JP4902161B2 - Method for producing polymer having acid anhydride group at terminal, and resin composition containing the polymer - Google Patents

Description

  The present invention relates to a method for producing a polymer having an acid anhydride group at a terminal and a resin composition containing the polymer. More specifically, the present invention relates to an acid anhydride at the terminal by producing a polymer having a diester group at the terminal under industrially advantageous conditions at room temperature or higher, and then converting the diester group to an acid anhydride group. The present invention relates to a method for producing a polymer having a group, a polymer having an acid anhydride group at the terminal obtained by the production method, a resin modifier comprising the polymer, and a resin composition containing the polymer and another thermoplastic resin. .

  A method for introducing a functional group into a polymer in order to impart reactivity or polarity to a nonpolar polymer is generally known. In particular, for the purpose of imparting reactivity to a nonpolar polymer, an acid anhydride group is generally introduced in the middle of the molecular chain of the polymer. For example, polyolefins such as polyethylene and polypropylene, polystyrene- (polyethylene / Polybutylene) -Elastomers in which acid anhydride groups are introduced in a pendant form into a polymer such as polystyrene are commercially available. Since the elastomer has a very high reactivity, a block copolymer or a graft copolymer can be easily produced by kneading with a resin having active hydrogen in the molecule, for example, polyamide, polyester, etc. It is known to show the effect of crystallization.

  As a method for introducing an acid anhydride group into a polymer, a method in which maleic anhydride is allowed to act on a polymer in the presence of a radical generator is generally known (for example, see Patent Documents 1 to 3). However, this method has a problem that, after the polymer is produced, a step of adding an acid anhydride group to the polymer is further required, and the production becomes complicated. In order for the polymer to have sufficient reactivity, it is necessary to introduce a relatively large amount of acid anhydride groups into the polymer. As a result, the properties and appearance of the polymer before and after the introduction of acid anhydride groups are improved. There may be a problem that they are different.

  In order to suppress the occurrence of this problem, a method using a terminal functionalized polymer having higher reactivity than a polymer in which an acid anhydride group is introduced in a pendant type is known (for example, see Non-Patent Document 1). However, a terminally functionalized polymer may not have sufficient effects and physical properties unless the number of terminal functional groups and the molecular weight distribution are controlled. Therefore, in the production of a terminal functionalized polymer, an anionic polymerization method, particularly a living anion polymerization method, is mainly used, and a method of introducing a functional group into the terminal of the obtained living polymer is employed.

  As a method for introducing a functional group into the terminal of the living polymer, for example, a method of reacting a functional capping agent with a living anion growth terminal is known. In particular, as a method of introducing an acid anhydride group, a functional capping is used. A method of performing a heat treatment after introducing a diester group at the end of a polymer using a maleic acid derivative as an agent is known (see Non-Patent Documents 2 to 4).

However, in the methods of Non-Patent Documents 2 to 4, when introducing a diester group to the terminal of the living polymer, an extremely low temperature of −78 ° C. or lower is necessary, or cooling to about 5 ° C. is performed to suppress side reactions. Currently, industrially disadvantageous conditions are adopted.
JP 50-56427 A JP-A-55-13720 JP 55-25315 A Macromolecules (2004), 37, 2563-2571. Macromolecules (1994), 27, 4914-4918. Polymer Preprint (1996), 37, 2, 653-654 Macromolecules (1997), 30, 5213-5219.

  The objective of this invention is providing the manufacturing method of the polymer which has an acid anhydride group at the terminal, and the resin composition containing this polymer. More specifically, a polymer having an acid anhydride group at the terminal is obtained by producing a polymer having a diester group at the terminal under industrially advantageous conditions at room temperature or higher, and then converting the diester group to an acid anhydride group. And a resin composition containing the polymer having an acid anhydride group at the terminal obtained by the production method, a resin modifier comprising the polymer, and the polymer and another thermoplastic resin. is there.

  As a result of intensive studies, the inventors of the present invention reacted a living polymer obtained by living anionic polymerization of a polymerizable monomer with a compound containing a specific typical metal element to form an art complex. A polymer having an acid anhydride group at the terminal under industrially advantageous conditions at room temperature or higher by introducing a diester group at the terminal of the living polymer by allowing a diester compound to act and then converting the diester group to an acid anhydride group Has been found, and the present invention has been completed.

