JP5340556B2 - Method for producing terminal hindered amino group-modified polymer - Google Patents

Description

  The present invention relates to a method for producing a terminal hindered amino group-modified polymer. More specifically, the terminal of a polymer chain comprising an aromatic vinyl compound unit and / or a conjugated diene compound unit is modified with a hindered amino group. The present invention relates to a method for producing a polymer.

  Various molded products of polymers used in agriculture, horticulture, fishing, building materials for inside and outside buildings, household goods, etc. may be directly or indirectly exposed to sunlight or in some cases exposed to wind and rain. It is important to provide light resistance and weather resistance. 2,2,6,6-Tetramethylpiperidine-based compounds conventionally used for improving the light resistance and weather resistance of various polymers, so-called hindered amine compounds, are excellent in the function of capturing radicals generated in the polymer, It is known to impart excellent weather resistance to molded articles made of various polymers and polymer compositions, and is widely used as a weather resistance improver. However, the low molecular weight compounds among these compounds have high volatility, so that the retention is insufficient even when added to various polymers, so-called bleed-out problems occur, and the effect of the addition is sustained. There was a problem. On the other hand, among the above hindered amine compounds, the oligomer type compounds have sufficient retention in the added polymer composition, but they are inferior in dispersibility when added to and mixed with the main polymer, and are uniform. There was a problem that sufficient weather resistance could not be obtained.

  In response to the above problems, for example, a polymer in which a 2,2,6,6-tetramethylpiperidine group is introduced into the side chain of the polymer has been reported (for example, see Patent Documents 1 to 3). However, these polymers are obtained by using a copolymerization reaction or a transesterification reaction, and there are problems such as a low degree of freedom in controlling the composition of the polymer, an increase in steps, and a complicated manufacturing process. I have it.

  In order to remedy this problem, polyolefins in which the ends of polymer chains are modified with 2,2,6,6-tetramethylpiperidine groups have been reported (see, for example, Patent Documents 4 and 5). These polyolefins have polymer chains composed of α-olefin units such as ethylene units and / or propylene units, and have 2,2,6,6-tetramethylpiperidine groups only at the ends. It is excellent in dispersibility in the polyolefin, which is the main component of the composition, and retention in the polymer composition. However, the modified polyolefin needs to be produced using toxic vanadium as a catalyst, and the polymerization process needs to be carried out at a low temperature of 0 ° C. or lower, so that the safety and industrial economy are inferior. .

  In addition to these, for example, a polymer in which the terminal of polybutadiene is modified with 1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine group has been reported (for example, see Patent Document 6). According to the method disclosed herein, a separately prepared terminal carboxylated polybutadiene is treated with oxalyl chloride and then reacted with 1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-ol. A polybutadiene having a terminal modified with a 1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine group can be obtained. However, in this method, it is necessary to use oxalyl chloride which has a risk of generating highly toxic phosgene due to decomposition and may corrode the reaction vessel, so it is difficult to say that it is excellent in safety and industrial economy.

JP 54-21489 A JP-A-57-180616 Japanese Patent No.2695971 Japanese Patent Laid-Open No. 11-246623 JP 2002-265693 A Japanese Patent No. 2913198

  The object of the present invention is to provide a terminal hindered amino group-modified polymer, more specifically, a polymer chain composed of an aromatic vinyl compound unit and / or a conjugated diene compound unit is modified with a hindered amino group. An object of the present invention is to provide a method for producing a polymer excellent in retention in a composition and excellent in industrial economic efficiency.

  As a result of intensive studies, the present inventors have made it possible to react a living polymer obtained by living anion polymerization with a specific hindered amino group-containing alkoxysilane compound, thereby producing a terminal hindered amino group in a method excellent in industrial economics. It has been found that a modified polymer can be obtained.

［式中、Polyは芳香族ビニル化合物単位、及び／又は共役ジエン系化合物単位からなる重合体鎖、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は独立して炭素数１〜３のアルキル基、Ｒ^５は水素原子、炭素数１〜６のアルキル基又はシクロアルキル基、Ｒ^６は炭素数１〜１０のアルキレン基、Ｒ^７は炭素数１〜５のアルキル基、Ｒ^８は水素原子または炭素数１〜５のアルキル基であり、ｎは０以上２以下の整数である。］
で表される末端ヒンダードアミノ基変性重合体の製造方法であって、
芳香族ビニル化合物、及び／又は共役ジエン化合物をリビングアニオン重合して得られるリビングポリマーと、下記一般式（II）；

［式中、Ｒ^１〜Ｒ^４およびＲ^６〜Ｒ^８は上記と同じ。Ｒ^５’は炭素数１〜６のアルキル基又はシクロアルキル基、若しくは炭素数３〜１２のトリアルキルシリル基、ｍは０以上２以下の整数である。］
で表されるアルコキシシラン化合物とを反応させる末端ヒンダードアミノ基変性重合体の製造方法である。
That is, the present invention provides the following general formula (I):

[Wherein, Poly is a polymer chain comprising an aromatic vinyl compound unit and / or a conjugated diene compound unit, R ¹ , R ² , R ³ and R ⁴ are each independently an alkyl group having 1 to 3 carbon atoms, R ⁵ is a hydrogen atom, an alkyl or cycloalkyl group having 1 to ⁶ carbon atoms, R ⁶ is an alkylene group having 1 to 10 carbon atoms, R ⁷ is an alkyl group having 1 to 5 carbon atoms, R ⁸ is a hydrogen atom or carbon N is an integer of 0 or more and 2 or less. ]
A process for producing a terminal hindered amino group-modified polymer represented by:
A living polymer obtained by living anionic polymerization of an aromatic vinyl compound and / or a conjugated diene compound, and the following general formula (II);

[Wherein, R ^{1 to} R ⁴ and R ^{6 to} R ⁸ are the same as above. R ⁵ 'is an alkyl group or a cycloalkyl group, or a trialkylsilyl group having 3 to 12 carbon atoms having a carbon number of 1 to 6, m is 0 to 2 integer. ]
The terminal hindered amino group modified polymer is made to react with the alkoxysilane compound represented by the formula:

  According to the production method of the present invention, the terminal hindered amino group-modified polymer is produced by a method excellent in industrial economics by using a living anion polymerization method and a mild alkoxysilane compound which are generally practiced industrially. Can be manufactured directly.

