JPH0616726A - Production of stereoregular methyl methacrylate polymer - Google Patents
Production of stereoregular methyl methacrylate polymerInfo
- Publication number
- JPH0616726A JPH0616726A JP4197717A JP19771792A JPH0616726A JP H0616726 A JPH0616726 A JP H0616726A JP 4197717 A JP4197717 A JP 4197717A JP 19771792 A JP19771792 A JP 19771792A JP H0616726 A JPH0616726 A JP H0616726A
- Authority
- JP
- Japan
- Prior art keywords
- methyl methacrylate
- polymerization
- water
- grignard reagent
- added
- 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.)
- Granted
Links
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229920000642 polymer Polymers 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000007818 Grignard reagent Substances 0.000 claims abstract description 18
- 150000004795 grignard reagents Chemical class 0.000 claims abstract description 18
- 238000010539 anionic addition polymerization reaction Methods 0.000 claims abstract description 15
- 229910001425 magnesium ion Inorganic materials 0.000 claims abstract description 7
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 3
- 239000003505 polymerization initiator Substances 0.000 claims description 18
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 6
- 230000005587 bubbling Effects 0.000 abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 21
- 239000000243 solution Substances 0.000 description 18
- 239000002904 solvent Substances 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- UKZCGMDMXDLAGZ-UHFFFAOYSA-M magnesium;2-methylpropane;bromide Chemical compound [Mg+2].[Br-].C[C-](C)C UKZCGMDMXDLAGZ-UHFFFAOYSA-M 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- PZIIGUMPOSVMSD-UHFFFAOYSA-M [Br-].C1=CC=C2C([Mg+])=CC=CC2=C1 Chemical compound [Br-].C1=CC=C2C([Mg+])=CC=CC2=C1 PZIIGUMPOSVMSD-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000003708 ampul Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- DLKQHBOKULLWDQ-UHFFFAOYSA-N 1-bromonaphthalene Chemical compound C1=CC=C2C(Br)=CC=CC2=C1 DLKQHBOKULLWDQ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- VPFPCNQBOYUQRG-UHFFFAOYSA-M [Br-].CC(C)(C)[Mg+] Chemical group [Br-].CC(C)(C)[Mg+] VPFPCNQBOYUQRG-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001347 alkyl bromides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000003869 coulometry Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- FUKUFMFMCZIRNT-UHFFFAOYSA-N hydron;methanol;chloride Chemical compound Cl.OC FUKUFMFMCZIRNT-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- YLOWTPHXXDJBAH-UHFFFAOYSA-N methyl 2-methylprop-2-enoate Chemical compound COC(=O)C(C)=C.COC(=O)C(C)=C YLOWTPHXXDJBAH-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- RKSOPLXZQNSWAS-UHFFFAOYSA-N tert-butyl bromide Chemical compound CC(C)(C)Br RKSOPLXZQNSWAS-UHFFFAOYSA-N 0.000 description 1
- BHAROVLESINHSM-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1.CC1=CC=CC=C1 BHAROVLESINHSM-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/22—Esters containing halogen
- C08F20/24—Esters containing halogen containing perhaloalkyl radicals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は、立体規則性メタクリ
ル酸メチル重合体の製造方法に関する。特に、高度にイ
ソタクチックな立体規則性に優れたメタクリル酸メチル
重合体の製法に関する。FIELD OF THE INVENTION The present invention relates to a method for producing a stereoregular methyl methacrylate polymer. In particular, it relates to a method for producing a methyl methacrylate polymer having a highly isotactic stereoregularity.
