JPH0411605A - Production of polystyrene having carboxyl group at one terminal - Google Patents
Production of polystyrene having carboxyl group at one terminalInfo
- Publication number
- JPH0411605A JPH0411605A JP11546190A JP11546190A JPH0411605A JP H0411605 A JPH0411605 A JP H0411605A JP 11546190 A JP11546190 A JP 11546190A JP 11546190 A JP11546190 A JP 11546190A JP H0411605 A JPH0411605 A JP H0411605A
- Authority
- JP
- Japan
- Prior art keywords
- polystyrene
- carboxyl group
- polymer
- styrene
- cyclohexane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004793 Polystyrene Substances 0.000 title claims abstract description 37
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 title description 23
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229920000642 polymer Polymers 0.000 claims abstract description 19
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 13
- ZMYIIHDQURVDRB-UHFFFAOYSA-N 1-phenylethenylbenzene Chemical group C=1C=CC=CC=1C(=C)C1=CC=CC=C1 ZMYIIHDQURVDRB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000002900 organolithium compounds Chemical class 0.000 claims abstract description 7
- 239000003999 initiator Substances 0.000 claims abstract description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 20
- 239000001569 carbon dioxide Substances 0.000 claims description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 10
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 abstract description 5
- 230000000379 polymerizing effect Effects 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 3
- 239000000539 dimer Substances 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002879 Lewis base Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 150000007527 lewis bases Chemical class 0.000 description 2
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- -1 i-propyllithium Chemical compound 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- ZLPHTMMGQHNDDQ-UHFFFAOYSA-N lithium;2-methylbutane Chemical compound [Li+].CC(C)C[CH2-] ZLPHTMMGQHNDDQ-UHFFFAOYSA-N 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical group C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は片末端にカルボキシル基を有するポリスチレン
の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing polystyrene having a carboxyl group at one end.
有機リチウムを開始剤としてスチレンのアニオン重合を
行い、得られた片末端にスチリルリチウム基を有するポ
リスチレンに炭酸ガスを反応させることにより、片末端
にカルボキシル基を有するポリスチレンを製造すること
は公知である（特公昭４２−２４１７４号公報； Ｊ、
Ｐｏ１ｙ＋ｗ、Ｓｃｉ、、ＰａｒｔＡ １９６Ｃ２，４
５４５； Ｊ、Ａｄｖ Ｐｏ１ｙｓ、Ｓｃｉ、、 １９
８４．５６．１等）。しかしながら、この反応は次に示
すような副反応によりスチレンが２量体、３量体化して
ケトンダイマー（Ａ）、トリメリックアルコール（Ｂ）
を副生しやすく、目的とする片末端にカルボキシル基を
有するポリスチレン（Ｃ）を選択的に高純度で得ること
は困難であった。It is known that polystyrene having a carboxyl group at one end can be produced by anionically polymerizing styrene using organolithium as an initiator and reacting the resulting polystyrene having a styryllithium group at one end with carbon dioxide gas. (Special Publication No. 42-24174; J.
Po1y+w, Sci,, Part A 196C2,4
545; J, Adv Polys, Sci, 19
84.56.1 etc.). However, this reaction causes styrene to dimerize and trimerize due to the following side reactions, resulting in ketone dimer (A) and trimeric alcohol (B).
is likely to be produced as a by-product, and it has been difficult to selectively obtain the desired polystyrene (C) having a carboxyl group at one end with high purity.
は酸処理を示す）
上記の問題点を解決するために、テトラヒドロフラン／
ベンゼン混合溶媒を使用したり、Ｎ、Ｎ。indicates acid treatment) In order to solve the above problems, tetrahydrofuran/
Using a benzene mixed solvent, N,N.
Ｎ’ Ｎ’−テトラメチレンジアミン（ＴＭＥＤＡ）
のようなルイス塩基を添加するなどして、カルボキシル
化された活性末端同士の会合を抑制する方法や、極低温
で凍結乾燥を行ってから炭酸ガスと反応させる方法が提
案されている（Ｊ、 Ｐｏｎｙｓ、 Ｓｃｉ 、 、
Ｐ。N'N'-tetramethylenediamine (TMEDA)
A method of suppressing the association between carboxylated active terminals by adding a Lewis base such as a Lewis base, and a method of freeze-drying at an extremely low temperature and then reacting with carbon dioxide gas have been proposed (J, Ponys, Sci, ,
P.