（式中、Ｒ^１は水素原子又は炭素数１〜５のアルキル基、Ｒ^２およびＲ^３はそれぞれ炭素数４〜１２の第３級アルキル基である。）で示されるジエステル化合物とを反応させ、該リビングポリマーの末端にジエステル基を導入する工程；及び
工程（４） 工程（３）で得られたポリマーの末端にあるジエステル基を酸無水物基に変換する工程；
を含む末端に酸無水物基を有するポリマーの製造方法、
〔２〕 典型金属元素を含有する化合物が、有機アルミニウム化合物である上記〔１〕に記載の末端に酸無水物基を有するポリマーの製造方法、
〔３〕 重合性モノマーが、ビニル芳香族化合物及び／又は共役ジエン化合物である上記〔１〕又は〔２〕に記載の末端に酸無水物基を有するポリマーの製造方法、
〔４〕 重合性モノマーが少なくとも共役ジエン化合物を含有し、更に以下の工程（５）：
工程（５） 工程（３）及び／又は工程（４）で得られたポリマーを水素添加する工程；
を含む上記〔３〕に記載の末端に酸無水物基を有するポリマーの製造方法、
〔５〕 リビングポリマーが、ビニル芳香族化合物重合体ブロック−共役ジエン化合物重合体ブロック−ビニル芳香族化合物重合体ブロックのトリブロック構造である上記〔４〕に記載の末端に酸無水物基を有するポリマーの製造方法、
に関する。 That is, the present invention
[1] A method for producing a polymer having an acid anhydride group at a terminal, the following steps (1) to (4):
Step (1) A step of obtaining a living polymer by living anionic polymerization of a polymerizable monomer;
Step (2) A step of reacting the living polymer with a compound containing a typical metal element selected from boron, aluminum, zinc and magnesium to form an art complex;
Step (3) The art complex and the following general formula

(Wherein R ¹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ² and R ³ are each a tertiary alkyl group having 4 to 12 carbon atoms). A step of introducing a diester group at the end of the living polymer; and a step (4) a step of converting the diester group at the end of the polymer obtained in step (3) into an acid anhydride group;
A process for producing a polymer having an acid anhydride group at the terminal containing
[2] The method for producing a polymer having an acid anhydride group at the terminal according to [1], wherein the compound containing a typical metal element is an organoaluminum compound,
[3] A method for producing a polymer having an acid anhydride group at the terminal according to [1] or [2], wherein the polymerizable monomer is a vinyl aromatic compound and / or a conjugated diene compound,
[4] The polymerizable monomer contains at least a conjugated diene compound, and the following step (5):
Step (5) Step of hydrogenating the polymer obtained in Step (3) and / or Step (4);
A process for producing a polymer having an acid anhydride group at the end thereof as described in [3] above,
[5] The living polymer has a triblock structure of vinyl aromatic compound polymer block-conjugated diene compound polymer block-vinyl aromatic compound polymer block, and has an acid anhydride group at the terminal according to the above [4] Production method of polymer ,
About the.

  According to the present invention, after producing a polymer having a diester group at the terminal under industrially advantageous conditions at room temperature or higher, the terminal has an acid anhydride group by converting the diester group into an acid anhydride group. Provided are a method for producing a polymer, a polymer having an acid anhydride group at the terminal obtained by the production method, a resin modifier comprising the polymer, and a resin composition containing the polymer and another thermoplastic resin. .

  The manufacturing method of the polymer which has an acid anhydride group at the terminal of this invention contains process (1)-(4), and also contains process (5) as needed. Hereinafter, it demonstrates for every process.

Process (1)
This step is a step of producing a living polymer that becomes a precursor of a polymer having an acid anhydride group at the end of the molecular chain by living anionic polymerization of a polymerizable monomer.

  The polymerizable monomer used in step (1) is not particularly limited as long as it is a monomer capable of living anion polymerization. For example, styrene, α-methylstyrene, 1-vinylnaphthalene, 4-methylstyrene, 4-ethylstyrene, Vinyl aromatic compounds such as 4-t-butylstyrene and divinylbenzene, 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 2-phenyl-1,3-butadiene, 1,3 -Conjugated diene compounds such as cyclohexadiene and the like are mentioned, and among them, styrene, 1,3-butadiene and isoprene are preferable from the viewpoint of industrial economy. These may be used alone or in combination of two or more.

When two or more kinds of polymerizable monomers are used in combination, the bonding form of the monomer units in the living polymer is not particularly limited, and may be any of a random shape, a block shape, or a tapered shape. The living polymer is composed of, for example, a block copolymer, and is composed of a polymer block (i) composed of vinyl aromatic compound units (hereinafter sometimes simply referred to as “(i)”) and a conjugated diene compound unit. A linear block consisting of a polymer block (ii) [hereinafter sometimes simply referred to as “(ii)”], a diblock structure represented by “(i)-(ii)”; A triblock structure represented by “(i)-(ii)-(i)”, a tetrablock structure represented by “(i)-(ii)-(i)-(ii)”, or (i) A multi-block structure in which (ii) and 5 or more are linearly bonded can be employed. Among these, from the viewpoint of the mechanical properties and compatibilizing effect of the polymer obtained, the bonding form of the polymer block should be a triblock structure represented by “(i)-(ii)-(i)”. preferable.
Examples of the triblock structure copolymer represented by the above “(i)-(ii)-(i)” include polystyrene-polyisoprene-polystyrene block copolymer, polystyrene-polybutadiene-polystyrene block copolymer, polystyrene-poly (isoprene / Butadiene) -polystyrene block copolymer.