【０００２】[0002]
【従来の技術】イソタクチックなメタクリル酸メチル重
合体は、非極性溶媒中で重合開始剤にグリニャール試薬
を用いてアニオン重合することにより得られており、こ
のような重合により得られた重合体の立体規則性は重合
開始剤であるグリニャール試薬の種類、重合溶媒の種
類、重合温度によるものである。このことは、たとえば
特開昭６１−１７９２１０およびＫ．Ｈａｔａｄａ，
Ｋ．Ｕｔｅ，Ｋ．Ｔａｎａｋａ，Ｙ．Ｏｋａｍｏｔｏ，
ａｎｄ Ｔ．Ｋｉｔａｙａｍａ；Ｐｏｌｙｍｅｒ Ｊｕ
ｏｒｎａｌ ，１８，１０３７（１９８６）；Ｐ．
Ｅ．Ｍ．Ａｌｌｅｎ，Ｄ．Ｒ．Ｇ．Ｗｉｌｌｉａｍｓ；
Ｉｎｄ．Ｅｎｇ．Ｃｈｅｍ．Ｐｒｏｄ．Ｒｅｓ．Ｄｅ
ｖ．，２４，３３４（１９８５）などによって報告され
ている。BACKGROUND OF THE INVENTION Isotactic methyl methacrylate polymers have been obtained by anionic polymerization using a Grignard reagent as a polymerization initiator in a non-polar solvent. The regularity depends on the type of Grignard reagent that is a polymerization initiator, the type of polymerization solvent, and the polymerization temperature. This is described, for example, in JP-A 61-179210 and K. Hatada,
K. Ute, K.M. Tanaka, Y .; Okamoto,
and T.C. Kitayama; Polymer Ju
oral, 18, 1037 (1986);
E. M. Allen, D.M. R. G. Williams;
Ind. Eng. Chem. Prod. Res. De
v. , 24, 334 (1985).
【０００３】また、重合開始剤にグリニャール試薬を用
いたメタクリル酸メチルのアニオン重合では、重合に用
いる試薬は充分に乾燥させたものを使用することが好ま
しいと考えられている。このことは、高分子実験学第４
巻「付加重合、開環重合−２章−アニオン重合」および
特開昭６１−１７９２１０などに記載されている。Further, in the anionic polymerization of methyl methacrylate using a Grignard reagent as a polymerization initiator, it is considered preferable to use a sufficiently dried reagent for the polymerization. This is the 4th
Volume "Additional Polymerization, Ring-Opening Polymerization-Chapter 2-Anionic Polymerization" and JP-A-61-179210.
【０００４】さらに、以上のように、重合開始剤にグリ
ニャール試薬を用いたアニオン重合により得られるメタ
クリル酸メチルの立体規則性の制御は、アニオン重合開
始剤であるグリニャール試薬の種類、重合溶媒の種類、
重合温度によりおこなわれ、また重合系内の水分はでき
るだけ除いて重合を行うのが現状である。Further, as described above, the stereoregularity of methyl methacrylate obtained by anionic polymerization using a Grignard reagent as a polymerization initiator can be controlled by the type of Grignard reagent as an anionic polymerization initiator and the type of polymerization solvent. ,
The present situation is that the polymerization is carried out depending on the polymerization temperature, and water in the polymerization system is removed as much as possible.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、上述
のような従来の技術に鑑み、従来できるだけ除かれてい
た水分の存在下にてアニオン重合を行い、より高度にイ
ソタクチックなメタクリル酸メチルの重合体の製造方法
を提供することである。SUMMARY OF THE INVENTION In view of the above-mentioned conventional techniques, the object of the present invention is to carry out anionic polymerization in the presence of water, which has been removed as much as possible in the past, to obtain a more highly isotactic methyl methacrylate. To provide a method for producing the polymer.
【０００６】[0006]
【課題を解決するための手段】すなわち、本発明は、メ
タクリル酸メチルを重合開始剤としてグリニャール試薬
を用い高度にイソタクチックなポリメタクリル酸メチル
を製造する方法において、重合開始剤であるグリニャー
ル試薬のマグネシウムイオンに対して、重合系内に水を
モル量で０．３倍以上共存させることを特徴とする。Means for Solving the Problems That is, the present invention provides a method for producing highly isotactic polymethylmethacrylate using methyl methacrylate as a polymerization initiator using methyl methacrylate as a polymerization initiator. It is characterized in that water is allowed to coexist in the polymerization system in a molar amount of 0.3 times or more with respect to ions.
