JPH04213307A - Production of functional group-terminated styrene polymer - Google Patents
Production of functional group-terminated styrene polymerInfo
- Publication number
- JPH04213307A JPH04213307A JP4730191A JP4730191A JPH04213307A JP H04213307 A JPH04213307 A JP H04213307A JP 4730191 A JP4730191 A JP 4730191A JP 4730191 A JP4730191 A JP 4730191A JP H04213307 A JPH04213307 A JP H04213307A
- Authority
- JP
- Japan
- Prior art keywords
- functional group
- polymer
- weight
- polymerization
- molecular weight
- 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.)
- Withdrawn
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 58
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title abstract description 38
- 125000000524 functional group Chemical group 0.000 claims abstract description 42
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 41
- 239000000178 monomer Substances 0.000 claims description 16
- 239000003505 polymerization initiator Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 7
- 239000007870 radical polymerization initiator Substances 0.000 claims description 6
- -1 peroxide compound Chemical class 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 13
- 239000003999 initiator Substances 0.000 abstract description 10
- 150000002978 peroxides Chemical class 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 229920001400 block copolymer Polymers 0.000 description 8
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000007796 conventional method Methods 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 101100490446 Penicillium chrysogenum PCBAB gene Proteins 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229920000578 graft copolymer Polymers 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- HXVNBWAKAOHACI-UHFFFAOYSA-N 2,4-dimethyl-3-pentanone Chemical compound CC(C)C(=O)C(C)C HXVNBWAKAOHACI-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- WHFHDVDXYKOSKI-UHFFFAOYSA-N 1-ethenyl-4-ethylbenzene Chemical compound CCC1=CC=C(C=C)C=C1 WHFHDVDXYKOSKI-UHFFFAOYSA-N 0.000 description 1
- JSZOAYXJRCEYSX-UHFFFAOYSA-N 1-nitropropane Chemical compound CCC[N+]([O-])=O JSZOAYXJRCEYSX-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- CISIJYCKDJSTMX-UHFFFAOYSA-N 2,2-dichloroethenylbenzene Chemical compound ClC(Cl)=CC1=CC=CC=C1 CISIJYCKDJSTMX-UHFFFAOYSA-N 0.000 description 1
- VUDVPVOIALASLB-UHFFFAOYSA-N 2-[(2-cyano-1-hydroxypropan-2-yl)diazenyl]-3-hydroxy-2-methylpropanenitrile Chemical compound OCC(C)(C#N)N=NC(C)(CO)C#N VUDVPVOIALASLB-UHFFFAOYSA-N 0.000 description 1
- FLKBKUFGKQPPRY-UHFFFAOYSA-N 2-[2-[2-[2-[1-(2-hydroxyethyl)-4,5-dihydroimidazol-2-yl]propan-2-yldiazenyl]propan-2-yl]-4,5-dihydroimidazol-1-yl]ethanol;dihydrochloride Chemical compound Cl.Cl.N=1CCN(CCO)C=1C(C)(C)N=NC(C)(C)C1=NCCN1CCO FLKBKUFGKQPPRY-UHFFFAOYSA-N 0.000 description 1
- QRYPVXBEPZJBRR-UHFFFAOYSA-N 2-[[1-amino-1-(4-hydroxyphenyl)imino-2-methylpropan-2-yl]diazenyl]-n'-(4-hydroxyphenyl)-2-methylpropanimidamide;dihydrochloride Chemical compound Cl.Cl.C=1C=C(O)C=CC=1NC(=N)C(C)(C)N=NC(C)(C)C(=N)NC1=CC=C(O)C=C1 QRYPVXBEPZJBRR-UHFFFAOYSA-N 0.000 description 1
- YMOONIIMQBGTDU-UHFFFAOYSA-N 2-bromoethenylbenzene Chemical compound BrC=CC1=CC=CC=C1 YMOONIIMQBGTDU-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- MKTOIPPVFPJEQO-UHFFFAOYSA-N 4-(3-carboxypropanoylperoxy)-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OOC(=O)CCC(O)=O MKTOIPPVFPJEQO-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 229960002380 dibutyl phthalate Drugs 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- XPBOFLGWLULIJL-UHFFFAOYSA-N dioxepane-3,7-dione Chemical compound O=C1CCCC(=O)OO1 XPBOFLGWLULIJL-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-N hexanedioic acid Natural products OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- WVFLGSMUPMVNTQ-UHFFFAOYSA-N n-(2-hydroxyethyl)-2-[[1-(2-hydroxyethylamino)-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCO WVFLGSMUPMVNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- SFXOHDOEOSCUCT-UHFFFAOYSA-N styrene;hydrochloride Chemical compound Cl.C=CC1=CC=CC=C1 SFXOHDOEOSCUCT-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000004260 weight control Methods 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Polymerization Catalysts (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、末端に反応性官能基を
有するスチレン系ポリマーの新規な製造法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel method for producing styrenic polymers having reactive functional groups at their ends.