［式中、Polyは芳香族ビニル化合物単位、及び／又は共役ジエン系化合物単位からなる重合体鎖、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は独立して炭素数１〜３のアルキル基、Ｒ^５は水素原子、炭素数１〜６のアルキル基又はシクロアルキル基、Ｒ^６は炭素数１〜１０のアルキレン基、Ｒ^７は炭素数１〜５のアルキル基、Ｒ^８は水素原子または炭素数１〜５のアルキル基であり、ｎは０以上２以下の整数である。］
で表される末端ヒンダードアミノ基変性重合体である。 The present invention is described in detail below.
The terminal hindered amino group-modified polymer produced by the production method of the present invention is represented by the following general formula (I):

[Wherein, Poly is a polymer chain comprising an aromatic vinyl compound unit and / or a conjugated diene compound unit, R ¹ , R ² , R ³ and R ⁴ are each independently an alkyl group having 1 to 3 carbon atoms, R ⁵ is a hydrogen atom, an alkyl or cycloalkyl group having 1 to ⁶ carbon atoms, R ⁶ is an alkylene group having 1 to 10 carbon atoms, R ⁷ is an alkyl group having 1 to 5 carbon atoms, R ⁸ is a hydrogen atom or carbon N is an integer of 0 or more and 2 or less. ]
Is a terminal hindered amino group-modified polymer represented by the formula:

［式中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は独立して炭素数１〜３のアルキル基、Ｒ^５は水素原子、炭素数１〜６のアルキル基又はシクロアルキル基である]
で表される基を指す。 In the present invention, the hindered amino group is the following general formula (III);

[Wherein R ¹ , R ² , R ³ and R ⁴ are independently an alkyl group having 1 to 3 carbon atoms, and R ⁵ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group]
The group represented by these.

  In the general formula (I), Poly represents a polymer chain composed of an aromatic vinyl compound unit and / or a conjugated diene compound unit. Examples of the aromatic vinyl compound include styrene, 4-methylstyrene, 4-t-butylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 4-t-butoxystyrene, vinylnaphthalene, and vinylanthracene. Styrene compounds which may have a substituent on the aromatic ring such as α-methylstyrene, α-ethylstyrene, α-substituted styrene compounds such as 1,1-diphenylethylene, 4, α-dimethylstyrene, etc. And a styrene-based compound having a substituent in the α-position and the aromatic ring. Of these, styrene, 4-methylstyrene, and α-methylstyrene are preferable from the viewpoint of ease of polymerization, and styrene is preferable from the viewpoint of industrial economy. These may be used alone or in combination of two or more.

  Examples of the conjugated diene compound include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 3,4-dimethyl-1,3-pentadiene, 1,3-cyclohexadiene, and the like. It is done. Among these, 1,3-butadiene and isoprene are preferable from the viewpoint of availability and industrial economic efficiency. These may be used alone or in combination of two or more.

  When the polymer chain is a copolymer composed of two or more types of structural units, the chain structure is not particularly limited, but examples of specific chain structures include random chain, block chain, and tapered chain. It is done. These can be appropriately determined according to the usage form and purpose of the terminal hindered amino group-modified polymer.

  When the polymer chain is a copolymer composed of two or more types of structural units, the composition ratio is not particularly limited, and can be appropriately determined according to the usage form and purpose of the terminal hindered amino group-modified polymer. it can.

In the hindered amino group in the general formula (I), R ¹ , R ² , R ³ and R ⁴ represent an alkyl group having 1 to 3 carbon atoms. These may all be the same or different, but are preferably all methyl groups from the viewpoint of industrial economy in the production of the terminal hindered amino group-modified polymer.

In the general formula (I), R ⁵ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group. Among these, a hydrogen atom or a methyl group is preferable from the viewpoint of performance as a weather resistance improver of the terminal hindered amino group-modified polymer, and a methyl group is preferable from the viewpoint of ease of production.

In the general formula (I), R ⁶ represents an alkylene group having 1 to 10 carbon atoms. There is no particular limitation as long as this condition is satisfied, but from the viewpoint of industrial economy in the production of the terminal hindered amino group-modified polymer, an alkylene group having 1 to 5 carbon atoms is preferable, and a propylene group It is more preferable.

In the general formula (I), R ⁷ represents an alkyl group having 1 to 5 carbon atoms. There is no particular limitation as long as this condition is satisfied, but it is preferably 1 to 3 carbon atoms, more preferably a methyl group from the viewpoint of ease of production of the terminal hindered amino group-modified polymer and industrial economy. is there.

In the general formula (I), R ⁸ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Although there is no particular limitation as long as this condition is satisfied, it is preferably a hydrogen atom, a methyl group, or an ethyl group from the viewpoint of ease of production of a terminal hindered amino group-modified polymer and industrial economy, and storage stability From the viewpoint of properties, an ethyl group is more preferable.