【０００７】本発明において、「高度にイソタクチック
な」とは、核磁気共鳴スペクトルにより測定されるトラ
イアッド表示によるイソタクチシチーが非常に大きいこ
と（例えば８０％以上）を意味する。In the present invention, "highly isotactic" means that the isotacticity by triad display measured by nuclear magnetic resonance spectrum is very large (for example, 80% or more).
【０００８】本発明に用いる水の量の範囲は、加える重
合開始剤であるグリニャール試薬のマグネシウムイオン
に対してモル量で０．３倍〜３倍程度である。重合系内
の水は多いほど得られるメタクリル酸メチル重合体のイ
ソタクチシチーは高くなる。また、得られるメタクリル
酸メチル重合体のイソタクチシチーは、共存する水の絶
対量に依存するものではなく、重合開始剤であるグリニ
ャール試薬のマグネシウムイオンとのモル比に依存する
ものである。たとえば、アニオン重合開始剤であるグリ
ニャール試薬のマグネシウムイオンのモル量に対して約
０．６倍量の水の存在下で重合せしめれば、水のない系
での重合で得られたメタクリル酸メチル重合体と比べ
て、イソタクチシチーをおよそ３％程度上昇させること
ができる。The amount of water used in the present invention is about 0.3 to 3 times the molar amount of magnesium ion of the Grignard reagent as a polymerization initiator to be added. The more water in the polymerization system, the higher the isotacticity of the obtained methyl methacrylate polymer. Further, the isotacticity of the obtained methyl methacrylate polymer does not depend on the absolute amount of coexisting water but on the molar ratio of the Grignard reagent as a polymerization initiator to magnesium ion. For example, if the polymerization is carried out in the presence of water in an amount of about 0.6 times the molar amount of magnesium ion of the Grignard reagent which is an anionic polymerization initiator, methyl methacrylate obtained by polymerization in a system without water Compared to the polymer, the isotacticity can be increased by about 3%.
【０００９】本発明で使用されるアニオン重合開始剤で
あるグリニャール試薬としては、一般式ＲＭｇＢｒで示
される化合物である。式中Ｒは炭素数Ｃ1 〜Ｃ10の炭化
水素基である。例えばメチル、エチル、プロピル、ブチ
ル、ペンチル、ヘキシル、ヘプチル、オクチル、ノニ
ル、およびデシルのような直鎖型および分岐型のアルキ
ル基；シクロヘキシル基のような脂環族アルキル基；な
らびにフェニル基及び置換芳香族炭化水素基が挙げられ
る。The Grignard reagent which is the anionic polymerization initiator used in the present invention is a compound represented by the general formula RMgBr. In the formula, R is a hydrocarbon group having 1 to 10 carbon atoms. Linear and branched alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl; alicyclic alkyl groups such as cyclohexyl; and phenyl and substituted An aromatic hydrocarbon group is mentioned.
【００１０】本発明で使用されるグリニャール試薬は、
対応するアルキルブロマイドを、好ましくは、充分に乾
燥したジエチルエーテル中で反応させることにより調整
できる。The Grignard reagent used in the present invention is
It can be prepared by reacting the corresponding alkyl bromide, preferably in fully dried diethyl ether.
【００１１】上述のように調整されたグリニャール試薬
は、溶液の形態で重合開始剤として使用できるし、また
トルエン等、別の溶媒に分散させた形態で使用してもよ
い。The Grignard reagent prepared as described above can be used as a polymerization initiator in the form of a solution, or may be used in the form of being dispersed in another solvent such as toluene.
【００１２】本発明で使用されるメタクリル酸メチルの
単量体及び重合反応溶媒は、例えば市販品を窒素気流下
で蒸留して精製して用いられる。使用する溶媒として
は、具体的にはベンゼン、トルエン、キシレン等の芳香
族炭化水素が挙げられる。The methyl methacrylate monomer and the polymerization reaction solvent used in the present invention are, for example, commercially available products that are purified by distillation under a nitrogen stream. Specific examples of the solvent used include aromatic hydrocarbons such as benzene, toluene and xylene.