１ｙｍ、Ｃｈｅｎ、Ｅｄ、１９８０．１８．１９４５
； Ｍａｋｒｏ＊ｏ１．Ｃｈｅ＋ｗ、 １９８２゜１Ｂ
３．２０７１ ； Ｍａｋｒｏｍｏｌｅｃｕｌｅｓ １
９８９．２２．８５）が、これらの方法は実験室的には
可能であっても、工業的には実施が非常に困難（極低温
での凍結乾燥）である、経済的に不利（混合溶媒の使用
）である、製品の精製が困難（ＴＨＥＤＡの除去）であ
る、等の問題を有していた。1ym, Chen, Ed, 1980.18.1945
; Makro*o1. Che+w, 1982゜1B
3.2071 ; Makromolecules 1
989.22.85), but although these methods are possible in the laboratory, they are very difficult to implement industrially (freeze-drying at cryogenic temperatures) and are economically disadvantageous (mixed solvents). There were problems such as difficulty in product purification (removal of THEDA) and difficulty in purifying the product (removal of THEDA).
しかして、本発明の目的は、工業的に実施可能で経済性
のある片末端カルボキシル基含有ポリスチレンの合成法
を提供しようとするものである。Therefore, an object of the present invention is to provide an industrially feasible and economical method for synthesizing polystyrene containing a carboxyl group at one end.
本発明によれば、上記目的は、有機リチウム化合物を開
始剤として用いてスチレンをアニオン重合させ、得られ
る重合物を１，１−ジフェニルエチレンで処理したのち
、シクロヘキサン中で炭酸ガスと反応させることによっ
て達成される。According to the present invention, the above object is to anionically polymerize styrene using an organolithium compound as an initiator, treat the resulting polymer with 1,1-diphenylethylene, and then react it with carbon dioxide gas in cyclohexane. achieved by.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明においてスチレンのアニオン重合に際し用いられ
る有機リチウム化合物は、式Ｒ−Ｌｉ（式中、Ｒは直鎖
状もしくは分校状の炭素数２〜６のアルキル基を示す）
で表わすことができ、その具体例としてエチルリチウム
、ｎ−プロピルリチウム、ｉ−プロピルリチウム、ｎ−
ブチルリチウム、Ｓ−ブチルリチウム、ｔ−ブチルリチ
ウム、ｎ −アミルリチウム、Ｓ−アミルリチウム、イ
ソアミルリチウム等が挙げれるが、重合反応の開始効率
、工業的な入手のしやすさの点からブチルリチウムが適
当であり、なかでもＳ−ブチルリチウムがスチレンに対
する重合開始能の点から最も好ましい。The organolithium compound used in the anionic polymerization of styrene in the present invention has the formula R-Li (wherein R represents a linear or branched alkyl group having 2 to 6 carbon atoms).
Specific examples thereof include ethyllithium, n-propyllithium, i-propyllithium, and n-propyllithium.
Examples include butyllithium, S-butyllithium, t-butyllithium, n-amyllithium, S-amyllithium, isoamyllithium, etc., but butyllithium is are suitable, and among them, S-butyllithium is the most preferred from the viewpoint of polymerization initiation ability for styrene.
有機リチウム化合物を開始剤とするスチレンのアニオン
重合は、水分および酸素のない状態で、活性水素を有し
ない極性または非極性の溶媒の存在下で行われる。この
ような重合溶媒として、テトラヒドロフラン、ジオキサ
ン、ジエチルエーテル、ベンゼン、トルエン、キシレン
、シクロヘキサン、メチルシクロヘキサン等が挙げられ
るが、後続の炭酸ガスとの反応がシクロヘキサン中で行
われることを考慮すると、シクロヘキサン中でスチレン
の重合反応を行うのが最も望ましい。The anionic polymerization of styrene using an organolithium compound as an initiator is carried out in the absence of moisture and oxygen in the presence of a polar or non-polar solvent without active hydrogen. Examples of such polymerization solvents include tetrahydrofuran, dioxane, diethyl ether, benzene, toluene, xylene, cyclohexane, and methylcyclohexane. Considering that the subsequent reaction with carbon dioxide gas is carried out in cyclohexane, It is most desirable to carry out the styrene polymerization reaction.