［式中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は独立して炭素数１〜３のアルキル基、Ｒ^５’は炭素数１〜６のアルキル基又はシクロアルキル基、若しくは炭素数３〜１２のトリアルキルシリル基、Ｒ^６は炭素数１〜１０のアルキレン基、Ｒ^７は炭素数１〜５のアルキル基、Ｒ^８は水素原子または炭素数１〜５のアルキル基であり、ｍは０以上２以下の整数である。］
で表されるアルコキシシラン化合物とを反応させる。
In the method for producing a terminal hindered amino group-modified polymer of the present invention, an aromatic vinyl compound, and / or from the viewpoint of being able to increase the number of hindered amino groups contained in one obtained polymer chain and ease of production, and / or Or a living polymer obtained by living anion polymerization of a conjugated diene compound, and the following general formula (II):

^{Wherein, R 1, R 2, R} 3 and ^{R 4} are independently an alkyl group having 1 to 3 carbon atoms, ^{R 5} 'is an alkyl group or a cycloalkyl group having a carbon number of 1-6, or 3 carbon 12 trialkylsilyl groups, R ⁶ is an alkylene group having 1 to 10 carbon atoms, R ⁷ is an alkyl group having 1 to 5 carbon atoms, R ⁸ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, m is It is an integer of 0 or more and 2 or less. ]
The alkoxysilane compound represented by these is made to react.

In the general formula (II), preferred chemical structures of R ¹ , R ² , R ³ , R ⁴ and R ⁶ , R ⁷ , R ⁸ are the same as those described in the general formula (I).

In the general formula (II), R ⁵ ′ represents an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group, or a trialkylsilyl group having 3 to 12 carbon atoms. When R ⁵ ′ is an alkyl group or a cycloalkyl group, there is no particular limitation as long as it has 1 to 6 carbon atoms, but carbon is used from the viewpoint of the performance as a weather resistance improver of the obtained terminal hindered amino group-modified polymer. A C 1-3 alkyl group is preferred, and a methyl group is more preferred.

  In the general formula (II), m is not particularly limited as long as m is an integer of 0 or more and 2 or less, but m is 1 or 2 from the viewpoint of suppressing the coupling reaction by 2 or 3 molecules of living polymer. M is preferably 1 from the viewpoint of industrial economy.

In living anion polymerization using an aromatic vinyl compound and / or a conjugated diene compound as a monomer, it is preferably 0 to 100 ° C. under an atmosphere of an inert gas such as nitrogen or argon under normal pressure or pressure. Is preferably employed at a temperature of 20 to 70 ° C. by adding an aromatic vinyl compound and / or a conjugated diene compound to an organic solvent solution of an anionic polymerization initiator.
As the anionic polymerization initiator at that time, conventionally known anionic polymerization initiators such as alkyllithium such as butyllithium, ethyllithium and methyllithium, and an alkyllithium bimolecular adduct of diisopropylbenzene can be used. These anionic polymerization initiators may be used alone or in combination of two or more. Among them, butyl lithium, particularly sec-butyl lithium, is preferably used from the viewpoint of the yield of the polymer, the polymerization initiation rate, and the like. The amount of the anionic polymerization initiator used is generally 0.05 to 7% by mass, particularly 0.08 to 3% by mass, based on the total mass of the monomers, such as the molecular weight of the resulting polymer. It is preferable from the point.
Examples of the organic solvent for conducting the living anion polymerization include hydrocarbon solvents such as cyclohexane, toluene, and benzene, ether solvents such as tetrahydrofuran and 1,4-dioxane, and the like. Or may be used in combination of two or more. Of these, hydrocarbon solvents such as cyclohexane and toluene are preferably used because they have few side reactions. The amount of the organic solvent used is preferably about 0.1 to 20 ml, particularly about 1 to 5 ml with respect to 1 g of the monomer, from the viewpoints of easiness of stirring, production cost and the like.
In conducting living anionic polymerization, a small amount of polar compound is added for the purpose of improving the polymerization rate, or for controlling the coupling mode of the conjugated diene compound and the chain mode of the aromatic vinyl compound and the conjugated diene compound. Examples thereof include diethyl ether, monoglyme, diglyme, tetrahydrofuran, dimethoxyethane, triethylamine, N, N, N ′, N′-tetramethylethylenediamine and the like. These may be used alone or in combination of two or more.

  In performing the reaction between the living polymer obtained above and the alkoxysilane compound represented by the general formula (II), a method of adding an organic solvent solution of the living polymer to the alkoxysilane compound, or an organic solvent solution thereof, or A method of adding alkoxysilane or an organic solvent solution thereof to the organic solvent solution of the living polymer can be employed. The reaction conditions such as the organic solvent, reaction temperature, and pressure used at this time are preferably in accordance with the above-described living anionic polymerization method in order to suppress side reactions and to promote the reaction effectively.

  In carrying out the reaction between the living polymer and the alkoxysilane compound, the ratio of the amount used is that the alkoxysilane compound is 0.5 to 10 mol with respect to 1 mol of the living polymer. It is preferable from the viewpoint of realization, and is preferably 1 to 10 mol from the viewpoint of suppression of the coupling reaction between living polymers. Furthermore, from the viewpoint of industrial economy, the amount of the alkoxysilane compound used is more preferably 1 to 3 moles per mole of living polymer.

  In the terminal hindered amino group-modified polymer obtained by the present invention, the terminal is modified with a hindered amino group as long as the effect is not significantly impaired in terms of the reaction rate of the reaction for introducing the hindered amino group. Although it may contain a polymer that has not been made, the number of hindered amino groups contained in one polymer chain is preferably 0.7 or more, and performance as a weather resistance improver From the viewpoint of the above, it is more preferably 0.8 or more. In addition, one polymer per molecule is added to both ends of the linear polymer chain and each end of the star polymer by a method such as producing a polymer with a bifunctional or higher polyfunctional living polymerization initiator. It may have more than hindered amino groups.

