JP2005179640A - Polymer having successive skeleton and chain skeleton and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a polymer having a successive skeleton and a chain skeleton and a polymer obtained by the method having the successive skeleton and the chain skeleton and excellent in melt molding. <P>SOLUTION: The polymer having the successive skeleton and the chain skeleton is produced by chain polymerizing an unsaturated monomer (D1) by using a high molecular compound (S) having an active structure (T) obtained by successive polymerization, initiating a radical polymerization of the unsaturated monomer and time-dependently increasing the molecular weight in the main chain as an initiator and reacting the same with another unsaturated monomer (D2) different from the unsaturated monomer (D1). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a polymer having a sequential skeleton and a chain skeleton in one molecule and a method for producing the same. Specifically, a polymer compound containing an active structure in the main chain, which is obtained by sequential polymerization, can initiate radical polymerization of unsaturated monomers and increase the molecular weight with polymerization time, is used as an initiator. The present invention relates to a polymer having a sequential skeleton and a chain skeleton obtained by chain polymerization of an unsaturated monomer and then reacting with another unsaturated monomer different from the unsaturated monomer, and a method for producing the polymer.

  As a method for synthesizing a polymer having a sequential skeleton and a chain skeleton in one molecule, for example, a polymer compound containing a functional group capable of generating a radical, such as an azo group, in the molecule is used as a radical polymerizable polymerization initiator. A method for polymerizing a polymerizable unsaturated monomer is known (for example, see Patent Document 1).

  In the method of polymerizing a polymerizable unsaturated monomer in the presence of a polymer compound having a diazo bond in one molecule according to Patent Document 1, the molecular weight cannot be increased with the polymerization time, and the length of the chain skeleton segment is increased. It is difficult to adjust the height.

  As another synthesis method, a synthesis method in which a vinyl monomer is polymerized using a urethane polymer compound or an ester polymer compound containing the following active structure in the main chain as an initiator has been proposed. (For example, see Patent Document 2).

（式中、Ｒ_a、Ｒ_b、Ｒ_cおよびＲ_dはＨまたは置換基を表す。）

(In the formula, R _a , R _b , R _c and R _d represent H or a substituent.)

  Reaction of sulfur compound having two amino groups or a mixture of this sulfur compound and diamine compound with diisocyanate compound or dicarboxylic acid dichloride compound that decomposes by light or heat used in the synthesis method according to Patent Document 2 When the polymer compound thus obtained is copolymerized with a vinyl monomer as an initiator, the molecular weight can be increased with the polymerization time, and the segment length of the skeleton or chain skeleton can be adjusted successively. However, the resulting block copolymer generates radicals in the main chain by heat or light. For this reason, when this is used as a melt-molding material, the main chain is decomposed, cleaved and altered.

JP-A-1-252611 Japanese Patent Publication No. 51-35514

  The present invention starts a polymer compound containing an active structure in the main chain, obtained by sequential polymerization, which initiates radical polymerization of unsaturated monomers and generates active sites capable of increasing the molecular weight with polymerization time. Provided is a method for producing a polymer having a sequential skeleton and a chain skeleton, in which the length of each segment of the sequential skeleton and the chain skeleton can be easily adjusted, and is excellent in thermal stability obtained by this method, and melt molding It is an object to provide a polymer having a sequential skeleton and a chain skeleton excellent in properties.

  The present invention relates to a polymer compound (S) obtained by sequential polymerization and containing an active structure (T) in the main chain that can initiate radical polymerization of an unsaturated monomer and increase the molecular weight with polymerization time. Obtained by chain polymerization of the unsaturated monomer (D1) and then reacting with another unsaturated monomer (D2) different from the unsaturated monomer (D1), as an initiator (U), A polymer having a sequential skeleton and a chain skeleton.

In addition, the present invention provides a polymer compound (S) obtained by sequential polymerization, which contains an active structure (T) in the main chain that can initiate radical polymerization of an unsaturated monomer and increase the molecular weight with polymerization time. ) As an initiator (U), a step of chain-polymerizing the unsaturated monomer (D1), and then a step of reacting another unsaturated monomer (D2) different from the unsaturated monomer (D1) It is a manufacturing method of the polymer containing this.

  According to the present invention, a polymer having a sequential skeleton and a chain skeleton, in which the length of each segment of the sequential skeleton and the chain skeleton is adjusted, excellent in thermal stability and excellent in melt moldability, is produced very easily in a simple reaction system. Can be provided.

Hereinafter, the present invention will be described in detail.
The polymer of the present invention is a polymer compound (S) obtained by sequential polymerization and containing an active structure (T) in the main chain that can initiate radical polymerization of unsaturated monomers and increase the molecular weight with the polymerization time. ) As an initiator (U), obtained by chain polymerization of the unsaturated monomer (D1), and then reacting with another unsaturated monomer (D2) different from the unsaturated monomer (D1). And a polymer having a sequential skeleton and a chain skeleton.

  The sequential skeleton constituting the main chain of the polymer of the present invention refers to a reaction product as a reaction reagent in the next step, as represented by polycondensation reaction and polyaddition reaction, and a series of elements between reactive functional groups. It means a polymer skeleton obtained by sequential polymerization, which is a polymerization that proceeds by repeating a so-called sequential reaction, in which the reaction takes place subsequently. The sequential skeleton in the polymer of the present invention is derived from the polymer compound (S) used as the initiator (U).

  Further, the chain skeleton constituting the main chain of the polymer of the present invention means a polymer skeleton obtained by chain polymerization in which the active structure (T) of the initiator repeats the addition reaction one after another to the monomer, The chain skeleton in the polymer of the present invention is an unsaturated monomer obtained by chain polymerization with an active structure (T) capable of initiating radical polymerization contained in the polymer compound (S) used as the initiator (U). It is mainly derived from the skeleton of the polymer (D1).

  The initiator (U) used in the present invention has, in the main chain, an active structure (T) obtained by sequential polymerization, which initiates radical polymerization of unsaturated monomers and can increase the molecular weight with the polymerization time. It is a high molecular compound (S) containing.

  In order to introduce the active structure (T) into the polymer compound (S), a compound (AM) having an active structure (T) in the molecule and another compound that sequentially polymerizes with this compound (AM) are combined. What is necessary is just to superpose | polymerize. The polymerization method of the polymer compound (S) is not particularly limited, and a suitable one may be selected from known polymerization methods according to the raw material compound used.

  Specific examples of the polymer compound (S) include, for example, a polyurethane having an active structure (T) in the main chain and a skeleton containing a urethane bond in the main chain (sometimes referred to as a urethane skeleton), an ester bond And a polyamide having a skeleton containing an amide bond in the main chain (sometimes referred to as an amide skeleton).