【０００２】0002
【従来の技術】従来、末端に反応性官能基を含有するス
チレン系ポリマーのラジカル重合法として、分解性二官
能連鎖移動剤の存在下に分解性二官能反応開始剤によっ
てラジカル重合を進行させる方法があり（特公昭３８−
５，９９３号公報）、また、官能基を有するメルカプタ
ン系の連鎖移動剤を連続的又は間欠的に供給してラジカ
ル重合する方法がある（特開昭６１−６４，７０５号公
報、特開昭６２−２１２，４０３号公報）。これらの方
法において、官能基を有する開始剤を用いたり、官能基
を有する連鎖移動剤を連続的又は間欠的に供給するのは
、分子量分布が比較的整っていると共に末端に官能基を
有するスチレン系ポリマーを製造するためである。この
様に、分子量分布が整っており、かつ、末端に官能基を
有するスチレン系ポリマーは、ブロック共重合体やグラ
フト共重合体の製造原料として最適なものであり、近年
高分子製造業界においてその重要性が広く認められてき
ている。[Prior Art] Conventionally, as a method for radical polymerization of styrenic polymers containing reactive functional groups at the terminals, radical polymerization is carried out using a degradable bifunctional reaction initiator in the presence of a degradable bifunctional chain transfer agent. There is (Special Public Service 1977-
5,993), there is also a method of radical polymerization by continuously or intermittently supplying a mercaptan-based chain transfer agent having a functional group (JP-A-61-64,705, JP-A-Sho 64,705). 62-212,403). In these methods, styrene, which has a relatively uniform molecular weight distribution and has a functional group at the end, is used to use an initiator having a functional group or to supply a chain transfer agent having a functional group continuously or intermittently. This is to produce a polymer. In this way, styrene-based polymers with a uniform molecular weight distribution and functional groups at the ends are optimal as raw materials for producing block copolymers and graft copolymers, and in recent years, styrene-based polymers have been gaining popularity in the polymer manufacturing industry. Its importance has been widely recognized.
【０００３】しかしながら、特公昭３８−５，９９３号
公報記載の製造法では、加圧下に４８時間重合させると
いう厳しい反応条件であるにかかわらず、モノマーのポ
リマーへの転化率が４０％前後と低いものである。また
、特開昭６１−６４，７０５号公報や特開昭６２−２１
２，４０３号公報に記載されている方法では、分子量の
コントロールが専ら官能基を有するメルカプタン系連鎖
移動反応に依存しており、その結果として１分子当りの
官能基の平均個数が１前後と少ない。そして、この様な
ポリマー１分子当りの官能基の平均個数の少ないスチレ
ン系ポリマーを、例えばポリエステル、ポリカーボネー
ト等とのブロック共重合体製造用の原料として使用する
と、充分にブロック共重合体が生成されず、ブロック共
重合体を製造するための原料としては適当でない。However, in the production method described in Japanese Patent Publication No. 38-5,993, the conversion rate of monomer to polymer is as low as around 40%, despite the severe reaction conditions of polymerization under pressure for 48 hours. It is something. Also, JP-A No. 61-64,705 and JP-A No. 62-21
In the method described in Publication No. 2,403, molecular weight control relies exclusively on mercaptan-based chain transfer reactions having functional groups, and as a result, the average number of functional groups per molecule is small at around 1. . When such a styrene polymer with a small average number of functional groups per polymer molecule is used as a raw material for producing a block copolymer with, for example, polyester, polycarbonate, etc., a sufficient amount of block copolymer is produced. First, it is not suitable as a raw material for producing block copolymers.
【０００４】一方、前記の問題点を解決する方法として
、特開昭６１−１９，６３０号公報には、官能基を有す
るアゾ系開始剤をスチレンの重合初期にのみ重合反応系
に添加する製造法が提案されている。しかしながら、こ
の方法においては、ポリマーを任意の分子量にコントロ
ールしたり、充分な転化率で製造することが困難である
。On the other hand, as a method for solving the above-mentioned problems, JP-A-61-19630 discloses a production method in which an azo initiator having a functional group is added to the polymerization reaction system only at the initial stage of styrene polymerization. A law is proposed. However, in this method, it is difficult to control the molecular weight of the polymer to a desired value or to produce it at a sufficient conversion rate.
【０００５】このように、従来の方法においては、ポリ
マー１分子当りの官能基の導入量が少ないことに起因し
て、得られたポリマーから規則性の高いブロック共重合
体を製造するのが困難であったり、あるいは、ポリマー
の分子量をコントロールすることやモノマーのポリマー
への充分な転化率を得ることが困難であるという問題が
あった。As described above, in the conventional method, it is difficult to produce a highly regular block copolymer from the obtained polymer due to the small amount of functional groups introduced per polymer molecule. Alternatively, there have been problems in that it is difficult to control the molecular weight of the polymer or to obtain a sufficient conversion rate of monomer to polymer.
【０００６】[0006]
【発明が解決しようとする課題】本発明の目的は、分子
量分布が狭く、制御された分子量を有し、しかも、ポリ
マー１分子当りの末端官能基の平均個数が２に近いスチ
レン系ポリマーを得ることができる新規な製造方法を提
供することにある。SUMMARY OF THE INVENTION An object of the present invention is to obtain a styrenic polymer having a narrow and controlled molecular weight distribution, and in which the average number of terminal functional groups per polymer molecule is close to 2. The objective is to provide a new manufacturing method that can.
【０００７】[0007]
【課題を解決するための手段】すなわち、本発明は、ス
チレン系モノマーを重合する際に、重合反応系内に官能
基を有するラジカル重合開始剤を連続的又は間欠的に供
給することを特徴とする末端に官能基を有するスチレン
系ポリマーの製造法である。[Means for Solving the Problems] That is, the present invention is characterized by continuously or intermittently supplying a radical polymerization initiator having a functional group into the polymerization reaction system when polymerizing a styrenic monomer. This is a method for producing styrenic polymers having functional groups at their terminals.