  The terminal hindered amino group-modified polymer obtained by the present invention preferably has a number average molecular weight in the range of 1000 to 100,000 in order to effectively exhibit the effect as a weather resistance improver. When the number average molecular weight is less than this range, the retentivity when the modified polymer is blended with another polymer to form a polymer composition may be insufficient, and bleed-out may easily occur. On the other hand, when the number average molecular weight exceeds this range, the amount of hindered amino groups is relatively lowered, and the effect as a weather resistance improver may be lowered. From these viewpoints, the number average molecular weight of the terminal hindered amino group-modified polymer is preferably in the range of 2000 to 80000, and more preferably in the range of 3000 to 50000.

In the general formula (II), when R ⁵ ′ is a trialkylsilyl group having 3 to 12 carbon atoms, the trialkylsilyl group acts as a protective group, and the reaction product of the living polymer and the alkoxysilane compound is removed. By adding a step of performing a protection reaction, it can be converted into a secondary hindered amino group, that is, an N—H bond can be generated. There is no particular limitation on the deprotecting agent to be used. For example, proton acidic compounds such as hydrochloric acid, sulfonic acid and carboxylic acid, Lewis acidic compounds such as boron trifluoride and tin tetrachloride, tetrabutylammonium fluoride, ammonium fluoride, An alkaline fluorine ion-containing compound such as potassium fluoride can be used. Among these, proton acidic compounds such as hydrochloric acid and sulfonic acid are preferably used from the viewpoint of easy deprotection reaction. Examples of the trialkylsilyl group include a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a tributylsilyl group, a tri-t-butylsilyl group, and a t-butyldimethylsilyl group. Among these, a trimethylsilyl group, a triethylsilyl group, and a t-butyldimethylsilyl group are preferable from the viewpoint of easy deprotection, and a t-butyldimethylsilyl group is preferable from the viewpoint of storage stability of the alkoxysilane compound. More preferably.

In the case where the terminal hindered amino group-modified polymer obtained by the present invention contains a conjugated diene compound unit, a step of hydrogenating a part or all thereof (hereinafter sometimes referred to as “hydrogenation”) is further performed. You may have. Thereby, the low polarity and the weather resistance improvement of the terminal hindered amino group modified polymer obtained can be aimed at. Examples of the hydrogenation method include a method in which a terminal hindered amino group-modified polymer is dissolved in an organic solvent and hydrogen is reacted in the presence of a hydrogenation catalyst. Examples of the organic solvent used at this time include hydrocarbon solvents such as cyclohexane, toluene, and benzene, ether solvents such as tetrahydrofuran and 1,4-dioxane, and these organic solvents can be used alone. Alternatively, two or more types may be used in combination, but cyclohexane is preferred from the viewpoint of a smooth hydrogenation reaction.
Examples of hydrogenation catalysts for hydrogenation include nickel-based Ziegler catalysts, Ziegler catalysts such as cobalt-based Ziegler catalysts, and metallocene catalysts such as titanocene catalysts. These hydrogenation catalysts can be used alone. Although it may be used, or two or more kinds may be used in combination, a nickel-based Ziegler catalyst is preferred from the viewpoint of industrial economy and ease of handling.
Although there is no restriction | limiting in particular in the preparation method of a nickel-type Ziegler catalyst, For example, it can prepare by making nickel salt of organic acid and a trialkylaluminum react.
The temperature at the time of hydrogenation is 0 to 100 ° C., the hydrogen pressure is 0.1 to 100 kgf / cm ² , and further 20 to 70 ° C. and the hydrogen pressure is 5 to 30 kgf / cm ² . It is preferable to carry out the process from the viewpoint of smooth hydrogenation reaction and industrial economy.

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

In addition, measuring instruments and measuring methods used in the following examples and the like are described.
(1) Analytical instrument for molecular structure of terminal hindered amino group-modified polymer by nuclear magnetic resonance spectrum ( ¹ H-NMR spectrum): JEOL nuclear magnetic resonance apparatus (JNM-LA400)
Solvent: Deuterated chloroform (2) Number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) measuring instrument by gel permeation chromatography (GPC): Tosoh gel permeation chromatograph (HLC-8020)
Column: Tosoh TSKgel GMHXL, G4000HXL and G5000HXL connected in series Eluent: Tetrahydrofuran, flow rate 1.0 ml / min Column temperature: 40 ° C
Calibration curve: Created using standard polystyrene Detection method: Differential refractive index (RI)
(3) Equipment for measuring the number of terminal hindered amino groups at the polymer end by high performance liquid chromatography (HPLC): Shimadzu Corporation high performance liquid chromatograph (LC-10AD)
Detector: Polymer Laboratories' Evaporative Light Scattering Detector (PL-EMD960)
Eluent: After holding for 5 minutes at ethyl acetate / cyclohexane = 30/70 (volume ratio), after linearly increasing the volume ratio of ethyl acetate to ethyl acetate / cyclohexane = 100/0 (volume ratio) over 35 minutes Hold for 20 minutes at 100/0, ethyl acetate / cyclohexane. Flow rate 1.0ml / min.
Column temperature: 40 ° C
(4) Crosslinking test of polymer composition
In accordance with JIS K6300, using a curast meter ("JSR type curast meter UMT-071" manufactured by Imanaka Kikai Kogyo Co., Ltd.)
In accordance with JIS K6250, measurement was performed using a hardness meter (“DUROMETER HARDNESS Type A” manufactured by Kobunshi Keiki Co., Ltd.), and 90% crosslinking time (T90) was measured.
(5) Measurement of modulus, tensile breaking strength, and tensile breaking elongation A dumbbell-shaped No. 3 test piece was punched from a 1 mm thick sheet produced by compression molding, and a universal material testing machine (in accordance with JIS K6251) Using “TM-MS-134” manufactured by Instron Japan Co., Ltd.), measurement was performed under the condition of 500 mm / min.
(6) Accelerated exposure test A dumbbell-shaped No. 3 test piece was punched out from a 1 mm thick sheet produced by compression molding, and an exposure test was conducted in accordance with JIS K7350-4. For the exposure test, a sunshine super long life weather meter ("WEL-SUN-HC-B" manufactured by Suga Test Instruments Co., Ltd.) was used, and the spray cycle was set to 12 minutes / 1 hour, humidity 50%, black panel temperature 63 ° C, An 800 hour accelerated exposure test was conducted. The modulus, tensile rupture strength, and tensile rupture elongation of the test piece after the accelerated exposure test were expressed as retention ratios when the value before the accelerated exposure test was taken as 100. When the modulus retention is less than 100, it means that the test piece is softened, and when it exceeds 100, it means that the test piece is cured, and the closer to 100, the better the flexibility retention. Further, when the tensile rupture strength and tensile rupture elongation retention ratio are less than 100, it indicates that the mechanical strength is lowered. The closer to 100, the better the mechanical strength retention.