The molecular weight of the living polymer obtained by the step (1) is not particularly limited, and the number average molecular weight (Mn) in a state where hydrogenation is not performed is in the range of 1,000 to 2,000,000. It is preferable from the point of property and handleability.
The number average molecular weight here refers to a value obtained from a standard polystyrene calibration curve by gel permeation chromatography (GPC).

  The living anionic polymerization in the step (1) can be performed by reacting a polymerizable monomer in an organic solvent using a polymerization initiator according to a usual method.

  The polymerization initiator used in the living anion polymerization in the step (1) is not particularly limited as long as the living anion polymerization can be performed. For example, organic alkali metal compounds such as organic lithium and organic sodium can be used. . Among these, an organolithium compound is preferable from the viewpoint of handleability and industrial economy, and alkyllithium and aryllithium are more preferable from the viewpoint of reactivity with the polymerizable monomer.

  Examples of the alkyl lithium include methyl lithium, ethyl lithium, propyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, isobutyl lithium, hexyl lithium, octyl lithium, tetramethylene dilithium, m-diiso Examples thereof include dilithiated products of propenylbenzene, and examples of the aryllithium include phenyllithium and tolyllithium. These may be used singly or in combination of two or more. From the viewpoint of handleability and industrial economy, n-butyllithium, sec-butyllithium and tert-butyllithium are preferable. From the viewpoint of reactivity, n-butyl lithium and sec-butyl lithium are more preferable.

  The organic solvent used in the living anion polymerization in the step (1) is not particularly limited as long as it is a nonpolar organic solvent that does not hinder the progress of the polymerization. For example, saturated aliphatic hydrocarbon compounds such as hexane, heptane, cyclohexane, Examples thereof include aromatic hydrocarbon compounds such as benzene, toluene, xylene and the like. These may be used alone or in combination of two or more.

  In the living anion polymerization in the step (1), for example, in order to control the bonding form of the monomer unit in the living polymer, a small amount of polar compound is added in the reaction system as long as it does not hinder the progress of the polymerization. It may be added. As the polar compound, a compound having no functional group that reacts with a carbanion such as a hydroxyl group or a carbonyl group and having an oxygen atom or a nitrogen atom can be used. For example, diethyl ether, monoglyme, diglyme, N, N , N ′, N′-tetramethylethylenediamine, dimethoxyethane, tetrahydrofuran and the like.

  It does not restrict | limit especially as reaction temperature in the living anion polymerization of a process (1), It is preferable that it is the range of -100 degreeC-100 degreeC, and it is the range of 0-60 degreeC from an industrial viewpoint. It is more preferable.

  As other reaction conditions in the living anion polymerization in the step (1), for example, from the viewpoint of suppressing side reactions, it is preferable to use a compound that has been sufficiently dehydrated and dried in advance. It is preferable to carry out in an inert gas atmosphere in which no etc. exist.

Process (2)
This step is a step of reacting the living polymer obtained in step (1) with a compound containing a typical metal element selected from boron, aluminum, zinc and magnesium to form an art complex.

  Examples of the compound containing a typical metal element selected from boron, aluminum, zinc and magnesium used in the step (2) include an organic boron compound, an organic aluminum compound, an organic zinc compound and an organic magnesium compound.

  Examples of the organoboron compound include alkylboranes such as triethylborane, tributylborane, diethylmethoxyborane, diisopropoxymethylborane, trimethylborate, triethylborate, triisopropylborate, tributylborate, 2-butyl-1,3. And boronic acid esters such as 2-dioxaborolinane.

  Examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisobutylaluminum, ethyldimethylaluminum, diisobutyl (2,6-di-t-butyl-4-methylphenoxy) aluminum, Examples thereof include isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum and aluminum triisopropoxide.

  Examples of the organic zinc compound include dimethyl zinc, diethyl zinc, dipropyl zinc, dibutyl zinc, and diphenyl zinc.

  Examples of the organomagnesium compound include dimethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, dicyclohexylmagnesium, and diphenylmagnesium.

  The above compound containing a typical metal element may be used alone or in combination of two or more. It is preferable to use an organoaluminum compound from the viewpoint of industrial economy, and triisobutyl from the viewpoint of handleability and the like. More preferably, aluminum or isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum is used.