  The active structure (T) is not particularly limited, and may have any structure. As an active structure (T) in this invention, what has a structure represented, for example by following General formula (1) is preferable.

（式中、Ｒ₁、Ｒ₂、Ｒ₃およびＲ₄は、各々独立に、水素または同一もしくは異なる置換基を表す。）

(Wherein R ₁ , R ₂ , R ₃ and R ₄ each independently represents hydrogen or the same or different substituent)

  Examples of the compound (AM) having an active structure (T) represented by the general formula (1) in the molecule include benzopinacol (1,2-dihydroxy-1,1,2,2-tetraphenylethane). , 1,4-diamino-2,2,3,3-tetraphenylbutane, etc., and a tetraphenylethane skeleton in which two carbon atoms substituted with two phenyl groups are connected and two in the molecule And compounds having various reactive functional groups such as a hydroxyl group and an amino group.

  When the polymer compound (S) is polyurethane, the compound (AM) having the above active structure is one of compounds having at least one tetraphenylethane skeleton and two hydroxyl groups in one molecule such as benzopinacol. It is preferable to obtain a polyaddition reaction by combining a species or two or more species and a diisocyanate compound and a diol compound as other compounds to be sequentially polymerized therewith.

  Specific examples of diisocyanate compounds that can be used include, for example, isophorone diisocyanate, methylcyclohexane-2,4-diisocyanate, methylcyclohexane-2,6-diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-methylenebis. (Cyclohexyl isocyanate), 1,3-di (isocyanatomethyl) cyclohexane, tetramethylene diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, hexamethylene diisocyanate, trimethylcyclohexane diisocyanate, tolylene diisocyanate and 1,3-bis (isocyanate) Mention may be made of diisocyanates such as natomethyl) benzene.

  Specific examples of the diol compound that can be used include, for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, 3-methyl-1,5- Examples include diols such as pentanediol, cyclohexanedimethanol, polyethylene glycol, polypropylene glycol, polyhexamethylene glycol, neopentyl glycol, bisphenol A and hydrogenated bisphenol; monocarboxyl diols such as dimethylolpropanoic acid, and the like.

  Moreover, these diisocyanate compounds and diol compounds may be used individually by 1 type, and may use 2 or more types together.

  In order to prepare the polymer compound (S) by sequential polymerization using these raw material compounds, for example, the compound (AM) having the above active structure, a short chain diol (molecular weight 50 to 200), and a long chain diol (molecular weight 200). And a diisocyanate compound, and the urethane polymer obtained preferably contains 5 to 95% by mass of a urethane moiety composed of a short-chain diol in the urethane polymer. It is preferable to use a catalyst for producing a generally known urethane bond such as dibutyltin dilaurate in an amount of 0.1 to 1 mol% based on the number of moles of isocyanate. As the solvent, 1-methyl-2-pyrrolidone, tetrahydrofuran, methyl ethyl ketone and the like are preferably used. The reaction temperature is preferably 60 to 100 ° C. The active structure contained in the sequential skeleton is preferably contained in the range of 0.1% by mass to 50% by mass. The number average molecular weight (sometimes expressed as Mn) is preferably 2000 or more.

  When the polymer compound (S) is a polyester, the polymer compound (S) is composed of at least one tetraphenylethane skeleton and two compounds in one molecule such as benzopinacol as the compound (AM) having the above active structure. It is preferable to use one or two or more compounds having a hydroxyl group, and polycondensation reaction of the compound with a dicarboxylic acid compound and a diol compound.

  Specific examples of dicarboxylic acid compounds that can be used include, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, Biphenyldicarboxylic acid, sodium 5-sulfoisophthalate and the like can be mentioned.

  Specific examples of the diol compound that can be used include, for example, ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1, 6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, cyclohexane 1 , 2-diol, cyclohexane 1,3-diol, cyclohexane 1,4-diol, cyclohexane 1,4-dimethanol, hydroquinone, 4,4-diphenol, and the like.

  These dicarboxylic acid compounds and diol compounds may be used alone or in combination of two or more.

  When the polymer compound (S) is polyamide, the polymer compound (S) is a compound (AM) having the above active structure such as 1,4-diamino-2,2,3,3-tetraphenylbutane. Using one or more compounds having at least one tetraphenylethane skeleton and two amino groups in one molecule, polycondensation reaction of this with a dicarboxylic acid compound or dicarboxylic acid halide and a diamine compound Preferably obtained.

  Specific examples of the dicarboxylic acid compound that can be used include terephthalic acid, isophthalic acid, glutaric acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, and the like.

  Specific examples of dicarboxylic acid halides that can be used include dichlorides of the above carboxylic acids, such as terephthalic acid dichloride, isophthalic acid dichloride, glutaric acid dichloride, adipic acid dichloride, sebacic acid dichloride, dodecane dicarboxylic acid dichloride, and the like. Mention may be made of dicarboxylic acid halides.

  Specific examples of the diamine compound that can be used include hexamethylenediamine, phenylenediamine, xylylenediamine, bis (3-methyl-4-amino-cyclohexyl) methane, and the like.

  These dicarboxylic acid compounds, dicarboxylic acid halides, and diamine compounds may be used singly or in combination of two or more.

  The unsaturated monomer (D1) that can be used in the present invention is not particularly limited, and may be appropriately selected according to required properties such as physical properties required for the polymer of the present invention.

  Examples of the unsaturated monomer (D1) that can be used in the present invention include (meth) acrylic monomers. Specific examples of the (meth) acrylic monomer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, (Meth) acrylates of linear or branched alkyl alcohols such as hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate; (meth) acrylates of cyclic alkyl alcohols such as cyclohexyl (meth) acrylate Phosphoric acid group-containing (meth) acrylates such as 2- (meth) acryloyloxyethyl acid phosphate; Hydroxyl group-containing (meth) such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate A Relates; Carbonyl group-containing (meth) acrylates such as acetoacetoxyethyl (meth) acrylate; Amino group-containing (meth) acrylates such as N-dimethylaminoethyl (meth) acrylate and N-diethylaminoethyl (meth) acrylate (Meth) acrylates such as

  Examples of the unsaturated monomer (D1) that can be used in the present invention include methacrylic acid, acrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 2-succinoloyloxyethyl methacrylate, Carboxyl group-containing monomers such as 2-malenoyloxyethyl methacrylate, 2-phthaloyloxyethyl methacrylate, 2-hexahydrophthaloyloxyethyl methacrylate; sulfonic acid group-containing monomers such as allyl sulfonic acid; acrylonitrile, methacrylate (Meth) acrylonitriles such as ronitrile and α-chloroacrylonitrile are listed.