Example 1 Production of terminal hindered amino group-modified polystyrene (I)
(1) 17 mL of cyclohexane was charged in a glass reaction vessel sufficiently purged with nitrogen, heated to 50 ° C., and then 0.5 mL of a cyclohexane solution of sec-butyllithium (0.65 mmol as sec-butyllithium). ) And 3.58 mL (31.2 mmol) of styrene were added and the polymerization reaction was continued for 30 minutes. Further, 10 mL of cyclohexane solution of 4- [3- (diethoxymethylsilyl) propoxy] -1,2,2,6,6-pentamethylpiperidine (manufactured by Shin-Etsu Chemical Co., Ltd.) (4- [3- ( Diethoxymethylsilyl) propoxy] -1,2,2,6,6-pentamethylpiperidine (1.3 mmol) is added and stirred at 50 ° C. for 5 minutes, followed by addition of a small amount of degassed methanol. Stopped. The obtained polymer solution was washed with water and then reprecipitated with a large excess of methanol to obtain terminal hindered amino group-modified polystyrene.
(2) As a result of GPC measurement on the obtained terminal hindered amino group-modified polystyrene, the number average molecular weight (Mn) was 5270, and the ratio of the weight average molecular weight (Mw) to Mn (hereinafter referred to as molecular weight distribution) was 1.06. The number of hindered amino groups per polystyrene molecule determined by HPLC measurement was 0.81.

Example 2 Production of terminal hindered amino group-modified polyisoprene (I)
(1) A terminal hindered amino group-modified polyisoprene was obtained in the same manner as in Example 1 except that 3.12 mL (31.2 mmol) of isoprene was used instead of styrene.
(2) As a result of GPC measurement of the obtained terminal hindered amino group-modified polyisoprene, Mn = 4980, Mw / Mn = 1.23, and a bimodal peak was observed. The area of the high molecular weight peak was 14%. The degree of vinylation determined by NMR measurement was 6%, and the number of hindered amino groups per molecule of polyisoprene determined by HPLC measurement was 0.78.

Example 3 Production of terminal hindered amino group-modified polyisoprene (II)
(1) In Example 2, instead of cyclohexane solution of 4- [3- (diethoxymethylsilyl) propoxy] -1,2,2,6,6-pentamethylpiperidine, 4- [3- (ethoxydimethylsilyl) ) Propoxy] -1,2,2,6,6-pentamethylpiperidine (manufactured by Shin-Etsu Chemical Co., Ltd.) in 10 mL of cyclohexane (4- [3- (ethoxydimethylsilyl) propoxy] -1,2,2,6, A terminal hindered amino group-modified polyisoprene was obtained in the same manner except that 1.3 mmol) was used as 6-pentamethylpiperidine.
(2) GPC measurement was performed on the obtained terminal hindered amino group-modified polyisoprene. As a result, Mn = 4740 and Mw / Mn = 1.05. The number of hindered amino groups per polyisoprene molecule determined by HPLC measurement was 0.69.

Example 4 Production of terminal hindered amino group-modified polystyrene (II)
(1) In Example 1, instead of a cyclohexane solution of 4- [3- (diethoxymethylsilyl) propoxy] -1,2,2,6,6-pentamethylpiperidine, 4- [3- (ethoxydimethylsilyl) ) Propoxy] -2,2,6,6-tetramethyl-1-trimethylsilylpiperidine (manufactured by Shin-Etsu Chemical Co., Ltd.) in 10 mL of cyclohexane (4- [3- (ethoxydimethylsilyl) propoxy] -2,2,6, A polymer solution was obtained in the same manner except that 1.3 mmol) was used as 6-tetramethyl-1-trimethylsilylpiperidine. A portion of the polymer solution obtained was collected, dried, and subjected to NMR measurement. As a result, it was confirmed that 0.8 trimethylsilyl groups were present per polystyrene molecule, and the N—H bond was protected by the trimethylsilyl groups. It was in a state that has been.
(2) To the obtained polymer solution, 10 mL of 0.1N hydrochloric acid aqueous solution was added, and after deprotection reaction by stirring at 30 ° C. for 2 hours, terminal hindered amino groups were reprecipitated with a large excess of methanol. Modified polystyrene was obtained.
(3) As a result of GPC measurement for the obtained terminal hindered amino group-modified polystyrene, Mn = 5390, Mw / Mn = 1.12 and a bimodal peak was observed. The area of the high molecular weight peak was 4% of the total peak area. Moreover, the peak derived from a trimethylsilyl group was not observed from NMR measurement, and it confirmed that the N-H bond was produced | generated. The number of hindered amino groups per polyisoprene molecule determined by HPLC measurement was 0.82.