【０００８】以下、本発明について詳細に説明する。本
発明で使用されるスチレン系モノマーを例示すると、ス
チレンの他に、例えばｏ−、ｍ−、ｐ−メチルスチレン
、ｏ−、ｍ−、ｐ−エチルスチレン、ｐ−ｔｅｒｔ−ブ
チルスチレン等のアルキル化スチレンや、ｏ−、ｍ−、
ｐ−クロルスチレン、ジクロルスチレン、モノブロムス
チレン、ジブロムスチレン等のハロゲン化スチレンや、
α−メチルスチレン等を挙げることができる。スチレン
系モノマーは、その何れか１種を単独で使用できるほか
、２種以上を混合して混合物として使用することもでき
る。The present invention will be explained in detail below. Examples of styrenic monomers used in the present invention include styrene and alkyl styrene such as o-, m-, p-methylstyrene, o-, m-, p-ethylstyrene, and p-tert-butylstyrene. Styrene chloride, o-, m-,
Halogenated styrenes such as p-chlorostyrene, dichlorostyrene, monobromstyrene, dibromstyrene,
Examples include α-methylstyrene. Any one of the styrene monomers can be used alone, or two or more of them can be used as a mixture.
【０００９】また、スチレン系モノマー以外の他のモノ
マーを少量併用使用して共重合させることもできる。こ
の共重合用モノマーとしては、例えばメタクリル酸エス
テル、アクリル酸エステル、アクリロニトリル、無水マ
レイン酸等が使用でき、その使用量としてはモノマー総
量に対して０〜４０重量％が好ましい。[0009] It is also possible to copolymerize by using a small amount of other monomers in addition to the styrene monomer. As the monomer for this copolymerization, for example, methacrylic acid ester, acrylic acid ester, acrylonitrile, maleic anhydride, etc. can be used, and the amount used is preferably 0 to 40% by weight based on the total amount of monomers.
【００１０】次に、本発明で使用されるラジカル重合開
始剤としては、例えば、コハク酸パーオキサイド、グル
タル酸パーオキサイド、アジピン酸パーオキサイド、ｔ
ｅｒｔ−ブチルパーオキサイドマレイン酸等の官能基を
有する過酸化物系化合物、及び４，４’−アゾビス−４
−シアノバレリックアシド（ＡＣＶＡ）、２，２’−ア
ゾビス−〔Ｎ−（４−ヒドロキシフェニル）−２−メチ
ルプロピオナミジン〕ジヒドロクロリド、２，２’−ア
ゾビス−〔Ｎ−（２−ヒドロキシエチル）−２−メチル
プロピオナミジン〕ジヒドロクロリド、２，２’−アゾ
ビス−〔２−（５−ヒドロ−３，４，５，６−テトラヒ
ドロピリミジン−２−イル）プロパン〕ジヒドロクロリ
ド、２，２’−アゾビス−｛２−〔１−（２−ヒドロキ
シエチル）−２−イミダゾリン−２−イル〕プロパン｝
ジヒドロクロリド、２，２’−アゾビス−〔２−メチル
−Ｎ−（２−ヒドロキシエチル）プロピオナミド〕、２
，２’−アゾビス−〔２−（ヒドロキシメチル）プロピ
オニトリル〕等のカルボキシル基、水酸基、アミノ基、
アミド基等の官能基を有するアゾ系開始剤があり、これ
らはその何れか１種を単独で使用できるほか、２種以上
の混合物として使用することもできる。Next, as the radical polymerization initiator used in the present invention, for example, succinic acid peroxide, glutaric acid peroxide, adipic acid peroxide, t
Peroxide compounds having functional groups such as ert-butyl peroxide maleic acid, and 4,4'-azobis-4
-cyanovaleric acid (ACVA), 2,2'-azobis-[N-(4-hydroxyphenyl)-2-methylpropionamidine] dihydrochloride, 2,2'-azobis-[N-(2-hydroxy ethyl)-2-methylpropionamidine]dihydrochloride, 2,2'-azobis-[2-(5-hydro-3,4,5,6-tetrahydropyrimidin-2-yl)propane]dihydrochloride, 2, 2'-azobis-{2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane}
Dihydrochloride, 2,2'-azobis-[2-methyl-N-(2-hydroxyethyl)propionamide], 2
, a carboxyl group such as 2'-azobis-[2-(hydroxymethyl)propionitrile], a hydroxyl group, an amino group,
There are azo initiators having a functional group such as an amide group, and any one of these can be used alone, or a mixture of two or more can be used.
【００１１】また、本発明においては、ポリマー１分子
が有する官能基の平均個数が１．２〜２．０となる範囲
である限り、上記の官能基を有するラジカル重合開始剤
の他に、通常の官能基を持たない過酸化物系開始剤やア
ゾ系開始剤を少量併用しても差し支えない。[0011] In addition, in the present invention, in addition to the radical polymerization initiator having the above-mentioned functional groups, as long as the average number of functional groups possessed by one polymer molecule is within the range of 1.2 to 2.0, There is no problem in using a small amount of a peroxide initiator or an azo initiator that does not have a functional group.