  Examples of the unsaturated monomer (D1) that can be used in the present invention include carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate; vinyl fluoride, vinyl chloride, vinyl bromide, and vinyl iodide. And vinylidene halides such as vinylidene fluoride, vinylidene chloride, vinylidene bromide, and vinylidene iodide; and conjugated diene compounds such as butadiene, isoprene, chloroprene, and 1-chlorobutadiene.

  The said unsaturated monomer can be used individually by 1 type or in combination of 2 or more types.

Among the unsaturated monomers, an unsaturated monomer satisfying the following conditions is preferably used as the unsaturated monomer (D1) in the present invention. That is, when the unsaturated monomer (D1) is represented by the following general formula (2), the bond bond indicated by the broken line in the molecular structure of the compound represented by the general formula (3) optimized by the molecular orbital method It is preferable to use an unsaturated monomer having a distance (Ri ¹ ) greater than 1.57 × 10 ⁻¹⁰ m.
Use of an unsaturated monomer having a bond distance (Ri ¹ ) greater than 1.57 × 10 ⁻¹⁰ m is preferred because the molecular weight increases with the polymerization time.

（式中、Ｒ₅、Ｒ₆、Ｒ₇およびＲ₈は、各々独立に、水素または同一もしくは異なる置換基を表す。）

(In the formula, R ₅ , R ₆ , R ₇ and R ₈ each independently represent hydrogen or the same or different substituent.)

(式中、Ｒ₅、Ｒ₆、Ｒ₇およびＲ₈は、各々独立に、水素または同一もしくは異なる置換基を表す。)

(In the formula, R ₅ , R ₆ , R ₇ and R ₈ each independently represent hydrogen or the same or different substituent.)

  Specific examples of the unsaturated monomer (D1) that satisfies the above conditions include, for example, a methacrylate monomer.

  As an unsaturated monomer (D2) which can be used for this invention, a styrene monomer can be mentioned, for example.

Further, as the unsaturated monomer (D2), when the unsaturated monomer (D2) is represented by the following general formula (4), the compound represented by the general formula (5) optimized by the molecular orbital method is used. It is preferable to use an unsaturated monomer having a bond distance (Ri ² ) of a bond indicated by a broken line in the molecular structure of 1.57 × 10 ⁻¹⁰ m or less.

（式中、Ｒ₉、Ｒ₁₀、Ｒ₁₁およびＲ₁₂は、各々独立に、水素または同一もしくは異なる置換基を表す。）

(In the formula, R ₉ , R ₁₀ , R ₁₁ and R ₁₂ each independently represent hydrogen or the same or different substituent.)

(式中、Ｒ₉、Ｒ₁₀、Ｒ₁₁およびＲ₁₂は、各々独立に、水素または同一もしくは異なる置換基を表す。)

(Wherein R ₉ , R ₁₀ , R ₁₁ and R ₁₂ each independently represents hydrogen or the same or different substituent).

The optimization by the molecular orbital method was carried out using MOPAC (AM1) (software used: ChemOffice Ultra 01 manufactured by CambridgeSoft) for both unsaturated monomers (D1) and (D2). The optimization by this software is a calculation method for calculating the bond distances Ri ¹ and Ri ² by calculating a structure with minimized energy. In the optimization method, the bond distances Ri ¹ and Ri calculated for the structures of the general formula (3) and the following general formula (6) or the structures of the general formula (5) and the following general formula (7) are calculated. ^{When 1 ′} or Ri ² and Ri ^{2 ′} are different, the longer one is defined as the coupling distance.

（式中、Ｒ₅、Ｒ₆、Ｒ₇およびＲ₈は、各々独立に、水素または同一もしくは異なる置換基を表す。）

(In the formula, R ₅ , R ₆ , R ₇ and R ₈ each independently represent hydrogen or the same or different substituent.)

（式中、Ｒ₉、Ｒ₁₀、Ｒ₁₁およびＲ₁₂は、各々独立に、水素または同一もしくは異なる置換基を表す。)

(Wherein R ₉ , R ₁₀ , R ₁₁ and R ₁₂ each independently represents hydrogen or the same or different substituent).

In the molecular structure of the compound represented by the general formula (5) optimized by the molecular orbital method, the bond length (Ri ² ) of the bond indicated by the broken line is 1.57 × 10 ⁻¹⁰ m or less. Specific examples of the monomer (D2) include styrene, α-methyl styrene, p-methyl styrene, vinyl toluene, o-methyl styrene, m-methyl styrene, p-methyl styrene, and the like.

  When the unsaturated monomer (D2) satisfying the above conditions is used, the thermal stability of the produced polymer having a sequential skeleton and a chain skeleton can be improved.

  For example, the radical structure of the unsaturated monomer obtained by sequential polymerization can be initiated and the molecular weight can be increased with the polymerization time. Polymer obtained by chain polymerization of unsaturated monomer (D1) using polymer compound (S) contained in chain as initiator (U) is 40 to 80 ° C. When heated, radicals are easily generated in the main chain of the polymer. This is also demonstrated from the fact that when the unsaturated monomer (D1) is further reacted with the polymer (U-D1), polymerization is performed while the molecular weight is increased, and stable radicals are detected by ESR measurement. For this reason, the polymer (U-D1) is inferior in thermal stability, and when used as a melt molding material, it is decomposed, cleaved, and altered.

However, when the unsaturated monomer (D2), preferably the unsaturated monomer (D2) is represented by the general formula (4), the structure of the general formula (5) is optimized by the molecular orbital method. In the polymer of the present invention obtained by reacting the unsaturated monomer (D2) having a bond distance (Ri ² ) of 1.57 × 10 ⁻¹⁰ m or less with the polymer (U-D1), the temperature is 200 ° C. It was confirmed by ESR measurement and the like that radicals were not generated even when heated to a low temperature.

The above results also indicate that the bond distance (Ri ² ) of the bond indicated by the broken line in the molecular structure of the unsaturated monomer (D2), particularly the compound represented by the general formula (5) optimized by the molecular orbital method. The unsaturated monomer (D2) having a value of 1.57 × 10 ⁻¹⁰ m or less indicates that it is a radically polymerizable unsaturated monomer excellent in the effect of promoting the chain polymerization termination reaction. is there.

Moreover, it is preferable that the polymer of the present invention has a tensile elastic modulus of not less than 5 kJ / m ^{2 and} an absorption energy value determined by a dynastat impact test of not less than 350 MPa.