  The amount of the compound containing the typical metal element is not particularly limited as long as the effect of the present invention is not impaired. From the viewpoint of suppressing side reactions in the step (3) described later, the step It is preferably in the range of 0.1-50 equivalents, more preferably in the range of 1-5 equivalents, relative to the polymerization initiator used in (1).

In the reaction of the step (2), the compound containing the typical metal element or the organic solvent solution containing the compound is added to the living polymer solution obtained in the step (1), and these are stirred and mixed. Can be done.
The progress of the reaction in the step (2) is observed, for example, by changing the color of the mixed liquid by utilizing that the living polymer having a color derived from carbanion changes to colorless when converted to an art complex. This can be easily confirmed.

  Reaction conditions such as the reaction temperature in step (2) and the type of organic solvent used as necessary are not particularly limited as long as the effects of the present invention are not impaired. It is preferable to match the reaction conditions employed in step (1).

（式中、Ｒ^１は水素原子又は炭素数１〜５のアルキル基、Ｒ^２およびＲ^３はそれぞれ炭素数４〜１２の第３級アルキル基である。）で示されるジエステル化合物とを反応させ、リビングポリマーの末端にジエステル基を導入する工程である。 Process (3)
This step includes the art complex obtained in step (2) and the following general formula:

(Wherein R ¹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ² and R ³ are each a tertiary alkyl group having 4 to 12 carbon atoms). In this step, a diester group is introduced at the end of the living polymer.

In said diester compound, R < ¹ > is a hydrogen atom or a C1-C5 alkyl group from a viewpoint with easy acquisition. R ² and R ³ are each a tertiary alkyl group having 4 to 12 carbon atoms, and examples thereof include a tert-butyl group, a tert-amyl group, a 2-methyl-2-pentyl group, and 2-methyl-2- A hexyl group, a 3-methyl-3-pentyl group, a 3-ethyl-3-pentyl group and the like can be mentioned. Among them, a tert-butyl group and a tert-amyl group are preferable from the viewpoint of facilitating the step (4) described below. preferable. When the number of carbon atoms in R ² and R ³ exceeds 13, removal of by-products generated in the step (4) described later becomes difficult, which is not preferable. Further, when R ² and R ³ are not tertiary alkyl groups such as primary or secondary alkyl groups, for example, prior to the step (4) described later, a diester group at the end of the polymer This is not preferable because it requires a pretreatment for converting to dicarboxylic acid by hydrolysis, which complicates the operation. Among them, di-t-butyl maleate is preferable as the diester compound, and the diester group to be introduced is preferably a di-t-butyl succinic acid-2-yl group.

  The reaction in the step (3) is performed by adding the diester compound or the organic solvent solution containing the compound to the art complex solution obtained in the step (2) and stirring and mixing them. it can.

  Reaction conditions such as the reaction temperature in step (3) and the type of organic solvent used as necessary are not particularly limited as long as the effects of the present invention are not impaired. It is preferable to match the reaction conditions employed in the steps (1) and (2).

  In the step (3), it is preferable to add a stopper such as methanol in order to stop the living anion polymerization after reacting the diester compound.

Step (4)
This step is a step of converting the diester group at the terminal of the living polymer obtained in step (3) into an acid anhydride group. As a conversion method, for example, the living polymer obtained in step (3) Heat treatment may be mentioned.

  As a heat treatment method in step (4), for example, heat treatment such as annealing without shearing operation, heating using a roll, Brabender mixer, Banbury mixer, single screw extruder, twin screw extruder, etc. Examples of the shearing treatment include heating treatment from the viewpoint of efficiently converting the diester group into an acid anhydride group.

  The heat treatment conditions in the step (4) can be appropriately selected according to the type of the apparatus for performing the heat treatment, etc., and it is usually preferably performed at a temperature of 100 to 500 ° C. for about 1 to 60 minutes, and prevention of deterioration of the polymer And from a viewpoint of economical efficiency, it is more preferable to carry out at the temperature of 180-300 degreeC for about 3 minutes-30 minutes.

  The polymer obtained by the production method of the present invention has an acid anhydride group at least at one end, but the terminal acid anhydride is taken into consideration when the reaction rate of the reaction for introducing the acid anhydride group at the end is not complete. The thing whose average content of a physical group is 0.2 or more per molecule is also included. The average content of terminal acid anhydride groups is more preferably 0.8 or more. If the average content of the terminal acid anhydride groups is less than 0.2 per molecule, the reactivity of the resulting polymer with other thermoplastic resins is not preferable. As the polymerization initiator, for example, when an organic dilithium compound that is a bifunctional initiator is used, a block copolymer having acid anhydride groups at both ends can be produced.