【００１２】この様なラジカル重合開始剤は、通常、有
機溶媒で希釈して重合反応系に添加される。この際の希
釈溶媒としては、スチレン、アルキルスチレン等のスチ
レン系モノマーや半重合物、あるいは重合開始剤に対す
る溶解性の良好な溶媒が好ましい。このような溶媒とし
ては、メチルエチルケトン、ジイソプロピルケトン、Ｎ
，Ｎ−ジメチルホルムアミド、ホルムアミド、テトラヒ
ドロフラン、ジメチルテトラヒドロフラン、１，４−ジ
オキサン、シクロヘキサノン、酢酸エチル、酢酸ブチル
、フタル酸メチル、フタル酸エチル、フタル酸ブチル、
１−ニトロプロパン、二硫化炭素、リン酸トリ−ｎ−ブ
チル等やこれらの混合物を挙げることができる。この際
の重合開始剤の希釈濃度は、希釈溶媒１００重量部に対
して重合開始剤１〜９０重量部、好ましくは３〜４０重
量部となる範囲がよい。Such a radical polymerization initiator is usually diluted with an organic solvent and added to the polymerization reaction system. As the diluting solvent in this case, a solvent having good solubility for styrene monomers and semi-polymers such as styrene and alkylstyrene, or a polymerization initiator is preferable. Such solvents include methyl ethyl ketone, diisopropyl ketone, N
, N-dimethylformamide, formamide, tetrahydrofuran, dimethyltetrahydrofuran, 1,4-dioxane, cyclohexanone, ethyl acetate, butyl acetate, methyl phthalate, ethyl phthalate, butyl phthalate,
Examples include 1-nitropropane, carbon disulfide, tri-n-butyl phosphate, and mixtures thereof. The dilution concentration of the polymerization initiator at this time is preferably in the range of 1 to 90 parts by weight, preferably 3 to 40 parts by weight, per 100 parts by weight of the diluent solvent.
【００１３】重合反応系に対するラジカル重合開始剤の
初期添加量は、全モノマー１００重量部に対して、通常
０．００５〜２５重量部、好ましくは０．０１〜２０重
量部の範囲がよい。０．００５重量部より少ないと重合
速度が低下し、反応に長時間を要することになる。また
、２５重量部を超えると重合速度が増加し、重合反応系
の温度をコンロールすることが困難になり好ましくない
。The initial amount of the radical polymerization initiator added to the polymerization reaction system is generally 0.005 to 25 parts by weight, preferably 0.01 to 20 parts by weight, based on 100 parts by weight of all monomers. If the amount is less than 0.005 parts by weight, the polymerization rate will decrease and the reaction will take a long time. Moreover, if it exceeds 25 parts by weight, the polymerization rate increases and it becomes difficult to control the temperature of the polymerization reaction system, which is not preferable.
【００１４】重合開始後の開始剤供給速度は、用いる重
合開始剤の種類及び初期添加量等により異なり、通常は
モノマー１００重量部に対して１．０×１０−５〜１．
０重量部／分である。一方、重合開始後の重合開始剤の
供給方法は、重合反応全般に亘って連続的に若しくは間
欠的に供給しなければならない。もし、開始剤の供給が
重合反応途中で絶たれると、重合反応系内の開始剤濃度
は反応と共に減少し、そのために高分子量のポリマーが
生成されて分子量分布が広がり、かつモノマーのポリマ
ーへの転化率は減少することになり好ましくない。The initiator supply rate after the start of polymerization varies depending on the type of polymerization initiator used and the initial amount added, and is usually 1.0 x 10 -5 to 1.
0 parts by weight/min. On the other hand, the method for supplying the polymerization initiator after the initiation of polymerization requires that it be supplied continuously or intermittently throughout the entire polymerization reaction. If the supply of initiator is cut off during the polymerization reaction, the initiator concentration in the polymerization reaction system will decrease with the reaction, resulting in the production of high molecular weight polymers, broadening the molecular weight distribution, and increasing the amount of monomer into polymer. This is not preferable because the conversion rate decreases.
【００１５】また、本発明の重合反応条件は、用いる重
合開始剤の種類、使用量等により異なり、通常は攪拌下
に反応温度５０〜２００℃、好ましくは６０〜１６０℃
の範囲で行なわれる。反応時の圧力は、通常、常圧下で
行なわれるが、減圧下でも差し支えない。所望ならば加
圧下にすることもできる。反応時間は、１０分〜２４時
間、好ましくは３０分〜１０時間である。Furthermore, the polymerization reaction conditions of the present invention vary depending on the type of polymerization initiator used, the amount used, etc., and usually the reaction temperature is 50 to 200°C, preferably 60 to 160°C, with stirring.
It is carried out within the range of The pressure during the reaction is usually carried out under normal pressure, but it may also be carried out under reduced pressure. It can also be under pressure if desired. The reaction time is 10 minutes to 24 hours, preferably 30 minutes to 10 hours.
【００１６】本発明方法によって得られる末端に官能基
を有するスチレン系ポリマーは、通常１分子当り平均１
．２個以上２．０個以下の官能基を有している。また、
ゲル浸透クロマトグラフィー（ＧＰＣ）を使用して測定
した数平均分子量（Ｍｎ）は、反応条件によって異なる
が、通常は２，０００〜２００，０００であり、そして
重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）の比（
Ｍｗ／Ｍｎ）は１．５〜４．０である。また、仕込モノ
マーのポリマーへの転化率は、５０％以上で得られる。The styrenic polymer having a functional group at the end obtained by the method of the present invention usually has an average of 1 per molecule.
