TG measurement of the polymer having a lactone ring structure, the weight reduction rate between 150 ° C. and 300 ° C. is measured, and the obtained actual weight reduction rate is defined as (X). On the other hand, from the composition of the polymer, all the hydroxyl groups contained in the polymer composition are involved in the formation of the lactone ring, so that it becomes an alcohol and is dealcoholized. (Y) is the weight loss rate calculated on the assumption that the% dealcoholization reaction has occurred. The theoretical weight reduction rate (Y) is more specifically the molar ratio of raw material monomers having a structure (hydroxyl group) involved in the dealcoholization reaction in the polymer, that is, the raw material unit in the polymer composition. It can be calculated from the content of the monomer. These values (X, Y) are calculated from the dealcoholization formula:
1- (actual weight reduction rate (X) / theoretical weight reduction rate (Y))
Substituting into, the value is obtained and expressed in% to obtain the dealcoholization reaction rate. Then, the content (weight ratio) in the polymer composition of the raw material monomer having a structure (hydroxyl group) involved in lactone cyclization, assuming that the predetermined lactone cyclization was performed by this dealcoholization reaction rate, By multiplying the dealcoholization reaction rate, the proportion of the lactone ring structure in the polymer can be calculated.

  As an example, the proportion of the lactone ring structure in the pellets obtained in Example 1 described later is calculated. When the theoretical weight loss rate (Y) of this polymer was determined, the molecular weight of methanol was 32, the molecular weight of methyl 2- (hydroxymethyl) acrylate was 116, and methyl 2- (hydroxymethyl) acrylate. Since the content (weight ratio) in the polymer is 25.0% by weight in terms of composition, (32/116) × 25.0≈6.90% by weight. On the other hand, the actual weight loss rate (X) by dynamic TG measurement was 0.22% by weight. When these values are applied to the above-described dealcoholization calculation formula, 1− (0.22 / 6.90) ≈0.968 is obtained, so that the dealcoholization reaction rate is 96.8%. And in the polymer, the content (25.0% by weight) of 2- (hydroxymethyl) methyl acrylate in the polymer, assuming that the predetermined lactone cyclization was performed by the dealcoholization reaction rate, When multiplied by the dealcoholization rate (96.8% = 0.968), the proportion of the lactone ring structure in the polymer is 24.2 (25.0 × 0.968) wt%.

<Weight average molecular weight>
The weight average molecular weight of the polymer was determined by polystyrene conversion of GPC (GPC system manufactured by Tosoh Corporation).
<Thermal analysis of resin>
The thermal analysis of the resin was performed using DSC (manufactured by Rigaku Corporation, apparatus name: DSC-8230) under the conditions of about 10 mg of sample, a heating rate of 10 ° C./min, and a nitrogen flow of 50 cc / min. The glass transition temperature (Tg) was determined by the midpoint method according to ASTM-D-3418.
<Melt flow rate>
The melt flow rate was measured at a test temperature of 240 ° C. and a load of 10 kg based on JIS-K6874.

[Example 1]
In a 30 L reaction kettle equipped with a stirrer, temperature sensor, cooling pipe, and nitrogen introduction pipe, 2500 g of 2- (hydroxymethyl) acrylic acid methyl, 7500 g of methyl methacrylate, 3800 g of methyl isobutyl ketone (MIBK), 950 g of methyl ethyl ketone (MEK) The initial monomer concentration was set to 68% by weight. When the temperature was raised to 100 ° C. while refluxing and refluxed, 6.4 g of tertiary butyl peroxyisopropyl carbonate was added as an initiator, and at the same time, 6.4 g of tertiary butyl peroxyisopropyl carbonate, 280 g of MIBK, and 70 g of MEK were comprised. While the solution was added dropwise over 4 hours, solution polymerization was performed under reflux (about 95 ° C. to 110 ° C.), followed by further aging over 4 hours. At this time, the mixed solvent (MIBK: MEK = 4: 1) was mixed at a rate of 2500 g / hr from 2 hours to 4 hours after the start of the polymerization reaction so that the polymer concentration in the solution was 45% by weight or less. From the time to 7 hours later, the solution was dropped at a rate of 1600 g / hr. A part of the reaction solution was taken out every 2 hours from the start of the reaction, and the polymerization reaction rate and the weight average molecular weight were analyzed. The results are shown in Table 1.