有機リチウム化合物の使用量は、目的とするポリスチレ
ンの重合度により異なるが、通常スチレンモノマー１モ
ルに対し０．１ミリモルないし１００ミリモルの範囲で
ある。重合温度は一１００°Ｃから１００°Ｃの範囲で
選択可能であり、低温にする方が分子量分布の狭いポリ
マーが得られるが、取り扱いやすさの点から室温付近で
重合を行うのが好ましい。The amount of the organolithium compound used varies depending on the degree of polymerization of the target polystyrene, but is usually in the range of 0.1 mmol to 100 mmol per mole of styrene monomer. The polymerization temperature can be selected within the range of -100°C to 100°C, and a polymer with a narrower molecular weight distribution can be obtained at a lower temperature, but from the viewpoint of ease of handling, it is preferable to carry out the polymerization at around room temperature.
重合時間は、重合温度、目的とするポリスチレンの重合
度等により異なってくるが、通常１０分〜１０時間であ
るスチレンアニオン重合により片末端にスチリルリチウ
ム基
を有するポリスチレンが得られる。該ポリスチレンの重
合度は特に限定されないが、通常平均分子量で１，００
０から１，０００，０００、好ましくは１０，０００か
ら５００，０００である。The polymerization time varies depending on the polymerization temperature, the desired degree of polymerization of polystyrene, etc., but is usually 10 minutes to 10 hours. Polystyrene having a styryllithium group at one end is obtained by styrene anion polymerization. The degree of polymerization of the polystyrene is not particularly limited, but usually has an average molecular weight of 1,00
0 to 1,000,000, preferably 10,000 to 500,000.
次に片末端にスチリルリチウム基を有するポリスチレン
に炭酸ガスを反応させて、目的とする片末端にカルボキ
シル基を有するポリスチレンを製造する方法について述
べる。Next, a method for producing the desired polystyrene having a carboxyl group at one end by reacting polystyrene having a styryllithium group at one end with carbon dioxide gas will be described.
片末端にスチリルリチウム基を有するポリスチレンの溶
液に、■、１−ジフェニルエチレンをスチルリチウム基
に対し好ましくは１〜５倍モル添加して、先ず活性末端
をジフェニルエチニルリチウム基
に変換する。続いて過剰の炭酸ガスを系に導入し、片末
端にジフェニルエチニルリチウム基を有するポリスチレ
ンと反応させて片末端にリチウムカルボキシレート基を
有するポリスチレンを得る。次にこれを常法にしたがっ
て酸で処理することにより、リチウムが離脱して片末端
にカルボキシル基を有するポリスチレンが得られる。To a solution of polystyrene having a styryllithium group at one end, 1,1-diphenylethylene is added, preferably from 1 to 5 times the mole of the styryllithium group, to first convert the active end to a diphenylethynyllithium group. Subsequently, excess carbon dioxide gas is introduced into the system and reacted with polystyrene having a diphenylethynyllithium group at one end to obtain polystyrene having a lithium carboxylate group at one end. Next, by treating this with an acid according to a conventional method, lithium is removed and polystyrene having a carboxyl group at one end is obtained.
１．１−ジフェニルエチレンの添加から炭酸ガスとの反
応までは、活性末端の失活を防ぐため、反応系中に水分
または酸素のない状態で行う必要があり、反応温度をシ
クロヘキサンの融点である６℃以上６０°Ｃ以下に保つ
のが好ましい。反応時間は通常１，１−ジフェニルエチ
レンの添加から炭酸ガスの導入までが１０分〜２時間で
あり、炭酸ガスの導入から停止までが１０分〜２時間で
ある。また、系中のポリスチレン濃度は高すぎると、前
述したケトンダイマー トリメリックアルコールへの副
反応が起こりやすくなるので３０％以下であるのが好ま
しい。1. The process from the addition of 1-diphenylethylene to the reaction with carbon dioxide gas must be carried out in the absence of moisture or oxygen in the reaction system in order to prevent deactivation of the active end, and the reaction temperature must be kept at the melting point of cyclohexane. It is preferable to maintain the temperature at 6°C or higher and 60°C or lower. The reaction time is usually 10 minutes to 2 hours from the addition of 1,1-diphenylethylene to the introduction of carbon dioxide gas, and 10 minutes to 2 hours from the introduction of carbon dioxide gas until it is stopped. Furthermore, if the polystyrene concentration in the system is too high, the side reaction to the ketone dimer trimeric alcohol described above tends to occur, so it is preferably 30% or less.