The tensile elastic modulus may be measured under the following test conditions according to JIS K-7113.
Testing equipment: Tensilon Universal Testing Machine 1250A (Orientec Co., Ltd .; trade name)
Measurement temperature: 25 ° C
Tensile speed: 200 mm / min
Initial sample length: 15 mm
Test specimen dimensions: width x length x thickness = 5 x 30 x 0.5 mm
The test piece is prepared by melt molding.

The value of the absorbed energy may be measured under the test conditions shown below in a Dynestat impact test according to BS-1330.
Test equipment: Dinestat tester (manufactured by Toyo Seiki Co., Ltd .; trade name)
Measurement temperature: 25 ° C
Angle: 60 °
Weight: Hammer only Test piece dimensions: Width x Length x Thickness = 10 x 20 x 0.5 mm
The test piece is prepared by melt molding.
The maximum moment that the hammer can have under the above test conditions is 2.5 kgf · cm, and the moment absorbed by the impact can be calculated by reading the scale of the discarded needle after impacting the test piece. When the test piece does not break in the dynastat impact test, the absorbed energy may be calculated assuming that the test piece has absorbed all the maximum moment 2.5 kgf · cm that the hammer can have under the above test conditions.

  The polymer of the present invention has excellent thermal stability and excellent melt moldability, and various articles can be produced very easily and efficiently using the polymer of the present invention. In general, acrylic polymers have low impact resistance, and it is known that the elongation decreases when tensile strength and tensile elastic modulus are improved. In the polymer of the present invention, the chain skeleton is an acrylic polymer. Even when the chain skeleton is used, it is possible to maintain the elongation and improve the tensile strength and the tensile elastic modulus. Further, since the absorbed energy at the time of impact increases, the impact resistance can be dramatically improved while maintaining the tensile elastic modulus to some extent.

Next, the manufacturing method of the polymer of this invention is demonstrated.
The method for producing a polymer of the present invention can initiate radical polymerization of an unsaturated monomer obtained by sequential polymerization and increase the molecular weight with the polymerization time, preferably the activity represented by the general formula (1) A step of chain-polymerizing unsaturated monomer (D1) using polymer compound (S) having structure (T) in the main chain as initiator (U), and then unsaturated monomer (D1) and It is a manufacturing method of a polymer including the process of reacting a different unsaturated monomer (D2).
By reacting the unsaturated monomer (D2), the radical polymerization of the unsaturated monomer (D1) is stopped to obtain the polymer of the present invention.

  The chain polymerization method of the unsaturated monomer (D1) in the method for producing the polymer of the present invention is not particularly limited. For example, it is carried out by a known chain polymerization method such as bulk polymerization, solution polymerization, emulsion polymerization or suspension polymerization. Can do.

  The polymerization conditions in the step of chain-polymerizing the unsaturated monomer (D1) are not particularly limited. Usually, the polymerization temperature may be 60 to 100 ° C., and the polymerization time may be 1 to 50 hours.

  Note that the length of the sequential skeleton depends on the amount in the polymer compound (S) of the active structure (T) that initiates radical polymerization of the unsaturated monomer and increases the molecular weight with the polymerization time, and the unsaturated monomer. It can be controlled by appropriately changing the amount of the polymer compound (S) used in the chain polymerization of (D1).

  Following the above step, a step of reacting with an unsaturated monomer (D2) different from the unsaturated monomer (D1) is performed. This step can be performed by introducing and reacting the unsaturated monomer (D2) to the reaction product after chain polymerization of the unsaturated monomer (D1).

  The conditions for reacting the unsaturated monomer (D2) are not particularly limited. Usually, the reaction temperature may be 60 to 100 ° C., and the reaction time may be 0.5 to 9 h. In addition, what is necessary is just to set a pressure suitably, such as a normal pressure.

  The method for recovering the polymer of the present invention is not particularly limited. In the case of solution polymerization, for example, it is precipitated in an appropriate organic solvent such as methanol, hexane, and filtered, and the polymer separated by filtration is washed and dried. In the case of the recovery method, suspension polymerization, for example, filtration, washing, drying and recovering, and in the case of emulsion polymerization, for example, using a known method such as spray drying or coagulation. It can be recovered.

  In the production method of the present invention, the length of the chain skeleton is appropriately changed by appropriately changing the amount of the active structure (T), the amount of the unsaturated monomer (D1), and the conversion rate of the unsaturated monomer (D1). Can be controlled. In addition, a polymer having a desired chain skeleton can be obtained.

  As described above, the polymer production method of the present invention can be synthesized by a very simple reaction system, and mass production is extremely easy.

  The polymer of the present invention is excellent in thermal stability and melt moldability as compared with the polymer of Patent Document 2. For this reason, it can be used for applications such as pressure-sensitive adhesives, adhesives, powder paints, and compatibilizers. It is also expected to have excellent properties as a thermoplastic elastomer. Thermoplastic elastomers, thermoplastic resins, impact modifiers, surfactants, release agents, membranes, slow-acting pharmaceutical carriers, packaging materials, pharmaceuticals It is expected that it can be widely used for applications such as medical tubes and ecological prostheses.

EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, this invention is not limited to the following Example.
“Conversion rate” and “number average molecular weight (Mn)” in the following examples and comparative examples were determined by the following methods, respectively, unless otherwise specified. Moreover, the thermal stability of the polymer was evaluated by the following method.

<Conversion rate>
It calculated from the residual ratio of each monomer by a gas chromatogram.

<Number average molecular weight>
It calculated | required from the calibration curve by a standard polystyrene using gel permeation chromatography.

<Evaluation of thermal stability based on solubility evaluation>
The polymers of Examples and Comparative Examples were melt-kneaded with the following evaluation apparatus a) under the melt-kneading conditions of b).
a) Evaluation equipment PL2000 type (Plavender, model number W-50E 2 zone type)
The screw is of the attached mixer type and the rotation direction is different. B) Melting and kneading conditions Setting temperature: 190 ° C
Kneading time: 3 min
Kneaded resin mass: 50 g
Screw rotation speed: 50rpm
The polymer melt kneaded product (sometimes referred to as a melt-molded product) of Examples and Comparative Examples was allowed to stand at 25 ° C. for 24 hours and dissolved in dimethylformamide (sometimes referred to as DMF) to obtain 0.04% by mass. A DMF solution was prepared, the solubility of the melt-kneaded products of the polymers of Examples and Comparative Examples was evaluated, and the solubility of the polymers of Examples and Comparative Examples before melt-kneading were compared and evaluated. The solubility of each polymer compound (S) was also evaluated in the same manner.
In addition, the solubility with respect to DMF was evaluated based on the following evaluation criteria.
○: In preparation of 0.04% by mass DMF solution, it was confirmed that it was completely dissolved by visual observation. X: In preparation of 0.04% by mass DMF solution, it was not completely dissolved by visual observation. confirmed

