JPH0459328B2 - - Google Patents
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- Publication number
- JPH0459328B2 JPH0459328B2 JP5801883A JP5801883A JPH0459328B2 JP H0459328 B2 JPH0459328 B2 JP H0459328B2 JP 5801883 A JP5801883 A JP 5801883A JP 5801883 A JP5801883 A JP 5801883A JP H0459328 B2 JPH0459328 B2 JP H0459328B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- polymer
- styrene
- molecular weight
- polymers
- 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.)
- Expired
Links
- 229920001002 functional polymer Polymers 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 description 20
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- -1 acyl peroxides Chemical class 0.000 description 5
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical group OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 150000003440 styrenes Chemical class 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000003708 ampul Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- BCCJBECBPZLHDY-UHFFFAOYSA-N 1-(1,2-dibromoethyl)-3-ethenylbenzene Chemical compound BrCC(Br)C1=CC=CC(C=C)=C1 BCCJBECBPZLHDY-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-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
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000013522 chelant Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- ZWKNLRXFUTWSOY-QPJJXVBHSA-N (e)-3-phenylprop-2-enenitrile Chemical compound N#C\C=C\C1=CC=CC=C1 ZWKNLRXFUTWSOY-QPJJXVBHSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DGIUXESWBSKTLI-UHFFFAOYSA-N 1-(1,2-dibromoethyl)-4-ethenylbenzene Chemical compound BrCC(Br)C1=CC=C(C=C)C=C1 DGIUXESWBSKTLI-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- VVKZCUGDWOHEBO-UHFFFAOYSA-N 2-[(2-ethoxy-2-oxoethyl)amino]acetic acid Chemical compound CCOC(=O)CNCC(O)=O VVKZCUGDWOHEBO-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- UWRZIZXBOLBCON-UHFFFAOYSA-N 2-phenylethenamine Chemical compound NC=CC1=CC=CC=C1 UWRZIZXBOLBCON-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- YMOONIIMQBGTDU-VOTSOKGWSA-N [(e)-2-bromoethenyl]benzene Chemical compound Br\C=C\C1=CC=CC=C1 YMOONIIMQBGTDU-VOTSOKGWSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-M hydroperoxide group Chemical group [O-]O MHAJPDPJQMAIIY-UHFFFAOYSA-M 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は新規な機能性線状高分子およびその製
造法に関するものであり、さらに詳しくは１，２
−ジハロゲノエチル基を有するスチレン誘導体の
重合体およびその製造法に関するものである。
従来からスチレン誘導体は数多く開発合成され
てきており、機能性高分子の合成に広く利用され
ている。たとえばシアノスチレン、アミノスチレ
ン等はラジカル重合により容易に高分子化し、各
種官能基を有する高分子を供給する。
またハロゲン原子を有するスチレン誘導体とし
ては、クロロスチレン、ブロモスチレン、クロロ
メチルスチレン、パラー（２−ブロモエチル）ス
チレン等が知られている。これらの化合物の重合
体は多数知られているが、１，２−ジハロゲノエ
チル基を有するスチレン誘導体の重合体は、これ
まで全く知られていない。
本発明者は、ハロゲン化アルキル基を側鎖に有
する機能性高分子化合物について種々の検討を加
えた結果、下記に示す新規な機能性重合体を見い
出すに至つた。
即ち本発明は、下記構造式（）で示される重
合単位よりなり、分子量が1000ないし2000000で
ある機能性重合体に関している。
The present invention relates to a novel functional linear polymer and a method for producing the same.
The present invention relates to a styrene derivative polymer having -dihalogenoethyl groups and a method for producing the same. Many styrene derivatives have been developed and synthesized to date, and are widely used in the synthesis of functional polymers. For example, cyanostyrene, aminostyrene, etc. are easily polymerized by radical polymerization to provide polymers having various functional groups. Further, as styrene derivatives having a halogen atom, chlorostyrene, bromostyrene, chloromethylstyrene, para-(2-bromoethyl)styrene, etc. are known. Although many polymers of these compounds are known, no polymers of styrene derivatives having 1,2-dihalogenoethyl groups have been known so far. The present inventor conducted various studies on functional polymer compounds having a halogenated alkyl group in the side chain, and as a result, discovered the novel functional polymer shown below. That is, the present invention relates to a functional polymer consisting of polymerized units represented by the following structural formula () and having a molecular weight of 1,000 to 2,000,000.