Process (5)
This step is a step that is included as necessary when the polymerizable monomer used in step (1) contains at least a conjugated diene compound. More specifically, this step is the step (3) and / or In this step, part or all of the polymer block composed of the conjugated diene compound in the polymer obtained in step (4) is hydrogenated (hereinafter sometimes referred to as “hydrogenation”).

The hydrogenation method is not particularly limited. For example, a polymer block comprising a conjugated diene compound in the presence of a hydrogenation catalyst such as a Ziegler catalyst comprising an alkylaluminum compound and cobalt, nickel, or a metallocene catalyst such as a titanocene compound. And a method of reacting a polymer having a hydrogen with hydrogen. The hydrogenation rate of the unsaturated double bond derived from the conjugated diene unit in the hydrogenated polymer is analyzed by iodine titration method, infrared spectroscopic measurement, nuclear magnetic resonance spectrum ( ¹ H-NMR spectrum) measurement, or the like. It can be calculated using means.

  Since the polymer obtained by the production method of the present invention has high reactivity, for example, it can not only be made into a resin composition by mixing and kneading with other thermoplastic resins, but also resin modification to other thermoplastic resins. It can function effectively as an agent, a compatibilizer, and a dispersibility improver for various fillers.

If the said resin composition finally contains the polymer which has an acid anhydride group at the terminal, there will be no restriction | limiting in the method which concerns on the manufacture, For example, the following (I) or (B):
(A) A method in which a polymer having an acid anhydride group at the terminal is produced by the above steps (1) to (4), and then another thermoplastic resin is added to the polymer and mixed and kneaded to obtain a resin composition. ;
(B) After producing a polymer having a diester group at the terminal by the above steps (1) to (3), another thermoplastic resin is added to the polymer and mixed and kneaded, and the above step (4) and the resin are mixed. A method of simultaneously producing the composition;
In addition to these methods, a method in which a step (5) is added according to the kind of the polymerizable monomer to be used can be used.

  The thermoplastic resin modified by the resin modifier is not particularly limited. For example, a polyamide resin, a polyester resin, a polycarbonate resin, a polyphenylene ether resin, an ionomer resin, a vinyl acetate resin (also a saponified product). Include), (meth) acrylic acid ester resins, polyurethane resins, olefin resins, styrene resins, and the like. These may be used alone or in combination of two or more.

  The resin to be compatibilized by the compatibilizer is not particularly limited, and examples thereof include polyamide resins, polyester resins, polycarbonate resins, polyphenylene ether resins, ionomer resins, vinyl acetate resins (including saponified products). ), Polar resins such as (meth) acrylic acid ester resins and polyurethane resins, and nonpolar resins such as olefin resins, styrene resins, ethylene-propylene rubber, ethylene-propylene-diene rubber, styrene block copolymer resins, etc. The combination with resin can be mentioned.

  There is no restriction | limiting in particular as a filler disperse | distributed by the said dispersibility improvement agent, For example, carbon black, a silica, an alumina, a talc, a calcium carbonate, a clay etc. can be mentioned, These may be used independently and 2 More than one type may be used in combination. In addition, there is no restriction | limiting in particular also about resin used as the matrix of the said dispersibility improvement agent, For example, resin described as resin modified with the said resin modifier can be used.

  EXAMPLES Hereinafter, although an Example etc. demonstrate this invention concretely, this invention is not limited by it at all. The chemicals used in the following examples and comparative examples were dried and purified by a conventional method, and the transfer and supply were performed in a nitrogen atmosphere.

In addition, measuring instruments used in the following Examples, Comparative Examples, and Reference Examples are described.
(1) Number average molecular weight (Mn), molecular weight distribution (Mw / Mn) and component ratio calculator by gel permeation chromatography (GPC): Gel permeation chromatograph (HLC-8020) manufactured by Tosoh Corporation
Column: TSKgel GMHXL, G4000HXL and G5000HXL manufactured by Tosoh Corporation connected in series Eluent: Tetrahydrofuran, flow rate 1.0 ml / min Column temperature: 40 ° C.
Calibration curve: prepared using standard polystyrene Detection method: differential refractive index (RI)

(2) Measuring instrument for the number of diester groups or acid anhydride groups at the polymer end by high performance liquid chromatography (HPLC): High performance liquid chromatograph (LC-10AD) manufactured by Shimadzu Corporation
Detector: Polymer Laboratories' Evaporative Light Scattering Detector (PL-EMD960)
Column: SUPELCOSIL LC-3-Si manufactured by SUPELCO
After eluent: ethyl acetate / cyclohexane = 50/50 (volume ratio) for 2 minutes, and then linearly increase the volume ratio of ethyl acetate to ethyl acetate / cyclohexane = 100/0 (volume ratio) over 18 minutes , Ethyl acetate / cyclohexane = 100/0, hold for 10 minutes. Flow rate 1.0 ml / min Column temperature: 40 ° C