<Evaluation of thermal stability by ESR>
The ESR measurement of the polymers of the examples and comparative examples was performed under the conditions of b) using the following evaluation apparatus a).
a) Measuring equipment JESOL JES-TE200 ESR SPECTROMETER (trade name)
b) Measurement condition measurement sample: Add about 100 mg of polymer to an ESR tube (NES-1; trade name) (manufactured by Japan Precision Science Co., Ltd.) and plug it.
Measurement temperature: 25 ° C to 200 ° C
Measuring method:
(I) The resonance frequency is searched for with constant power (4.0 mW).
(Ii) Determine the Center Field. (335 mT in the present invention)
(Iii) Set Sweep Width. (± 500mT)
(Iv) Set Amp (50-100 times) and Field Modulation Width (0.2mT) to increase sensitivity.
(V) Set Time Const. (0.03s in the present invention)
(Vi) When the waveform is determined, measure.
c) Evaluation criteria:
When a peak is detected in the range of −150 mT to 800 mT, it is assumed that there is a stable radical in the polymer, and when no peak is detected, it is assumed that there is no stable radical in the obtained polymer.

(Reference example)
To a flask purged with nitrogen was charged 1.92 g (5.23 mmol) of benzopinacol and 0.19 g (0.3 mmol) of di-n-butyltin dilaurate, and 23.4 g of 1-methyl-2-pyrrolidone was added. Dissolved. To this, 3.57 g (30.0 mmol) of phenyl isocyanate was added at room temperature, then they were reacted at a reaction temperature of 25 ° C. for 48 hours, and 1.04 g (22.6 mmol) of ethanol was added at a reaction temperature of 25 ° C. The reaction was further continued for 3 hours to obtain a solution of an isocyanate compound.
To this isocyanate compound solution, 262.82 g (2.62 mol) of methyl methacrylate and 232.2 g of 1-methyl-2-pyrrolidone were added, and then they were reacted at a reaction temperature of 80 ° C. for 12 hours. The conversion was 80%. Mn of the obtained polymer was 56000 g / mol.
On the other hand, sampling was performed every hour during the polymerization, and the conversion rate and Mn of the methyl methacrylate were measured. The results of plotting with Mn on the vertical axis and methyl methacrylate conversion on the horizontal axis are shown in FIG. It can be confirmed that Mn increases with the polymerization time.
Here, the tetraphenylethane skeleton in the isocyanate compound is the active structure (T). The number of methyl methacrylate molecules in the reaction solution is about 500 times the number of active structures (T), and if the active structure (T) reacts with methacrylate and the molecular weight increases with time, the molecular weight of the polymer is 50000 g / About mol. In the system of this example, the number average molecular weight was slightly higher than this value, but it was demonstrated that the active structure (T) having a tetraphenylethane skeleton reacts with methacrylate along with the polymerization time, and the molecular weight increases. It was done. Incidentally, the NCO content in the obtained polymer is about 0.1 wt%, which does not significantly affect the molecular weight of the polymer produced.

(Example 1)
<Synthesis of polymer compound (S)>
In a nitrogen-substituted flask, 0.8 g (0.0023 mol) of benzopinacol (sometimes referred to as BP) and 1.3 g (0.002 mol) of di-n-butyltin dilaurate (sometimes referred to as DBDSL) Was dissolved in 162.6 g of 1-methyl-2-pyrrolidone (may be referred to as MP). Then, 18.8 g (0.1 mol) of 1,3-bis (isocyanatomethyl) benzene (sometimes referred to as XDI) was added to this solution at room temperature, and they were reacted at a reaction temperature of 25 ° C. for 24 hours. Thus, a solution of the isocyanate compound was obtained.
Next, a reaction vessel comprising a flask purged with nitrogen in advance and a dropping funnel was prepared. The above-mentioned isocyanate compound solution was placed in the dropping funnel, and 9.0 g of 1,4-butanediol (sometimes referred to as BD) was placed in the flask. (0.1002 mol) was added, the polymerization temperature was set to 60 ° C., and the obtained isocyanate compound solution was added dropwise over 2 hours. Thereafter, the temperature of the reaction solution was raised to 80 ° C. and reacted for 1 hour to obtain a solution of the target polymer compound (S).

<Polymer synthesis>
Into a flask previously purged with nitrogen, a mixture of 174.4 g of 1-methyl-2-pyrrolidone and 143.8 g (1.01 mol) of n-butyl methacrylate (sometimes referred to as n-BMA) was added, 192.5 g of the polymer compound (S) solution was added and dissolved.
Thereafter, polymerization was carried out at a polymerization temperature of 80 ° C. in a nitrogen atmosphere, and 24.0 g (0.23 mol) of a styrene monomer (sometimes referred to as St) was charged when the conversion rate of n-BMA reached 80%. Subsequently, the same temperature was maintained for 9 hours.
The resulting solution was poured into a large excess of methanol to precipitate the polymer in methanol, which was filtered, washed with water, and vacuum dried at 80 ° C. for 24 hours to obtain a polymer.

(Examples 2 to 8)
A polymer was synthesized in the same manner as in Example 1 except that the composition, composition ratio, and mass ratio of the polymer compound and the unsaturated monomer shown in Table 1 were used. The ratio of the number of moles of isocyanate (0.1 mol) used in the synthesis to the number of moles of all diol compounds of benzopinacol and 1,4-butanediol (0.1025 mol) was 100: 102.5.
In Example 6, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (sometimes referred to as IPDI) was used as the diisocyanate compound. In Example 7, 4,4′-diphenylmethane diisocyanate (MDI and May be used). In Example 8, acrylate ester SL (CH ₂ ═C (CH ₃ ) COOC _n CH _2n +1 [n = 12, 13], which is a methacrylate of a linear alkyl alcohol, as the unsaturated monomer (D1), Mitsubishi Rayon Co., Ltd. (trade name) (sometimes referred to as SLMA) was used.
For reference, FIGS. 2 to 4 show the changes in the number average molecular weight associated with the polymerization times of Examples 2, 3 and 4, respectively.
When the n-BMA monomer, that is, the unsaturated monomer (D1) is polymerized, the molecular weight increases with the polymerization time. By adding styrene, that is, an unsaturated monomer (D2), the molecular weight is not increased. This means that the polymerization has stopped.