．． It has 2 or more and 2.0 or less functional groups. Also,
The number average molecular weight (Mn) measured using gel permeation chromatography (GPC) is typically between 2,000 and 200,000, depending on the reaction conditions, and the weight average molecular weight (Mw) and number average molecular weight (Mn) ratio (
Mw/Mn) is 1.5 to 4.0. Further, the conversion rate of the charged monomer to the polymer is obtained at 50% or more.
【００１７】本発明により得られる末端に官能基を有す
るスチレン系ポリマーは、それ自体を機能性樹脂として
利用できるばかりでなく、ブロックコポリマー、グラフ
トコポリマー等の原料としても利用することができる。
従って、この重合体は接着剤、塗料、成形品、樹脂、ア
スファルト類等の改質に極めて有用である。また、本発
明を製法上の立場から見ると、従来法と比較して、常圧
下、短時間で分子量分布が狭いポリマーを高収率で得る
ことが可能である。この結果、純度の高いブロック共重
合体、グラフトポリマー共重合体の原料として利用でき
、かつ工業的な生産性も向上するという特徴を有してい
る。The styrenic polymer having a functional group at the end obtained by the present invention can be used not only as a functional resin itself, but also as a raw material for block copolymers, graft copolymers, etc. Therefore, this polymer is extremely useful for modifying adhesives, paints, molded products, resins, asphalts, etc. Furthermore, when the present invention is viewed from a production method standpoint, it is possible to obtain a polymer with a narrow molecular weight distribution in a high yield in a short time under normal pressure, compared to conventional methods. As a result, it can be used as a raw material for highly pure block copolymers and graft polymer copolymers, and has the characteristics of improved industrial productivity.
【００１８】[0018]
【実施例】以下、実施例及び比較例に基づいて、本発明
を具体的に説明する。なお、以下の実施例及び比較例に
おいて、得られたスチレン系ポリマーのＭｎ及びＭｗは
、単分散ポリスチレン（ウォーターズ社製）でキャリブ
レーションしたゲル浸透クロマトグラフィー（ＧＰＣ）
により、移動相としてテトラヒドロフランを、また、検
出器としてＲＩ検出器を使用し、溶出速度１．０ｍｌ／
ｍｉｎの条件で測定した。また、ポリマー１分子が有す
る末端官能基の平均個数は、実施例１〜６おいては自動
滴定装置〔三菱化成工業（株）製ＧＴ−０５型〕を使用
し、ポリマー溶液を水酸化ナトリウム水溶液で中和滴定
することにより定量した。また、実施例７〜１１おいて
は、以下の様な方法で末端をシリルエーテル化したポリ
マーの １Ｈ−ＮＭＲを測定して末端官能基の平均個数
を定量した。すなわち、ポリスチレン１重量部にＴＨＦ
２０重量部、トリメチルクロルシラン１重量部及びトリ
エチルアミン１重量部を混合し、８０℃で３時間反応さ
せ、次いでエバポレーターでＴＨＦを除去し、２重量部
のクロロホルムに溶解させた後、５０重量部のメタノー
ルに投入してポリマーを沈澱させ、沈澱したポリマーを
ろ別し、続いて１ｍｍＨｇ、５０℃で１日間脱気して蒸
発分を除去し、末端がシリルエーテル化されたポリマー
を得、これを １Ｈ−ＮＭＲで測定した。[Examples] The present invention will be specifically explained below based on Examples and Comparative Examples. In the following Examples and Comparative Examples, Mn and Mw of the obtained styrenic polymers were determined by gel permeation chromatography (GPC) calibrated with monodisperse polystyrene (manufactured by Waters).
Using tetrahydrofuran as the mobile phase and an RI detector as the detector, the elution rate was 1.0 ml/
The measurement was performed under the condition of min. In addition, in Examples 1 to 6, the average number of terminal functional groups possessed by one polymer molecule was determined using an automatic titrator [GT-05 type manufactured by Mitsubishi Chemical Industries, Ltd.]. It was determined by neutralization titration. Further, in Examples 7 to 11, the average number of terminal functional groups was determined by measuring 1H-NMR of the polymer whose terminal was silyl etherified in the following manner. That is, THF is added to 1 part by weight of polystyrene.
20 parts by weight, 1 part by weight of trimethylchlorosilane and 1 part by weight of triethylamine were mixed and reacted at 80°C for 3 hours, then THF was removed with an evaporator, dissolved in 2 parts by weight of chloroform, and 50 parts by weight of The polymer was precipitated by pouring it into methanol, and the precipitated polymer was filtered, followed by degassing at 1 mmHg and 50°C for 1 day to remove the evaporated content, to obtain a polymer whose terminal was silyl etherified. Measured by 1H-NMR.