こうして得られた片末端にリチウムカルボキシレート基
を有するポリスチレンのシクロヘキサン溶液を塩酸で酸
性にした大量のメタノール中に注いで片末端にカルボキ
シル基を有するポリスチレンを沈澱させ、濾過して取り
出したポリマーを水洗して、生成したＬｉＣｊ！を除去
した後ポリマーを乾燥すれば、目的とする片末端にカル
ボキシル基を有するポリスチレンが得られる。The thus obtained cyclohexane solution of polystyrene having a lithium carboxylate group at one end was poured into a large amount of methanol acidified with hydrochloric acid to precipitate polystyrene having a carboxyl group at one end, and the polymer was filtered out and washed with water. Then, the generated LiCj! By drying the polymer after removing it, the desired polystyrene having a carboxyl group at one end can be obtained.
本発明により、副反応が抑制され、純度の高い片末端カ
ルボキシル基含有ポリスチレンが得られるが、その理由
は、炭酸ガスによるカルボキシル化反応を極端に抑制し
ない程度に活性末端の反応性が弱められ、活性末端同士
の反応による２量化（ケトンダイマーの生成）、３量化
（トリメリックアルコールの生成）が抑制されるためと
考えられる。According to the present invention, side reactions are suppressed and highly pure polystyrene containing a carboxyl group at one end can be obtained. This is thought to be because dimerization (generation of ketone dimer) and trimerization (generation of trimeric alcohol) due to reactions between active ends are suppressed.
本発明によって製造される片末端にカルボキシル基を有
するポリスチレンは、末端のカルボキシル基の反応性を
利用してグラフトポリマー、ブロックポリマーの合成や
プラスチックスゴムの改質剤、あるいはアロイ化成分と
して有用である。Polystyrene having a carboxyl group at one end produced by the present invention is useful for synthesizing graft polymers and block polymers, as a modifier for plastics rubber, or as an alloying component by utilizing the reactivity of the carboxyl group at one end. be.
以下実施例により本発明を具体的に説明する。The present invention will be specifically explained below using Examples.
（実施例１）
あらかじめ乾燥窒素置換した１！オートクレーブに、乾
燥窒素雰囲気下、モレキュラシーブで脱水したシクロヘ
キサン２２０ｇ、ｓ−ブチルリチウムの１２％ヘキサン
溶液１．８６ｍｆ （２，７２５Ｘ１０−３モル）を注
入した。(Example 1) 1 which was replaced with dry nitrogen in advance! 220 g of cyclohexane dehydrated with a molecular sieve and 1.86 mf (2,725×10 −3 mol) of a 12% hexane solution of s-butyllithium were injected into the autoclave under a dry nitrogen atmosphere.
室温で１０分間撹拌後、活性アルミナで脱水したスチレ
ンモノマー５４ ｇ （０，５２４モル） ヲ加工た。After stirring for 10 minutes at room temperature, 54 g (0,524 mol) of styrene monomer dehydrated with activated alumina was processed.
室温（２０〜３０℃）で９０分間攪拌してスチレンの重
合反応を行った後、１．１〜ジフェニルエチレン０．９
６ ｍｌ （５，４５Ｘ １０−３モル）を加え、さら
に３０分間撹拌を行った。続いて乾燥ＣＯ□ガスを反応
器内に導入し、反応液の暗赤色（ジフェニルエチニルア
ニオンに由来）が消えてから更に１０分間攪拌を続けた
。１．１−ジフェニルエチレンの添加からＣＯ□ガスと
の反応までは室温で行った。After stirring at room temperature (20-30°C) for 90 minutes to perform a styrene polymerization reaction, 1.1 to 0.9 diphenylethylene
6 ml (5,45×10 −3 mol) was added and stirring was continued for an additional 30 minutes. Subsequently, dry CO□ gas was introduced into the reactor, and stirring was continued for an additional 10 minutes after the dark red color (derived from diphenylethynyl anion) of the reaction solution disappeared. The steps from addition of 1.1-diphenylethylene to reaction with CO□ gas were carried out at room temperature.