Example 9
<Synthesis of polymer compound (S)>
Into a flask purged with nitrogen, 0.48 g (0.0013 mol) of benzopinacol and 0.6 g (0.001 mol) of di-n-butyltin dilaurate were blended to make 65.8 g of 1-methyl-2-pyrrolidone. Dissolved. Next, 18.8 g (0.1 mol) of 1,3-bis (isocyanatomethyl) benzene was charged into this solution at room temperature, and they were reacted at a reaction temperature of 25 ° C. for 24 hours to obtain a solution of an isocyanate compound. .
Next, a reaction vessel consisting of a flask purged with nitrogen in advance and a dropping funnel was prepared. The dropping funnel was charged with the above isocyanate compound solution, and the flask was charged with 8.9 g (0.0987 mol) of 1,4-butanediol. Then, the polymerization temperature was set to 60 ° C., and an isocyanate compound solution obtained over 4 hours was added dropwise. Thereafter, the temperature of the reaction solution was raised to 80 ° C. and reacted for 1 hour to obtain a solution of the target polymer compound (S).

<Polymer synthesis>
A mixture of 194.6 g of 1-methyl-2-pyrrolidone and 82.2 g (0.56 mol) of n-butyl methacrylate was put into a flask which had been previously purged with nitrogen, and then a solution 94 of the above polymer compound (S) 94 .6 g was added and dissolved.
Thereafter, polymerization was carried out in a nitrogen atmosphere at a polymerization temperature of 80 ° C., and when the conversion rate of n-BMA reached 80%, 13.2 g (0.13 mol) of styrene monomer was added, and then maintained at that temperature for 9 hours. did.
The resulting solution was poured into a large excess of methanol to precipitate the polymer in methanol, which was filtered, washed with water, and vacuum dried at 80 ° C. for 24 hours to obtain a polymer.

(Examples 10 to 13)
A polymer was synthesized in the same manner as in Example 9 except that the composition, composition ratio, and mass ratio of the polymer compound and the unsaturated monomer shown in Table 2 were used. The molar ratio of the number of moles of isocyanate used in the synthesis (0.1 mol) and the number of moles of diol compounds of benzopinacol and 1,4-butanediol (0.1 mol) was 100: 100.
In Examples 10, 11 and 12, as the diisocyanate compound, tolylene diisocyanate (sometimes represented as TDI), hexamethylene diisocyanate (sometimes represented as HDI) and dicyclohexylmethane-4,4-diisocyanate ( HMDI) may be used.

(Example 14)
<Synthesis of polymer compound (S)>
In a flask purged with nitrogen, 0.42 g (0.0011 mol) of benzopinacol, 30.8 g (0.015 mol) of polyethylene glycol (molecular weight 2000 g / mol, hydroxyl groups at both ends) (sometimes referred to as PEG2000) and di -N-butyltin dilaurate 0.6g (0.001mol) was mix | blended and it was made to melt | dissolve in 14.7g of 1-methyl-2- pyrrolidone. Then, 18.8 g (0.1 mol) of 1,3-bis (isocyanatomethyl) benzene was charged into this solution at room temperature, and they were reacted at a reaction temperature of 25 ° C. for 24 hours to obtain a solution of an isocyanate compound. .
Next, a reaction vessel consisting of a flask and a dropping funnel previously purged with nitrogen was prepared. The above-mentioned isocyanate compound solution was charged into the dropping funnel, and 7.8 g (0.084 mol) of 1,4-butanediol was charged into the flask. Then, the polymerization temperature was set to 60 ° C., and an isocyanate compound solution obtained over 4 hours was added dropwise. Thereafter, the temperature of the reaction solution was raised to 80 ° C. and reacted for 1 hour to obtain a solution of the target polymer compound (S).

<Polymer synthesis>
Into a flask purged with nitrogen in advance, a mixture of 167.2 g of 1-methyl-2-pyrrolidone and 71.6 g (0.71 mol) of methyl methacrylate (sometimes referred to as MMA) was added. 185.4 g of the solution of S) was added and dissolved.
Thereafter, polymerization was carried out at a polymerization temperature of 80 ° C. in a nitrogen atmosphere. When the conversion rate of MMA reached 80%, 11.5 g (0.11 mol) of styrene monomer was added, and the mixture was maintained at the same temperature for 9 hours.
The resulting solution was poured into a large excess of methanol to precipitate the polymer in methanol, which was filtered, washed with water, and vacuum dried at 80 ° C. for 24 hours to obtain a polymer.

(Examples 15 to 16)
A polymer was synthesized in the same manner as in Example 14 except that the composition, composition ratio, and mass ratio of the polymer compound and the unsaturated monomer shown in Table 3 were used. The molar ratio of the number of moles of isocyanate (0.1 mol) used in the synthesis and the number of moles (0.1 mol) of all diol compounds of benzopinacol and 1,4-butanediol was 100: 100.

(Comparative example 1) (Additional examination of patent document 2)
After dissolving 0.566 g (0.0023 mol) of 4,4′-diaminodiphenyl disulfide and 9.0 g (0.1002 mol) of 1,4-butanediol in 161.0 g of dimethylacetamide dried and purified under reduced pressure, 1-8 g (0.1 mol) of 1,3-bis (isocyanatomethyl) benzene was added while maintaining the temperature at 5 to 10 ° C., and the mixture was reacted at 25 ° C. for 8 hours.
After completion of the reaction, the obtained reaction solution was poured into 1000 g of water to precipitate a polymer compound. This polymer compound was washed twice with methanol and twice with ether, and dried under reduced pressure at 25 ° C. to obtain a polymer compound. The series of reaction procedures were all performed under light-shielding conditions.
Next, 20 g of the resulting polymer compound was dissolved in 280 g of dimethylacetamide, 100 g (0.703 mol) of n-butyl methacrylate was added, and polymerization was performed at 80 ° C. When the conversion rate reached 80%, 20 ° C. Water-cooled to the following.
The obtained solution was poured into a large excess of methanol to elute the polymer into methanol, and it was further washed with water and vacuum dried at 40 ° C. for 48 hours to obtain a polymer. When the obtained polymer was heated to room temperature or higher, it was confirmed by measurement by ESR or the like that radicals were generated in the main chain of the polymer.
This polymer is inferior in thermal stability, and when used as a melt molding material, it was proved from thermal stability evaluation that the main chain of the polymer is decomposed, cleaved and altered.

(Comparative Examples 2 to 17)
In Examples 1 to 16, the polymer compound (S) solution was added to n-butyl methacrylate for dissolution and polymerization, or the styrene monomer was added and kept at the same temperature for no reaction. In place of the polymer solution, the polymer compound (S) solution is poured into a large excess of methanol to precipitate the polymer compound (S) in methanol, which is filtered and washed with water. The polymer compound (S) was obtained in the same manner as in each of the examples except that it was recovered by vacuum drying at 80 ° C. for 24 hours, and each was made into the polymer compound (S) of Comparative Examples 2 to 17, and styrene monomer A polymer was obtained in the same manner as in each of the Examples except that the reaction was not carried out by adding and each of the polymers was used as a polymer of Comparative Examples 2 to 17.