A mixture of stearyl phosphate / distearyl phosphate (“Phoslex A-18” manufactured by Sakai Chemical Co., Ltd.) in an amount of 0.005 g per 1 g of the polymer (1a) in the polymer solution obtained as described above was used. In addition to the combined solution, a cyclization condensation reaction was carried out under reflux (about 80 to 100 ° C.) for 5 hours while introducing nitrogen. A part of the obtained reaction solution was taken out and the dynamic TG was measured by the method described above, and a weight loss of 0.43% by weight was detected.
Next, the polymer solution obtained by the above cyclization condensation reaction was subjected to a barrel temperature of 260 ° C., a rotation speed of 100 rpm, a degree of vacuum of 13.3 to 400 hPa (10 to 300 mmHg), a rear vent number of 1 and a forevent number of 4 Introduced into a bent type screw twin screw extruder (φ = 29.75 mm, L / D = 30) at a processing rate of 2.0 kg / hour in terms of resin amount, and cyclization condensation reaction and devolatilization in the extruder And extruding to obtain a transparent pellet (1A).

When the obtained pellet (1A) was measured for dynamic TG, a weight reduction rate of 0.22% by weight was detected. Moreover, the weight average molecular weight of pellet (1A) was 244000, the melt flow rate was 3.90 g / 10min, and the glass transition temperature was 134 degreeC.
[Example 2]
The same as in Example 1 except that 3000 g of methyl 2- (hydroxymethyl) acrylate, 7000 g of methyl methacrylate, 3800 g of methyl isobutyl ketone (MIBK), and 950 g of methyl ethyl ketone (MEK) were charged and the initial monomer concentration was 68% by weight. Polymerization was carried out by the method. A part of the reaction solution was taken out every 2 hours from the start of the reaction, and the polymerization reaction rate and the weight average molecular weight were analyzed. The results are shown in Table 1.

The amount of 0.005 g of stearyl phosphate / distearyl phosphate mixture (“Phoslex A-18” manufactured by Sakai Chemical Co., Ltd.) in an amount of 0.005 g is added to 1 g of the polymer (2a) in the polymer solution obtained as described above. In addition to the combined solution, a cyclization condensation reaction was carried out under reflux (about 80 to 100 ° C.) for 5 hours while introducing nitrogen. A part of the obtained reaction solution was taken out and the dynamic TG was measured by the method described above, and a weight loss of 0.55% by weight was detected.
Next, the polymer solution obtained by the cyclization condensation reaction was subjected to cyclization condensation reaction and devolatilization in an extruder in the same manner as in Example 1 and extruded to obtain transparent pellets (2A).
When the obtained pellet (2A) was measured for dynamic TG, a weight reduction rate of 0.23% by weight was detected. Moreover, the weight average molecular weight of this pellet (2A) was 227000, the melt flow rate was 3.81 g / 10min, and the glass transition temperature was 139 degreeC.

Example 3
In a 30 L reaction kettle equipped with a stirrer, temperature sensor, cooling tube, and nitrogen introduction tube, 2500 g of methyl 2- (hydroxymethyl) acrylate, 7000 g of methyl methacrylate, 500 g of methacrylic acid, 3400 g of methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK) 850 g was charged, and the initial monomer concentration was set to 70% by weight. The solution was heated to 100 ° C. while refluxing nitrogen and refluxed. A solution consisting of 15 g of dimethyl 2,2′-azobisisobutyrate, MIBK 560 g, and MEK 125 g as an initiator was dropped over 6 hours under reflux (about The solution polymerization was performed at 90 ° C. to 110 ° C., and further aging was performed for 2 hours. The mixed solvent (MIBK: MEK = 4: 1) was mixed at a rate of 2000 g / hr from 1 hour to 4 hours after the start of the polymerization reaction so that the polymer concentration in the solution was 45% by weight or less. It was dropped at a rate of 1300 g / hr until 7 hours later. A part of the reaction solution was taken out every 2 hours from the start of the reaction, and the polymerization reaction rate and the weight average molecular weight were analyzed. The results are shown in Table 1.