【００１３】重合系内に共存させる水は、たとえばメタ
クリル酸メチルまたは、メタクリル酸メチルを重合溶媒
に溶解した溶液に直接添加するか、水を含ませた窒素に
よりバブリングするなどして加えることができる。The water coexisting in the polymerization system can be added, for example, by adding it directly to a solution of methyl methacrylate or methyl methacrylate dissolved in a polymerization solvent, or by bubbling with nitrogen containing water. .
【００１４】メタクリル酸メチルの重合反応は、メタク
リル酸メチルまたは、メタクリル酸メチルを重合溶媒に
溶解した溶液を−１００℃〜＋５０℃に設定した後に重
合開始剤を加えることにより重合を開始する。重合温度
は、水が共存することによる停止反応を押さえるために
より低温であることが好ましい。The polymerization reaction of methyl methacrylate is initiated by adding a polymerization initiator after setting methyl methacrylate or a solution of methyl methacrylate dissolved in a polymerization solvent at -100 ° C to + 50 ° C. The polymerization temperature is preferably lower so as to suppress the termination reaction due to the coexistence of water.
【００１５】重合の停止は、メタノールまたは、少量の
酸を含むメタノールを加えて行うことができる。The termination of the polymerization can be carried out by adding methanol or methanol containing a small amount of acid.
【００１６】得られたメタクリル酸メチル重合体は常法
によって回収される。例えば、生成したメタクリル酸メ
チル重合体溶液をメタクリル酸メチル重合体の貧溶媒で
あるメタノール、ヘキサン等に再沈澱せしめて、沈澱せ
しめた重合体を充分に洗浄し、乾燥することによって回
収できる。The obtained methyl methacrylate polymer is recovered by a conventional method. For example, it can be recovered by reprecipitating the produced methyl methacrylate polymer solution in methanol, hexane or the like which is a poor solvent for the methyl methacrylate polymer, washing the precipitated polymer sufficiently, and drying.
【００１７】[0017]
【実施例】以下、メタクリル酸メチル、溶媒およびアニ
オン重合開始剤として用いるグリニャール試薬の調製
例、ならびに重合系内に水を添加してメタクリル酸メチ
ルを重合した実施例、および重合系内に水を添加せずに
メタクリル酸メチルを重合した比較例を示す。[Examples] The following are preparation examples of methyl methacrylate, a solvent and a Grignard reagent used as an anionic polymerization initiator, an example in which water is added to the polymerization system to polymerize methyl methacrylate, and water is added to the polymerization system. A comparative example in which methyl methacrylate is polymerized without addition is shown.
【００１８】Ａ．メタクリル酸メチルおよび溶媒の調製
例 １）メタクリル酸メチル メタクリル酸メチルは常法により精製した後、精留し
た。これをＣａＨ2 で乾燥したものを真空蒸留し、４Ａ
モレキュラーシーブスを加えて室温にて３日間乾燥させ
た。 ２）トルエン トルエンは常法により精製した後、精留した。これを金
属ナトリウムで乾燥させたもの蒸留し、４Ａモレキュラ
ーシーブスを加え室温にて３日間乾燥させた。A. Preparation Example of Methyl Methacrylate and Solvent 1) Methyl Methacrylate Methyl methacrylate was purified by a conventional method and then rectified. This was dried with CaH 2 and vacuum distilled to give 4A
Molecular sieves were added and the mixture was dried at room temperature for 3 days. 2) Toluene Toluene was purified by a conventional method and then rectified. This was dried with sodium metal, distilled, and added with 4A molecular sieves, and dried at room temperature for 3 days.