  The polymers of Examples 1 to 8 and Comparative Examples 1 to 9 were evaluated for thermal stability based on the solubility evaluation. Moreover, the solubility with respect to DMF was similarly evaluated about the high molecular compound (S) and polymer which were not melt-kneaded of these Examples and Comparative Examples. The obtained results are shown in Table 4 together with the solubility results of the polymer compound (S).

  The polymers of Examples 1 to 8 were not melt-kneaded (shown as “Polymer” in Table 4) and the melt-molded product was completely dissolved to form a DMF solution having a concentration of 0.04% by mass. I was able to. However, all the polymers that were not melt-kneaded in Comparative Examples 1 to 9 (indicated as “polymer” in Table 4) were completely dissolved in DMF, but the melt-molded products except for Comparative Examples 4, 5, and 7 Insoluble matter was confirmed without dissolving.

The polymer compounds (S) of Comparative Examples 4, 5, and 7 are dissolved in DMF, and the homopolymer composed of 1,3-bis (isocyanatomethyl) benzene and 1,4-butanediol has a number average molecular weight of 0. If it is 5 × 10 ⁴ g / mol or less, it can be dissolved in DMF to make a DMF solution with a concentration of 0.04% by mass, but if it has a number average molecular weight of 1.2 × 10 ⁴ g / mol or more, it will not dissolve. Was confirmed. Furthermore, a urethane homopolymer composed of IPDI and 1,4-butanediol can be dissolved in DMF to form a DMF solution having a concentration of 0.04% by mass when the number average molecular weight is 1.5 × 10 ⁴ g / mol or less. It was also confirmed that it was possible. Therefore, when the polymer of the comparative example 1 (synthesis method by patent document 2) or the polymer of the comparative examples 2-9 is used as a melt molding material, it turned out that it decomposes | disassembles and tears and changes in quality.
On the other hand, the polymer of the present invention was found to be a polymer that is not thermally changed after melt kneading, is thermally stable, and has excellent melt moldability.

The length of one segment of the sequential skeleton shown in Table 4 corresponds to the number average molecular weight [g / mol] of the polymer compound (S), and a value obtained by dividing this by 10 ⁴ is shown.

Moreover, the thermal stability by ESR was evaluated about the polymer of Examples 1-16 and Comparative Examples 1-17.
Stable radicals were not detected in the polymers of Examples 1 to 16, but stable radicals were detected in the polymers of Comparative Examples 1 to 17.

From the above evaluation results, the polymer obtained by the synthesis method according to Patent Document 2 of Comparative Example 1 and the polymer of Comparative Examples 2 to 17 not reacted with the unsaturated monomer (D2) were compared with the polymer of the Example. It has been demonstrated that when the heat stability is low, polymer decomposition and cleavage occur when heated.
On the other hand, the polymer of the present invention has high thermal stability, and even when heated, stable radicals that promote decomposition and cleavage are not detected, and the thermal stability is excellent.

(Example 17)
<Synthesis of polymer compound (S)>
Into a nitrogen-substituted flask, 0.27 g (0.0007 mol) of benzopinacol and 8.85 g (0.0044 mol) of polyethylene glycol (molecular weight 2000 g / mol, hydroxyl groups at both ends) (sometimes referred to as PEG2000) -1.2 g (0.002 mol) of n-butyltin dilaurate was blended and dissolved in 85.5 g of 1-methyl-2-pyrrolidone. Then, 18.8 g (0.1 mol) of 1,3-bis (isocyanatomethyl) benzene was charged into this solution at room temperature, and they were reacted at a reaction temperature of 25 ° C. for 24 hours to obtain a solution of an isocyanate compound. .
Next, a reaction vessel consisting of a flask and a dropping funnel previously purged with nitrogen was prepared. The above-mentioned isocyanate compound solution was charged into the dropping funnel, and 8.7 g (0.0948 mol) of 1,4-butanediol was charged into the flask. Then, the polymerization temperature was set to 60 ° C., and an isocyanate compound solution obtained over 4 hours was added dropwise. Thereafter, the temperature of the reaction solution was raised to 80 ° C. and reacted for 1 hour to obtain a solution of the target polymer compound (S).

<Polymer synthesis>
Into a flask purged with nitrogen in advance, a mixture of 167.2 g of 1-methyl-2-pyrrolidone and 45.5 g (0.45 mol) of methyl methacrylate (sometimes referred to as MMA) was added, and then the above polymer compound ( 123.4 g of the solution of S) was added and dissolved.
Thereafter, polymerization was carried out at a polymerization temperature of 80 ° C. in a nitrogen atmosphere. When the conversion rate of MMA reached 80%, 7.3 g (0.07 mol) of styrene monomer was added, and the mixture was maintained at the same temperature for 9 hours.
The resulting solution was poured into a large excess of methanol to precipitate the polymer in methanol, which was filtered, washed with water, and vacuum dried at 80 ° C. for 24 hours to obtain a polymer.

  The obtained polymer is melt-molded to prepare test pieces, and the value of absorbed energy of these test pieces is measured by the above-described Dynestat impact test, and the tensile fracture strength and tensile strength are measured by the tensile test described above. The elongation at break and tensile modulus were determined. The obtained results are shown in Table 5. Moreover, although the thermal stability by said ESR was evaluated about the obtained polymer, the stable radical was not detected.

(Examples 18 to 19)
A polymer was synthesized in the same manner as in Example 17 except that the composition, the composition ratio, and the mass ratio between the polymer compound and the unsaturated monomer shown in Table 5 were used. In Table 5, “PPG2000” represents polypropylene glycol having a molecular weight of 2000 g / mol having hydroxyl groups at both ends, and “PO” represents polyoxyalkylene glycol. The molar ratio of the number of moles of isocyanate (0.1 mol) used in the synthesis to the number of moles (0.1 mol) of all diol compounds of benzopinacol, 1,4-butanediol and polyether diol was 100: 100.
Further, in the same manner as in Example 17, the absorption energy value, tensile fracture strength, tensile fracture elongation and tensile elastic modulus of the obtained polymer were determined, and thermal stability was evaluated by ESR. Table 6 shows the results of measurement such as the value of absorbed energy and tensile modulus. Moreover, no stable radical was detected in any polymer in the evaluation of thermal stability by ESR.