When a part of the solution after the reaction for 8 hours was taken out and the dynamic TG was measured by the method described above, a weight loss of 1.22% by weight was detected.
Subsequently, the polymer solution containing the obtained polymer (3a) was subjected to cyclization condensation reaction and devolatilization in an extruder in the same manner as in Example 1, and extruded to obtain transparent pellets (3A).
When the obtained pellet (3A) was measured for dynamic TG, a weight reduction rate of 0.15% by weight was detected. Moreover, the weight average molecular weight of this pellet (3A) was 263000, the melt flow rate was 0.52 g / 10min, and the glass transition temperature was 138 degreeC.

Example 4
2- (hydroxymethyl) methyl acrylate 1500 g, methyl methacrylate 8500 g, methyl isobutyl ketone (MIBK) 3800 g, methyl ethyl ketone (MEK) 950 g were charged to an initial monomer concentration of 68% by weight, and tertiary amyl as an initiator Polymerization was carried out in the same manner as in Example 1 except that 3,5,5-trimethylhexanoate was used and both the addition amount at reflux and the subsequent dropwise addition amount were 7.0 g. A part of the reaction solution was taken out every 2 hours from the start of the reaction, and the polymerization reaction rate and the weight average molecular weight were analyzed. The results are shown in Table 1.

The amount of 0.005 g of stearyl phosphate / distearyl phosphate mixture (“Phoslex A-18” manufactured by Sakai Chemical Co., Ltd.) in an amount of 0.005 g is added to 1 g of the polymer (4a) in the polymer solution obtained as described above. In addition to the combined solution, a cyclization condensation reaction was carried out under reflux (about 80 to 100 ° C.) for 5 hours while introducing nitrogen. A part of the obtained reaction solution was taken out and the dynamic TG was measured by the method described above, and a weight loss of 0.71% by weight was detected.
Next, the polymer solution obtained by the cyclization condensation reaction was subjected to cyclization condensation reaction and devolatilization in an extruder in the same manner as in Example 1, and extruded to obtain transparent pellets (4A).
When the obtained pellet (4A) was measured for dynamic TG, a weight reduction rate of 0.13% by weight was detected. Moreover, the weight average molecular weight of this pellet (4A) was 307000, the melt flow rate was 1.06 g / 10min, and the glass transition temperature was 128 degreeC.

Example 5
In a 30 L reaction kettle equipped with a stirrer, temperature sensor, cooling pipe, and nitrogen introduction pipe, 1500 g of methyl 2- (hydroxymethyl) acrylate, 8000 g of methyl methacrylate, 500 g of methacrylic acid, 6080 g of methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK) 1520 g was charged, and the initial monomer concentration was 57% by weight. When this was heated to 100 ° C. while refluxing nitrogen and refluxed, 7.0 g of tertiary amyl-3,5,5-trimethylhexanoate was added as an initiator, and at the same time, tertiary amyl-3,5,5 -Solution polymerization was performed under reflux (about 90 ° C to 110 ° C) while dropping a solution composed of 7.0 g of trimethylhexanoate, 280 g of MIBK, and 70 g of MEK over 4 hours, followed by further aging for 6 hours. The mixed solvent (MIBK: MEK = 4: 1) was mixed at a rate of 600 g / hr from 1 hour to 4 hours after the start of the polymerization reaction so that the polymer concentration in the solution was 45% by weight or less after 4 hours. It was dropped at a rate of 970 g / hr until 7 hours later. A part of the reaction solution was taken out every 2 hours from the start of the reaction, and the polymerization reaction rate and the weight average molecular weight were analyzed. The results are shown in Table 1.