【００１９】
実施例１〜６
攪拌器、還流冷却器、滴下ロート、熱電対、重合開始剤
供給口、及び窒素ガス吹き込み口を備えたガラスフラス
コにモノマーとしてスチレンを仕込み、窒素ガス導入下
に９０℃で、１，４−ジオキサンに溶解した重合開始剤
〔４，４’−アゾビス−４−シアノバレリックアシド（
ＡＣＶＡ）〕を滴下ロートより添加し、重合を開始した
。Examples 1 to 6 Styrene was charged as a monomer into a glass flask equipped with a stirrer, a reflux condenser, a dropping funnel, a thermocouple, a polymerization initiator supply port, and a nitrogen gas inlet, and the mixture was heated to 90°C while nitrogen gas was being introduced. The polymerization initiator [4,4'-azobis-4-cyanovaleric acid (
ACVA] was added from the dropping funnel to initiate polymerization.
【００２０】一方、重合開始直後より、ＡＣＶＡの１，
４−ジオキサン溶液を定量ポンプにて連続的に供給した
。 所定の反応時間が経過した後、重合反応系を９０
℃に保持しながら３時間攪拌し、残留重合開始剤ＡＣＶ
Ａを分解した。このときには重合開始剤溶液の供給を停
止した。On the other hand, immediately after the start of polymerization, 1,
The 4-dioxane solution was continuously supplied using a metering pump. After the predetermined reaction time has elapsed, the polymerization reaction system is heated to 90%
Stir for 3 hours while maintaining at ℃ to remove residual polymerization initiator ACV.
A was disassembled. At this time, the supply of the polymerization initiator solution was stopped.
【００２１】残留ＡＣＶＡの分解終了後、１，４−ジオ
キサンに溶解した重合禁止剤（ターシャリブチルカテコ
ール）を加え、重合反応を停止させた。得られた重合混
合物に６００重量部のクロロホルムを加え、これを２，
８００重量部のメタノール中に添加し、反応混合物中の
ポリマーを沈澱させた。その後、ポリマーをろ別し、続
いて、１ｍｍＨｇ、７０℃で３日間脱気を行い、蒸発分
を除去した。重合反応条件及び重合反応結果、並びに得
られたスチレン系ポリマーの物性をそれぞれ表１に示す
。After the residual ACVA was completely decomposed, a polymerization inhibitor (tert-butylcatechol) dissolved in 1,4-dioxane was added to stop the polymerization reaction. 600 parts by weight of chloroform was added to the obtained polymerization mixture, and 2.
It was added to 800 parts by weight of methanol to precipitate the polymer in the reaction mixture. Thereafter, the polymer was filtered off, followed by deaeration at 1 mmHg and 70° C. for 3 days to remove evaporated components. Table 1 shows the polymerization reaction conditions, polymerization reaction results, and physical properties of the obtained styrenic polymer.
【００２２】[0022]
【表１】[Table 1]
【００２３】
実施例７〜１１
攪拌器、還流冷却器、滴下ロート、熱電対、重合開始剤
供給口、及び窒素ガス吹き込み口を備えたガラスフラス
コに、モノマーとしてスチレンを仕込み、窒素ガス導入
下に１１０℃で、ＤＭＦに溶解した重合開始剤（２，２
’−アゾビス〔２−（ヒドロキシメチル） プロピオニ
トリル〕（ＡＨＰＮ））を滴下ロートより添加し、重合
を開始した。一方、重合開始直後より、ＡＨＰＮのＤＭ
Ｆ溶液を定量ポンプにて連続的に供給した。Examples 7 to 11 Styrene was charged as a monomer into a glass flask equipped with a stirrer, a reflux condenser, a dropping funnel, a thermocouple, a polymerization initiator supply port, and a nitrogen gas inlet, and the flask was heated under nitrogen gas introduction. Polymerization initiator (2,2
'-Azobis[2-(hydroxymethyl)propionitrile] (AHPN)) was added from the dropping funnel to initiate polymerization. On the other hand, immediately after the start of polymerization, DM of AHPN
The F solution was continuously supplied using a metering pump.
【００２４】所定の反応時間が経過した後、重合反応系
を１１０℃に保持しながら３時間攪拌し、残留重合開始
剤ＡＨＰＮを分解した。このときには重合開始剤溶液の
供給は停止した。残留ＡＨＰＮの分解終了後、冷却し、
重合反応を停止させた。得られた重合混合物に５０重量
部のクロロホルムを加え、これを５００重量部のメタノ
ール中に添加し、反応混合物中のポリマーを沈澱させた
。その後、ポリマーをろ別し、続いて、１ｍｍＨｇ、７
０℃にて、３日間脱気を行い、蒸発分を除去した。重合
反応条件及び重合反応結果並びに得られたスチレン系ポ
リマーの物性を表２に示す。After the predetermined reaction time had elapsed, the polymerization reaction system was stirred for 3 hours while being maintained at 110° C. to decompose the residual polymerization initiator AHPN. At this time, the supply of the polymerization initiator solution was stopped. After the residual AHPN has been decomposed, it is cooled,
The polymerization reaction was stopped. 50 parts by weight of chloroform was added to the obtained polymerization mixture, which was then added to 500 parts by weight of methanol to precipitate the polymer in the reaction mixture. Thereafter, the polymer was filtered off, followed by 1 mmHg, 7
Deaeration was performed at 0° C. for 3 days to remove evaporated components. Table 2 shows the polymerization reaction conditions, polymerization reaction results, and physical properties of the obtained styrenic polymer.