Example 5 Production of terminal hindered amino group-modified polystyrene-b-polybutadiene-b-polystyrene (1) 750 mL of cyclohexane and 6.41 mL of a cyclohexane solution of sec-butyllithium in a 1.5 L autoclave sufficiently substituted with nitrogen (8.33 mmol as sec-butyllithium) and 2.03 mL (25 mmol) of tetrahydrofuran were charged and heated to 50 ° C., and then 37.5 g (360 mmol) of styrene was added to the vessel to complete the polymerization reaction. Next, 175 g (3.24 mol) of butadiene was added to the vessel to complete the polymerization reaction. Thereafter, 37.5 g (360 mmol) of styrene was added to the vessel to complete the polymerization reaction. Furthermore, 34.6 g (10 mmol) of 4- [3- (diethoxymethylsilyl) propoxy] -1,2,2,6,6-pentamethylpiperidine was added to the vessel and stirred at 50 ° C. for 5 minutes. The reaction was stopped by adding a small amount of degassed methanol.
(2) The obtained polymer solution was washed with water and then reprecipitated with a large excess of methanol / acetone mixed solvent to obtain terminal hindered amino group-modified polystyrene-b-polybutadiene-b-polystyrene.
(3) As a result of performing GPC measurement about the obtained terminal hindered amino group modified polystyrene-b-polybutadiene-b-polystyrene, it was Mn = 47100 and Mw / Mn = 1.02. The degree of vinylation determined by NMR measurement was 39%, and the number of hindered amino groups per molecule of polystyrene-b-polybutadiene-b-polystyrene determined by HPLC measurement was 0.89.

<< Example 6 >> Production of terminal hindered amino group-modified polystyrene-b-hydrogenated polybutadiene-b-polystyrene (1) Terminal hindered amino group-modified polystyrene-b- was prepared in the same manner as in Example 5 (1). A cyclohexane solution of polybutadiene-b-polystyrene was obtained.
(2) The obtained polymer solution was transferred to a 3 L autoclave and further diluted with 1 L of cyclohexane. Here, a Ziegler catalyst obtained by reacting nickel octylate and triisobutylaluminum was charged, and the hydrogenation reaction was carried out at 60 ° C. for 8 hours, followed by heating to 80 ° C., followed by 3 hours of hydrogenation reaction. Next, the solution after the reaction was washed to remove the catalyst, and then reprecipitated with a large excess of acetone / methanol mixed solvent to obtain terminal hindered amino group-modified polystyrene-b-hydrogenated polybutadiene-b-polystyrene. .
(3) GPC measurement was performed on the obtained terminal hindered amino group-modified polystyrene-b-hydrogenated polybutadiene-b-polystyrene. As a result, Mn = 48200 and Mw / Mn = 1.02. The number of hindered amino groups per molecule of polystyrene-b-hydrogenated polybutadiene-b-polystyrene determined by HPLC measurement was 0.88.

Example 7 Production of terminal hindered amino group-modified poly (styrene / butadiene) (1) In a 10 L autoclave sufficiently substituted with nitrogen, 4L of cyclohexane, 289.9 mL of cyclohexane solution of sec-butyllithium (sec-butyl) 376.9 mmol as lithium), 28.9 mL (191.4 mmol) of N, N, N ′, N′-tetramethylethylenediamine were charged, heated to 35 ° C., and 275 g of styrene and butadiene previously mixed in the vessel 825 g was intermittently added to complete the polymerization reaction. Thereafter, 140 g (405 mmol) of 4- [3- (diethoxymethylsilyl) propoxy] -1,2,2,6,6-pentamethylpiperidine was added to the vessel and stirred at 35 ° C. for 10 minutes. The reaction was stopped by adding a small amount of degassed methanol.
(2) The obtained polymer solution was washed with water and then reprecipitated with a large excess of methanol / acetone mixed solvent to obtain terminal hindered amino group-modified poly (styrene / butadiene).
(3) GPC measurement was performed on the obtained terminal hindered amino group-modified poly (styrene / butadiene). As a result, Mn = 4770 and Mw / Mn = 1.09. Further, the styrene unit content of the polymer determined by NMR measurement was 27% by mass, and the degree of vinylation of the butadiene portion was 69%. The number of hindered amino groups per molecule of poly (styrene / butadiene) determined by HPLC measurement was 0.85.

<< Example 8 >> Production of terminal hindered amino group-modified hydrogenated poly (styrene / butadiene) (1) The same operation as in Example 7 (1) was carried out to prepare a terminal hindered amino group-modified poly (styrene / butadiene). A cyclohexane solution was obtained.
(2) The obtained polymer solution was diluted with 1.5 L of cyclohexane. Here, a Ziegler catalyst obtained by reacting nickel octylate and triisobutylaluminum was charged, and a hydrogenation reaction was carried out at 35 ° C. for 2 hours. Next, the solution after the reaction was washed to remove the catalyst, and then reprecipitated with a large excess of acetone / methanol mixed solvent to obtain a terminal hindered amino group-modified hydrogenated poly (styrene / butadiene).
(3) The obtained terminal hindered amino group-modified poly (styrene / butadiene) was subjected to GPC measurement. The results were Mn = 4820 and Mw / Mn = 1.09. From NMR measurement, 49% of the butadiene units were hydrogenated. The number of hindered amino groups per molecule of poly (styrene / butadiene) determined by HPLC measurement was 0.85.