(3) Measurement of Polymer Hydrogenation Rate and Number of Diester Groups at Polymer Terminal by Nuclear Magnetic Resonance Spectrum ( ¹ H-NMR Spectrum) The number of terminal diester groups of the polymer was also confirmed by nuclear magnetic resonance spectrum.
Equipment: JEOL nuclear magnetic resonance apparatus (JNM-LA400)
Solvent: deuterated chloroform

(4) Measuring device for Izod impact strength in accordance with JIS K7110: DG-UB digital impact tester test piece manufactured by Toyo Seiki Co., Ltd. From a sheet hot-pressed to 2 mm thickness, a length of 31.5 mm and a width of 6.2 mm Cut out a strip and create a notch with a depth of 1.2mm using a notching machine

<< Production Example 1 >> Production of di-t-butyl maleate 34.8 g (0.3 mol) of maleic acid was charged into a dry 200 mL glass pressure vessel, and the gas in the vessel was replaced with nitrogen gas. Next, 60 mL of dichloromethane as a solvent and 2 mL of concentrated sulfuric acid as a catalyst were added and stirred to sufficiently disperse maleic acid. Thereto was added 40.4 g (0.72 mol) of isobutylene. The reaction started at room temperature and increased up to 32 ° C. As the reaction proceeded, isobutylene was consumed, the pressure in the vessel was lowered, and maleic acid insoluble in dichloromethane gradually decreased. When pressure was reduced (0.5 MPa) with nitrogen gas three times and the stirring was continued for 15 hours to reduce the pressure, the reaction vessel was completely homogenized and the reaction was completed. The resulting solution was diluted with diethyl ether, neutralized with aqueous sodium bicarbonate, and washed with water. The obtained solution was dried over magnesium sulfate overnight, then the magnesium sulfate was filtered off, and the solution was concentrated to obtain white crystals. The obtained crystals were dissolved in hexane, cooled to −78 ° C., recrystallized and purified to obtain di-t-butyl maleate.

<< Example 1 >> Production of polystyrene (1) having an acid anhydride group at its terminal 30 mL of cyclohexane was charged in a glass reaction vessel sufficiently substituted with nitrogen, heated to 50 ° C., and sec. -0.23 mL of cyclohexane solution of butyl lithium (0.3 mmol as sec-butyl lithium) and 1.5 g of styrene were added, and the polymerization reaction was continued for 30 minutes. Further, 0.38 mL of triisobutylaluminum in cyclohexane solution (0.3 mmol as triisobutylaluminum) was added to the vessel and stirred for 5 minutes, and the cyclohexane solution of di-t-butyl maleate obtained in Production Example 1 was added. (0.6 mmol as di-t-butyl maleate) was added and the reaction was continued for 10 minutes, and then 0.1 mL of methanol was added to the vessel to stop the reaction. The resulting polymer solution is sufficiently washed with water containing a small amount of sulfuric acid and water, and then reprecipitated with a large excess of methanol, thereby having polystyrene having a diester group at the end [hereinafter referred to as (1-1)]. Got. Next, 1 g of (1-1) was placed in a glass reaction vessel, heated at 230 ° C. for 20 minutes while degassing with a vacuum pump, and then slowly cooled to room temperature, whereby polystyrene having an acid anhydride group at the end [ Hereinafter referred to as (1-2)]. For the obtained (1-1) and (1-2), the number average molecular weight, molecular weight distribution, component ratio, the number of terminal diester groups or the number of acid anhydride groups were measured and calculated, as shown in Table 1. there were.

<< Example 2 >> Production of polystyrene (2) having an acid anhydride group at its terminal The amount of triisobutylaluminum in cyclohexane solution used in Example 1 was changed from 0.38 mL to 3.8 mL (0. 3 as triisobutylaluminum). Except for changing from 3 mmol to 3 mmol), the same operation as in Example 1 was performed, and polystyrene having a diester group at the end [hereinafter referred to as (2-1)] and polystyrene having an acid anhydride group at the end [hereinafter referred to as And (2-2)]. For the obtained (2-1) and (2-2), the number average molecular weight, molecular weight distribution, component ratio, terminal diester group number or acid anhydride group number were measured and calculated, as shown in Table 1. there were.