【００２５】[0025]
【表２】[Table 2]
【００２６】
比較例１
スチレン３３３重量部をガラスフラスコ内に仕込み、窒
素ガス導入下に攪拌しながら１４６℃まで加熱した。重
合反応系が１４６℃に到達した時点で滴下ロートより３
−メルカプトプロピオン酸（以下、ＭＰＡと略称する）
３．２重量部を加え、重合を開始した。重合開始と同時
に定量ポンプを使用してスチレン６６７重量部とＭＰＡ
３．２重量部とからなる溶液を４時間かけて反応系に供
給した。この間、反応温度は１４６℃から徐々に上昇し
、１７０℃に達した時点で以後一定に保持した。供給終
了後、更にＭＰＡ３．２重量部を３時間かけて連続的に
反応系に供給した。更に、３時間保持して反応を終了し
、重合反応混合物中にクロロホルム１，０００重量部を
添加し、これを６，０００重量部のメタノール中に添加
してポリマーを沈澱させ、ろ別した。得られたポリマー
を１ｍｍＨｇ、７０℃にて３日間脱気を行い、蒸発分を
除去した。得られたポリマーの数平均分子量（Ｍｎ）は
５，４００、重量平均分子量（Ｍｗ）は１３，０００、
Ｍｗ／Ｍｎは２．４１であった。また、このスチレン系
ポリマーの１分子当りの官能基の平均個数は０．６７で
あった。Comparative Example 1 333 parts by weight of styrene was placed in a glass flask and heated to 146° C. while stirring while introducing nitrogen gas. When the polymerization reaction system reached 146°C, 3
-Mercaptopropionic acid (hereinafter abbreviated as MPA)
3.2 parts by weight was added to start polymerization. At the same time as polymerization started, 667 parts by weight of styrene and MPA were added using a metering pump.
A solution consisting of 3.2 parts by weight was supplied to the reaction system over 4 hours. During this time, the reaction temperature gradually rose from 146°C, and was kept constant after reaching 170°C. After the supply was completed, 3.2 parts by weight of MPA was further continuously supplied to the reaction system over 3 hours. The reaction was further maintained for 3 hours to complete the reaction, and 1,000 parts by weight of chloroform was added to the polymerization reaction mixture, and this was added to 6,000 parts by weight of methanol to precipitate the polymer, which was filtered. The obtained polymer was degassed at 1 mmHg and 70° C. for 3 days to remove evaporated components. The number average molecular weight (Mn) of the obtained polymer was 5,400, the weight average molecular weight (Mw) was 13,000,
Mw/Mn was 2.41. Further, the average number of functional groups per molecule of this styrenic polymer was 0.67.
【００２７】
比較例２
スチレン２００重量部を、ＡＣＶＡ２重量部及びクロル
ベンゼン２００重量部をガラスフラスコ内に仕込み、窒
素ガス導入下に攪拌しながら９０℃に昇温せて１４時間
重合反応を行った。重合反応終了後、重合反応混合物中
にクロロホルム２００重量部を添加し、これを３，００
０重量部のメタノール中に添加してポリマーを沈澱させ
、ろ別した。得られたポリマーを１ｍｍＨｇ、７０℃に
て３日間脱気を行い、蒸発分を除去した。得られたポリ
マーの数平均分子量（Ｍｎ）は６０，０００、重量平均
分子量（Ｍｗ）は１４５，０００、Ｍｗ／Ｍｎは２．４
２であった。また、ポリマーへの転化率は３３．０％で
あった。更に、このスチレン系ポリマーの１分子当りの
官能基の平均個数は１．８８であった。Comparative Example 2 200 parts by weight of styrene, 2 parts by weight of ACVA, and 200 parts by weight of chlorobenzene were placed in a glass flask, and the temperature was raised to 90° C. with stirring while introducing nitrogen gas to conduct a polymerization reaction for 14 hours. . After the polymerization reaction was completed, 200 parts by weight of chloroform was added to the polymerization reaction mixture, and 3,00 parts by weight of chloroform was added to the polymerization reaction mixture.
The polymer was precipitated by adding it to 0 parts by weight of methanol and filtered. The obtained polymer was degassed at 1 mmHg and 70° C. for 3 days to remove evaporated components. The number average molecular weight (Mn) of the obtained polymer was 60,000, the weight average molecular weight (Mw) was 145,000, and the Mw/Mn was 2.4.
It was 2. Moreover, the conversion rate to polymer was 33.0%. Furthermore, the average number of functional groups per molecule of this styrene polymer was 1.88.
【００２８】上記実施例１〜１１及び比較例１の結果か
ら、従来法により得られた末端に官能基を有するスチレ
ン系ポリマーの１分子当りの官能基の平均個数が０．６
７であるのに対し、本発明法により得られたポリスチレ
ンでは１．４０〜１．９８となっており、ポリマー１分
子当りの官能基の平均個数が多くなっていることが判明
した。また、比較例２との結果から、従来法ではモノマ
ーの転化率が３３．０％であったのに対し、本発明方法
では平均７５％と転化率が増加することが判明した。From the results of Examples 1 to 11 and Comparative Example 1, it is clear that the average number of functional groups per molecule of the styrenic polymer having functional groups at the ends obtained by the conventional method was 0.6.
7, whereas the polystyrene obtained by the method of the present invention has a value of 1.40 to 1.98, indicating that the average number of functional groups per polymer molecule is large. Further, from the results of Comparative Example 2, it was found that while the monomer conversion rate was 33.0% in the conventional method, the conversion rate increased to an average of 75% in the method of the present invention.