こうして得られた片末端にジフェニルエチニルリチウム
基を有するポリスチレンのシクロヘキサン溶液（ポリマ
ー濃度２０％）を、塩酸で酸性にしたメタノール３ｊ！
中で沈澱させ、濾過して得られたポリマーをメタノール
と水で洗浄後、６０’Ｃで真空乾燥して片末端にカルボ
キシル基を有するスチレンポリマー５４．４ ｇが得ら
れた。The thus obtained cyclohexane solution (polymer concentration 20%) of polystyrene having a diphenylethynyllithium group at one end was acidified with hydrochloric acid and added to methanol 3j!
The polymer obtained by precipitation and filtration was washed with methanol and water, and then vacuum dried at 60'C to obtain 54.4 g of a styrene polymer having a carboxyl group at one end.
こうして得られたポリマーの分析結果を以下に示す。The analysis results of the polymer thus obtained are shown below.
■ゲル透過クロマトグラフィー（ＧＰＣ）による分子量
測定
Ｍｎ＝２．１５Ｘ１０’
（標準ポリスチレンで検量した数平均分子量）Ｍｗ＝２
．３６Ｘ１０’
（標準ポリスチレンで検量した重量平均分子量）■酸価
の測定
フェノールフタレインを指示薬とするＮ ／１０ＫＯＨ
による滴定による。■ Molecular weight measurement by gel permeation chromatography (GPC) Mn = 2.15X10' (number average molecular weight calibrated with standard polystyrene) Mw = 2
．． 36X10' (weight average molecular weight calibrated with standard polystyrene) Measurement of acid value N/10KOH using phenolphthalein as indicator
By titration.
２５９細ｇＫＯＨ／ １００ ｇポリマー■、■より得
られたポリスチレンのカルボキシル基の含有割合は、ｆ
値（官能基価）で０．９９となり、はぼ１（片末端官能
基含有の場合ｆ＝１）に近いものであった。The content of carboxyl groups in the polystyrene obtained from 259 fine g KOH/100 g polymers ■ and ■ is f
The value (functional group value) was 0.99, which was close to 1 (f=1 in the case of one terminal containing a functional group).
（実施例２）
実施例１においてＳ−ブチルリチウムの代わりにｎ−ブ
チルリチウムの１２％ヘキサン溶液０．４０ｍ１（０，
５８６Ｘ １０−’モル）を用い、シクロヘキサン、１
，１−ジフェニルエチレンの量をそれぞれ３０５ｇ、０
．３１ ｔａｉ、（１，７６Ｘ１０−”モル）とする以
外は実施例１と同様にして片末端カルボキシル基含有ポ
リスチレンの合成を行った。得られたポリマー５４．１
ｇの分析値は
Ｍｎ ＝１０．４Ｘ１０’ （ＧＰＣ）Ｍｗ−１１，
９Ｘ１０’ （ＧＰＣ）酸価５２．９ｍｇ ＲＯＢ／
１００ ｇポリマーであり、含有カルボキシル基のｆ
値−０，９８となり、はぼ１に近いものであった。(Example 2) In Example 1, instead of S-butyllithium, 0.40ml of a 12% hexane solution of n-butyllithium (0,
cyclohexane, 1
, 1-diphenylethylene in amounts of 305g and 0, respectively.
．． Polystyrene containing a carboxyl group at one end was synthesized in the same manner as in Example 1, except that the polystyrene was adjusted to 31 tai (1,76 x 10-'' moles).The resulting polymer 54.1
The analysis value of g is Mn = 10.4X10' (GPC) Mw-11,
9X10' (GPC) acid value 52.9mg ROB/
100 g polymer, containing carboxyl group f
The value was -0.98, which was close to 1.