<< Example 3 >> Production of polymer (3) having an acid anhydride group at its end In a 1.5 L autoclave sufficiently substituted with nitrogen, 750 mL of cyclohexane and 6.41 mL of a cyclohexane solution of sec-butyllithium (sec- After charging 8.33 mmol) as butyl lithium and heating to 50 ° C., 37.5 g of styrene was added to the vessel to complete the polymerization reaction. Subsequently, 88 g of isoprene and 88 g of butadiene were added to the vessel to complete the polymerization reaction. Thereafter, 37.5 g of styrene was added to the vessel to complete the polymerization reaction, thereby obtaining a cyclohexane solution of polystyrene-poly (isoprene / butadiene) -polystyrene block copolymer. To this solution, 15.8 mL of triisobutylaluminum in cyclohexane solution (12.5 mmol as triisobutylaluminum) was added and stirred for 15 minutes, and then a solution of di-t-butyl maleate in cyclohexane (as di-t-butyl maleate). 16.7 mmol) was added and the reaction was continued for 10 minutes, and then 1 mL of methanol was added to the vessel to stop the reaction. The obtained polymer solution is sufficiently washed with water containing a small amount of sulfuric acid and water, and then reprecipitated with a large excess of methanol, whereby a polymer having a diester group at the end [hereinafter referred to as (3-1)] Got. Next, 1 g of (3-1) was placed in a glass reaction vessel, heated at 230 ° C. for 20 minutes while being deaerated with a vacuum pump, and then slowly cooled to room temperature, whereby the polymer having an acid anhydride group at the end [ Hereinafter, (3-2)] was obtained. For the obtained (3-1) and (3-2), the number average molecular weight, molecular weight distribution, component ratio, terminal diester group number or acid anhydride group number were measured and calculated, as shown in Table 1. there were.

  In addition, 125 g of (3-1) was charged into a 5 L autoclave sufficiently purged with nitrogen, and 1 L of cyclohexane was added to obtain a solution. The solution was charged with a nickel catalyst prepared from nickel octylate and triisobutylaluminum, and a hydrogenation reaction was performed at 60 ° C. for 5 hours. Next, the solution after the reaction is washed to remove the catalyst, and then reprecipitated with a large excess of acetone / methanol mixed solution, whereby a polymer having a diester group at the end and hydrogenated [hereinafter referred to as (3- 3)] was obtained. The obtained (3-3) was measured and calculated for the number average molecular weight, molecular weight distribution, component ratio, number of terminal diester groups, and hydrogenation rate, and the results were as shown in Table 1.

  Furthermore, the above (3-3) is charged into a boplast mill (manufactured by Toyo Seiki Co., Ltd.) and masticated for 5 minutes under the conditions of 230 ° C. and rotor rotation speed of 100 rpm, thereby having an acid anhydride group at the terminal and hydrogenation. The obtained polymer [hereinafter referred to as (3-4)] was obtained. The obtained (3-4) was measured for the number average molecular weight, molecular weight distribution, component ratio, and number of terminal acid anhydride groups as shown in Table 1.

«Comparative Example 1» Production of polystyrene (4) having an acid anhydride group at the terminal The same operation as in Example 1 was performed except that the cyclohexane solution of triisobutylaluminum used in Example 1 was not used. Polystyrene having a diester group [hereinafter referred to as (4-1)] and polystyrene having an acid anhydride group at the terminal [hereinafter referred to as (4-2)] were obtained. For the obtained (4-1) and (4-2), the number average molecular weight, molecular weight distribution, component ratio, terminal diester group number or acid anhydride group number were measured and calculated, as shown in Table 1. there were.

Comparative Example 2 Production of Polystyrene (5) Having a Functional Group at the Terminal In Example 1 above, the same operation as in Example 1 was performed except that dimethyl maleate was used instead of di-t-butyl maleate. A polystyrene having a diester group at the end [hereinafter referred to as (5-1)] was obtained. Next, 1 g of (5-1) was placed in a glass reaction vessel, heated at 230 ° C. for 20 minutes while being degassed with a vacuum pump, and then slowly cooled to room temperature, whereby polystyrene [hereinafter referred to as (5-2) and To get]. For the obtained (5-1) and (5-2), the number average molecular weight, molecular weight distribution, component ratio, terminal diester group number or acid anhydride group number were measured and calculated, as shown in Table 1. there were.

Reference Example 1 Production of Polystyrene (6) 30 mL of cyclohexane was charged into a dry glass reaction vessel and heated to 50 ° C., and then 0.23 mL (sec-butyl) of a cyclohexane solution of sec-butyllithium in the vessel. 0.3 mmol) as lithium and 1.5 g of styrene were added and the polymerization reaction was continued for 30 minutes. Thereafter, 0.1 mL of methanol was added to the vessel to stop the reaction. The resulting polymer solution was sufficiently washed with water containing a small amount of sulfuric acid and water, and then reprecipitated with a large excess of methanol to obtain polystyrene [hereinafter referred to as (6-1)]. Next, 1 g of (6-1) was placed in a glass reaction vessel, heated at 230 ° C. for 20 minutes while degassing with a vacuum pump, and then slowly cooled to room temperature, thereby polystyrene [hereinafter referred to as (6-2) and To get]. For the obtained (6-1) and (6-2), the number average molecular weight, molecular weight distribution, component ratio, terminal diester group number or acid anhydride group number were measured and calculated, as shown in Table 1. there were.