Comparative Example 1 Production of Terminal Hindered Amino Group-Modified Polystyrene (III)
(1) 17 mL of cyclohexane was charged in a glass reaction vessel sufficiently purged with nitrogen, heated to 50 ° C., and then 0.5 mL of a cyclohexane solution of sec-butyllithium (0.65 mmol as sec-butyllithium). ) And 3.58 mL (31.2 mmol) of styrene were added to continue the polymerization reaction for 30 minutes, and then a small amount of degassed methanol was added to stop the living polymerization. Furthermore, 10 mL of 4- [3- (diethoxymethylsilyl) propoxy] -1,2,2,6,6-pentamethylpiperidine in cyclohexane (4- [3- (diethoxymethylsilyl) propoxy] After adding 1.3 mmol) as -1,2,2,6,6-pentamethylpiperidine and stirring at 50 ° C. for 5 minutes, a small amount of degassed methanol was added to stop the reaction. The obtained polymer solution was washed with water and then reprecipitated with a large excess of methanol to obtain terminal hindered amino group-modified polystyrene.
(2) As a result of performing GPC measurement about the obtained terminal hindered amino group modified polystyrene, it was Mn = 5140 and Mw / Mn = 1.06. The number of hindered amino groups per polystyrene molecule determined by HPLC measurement was 0.

<Comparative Example 2> Production of terminal hindered amino group-modified polystyrene (IV)
(1) 17 mL of cyclohexane was charged in a glass reaction vessel sufficiently purged with nitrogen, heated to 50 ° C., and then 0.5 mL of a cyclohexane solution of sec-butyllithium (0.65 mmol as sec-butyllithium). ), And 4- [3- (diethoxymethylsilyl) propoxy] -1,2,2,6,6-pentamethylpiperidine in cyclohexane 10 mL (4- [3- (diethoxymethylsilyl) propoxy] -1 , 2,2,6,6-pentamethylpiperidine (1.3 mmol) was added and stirred at 50 ° C. for 5 minutes. Further, 3.58 mL (31.2 mmol) of styrene was added to the vessel and the polymerization reaction was continued at 50 ° C. for 30 minutes, and then a small amount of degassed methanol was added to terminate the polymerization.
(2) As a result of collecting a part of the obtained solution and performing GPC measurement, no polymer was obtained.

Comparative Example 3 Production of terminal hindered amino group-modified polystyrene (V)
(1) 17 mL of cyclohexane was charged in a glass reaction vessel sufficiently purged with nitrogen, heated to 50 ° C., and then 0.5 mL of a cyclohexane solution of sec-butyllithium (0.65 mmol as sec-butyllithium). ) And 3.58 mL of styrene were added and the polymerization reaction was continued for 30 minutes. Further, 10 mL of a tetrahydrofuran solution of 1,2,2,6,6-pentamethyl-4-hydroxypiperidine (1.3 mmol as 1,2,2,6,6-pentamethyl-4-hydroxypiperidine) was added to the container, After continuing the reaction at 50 ° C. for 5 minutes, a small amount of degassed methanol was added to stop the reaction.
(2) As a result of performing GPC measurement about the obtained terminal hindered amino group modified polystyrene, it was Mn = 5160 and Mw / Mn = 1.05. The number of hindered amino groups per polystyrene molecule determined by HPLC measurement was 0.

Comparative Example 4 Production of terminal hindered amino group-modified polystyrene (VI)
(1) In Comparative Example 3, instead of 10 mL of tetrahydrofuran solution of 1,2,2,6,6-pentamethyl-4-hydroxypiperidine, 10 mL of cyclohexane solution of 1,2,2,6,6-pentamethylpiperidine ( A terminal hindered amino group-modified polystyrene was obtained in the same manner as in Comparative Example 3 except that 1.3 mmol) was used as 1,2,2,6,6-pentamethylpiperidine.
(2) As a result of performing GPC measurement about the obtained terminal hindered amino group modified polystyrene, it was Mn = 5230 and Mw / Mn = 1.05. The number of hindered amino groups per polystyrene molecule determined by HPLC measurement was 0.

  As described above, a terminal hindered amino group-modified polymer can be obtained by reacting a living polymer obtained by living anion polymerization with a specific compound. However, when a living polymer is not used, a specific compound is used. If it is not present, it can be seen that a terminal hindered amino group-modified polymer cannot be obtained.

<< Reference Production Example 1 >> Production of poly (styrene / butadiene) (1) In Example 7, 4- [3- (diethoxymethylsilyl) propoxy] -1,2,2,6,6-pentamethylpiperidine was added. A poly (styrene / butadiene) was obtained in the same manner as above except that it was not used.
(2) GPC measurement was performed on the obtained poly (styrene / butadiene). As a result, Mn = 4830 and Mw / Mn = 1.08. The polymer determined by NMR measurement had a styrene unit content of 27% by mass and a butadiene part vinylation degree of 71%.

<< Use Example 1 >> Production of Molded Body (I) Consisting of Polymer Composition (1) Styrene Butadiene Rubber (Emulsion Polymerization SBR1502 manufactured by JSR) 100g, Zinc Hua 1 (Mitsui Metal Mining Co., Ltd.) 3g, stearic acid ( Nippon Oil & Fats Co., Ltd. 1 g, Carbon Black (Showa Cabot Co., Ltd., Shiyo Black N330) 30 g, Aging Prevention Agent (Ouchi Shinsei Chemical Co., Ltd. Nocrack 6C) 1 g, terminal hindered amino group-modified poly produced in Example 7 ( 10 g of styrene / butadiene (containing 1.78 mmol of hindered amino groups) was charged in a lab plast mill (manufactured by Toyo Seiki Co., Ltd.), and kneaded for 5 minutes under the conditions of 150 ° C. and rotor rotation speed 50 rpm. After cooling the obtained kneaded material to room temperature, roll kneading was carried out and a vulcanization accelerator and sulfur were blended to obtain a polymer composition sheet having a thickness of 1 mm.
(2) A part of the obtained sheet was sampled and subjected to a crosslinkability test. The obtained 90% cross-linking time was heat-compressed at 155 ° C. for 5 minutes longer, and a terminal hindered amino group-modified polymer and SBR were co-cross-linked to obtain a molded body comprising a polymer composition having a thickness of 1 mm. .
(3) The obtained molded body was measured for the modulus, tensile strength at break, tensile elongation at break and accelerated exposure test, and the results were as shown in Table 2.