【００２９】[0029]
【発明の効果】本発明方法によれば、従来法に比較して
ポリマー１分子が有する官能基の平均個数が大きなポリ
スチレンを高収率で製造することができ、また、分子量
を広い範囲にわたって自由にコントロールすることがで
き、分子量分布も狭い範囲に制御できる。従って、本発
明方法によって得られるポリマーは、１分子当りに有す
る官能基の平均個数が大きいことから、規則性の高いブ
ロック共重合体やグラフト共重合体を得るための製造原
料に供することができるだけでなく、更にそれ自体機能
性樹脂として利用可能であり、接着剤、塗料、成形品、
樹脂、アスファルト類等の改質に極めて有用である。Effects of the Invention According to the method of the present invention, polystyrene having a larger average number of functional groups per polymer molecule can be produced in high yield compared to conventional methods, and the molecular weight can be freely adjusted over a wide range. The molecular weight distribution can also be controlled within a narrow range. Therefore, since the polymer obtained by the method of the present invention has a large average number of functional groups per molecule, it can be used as a raw material for producing highly regular block copolymers and graft copolymers. In addition, it can be used as a functional resin itself, such as adhesives, paints, molded products,
Extremely useful for modifying resins, asphalts, etc.
Claims (3)
重合反応系内に官能基を有するラジカル重合開始剤を連
続的又は間欠的に供給することを特徴とする末端に官能
基を有するスチレン系ポリマーの製造法。Claim 1: When polymerizing a styrenic monomer,
1. A method for producing a styrenic polymer having a functional group at its terminal, which comprises continuously or intermittently supplying a radical polymerization initiator having a functional group into a polymerization reaction system.
数平均分子量（Ｍｎ）が１，０００〜２００，０００で
あり、重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）
との比（Ｍｗ／Ｍｎ）が１．５〜４．０であり、かつ、
ポリマー１分子が有する官能基の平均個数が１．２〜２
．０である請求項１記載の末端に官能基を有するスチレ
ン系ポリマーの製造法。2. The styrenic polymer having a functional group has a number average molecular weight (Mn) of 1,000 to 200,000, and a weight average molecular weight (Mw) and a number average molecular weight (Mn)
The ratio (Mw/Mn) is 1.5 to 4.0, and
The average number of functional groups per polymer molecule is 1.2 to 2.
．． 2. The method for producing a styrenic polymer having a terminal functional group according to claim 1, wherein
物系化合物又は官能基を有するアゾ系化合物若しくはこ
れらの混合物である請求項１記載の末端に官能基を有す
るスチレン系ポリマーの製造法。3. The method for producing a styrenic polymer having a terminal functional group according to claim 1, wherein the polymerization initiator is a peroxide compound having a functional group, an azo compound having a functional group, or a mixture thereof. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4730191A JPH04213307A (en) | 1990-04-20 | 1991-02-21 | Production of functional group-terminated styrene polymer |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10292290 | 1990-04-20 | ||
| JP2-102922 | 1990-04-20 | ||
| JP4730191A JPH04213307A (en) | 1990-04-20 | 1991-02-21 | Production of functional group-terminated styrene polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04213307A true JPH04213307A (en) | 1992-08-04 |
Family
ID=26387468
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4730191A Withdrawn JPH04213307A (en) | 1990-04-20 | 1991-02-21 | Production of functional group-terminated styrene polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04213307A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4912120A (en) * | 1986-03-14 | 1990-03-27 | Syntex (U.S.A.) Inc. | 3,5-substituted 4,5-dihydroisoxazoles as transglutaminase inhibitors |
| JPH059354A (en) * | 1991-07-03 | 1993-01-19 | Sanyo Chem Ind Ltd | Compatibilizing agent for resin and resin composition |
| JP2002080514A (en) * | 2000-09-05 | 2002-03-19 | Daicel Chem Ind Ltd | Complex-based polymerization initiator |
| WO2002085957A1 (en) * | 2001-04-24 | 2002-10-31 | Ppg Industries Ohio, Inc. | Synthesis of vinyl polymers by controlled radical polymerization |
-
1991
- 1991-02-21 JP JP4730191A patent/JPH04213307A/en not_active Withdrawn
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4912120A (en) * | 1986-03-14 | 1990-03-27 | Syntex (U.S.A.) Inc. | 3,5-substituted 4,5-dihydroisoxazoles as transglutaminase inhibitors |
| JPH059354A (en) * | 1991-07-03 | 1993-01-19 | Sanyo Chem Ind Ltd | Compatibilizing agent for resin and resin composition |
| JP2002080514A (en) * | 2000-09-05 | 2002-03-19 | Daicel Chem Ind Ltd | Complex-based polymerization initiator |
| WO2002085957A1 (en) * | 2001-04-24 | 2002-10-31 | Ppg Industries Ohio, Inc. | Synthesis of vinyl polymers by controlled radical polymerization |
| US6875832B2 (en) | 2001-04-24 | 2005-04-05 | Ppg Industries Ohio, Inc. | Synthesis of vinyl polymers by controlled radical polymerization |
| US7351781B2 (en) | 2001-04-24 | 2008-04-01 | Ppg Industries Ohio, Inc. | Synthesis of vinyl polymers by controlled radical polymerization |
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|---|---|---|---|
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