A part of the solution after the reaction for 10 hours was taken out and the dynamic TG was measured by the method described above, and a weight loss of 1.34% by weight was detected.
Subsequently, the polymer solution containing the obtained polymer (5a) was subjected to cyclization condensation reaction and devolatilization in an extruder in the same manner as in Example 1, and extruded to obtain transparent pellets (5A).
When the obtained pellet (5A) was measured for dynamic TG, a weight reduction rate of 0.17% by weight was detected. Moreover, the weight average molecular weight of this pellet (5A) was 326000, the melt flow rate was 0.38 g / 10min, and the glass transition temperature was 135 degreeC.

[Comparative Example 1]
A 30 L reaction kettle equipped with a stirrer, temperature sensor, cooling pipe, and nitrogen introduction pipe was charged with 1600 g of methyl 2- (hydroxymethyl) acrylate, 6400 g of methyl methacrylate, and 8000 g of toluene, and the initial monomer concentration was 50% by weight. did. When the temperature was raised to 100 ° C. while refluxing nitrogen and refluxed, 32 g of tertiary butyl peroxyisopropyl carbonate was added as an initiator, and solution polymerization was performed under reflux (100 to 110 ° C.) over 5 hours. Aged. The polymerization reaction rate was 95.0%, and the weight average molecular weight was 150,000.

37.5 g of methyl isobutyl ketone per 100 g of polymer (c1a) in the polymer solution obtained as described above, and 0.1 g of methyl phosphate / phosphorus per 100 g of polymer (c1a) A dimethyl acid mixture (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the polymer solution, and a cyclization condensation reaction was performed for 5 hours under reflux (95 to 100 ° C.) through nitrogen. When a part of the obtained reaction solution was taken out and the dynamic TG was measured, a weight reduction rate of 0.62% by weight was detected.
Subsequently, the obtained polymer solution was subjected to cyclization condensation reaction and devolatilization in an extruder in the same manner as in Example 1, and extruded to obtain transparent pellets (c1A).

When the obtained pellet (c1A) was measured for dynamic TG, a weight reduction rate of 0.2% by weight was detected. Moreover, the weight average molecular weight of this pellet (c1A) was 165000, the melt flow rate was 10.80 g / 10min, and the glass transition temperature was 134 degreeC.
[Comparative Example 2]
In a 30 L reaction kettle equipped with a stirrer, temperature sensor, cooling pipe, and nitrogen introduction pipe, 7500 g of methyl 2- (hydroxymethyl) acrylate, 2500 g of methyl methacrylate, 3800 g of methyl isobutyl ketone (MIBK), 950 g of methyl ethyl ketone (MEK) The initial monomer concentration was set to 68% by weight. When the temperature was raised to 100 ° C. while refluxing and refluxed, 6.4 g of tertiary butyl peroxyisopropyl carbonate was added as an initiator, and at the same time, 6.4 g of tertiary butyl peroxyisopropyl carbonate, 280 g of MIBK, and 70 g of MEK were comprised. Solution polymerization was carried out under reflux (about 95 ° C. to 110 ° C.) while the solution was added dropwise over 4 hours, followed by further aging for 4 hours. From 3 hours after the start of the reaction, the viscosity of the solution gradually increased and stirring became impossible. The resulting polymerization solution was diluted with methyl ethyl ketone, but an insoluble solid was formed.