【式】
（式中X1、X2はハロゲンを表わす。）
構造式（）においてX1、X2の好ましい態様
は、塩素、臭素およびヨウ素のうち同一または異
なる組合せである。また主鎖と１，２−ジハロゲ
ノエチル基の好ましい位置関係は、メタ位または
パラ位またはそれらの混合物である。
本発明における機能性重合体の分子量は1000な
いし2000000であるが、より好ましくは、10000な
いし2000000である。
本発明の機能性重合体は構造式（）で示され
る単量体を重合させることによつて得ることがで
きる。[Formula] (In the formula, X 1 and X 2 represent halogen.) In the structural formula (), a preferred embodiment of X 1 and X 2 is the same or different combination of chlorine, bromine and iodine. Further, a preferable positional relationship between the main chain and the 1,2-dihalogenoethyl group is the meta position, the para position, or a mixture thereof. The molecular weight of the functional polymer in the present invention is from 1,000 to 2,000,000, more preferably from 10,000 to 2,000,000. The functional polymer of the present invention can be obtained by polymerizing monomers represented by the structural formula ().
【式】
（式中X1、X2はハロゲンを表わす。）
上記単量体は例えば、ジビニルベンゼンまたは
その置換体とハロゲン分子を不活性化したハロゲ
ン化剤とを反応させることにより得ることができ
る。
重合方法には特に制限はなく、加熱による重合
でも充分可能であるが、重合開始剤を利用するこ
とが好ましい場合が多い。重合開始剤として用い
られるのは、過酸化ベンゾイル、過酸化ラウロイ
ル等の過酸化アシル類、アゾビスイソブチロニト
リル、２，2′−アゾビス（２，４−ジメチルマレ
ロニトリル）等のアゾニトリル類、過酸化ジター
シヤリーブチル、過酸化ジクミル、メチルエチル
ケトンパーオキシド等の過酸化物、クメンヒドロ
ペンオキシド、ターシヤリーヒドロペルオキシド
等のヒドロペルオキシド類である。
本発明における重合体は、不活性液体の存在下
で重合を行つて製造することも可能である。不活
性液体としてはノルマルーペンタン、ノルマルー
ヘキサン、ノルマルーヘプタン、ノルマルーオク
タンを始めとする脂肪族炭化水素類、メタノー
ル、エタノール、イソプロピルアルコールなどの
アルコール類、アセトン、メチルエチルケトン、
ジエチレケトンなどのケトン類、ジエチルエーテ
ル、メチルエチルエーテル、ジブチルエーテル、
ジオキサン、テトラヒドロフラン等のエーテル
類、ベンゼン、トルエン、キシレン等の芳香族炭
化水素類、ギ酸エチル、酢酸エチル、酢酸ブチル
等のエステル類、ジメチルホルムアミド、ジメチ
ルアセトアミドを始めとするアミド類、クロロホ
ルム、塩化メチレン、ジクロルエタン等の脂肪族
ハロゲン化物、クロルベンゼンを始めとする芳香
族ハロゲン化物、またジメチルスルホキシド等の
極性液体も用いることができる。尚これらの液体
は単独ないしは二つ以上の液体の混合物として用
いることもできる。
反応の温度に制限はないが、20℃から120℃程
度が好ましく、さらに好ましくは60℃から100℃
程度である。
本発明の重合体は、隣接する炭素に１個づつハ
ロゲンを有するアルキル置換フエニル基、即ち
１，２−ジハロゲノエチルフエニル基を側鎖に有
し、各種反応により種々の官能基に変換すること
が可能であり、機能性高分子として有用である。
たとえば窒素化合物との反応により、アニオン交
換を有する高分子を生成したり、また、イミノジ
酢酸基[Formula] (In the formula, X 1 and X 2 represent halogen.) The above monomer can be obtained, for example, by reacting divinylbenzene or its substituted product with a halogenating agent that has inactivated the halogen molecule. can. There are no particular restrictions on the polymerization method, and polymerization by heating is sufficient, but it is often preferable to use a polymerization initiator. The polymerization initiators used include acyl peroxides such as benzoyl peroxide and lauroyl peroxide, azonitrile such as azobisisobutyronitrile and 2,2'-azobis(2,4-dimethylmaleronitrile), These are peroxides such as ditertiary butyl peroxide, dicumyl peroxide, and methyl ethyl ketone peroxide, and hydroperoxides such as cumene hydropene oxide and tertiary hydroperoxide. The polymer in the present invention can also be produced by polymerizing in the presence of an inert liquid. Examples of inert liquids include aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, and n-octane, alcohols such as methanol, ethanol, and isopropyl alcohol, acetone, methyl ethyl ketone,
Ketones such as diethyleketone, diethyl ether, methyl ethyl ether, dibutyl ether,