<< Comparative Use Example 1 >> Production of Molded Body (II) Consisting of Polymer Composition (1) In Use Example 1, poly produced in Reference Production Example 1 instead of terminal hindered amino group-modified poly (styrene / butadiene) The same operation was performed except that 10 g of (styrene / butadiene) was used to obtain a polymer composition sheet and a molded body.
(2) The obtained molded body was measured for the modulus, tensile strength at break, tensile elongation at break, and accelerated exposure test, and the results were as shown in Table 2.

<< Comparative Use Example 2 >> Production of Molded Product (III) Containing Polymer Composition (1) In Comparative Use Example 1, 0.53 g of a low molecular weight hindered amine light stabilizer (Tinubin 765 manufactured by Ciba Specialty Chemicals) A polymer composition sheet and a molded product were obtained in the same manner except that 509 having a molecular weight of 509 and a hindered amino group of 2.08 mmol was added.
(2) The obtained molded body was measured for the modulus, tensile strength at break, tensile elongation at break, and accelerated exposure test, and the results were as shown in Table 2.

<< Comparative Use Example 3 >> Production of Molded Product (IV) Consisting of Polymer Composition (1) In Comparative Use Example 1, 0.6 g of medium molecular weight hindered amine light stabilizer (Simasorb 119FL, manufactured by Ciba Specialty Chemicals) A polymer composition sheet and a molded product were obtained in the same manner except that a molecular weight of 2286 and a hindered amino group of 2.10 mmol were added).
(2) The obtained molded body was measured for the modulus, tensile strength at break, tensile elongation at break, and accelerated exposure test, and the results were as shown in Table 2.

  From Table 2, use example 1 using terminal hindered amino group-modified poly (styrene / butadiene) is an accelerated exposure test compared to comparative use example 1 using poly (styrene / butadiene) having no hindered amino group. The retention rate of the tensile strength at break and the tensile elongation at break is significantly high, and the terminal hindered amino group-modified poly (styrene / butadiene) obtained by the present invention can be provided with weather resistance by blending with other polymers. It can be seen that the polymer composition containing the modified polymer of the present invention and the molded product thereof have high weather resistance.

  Furthermore, from Table 2, the use of terminal hindered amino group-modified poly (styrene / butadiene) is used for Comparative Use Example 2 and Comparative Use Example 3 in which a hindered amine light stabilizer having an equivalent amount of hindered amino groups is blended. In Example 1, it can be seen that the modulus retention after the accelerated exposure test is significantly low, and the flexibility retention is excellent. Also in the comparison of the tensile breaking strength and the tensile breaking elongation retention rate after the accelerated exposure test, it is found that the usage example 1 is significantly higher than the comparative usage example 2 and the comparative usage example 3, and the mechanical strength is maintained for a long time. . From these facts, the terminal hindered amino group-modified poly (styrene / butadiene) obtained by the present invention has improved retention in the polymer composition as compared with the low molecular weight and medium molecular weight hindered amine light stabilizers. It can be seen that the polymer composition and the molded product have high weather resistance.

  INDUSTRIAL APPLICABILITY According to the present invention, a terminal hindered amino group-modified polymer that can express high weather resistance over a long period of time in a polymer composition and a molded product thereof is provided by a method excellent in industrial economy.

Claims (3)

The following general formula (I);

[Wherein, Poly is a polymer chain comprising an aromatic vinyl compound unit and / or a conjugated diene compound unit, R ¹ , R ² , R ³ and R ⁴ are each independently an alkyl group having 1 to 3 carbon atoms, R ⁵ is a hydrogen atom, an alkyl or cycloalkyl group having 1 to ⁶ carbon atoms, R ⁶ is an alkylene group having 1 to 10 carbon atoms, R ⁷ is an alkyl group having 1 to 5 carbon atoms, R ⁸ is a hydrogen atom or carbon N is an integer of 0 or more and 2 or less. ]
A process for producing a terminal hindered amino group-modified polymer represented by:
A living polymer obtained by living anionic polymerization of an aromatic vinyl compound and / or a conjugated diene compound, and the following general formula (II);

[Wherein, R ^{1 to} R ⁴ and R ^{6 to} R ⁸ are the same as above. R ⁵ 'is an alkyl group or a cycloalkyl group, or a trialkylsilyl group having 3 to 12 carbon atoms having a carbon number of 1 to 6, m is 0 to 2 integer. ]
The manufacturing method of the terminal hindered amino-group modified polymer with which the alkoxysilane compound represented by these is made to react.
  The production of a terminal hindered amino group-modified polymer according to claim 1, wherein the aromatic vinyl compound is styrene, the conjugated diene compound is butadiene or isoprene, and the resulting polymer has a number average molecular weight of 1,000 to 100,000. Method.   The method for producing a terminal hindered amino group-modified polymer according to claim 1 or 2, wherein the terminal hindered amino group-modified polymer is produced by using at least a conjugated diene compound and further hydrogenating a part or all of the conjugated diene compound unit of the polymer chain.