<< Example 4 >> Production of resin composition containing polymer having acid anhydride group at terminal (3-4) obtained in Example 3 and UBE nylon 6 1022B (manufactured by Ube Industries, Ltd .; polyamide 6; , PA6) at a ratio shown in Table 2 and charged into a lab plast mill (manufactured by Toyo Seiki Co., Ltd.), and kneaded for 5 minutes at 260 ° C. and a rotor rotational speed of 100 rpm to obtain a resin composition. The above-mentioned Izod impact strength of the resin composition was measured and as shown in Table 2.

<< Comparative Examples 3 to 7 >> Production of resin composition containing polymer having no acid anhydride group at terminal In Example 4, in place of (3-4), the following (A) to (E) Any kind of resin:
(A) Septon 2002 (manufactured by Kuraray Co., Ltd .; styrene block polymer; hereinafter referred to as SEEPS)
(B) Septon HG-252 (manufactured by Kuraray Co., Ltd .; styrene block polymer having a hydroxyl group at the terminal; hereinafter referred to as SEPS-OH);
(C) Tuftec M1911 (manufactured by Asahi Kasei Chemicals; side chain maleic acid-modified styrene block polymer; hereinafter referred to as MAn-SEBS1);
(D) Tuftec M1913 (manufactured by Asahi Kasei Chemicals; side chain maleic acid-modified styrene block polymer; hereinafter referred to as MAn-SEBS2); MAn-EPR);
A resin composition was obtained in the same manner as in Example 4 except that was used. The above-mentioned Izod impact strength of the resin composition was measured and as shown in Table 2.

≪Reference example 2≫
Table 2 shows the Izod impact strength measured for the above PA6 only in a Laboplast mill (manufactured by Toyo Seiki Co., Ltd.) and kneaded for 5 minutes under the conditions of 260 ° C. and rotor rotation speed 100 rpm. It was street.

  From the results of Table 1, the polymers obtained by the production methods of Examples 1 to 3 that satisfy all the constituent requirements of the present invention contain typical metal elements selected from boron, aluminum, zinc and magnesium specified in the present invention. For the polymer obtained by the production method of Comparative Example 1 that did not use the compound and the polymer obtained by the production method of Comparative Example 2 that did not use the diester compound specified in the present invention, The generation is suppressed, and the number of acid anhydride groups introduced into the ends of the polymer is high, indicating that the target polymer is obtained.

  From the results of Table 2, the resin composition of Example 4 that satisfies all the constituent requirements of the present invention is a comparative example that does not satisfy the constituent requirements of the present invention in that it does not contain a polymer having an acid anhydride group at the terminal. It can be seen that the impact resistance is improved with respect to the resin compositions of 3 to 7.

INDUSTRIAL APPLICABILITY According to the present invention, a method for producing a polymer having an acid anhydride group at the terminal under industrially advantageous conditions at room temperature or higher, a polymer having an acid anhydride group at the terminal obtained by the production method, and a resin modification comprising the polymer An agent and a resin composition containing the polymer and another thermoplastic resin are provided.

Claims (5)

A method for producing a polymer having an acid anhydride group at the terminal, wherein the following steps (1) to (4):
Step (1) A step of obtaining a living polymer by living anionic polymerization of a polymerizable monomer;
Step (2) A step of reacting the living polymer with a compound containing a typical metal element selected from boron, aluminum, zinc and magnesium to form an art complex;
Step (3) The art complex and the following general formula

(Wherein R ¹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ² and R ³ are each a tertiary alkyl group having 4 to 12 carbon atoms). A step of introducing a diester group at the end of the living polymer; and a step (4) a step of converting the diester group at the end of the polymer obtained in step (3) into an acid anhydride group;
The manufacturing method of the polymer which has an acid anhydride group in the terminal containing.   The method for producing a polymer having an acid anhydride group at a terminal according to claim 1, wherein the compound containing a typical metal element is an organoaluminum compound.   The method for producing a polymer having an acid anhydride group at a terminal according to claim 1 or 2, wherein the polymerizable monomer is a vinyl aromatic compound and / or a conjugated diene compound. The polymerizable monomer contains at least a conjugated diene compound, and the following step (5):
Step (5) Step of hydrogenating the polymer obtained in Step (3) and / or Step (4);
The manufacturing method of the polymer which has an acid anhydride group at the terminal of Claim 3 containing this. The method for producing a polymer having an acid anhydride group at a terminal according to claim 4, wherein the living polymer has a triblock structure of vinyl aromatic compound polymer block-conjugated diene compound polymer block-vinyl aromatic compound polymer block. .