Example 6
Using the pellets (1A to 5A, c1A) obtained in Examples 1 to 5 and Comparative Example 1, a film winding test having a thickness of about 400 μm and 20 m was performed. The results are shown in Table 2.
The film forming conditions were as follows.
Screw diameter: φ50mm
Barrel temperature: 270 ° C
Die: temperature 260 ° C, width 1000mm
Three roll temperature with gloss: first roll 125 ° C., second roll 142 ° C., third roll 118 ° C.
Take-off speed: 1.5 m / min

Example 7
The pellet (1A) obtained in Example 1 and ASA resin (“Dialac S210B” manufactured by UMG ABS) were coextruded to produce a two-layer laminate.
The coextrusion conditions were as follows.
Screw diameter: ASA resin side φ50mm, pellet (1A) side φ20mm
Barrel temperature: ASA resin side 240 ° C, pellet (1A) side 260 ° C
Three roll temperature with gloss: first roll 125 ° C., second roll 142 ° C., third roll 118 ° C.
Take-off speed: 1.5 m / min
The surface properties of the obtained laminate were good, the thickness of the pellet (1A) layer was 95 μm, and the thickness of the ASA resin layer was 2 mm.

Example 8
In Example 2, methyl ethyl ketone (MEK) was further added to the polymer solution obtained after the cyclization condensation reaction under reflux (about 80 to 100 ° C.) for 5 hours to adjust the concentration of the polymer (2a) to 25% by weight. To obtain a coating resin solution. In the adjustment of the polymer concentration, a part of the polymer solution before adjustment was added to a large amount of methanol to reprecipitate the polymer, filtered under reduced pressure, and then vacuum dried at 80 ° C. From the weight of the polymer, the polymer concentration of the polymer solution before adjustment was converted, and the amount of MEK necessary for adjusting the polymer concentration was determined.
The obtained coating resin solution was applied to various substrates such as a plastic substrate, a glass substrate, and a metal plate and evaporated and dried, whereby a surface protective film could be formed on these various substrates.

  The lactone ring-containing polymer according to the present invention has both high transparency and heat resistance, and is excellent in molding processability to a film and the like, and can give a molded product having high physical properties such as mechanical strength. Since it is a polymer containing a high-molecular weight lactone ring, for example, a transparent optical lens, an optical element (for example, a light guide that can be used for illumination of various instruments or various displays and signboard illumination, a plastic optical fiber, a light diffusing surface, etc. Transparent molded parts (such as lenses for laser beam printers, lamp lenses used in vehicle headlamps, fog lamps, signal lights, etc.), building materials and glazing materials for vehicles, and depainting Can be suitably used as a sheet for thermoforming, a coating material, an optical film material, and an optical laminate material.

Claims (4)

After polymerizing the monomer component containing the monomer (1) represented by the following general formula and the (meth) acrylic acid ester , or simultaneously with the polymerization, the lactone cyclocondensation reaction is performed, so that the weight average molecular weight is 180,000 to 500,000. A process for producing a lactone ring-containing polymer having a melt flow rate of 0.2 to 7.0 g / 10 min ,
Using a ketone solvent and / or an ether solvent as a polymerization solvent,
The initial charge concentration of the monomer component to be subjected to polymerization is 55 to 95% by weight,
Polymerization is performed by adding a polymerization solvent to the polymerization reaction mixture so that the concentration of the produced polymer in the polymerization reaction mixture is 50% by weight or less.
A process for producing a lactone ring-containing polymer.

(In the formula, R ¹ and R ² each independently represents a hydrogen atom or an organic residue having 1 to 20 carbon atoms.) The lactone according to claim 1 , wherein the content ratio of the monomer (1) in all monomer components to be subjected to polymerization is 10 to 50 wt% , and the ratio of (meth) acrylic acid ester is 90 to 50 wt% . A method for producing a ring-containing polymer. The manufacturing method of the lactone ring containing polymer of Claim 1 or 2 whose said (meth) acrylic acid ester is methyl methacrylate. The monomer (1) represented by the general formula is methyl 2- (hydroxymethyl) acrylate, ethyl 2- (hydroxymethyl) acrylate, isopropyl 2- (hydroxymethyl) acrylate, 2- (hydroxymethyl) The method for producing a lactone ring-containing polymer according to any one of claims 1 to 3, which is either normal butyl acrylate or tertiary butyl 2- (hydroxymethyl) acrylate.