（比較例１）
実施例１において、１．１−ジフェニルエチレンによる
活性末端の変換を行わない以外は実施例１と同様にして
、片末端カルボキシル基含有ポリスチレンの合成を行っ
た。得られたポリマー５４．２ ｇの分析値は、
Ｍｎ＝２．１０Ｘ１０’
Ｍｗ ＝２．３１ Ｘ １０’
ｆ＝０．４８
と片末端カルボキシル基含有率の低いポリスチレンであ
った。(Comparative Example 1) Polystyrene containing a carboxyl group at one end was synthesized in the same manner as in Example 1 except that the active end was not converted with 1,1-diphenylethylene. The analysis values of 54.2 g of the obtained polymer were as follows: Mn = 2.10 x 10' Mw = 2.31 x 10' f = 0.48, indicating that it was polystyrene with a low content of one terminal carboxyl group.
（比較例２）
実施例１において、溶媒としてシクロヘキサンの代わり
にトルエンを用いる以外は実施例１と同様にして、片末
端カルボキシル基含有ポリスチレンの合成を行った。得
られたポリマー５４．３ ｇの分析値は、
Ｍｎ ＝２．２６ Ｘ １０’
Ｍ何＝２．５３Ｘ１０’
Ｊ＝０．５４
であり、片末端カルボキシル基含有率の低いポリスチレ
ンであった。(Comparative Example 2) Polystyrene containing a carboxyl group at one end was synthesized in the same manner as in Example 1 except that toluene was used instead of cyclohexane as the solvent. The analytical values of 54.3 g of the obtained polymer were as follows: Mn = 2.26 x 10' M = 2.53 x 10' J = 0.54, indicating that it was polystyrene with a low content of one terminal carboxyl group.
（比較例３）
実施例１において、溶媒としてシクロヘキサンの代わり
にテトラヒドロフランを用いる以外は実施例１と同様に
して、片末端カルボキシル基含有ポリスチレンの合成を
行った。得られたポリマー５３、９ ｇの分析値は、
Ｍｎ ＝２．０３ Ｘ １０’
Ｍｙ ＝２．２１ Ｘ １０’
Ｊ＝０．３２
と、片末端カルボキシル基含有率の低いポリスチレンで
あった。(Comparative Example 3) Polystyrene containing a carboxyl group at one end was synthesized in the same manner as in Example 1 except that tetrahydrofuran was used instead of cyclohexane as a solvent. The analysis values of 53.9 g of the obtained polymer were as follows: Mn = 2.03 x 10' My = 2.21 x 10' J = 0.32, indicating that it was polystyrene with a low content of one terminal carboxyl group.
（発明の効果）
上記実施例、比較例に示されるが如く、本発明によって
工業的に実施可能でかつ経済的な、高純度の片末端にカ
ルボキシル基を含有するポリスチレンの製造方法が提供
される。(Effects of the Invention) As shown in the above Examples and Comparative Examples, the present invention provides an industrially feasible and economical method for producing polystyrene containing a carboxyl group at one end with high purity. .
Claims (1)
ニオン重合させ、得られる重合物を１，１−ジフェニル
エチレンで処理したのち、シクロヘキサン中で炭酸ガス
と反応させることを特徴とする片末端にカルボキシル基
を有するポリスチレンの製造方法。Styrene is anionically polymerized using an organolithium compound as an initiator, the resulting polymer is treated with 1,1-diphenylethylene, and then reacted with carbon dioxide gas in cyclohexane. A method for producing polystyrene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11546190A JPH0411605A (en) | 1990-04-30 | 1990-04-30 | Production of polystyrene having carboxyl group at one terminal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11546190A JPH0411605A (en) | 1990-04-30 | 1990-04-30 | Production of polystyrene having carboxyl group at one terminal |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0411605A true JPH0411605A (en) | 1992-01-16 |
Family
ID=14663121
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11546190A Pending JPH0411605A (en) | 1990-04-30 | 1990-04-30 | Production of polystyrene having carboxyl group at one terminal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0411605A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010052916A1 (en) | 2008-11-07 | 2010-05-14 | 日本曹達株式会社 | Process for production of polymers having functional groups, and star polymers obtained thereby |
-
1990
- 1990-04-30 JP JP11546190A patent/JPH0411605A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010052916A1 (en) | 2008-11-07 | 2010-05-14 | 日本曹達株式会社 | Process for production of polymers having functional groups, and star polymers obtained thereby |
| US8481650B2 (en) | 2008-11-07 | 2013-07-09 | Nippon Soda Co., Ltd. | Process for production of polymers having functional groups, and star polymers obtained thereby |
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