  From the results shown in Table 6, the polymer of the present invention has a Dynestat impact while maintaining a tensile elastic modulus equivalent to that of PMMA composed of a PMMA chain skeleton (for example, BR-085 (manufactured by Mitsubishi Rayon Co., Ltd .; trade name)). It can be confirmed that the absorbed energy required in the test is improved.

The polymer of the present invention has a sequential skeleton and a chain skeleton, can easily adjust the length of each segment, and is excellent in thermal stability. It also contributes to toughening acrylic resin. Thereby, the polymer of the present invention is excellent in thermal stability, excellent in melt moldability, and can be used for applications such as pressure-sensitive adhesives, adhesives, powder coatings, and compatibilizing agents. It is also expected to have excellent properties as a thermoplastic elastomer. Thermoplastic elastomers, thermoplastic resins, impact modifiers, surfactants, release agents, membranes, slow-acting pharmaceutical carriers, packaging materials, pharmaceuticals It is expected to be widely used for applications such as medical tubes and ecological prostheses.
Moreover, if the manufacturing method of this invention is used, the polymer of this invention can be obtained very easily by a simple reaction system, and the manufacturing method of this invention is suitable for mass production of the polymer of this invention.

It is the figure which showed the relationship between the number average molecular weight of a polymer at the time of carrying out chain polymerization of the unsaturated monomer (D1) in a reference example, and a conversion rate. In Example 2, it is the figure which represented the conversion rate and the number average molecular weight of the obtained polymer with respect to superposition | polymerization time in superposition | polymerization of n-BMA by the high molecular compound (S). The time when styrene was added is represented by →. In Example 3, it is the figure which represented the conversion rate and the number average molecular weight of the obtained polymer with respect to superposition | polymerization time by superposition | polymerization of n-BMA by the high molecular compound (S). The time when styrene was added is represented by →. In Example 4, it is the figure which represented the conversion rate and the number average molecular weight of the obtained polymer with respect to superposition | polymerization time by superposition | polymerization of n-BMA by the high molecular compound (S). The time when styrene was added is represented by →.

Claims (15)

  A polymer compound (S) obtained by sequential polymerization and containing an active structure (T) in the main chain that can initiate radical polymerization of an unsaturated monomer and increase the molecular weight with the polymerization time is represented by an initiator (U ), Chain-polymerize the unsaturated monomer (D1), and then react with another unsaturated monomer (D2) different from the unsaturated monomer (D1). A polymer having a skeleton. The polymer according to claim 1, wherein the active structure (T) is a structure represented by the following general formula (1).

(Wherein R ₁ , R ₂ , R ₃ and R ₄ each independently represents hydrogen or the same or different substituent)   The polymer according to claim 1 or 2, wherein the polymer compound (S) is polyurethane, polyamide or polyester. When the unsaturated monomer (D1) is represented by the following general formula (2), the compound represented by the general formula (3) optimized by the molecular orbital method is used. The polymer according to any one of claims 1 to 3, which is an unsaturated monomer having a bond distance (Ri ¹ ) of a bond indicated by a broken line in the molecular structure that is greater than 1.57 x 10 ^-10 m.

(In the formula, R ₅ , R ₆ , R ₇ and R ₈ each independently represent hydrogen or the same or different substituent.)

(In the formula, R ₅ , R ₆ , R ₇ and R ₈ each independently represent hydrogen or the same or different substituent.) When the unsaturated monomer (D2) is represented by the following general formula (4), the unsaturated monomer (D2) is a compound represented by the general formula (5) optimized by the molecular orbital method. The polymer according to any one of claims 1 to 3, which is an unsaturated monomer having a bond distance (Ri ² ) of a bond indicated by a broken line in the molecular structure having a value of 1.57 × 10 ^-10 m or less.

(In the formula, R ₉ , R ₁₀ , R ₁₁ and R ₁₂ each independently represent hydrogen or the same or different substituent.)

(Wherein R ₉ , R ₁₀ , R ₁₁ and R ₁₂ each independently represents hydrogen or the same or different substituent).   The polymer according to any one of claims 1 to 3, wherein the unsaturated monomer (D1) is methacrylate.   The polymer according to any one of claims 1 to 3, wherein the unsaturated monomer (D2) is styrene. The polymer according to any one of claims 1 to 7, which has a tensile elastic modulus of not less than 5 kJ / m ^{2 and} an absorption energy obtained by a dynastat impact test of not less than 350 MPa.   A polymer compound (S) obtained by sequential polymerization and containing an active structure (T) in the main chain that can initiate radical polymerization of an unsaturated monomer and increase the molecular weight with the polymerization time is represented by an initiator (U ), A method for producing a polymer comprising a step of chain-polymerizing an unsaturated monomer (D1) and then a step of reacting another unsaturated monomer (D2) different from the unsaturated monomer (D1) . The method for producing a polymer according to claim 9, wherein the active structure (T) is a structure represented by the general formula (1).

(Wherein R ₁ , R ₂ , R ₃ and R ₄ each independently represents hydrogen or the same or different substituent)   The method for producing a polymer according to claim 9 or 10, wherein the polymer compound (S) is polyurethane, polyamide or polyester. When the unsaturated monomer (D1) is represented by the following general formula (2), the compound represented by the general formula (3) optimized by the molecular orbital method is used. bond length bond shown by a broken line in the molecular structure (Ri ¹⁾ a polymer according to any one of claims 9 to 11 which is an unsaturated monomer to a value greater than 1.57 × 10 ^-10 m Production method.

(In the formula, R ₉ , R ₁₀ , R ₁₁ and R ₁₂ each independently represent hydrogen or the same or different substituent.)

(Wherein R ₉ , R ₁₀ , R ₁₁ and R ₁₂ each independently represents hydrogen or the same or different substituent). When the unsaturated monomer (D2) is represented by the following general formula (4), the unsaturated monomer (D2) is a compound represented by the general formula (5) optimized by the molecular orbital method. The polymer production according to any one of claims 9 to 11, which is an unsaturated monomer having a bond distance (Ri ² ) of a bond indicated by a broken line in the molecular structure of 1.57 x 10 ^-10 m or less. Method.

(In the formula, R ₉ , R ₁₀ , R ₁₁ and R ₁₂ each independently represent hydrogen or the same or different substituent.)

(Wherein R ₉ , R ₁₀ , R ₁₁ and R ₁₂ each independently represents hydrogen or the same or different substituent).   The method for producing a polymer according to any one of claims 9 to 11, wherein the unsaturated monomer (D1) is methacrylate. The method for producing a polymer according to any one of claims 9 to 11, wherein the unsaturated monomer (D2) is styrene.

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