Ethers such as dioxane and tetrahydrofuran, aromatic hydrocarbons such as benzene, toluene and xylene, esters such as ethyl formate, ethyl acetate and butyl acetate, amides such as dimethylformamide and dimethylacetamide, chloroform and methylene chloride. , aliphatic halides such as dichloroethane, aromatic halides such as chlorobenzene, and polar liquids such as dimethyl sulfoxide can also be used. Note that these liquids can be used alone or as a mixture of two or more liquids. There is no limit to the reaction temperature, but it is preferably about 20°C to 120°C, more preferably 60°C to 100°C.
That's about it. The polymer of the present invention has an alkyl-substituted phenyl group having one halogen on each adjacent carbon, that is, a 1,2-dihalogenoethyl phenyl group in the side chain, and can be converted into various functional groups by various reactions. Therefore, it is useful as a functional polymer.
For example, by reaction with nitrogen compounds, polymers with anion exchange can be produced, and iminodiacetic acid groups can be produced.
【式】を導入すること
により各種金属にキレート能を有する高分子を生
成することが可能である。
この場合と同様に、ハロゲン原子１個を有する
アルキル置換スチレン、例えばパラー（２−ブロ
モエチル）スチレンやクロロメチルスチレンの重
合体も同様な高分子の合成が可能である。しか
し、合成される高分子の性能には非常に大きな質
的な差がある。たとえばイミノジ酢酸基を導入し
たキレート高分子において、その差は明らかであ
る。
１，２−ジハロゲノエチルスチレンより生成す
る高分子にイミノジ酢酸基を導入した場合イミノ
ジ酢酸基が２個並んだ側鎖が成形する。それは、
下記の構造式（）で示される。
これに対し、たとえばクロロメチルスチレンよ
り生成する高分子にイミノジ酢酸基を導入した場
合は、下記の構造式（）のようになる。
ここで、構造式（）と（）の側鎖を比較す
ると、（）の方が錯形性能が大きく、本発明の
重合体より合成されるキレート高分子が、金属除
去剤として非常に有効であることがわかる。
また、本発明の重合体は、側鎖にハロゲン原子
２個を有するため難燃性高分子としても有用であ
る。
以下に本発明の実施例を示すがこれらは本発明
を制限するものではない。
実施例 １
50mlのアンプルに5.0ｇの３−（１，２−ジブロ
モエチル）スチレン、20mlのキシレン及び0.05
ｇ）のアゾビスイソブチロニトリルを入れ、充分
混合溶解されたのちアンプル管内を窒素パージし
て封管した。これを90℃の水浴中に24時間浸漬し
た。冷却後、封管を割つて内容物をヘキサン中に
あけて沈澱を濾別し、ヘキサンで充分洗浄した
後、真空乾燥して重量を測定したところ4.9ｇで
あつた。この生成物の元素分析値および赤外吸収
スペクトルにおける主なピークは次のとおりであ
る。
元素分析値（括孤内は論理値を表わす。）
Ｃ；41.38（41.42）Ｈ；3.42（3.48）Br；55.20
（55.11）
赤外線級数スペクトル（cm-1）
3020、2970、1600、1510、1480、1215、800、
690
単量体におけるＣ＝C2重結合に由来する吸収
が消失していることから重合体になつていること
が確認された。このものを、ゲルパーミエイシヨ
ンクロマトグラフイーによつて、ポリスチレンを
検量線として用いることによつて分子量を測定し
たところ、分子量は1100000であつた。
実施例 ２
３−（１，２−ジブロモエチル）スチレンの代
りに４−（１，２−ジブロモエチル）スチレンを
用いたこと以外は、実施例１とまつたく同様に反
応、操作を行なつた。得られた生成物の収量は
4.8ｇであり、その元素分析値および赤外吸収ス
ペクトルにおける主なピークは次のとおりであ
る。
元素分析値（括孤内は論理値を表わす。）
Ｃ；41.35（41.42）、Ｈ；3.39（3.48）Br；55.26
（55.11）
赤外吸収スペクトル（cm-1）
3020、2910、1600、1510、1430、1230、835、
695
また分子量を実施例１と同様に測定したとこ
ろ、分子量は900000であつた。
実施例 ３
50mlのアンプルに10.0ｇの３−（１，２−ジブ
ロモエチル）スチレン、20mlのプロパノール及び
0.05ｇのアソビスイソブチロニトリルを入れ、充
分混合溶解させたのち、アンプル管内を窒素パー
ジして封管した。これを90℃の水浴中に24時間浸
漬した。冷却後、封管を割つて内容物を温度計、
還流器および撹拌器を備えた300mlの４口フラス
コに入れた。続いてイミノジ酢酸エチルエステル
26.1ｇを溶解したエタノール100mlを加え、内温
を70℃に保つて24時間撹拌を続けた。続いて水酸
化ナトリウム6.6ｇを溶解した純水100mlを加え、
90℃でさらに５時間撹拌を続けた。冷却一洗浄後
次に示すように金属の除去能を調べた。
Cuの２価およびFeの３価の塩化物を純水に溶
解し、各金属100mgを含有する水溶液１を用意
した。この水溶液に上記のようにして合成した重
合体5.0ｇを加え24時間浸漬後、水溶液に残存す
る金属イオン量を測定すると、Cu、Feともに0.1
mg以下であつた。By introducing the formula, it is possible to produce polymers that have the ability to chelate various metals. Similarly to this case, it is also possible to synthesize polymers of alkyl-substituted styrene having one halogen atom, such as para-(2-bromoethyl)styrene and chloromethylstyrene. However, there are very large qualitative differences in the performance of the synthesized polymers. For example, the difference is obvious in chelate polymers into which iminodiacetic acid groups have been introduced. When iminodiacetic acid groups are introduced into a polymer produced from 1,2-dihalogenoethylstyrene, a side chain in which two iminodiacetic acid groups are arranged is formed. it is,
It is represented by the structural formula () below. On the other hand, when iminodiacetic acid groups are introduced into a polymer produced from chloromethylstyrene, for example, the following structural formula () is obtained. Comparing the side chains of structural formulas () and (), the complexing performance of () is greater, and the chelate polymer synthesized from the polymer of the present invention is extremely effective as a metal removal agent. I understand that there is something. Furthermore, since the polymer of the present invention has two halogen atoms in the side chain, it is useful as a flame-retardant polymer. Examples of the present invention are shown below, but these are not intended to limit the invention. Example 1 In a 50 ml ampoule, 5.0 g of 3-(1,2-dibromoethyl)styrene, 20 ml of xylene and 0.05
After the azobisisobutyronitrile (g) was added and thoroughly mixed and dissolved, the inside of the ampoule tube was purged with nitrogen and the tube was sealed. This was immersed in a 90°C water bath for 24 hours. After cooling, the sealed tube was broken and the contents were poured into hexane, and the precipitate was filtered out, thoroughly washed with hexane, dried under vacuum, and weighed to be 4.9 g. The elemental analysis values and main peaks in the infrared absorption spectrum of this product are as follows. Elemental analysis value (The value in parentheses represents a logical value.) C; 41.38 (41.42) H; 3.42 (3.48) Br; 55.20
(55.11) Infrared series spectrum (cm -1 ) 3020, 2970, 1600, 1510, 1480, 1215, 800,
690 It was confirmed that the absorption derived from the C═C double bond in the monomer had disappeared, indicating that it had become a polymer. The molecular weight of this product was measured by gel permeation chromatography using polystyrene as a calibration curve, and the molecular weight was found to be 1,100,000. Example 2 The reaction and operation were carried out in the same manner as in Example 1, except that 4-(1,2-dibromoethyl)styrene was used instead of 3-(1,2-dibromoethyl)styrene. . The yield of the product obtained is
It weighs 4.8g, and its elemental analysis values and main peaks in the infrared absorption spectrum are as follows. Elemental analysis value (The value in parentheses represents a logical value.) C: 41.35 (41.42), H: 3.39 (3.48) Br: 55.26
(55.11) Infrared absorption spectrum (cm -1 ) 3020, 2910, 1600, 1510, 1430, 1230, 835,
695 Furthermore, when the molecular weight was measured in the same manner as in Example 1, the molecular weight was 900,000. Example 3 In a 50 ml ampoule, 10.0 g of 3-(1,2-dibromoethyl)styrene, 20 ml of propanol and
After adding 0.05 g of asobisisobutyronitrile and thoroughly mixing and dissolving it, the inside of the ampoule tube was purged with nitrogen and the tube was sealed. This was immersed in a 90°C water bath for 24 hours. After cooling, break the sealed tube and measure the contents with a thermometer.
It was placed in a 300ml 4-necked flask equipped with a reflux and a stirrer. followed by iminodiacetic acid ethyl ester
100 ml of ethanol in which 26.1 g of ethanol was dissolved was added, and stirring was continued for 24 hours while keeping the internal temperature at 70°C. Next, add 100ml of pure water in which 6.6g of sodium hydroxide has been dissolved.
Stirring was continued for an additional 5 hours at 90°C. After cooling and cleaning, the ability to remove metals was examined as shown below. Divalent Cu chloride and trivalent Fe chloride were dissolved in pure water to prepare an aqueous solution 1 containing 100 mg of each metal. 5.0 g of the polymer synthesized as described above was added to this aqueous solution, and after immersion for 24 hours, the amount of metal ions remaining in the aqueous solution was measured. Both Cu and Fe were 0.1
It was less than mg.
Claims (1)
り分子量が1000ないし2000000である機能性重合
体。 （式中、X1、X2はハロゲンを表わす。） ２ 下記構造式（）で示される単量体を重合さ
せることを特徴とする、下記構造式（）で示さ
れる重合単位より成り分子量が1000ないし
2000000である機能性重合体の製造法。 【式】【式】 （式中、X1、X2はハロゲンを表わす。）[Claims] 1. A functional polymer consisting of polymerized units represented by the following structural formula () and having a molecular weight of 1,000 to 2,000,000. (In the formula, X 1 and X 2 represent halogen.) 2. A monomer represented by the following structural formula () is composed of polymerized units represented by the following structural formula (), and the molecular weight is 1000 or so
2,000,000 production method of functional polymer. [Formula] [Formula] (In the formula, X 1 and X 2 represent halogen.)
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5801883A JPS59184212A (en) | 1983-04-04 | 1983-04-04 | Functional polymer and its production |
| DE3448168A DE3448168C2 (en) | 1983-04-01 | 1984-03-30 | |
| DE3411763A DE3411763C2 (en) | 1983-04-01 | 1984-03-30 | Linear or cross-linked polymers based on styrene derivatives and processes for their preparation |
| FR8405092A FR2543541B1 (en) | 1983-04-01 | 1984-03-30 | STYRENE DERIVATIVE, POLYMER THEREOF AND PROCESS FOR PRODUCING THE SAME |
| GB08408208A GB2140413B (en) | 1983-04-01 | 1984-03-30 | Styrene derivatives and polymers thereof |
| US06/924,724 US4791183A (en) | 1983-04-01 | 1986-10-30 | Styrene derivative, polymer thereof and production of same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5801883A JPS59184212A (en) | 1983-04-04 | 1983-04-04 | Functional polymer and its production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59184212A JPS59184212A (en) | 1984-10-19 |
| JPH0459328B2 true JPH0459328B2 (en) | 1992-09-22 |
Family
ID=13072221
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5801883A Granted JPS59184212A (en) | 1983-04-01 | 1983-04-04 | Functional polymer and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59184212A (en) |
-
1983
- 1983-04-04 JP JP5801883A patent/JPS59184212A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59184212A (en) | 1984-10-19 |
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