【００１９】Ｂ．グリニャール試薬の調製例 １）ｔｅｒｔ−ブチルマグネシウムブロマイド 滴下ロートと還流冷却管を付した１００ｍｌの４つ口フ
ラスコを乾燥窒素で満たし、これにマグネシウムリボン
を紙やすりで磨いた後細かく切ったものを、４．１ｇ
と、金属ナトリウムから直前に蒸留し得た乾燥ジエチル
エーテルを約１０ｍｌ加えた。滴下ロートには先の乾燥
ジエチルエーテルを約４０ｍｌと、臭化ｔｅｒｔ−ブチ
ルを２０．７ｇ入れ、これを約１時間でフラスコに攪拌
しながら滴下した。滴下終了後、さらに１時間還流を続
けた。反応液をしばらく静置し、未反応のマグネシウム
を沈殿させた後、上澄み液を開始剤溶液とした。この溶
液の濃度は滴定により決定した。すなわち溶液の一部を
注射器にて取り出し過剰の０．１Ｎ塩酸を加えた後、
０．１Ｎ水酸化トナリウム水溶液で逆滴定した。ｔｅｒ
ｔ−ブチルマグネシウムブロマイド基の濃度は０．７３
５ｍｏｌ／ｌであった。B. Preparation example of Grignard reagent 1) tert-butylmagnesium bromide A 100 ml four-necked flask equipped with a dropping funnel and a reflux condenser was filled with dry nitrogen, and a magnesium ribbon was sanded and then finely chopped. 4.1 g
Then, about 10 ml of dry diethyl ether obtained by distillation from metal sodium immediately before was added. About 40 ml of the above dry diethyl ether and 20.7 g of tert-butyl bromide were put into the dropping funnel, and this was added dropwise to the flask while stirring for about 1 hour. After the dropping was completed, the reflux was continued for another hour. The reaction solution was allowed to stand for a while to precipitate unreacted magnesium, and the supernatant was used as an initiator solution. The concentration of this solution was determined by titration. That is, after taking out a part of the solution with a syringe and adding excess 0.1N hydrochloric acid,
Back titration was carried out with a 0.1 N aqueous solution of tonarium hydroxide. ter
The concentration of t-butylmagnesium bromide group is 0.73.
It was 5 mol / l.
【００２０】２）１−ナフチルマグネシウムブロマイド ｔｅｒｔ−ブチルマグネシウムブロマイドと同様の操作
で調製を行った。すなわち、滴下ロートと還流冷却管を
付した１００ｍｌの４つ口フラスコを乾燥窒素で満た
し、これにマグネシウムリボンを紙やすりで磨いた後細
かく切ったものを２．８ｇと、金属ナトリウムから直前
に蒸留し得た乾燥ジエチルエーテルを約１０ｍｌ加え
た。滴下ロートには先の乾燥ジエチルエーテルを約４０
ｍｌと、１−ナフチルブロマイドを２０．２ｇ入れ、こ
れを約１時間でフラスコに攪拌しながら滴下した。滴下
終了後、さらに１時間還流を続けた。反応液をしばらく
静置し、未反応のマグネシウムおよび不溶物を沈澱させ
た後、上澄み液を開始剤溶液とした。2) 1-Naphthylmagnesium bromide Preparation was carried out in the same manner as tert-butylmagnesium bromide. That is, a 100 ml four-necked flask equipped with a dropping funnel and a reflux condenser was filled with dry nitrogen, and a magnesium ribbon was sanded and finely chopped into 2.8 g. About 10 ml of the obtained dry diethyl ether was added. Approximately 40 parts of the above dry diethyl ether was added to the dropping funnel.
ml and 1-naphthyl bromide (20.2 g) were added, and this was added dropwise to the flask with stirring for about 1 hour. After the dropping was completed, the reflux was continued for another hour. The reaction solution was allowed to stand for a while to precipitate unreacted magnesium and insoluble matter, and then the supernatant was used as an initiator solution.
【００２１】この溶液の濃度もｔｅｒｔ−ブチルマグネ
シウムブロマイドと同様の操作で決定した。すなわち溶
液の一部を注射器にて取り出し過剰の０．１Ｎ塩酸を加
えた後、０．１Ｎ水酸化ナトリウム水溶液で逆滴定し
た。１−ナフチルマグネシウムブロマイド基の濃度は
０．０４３ｍｏｌ／ｌであった。The concentration of this solution was also determined by the same operation as for tert-butylmagnesium bromide. That is, a part of the solution was taken out with a syringe, excess 0.1N hydrochloric acid was added, and then back titration was performed with a 0.1N aqueous sodium hydroxide solution. The concentration of 1-naphthylmagnesium bromide group was 0.043 mol / l.
【００２２】Ｃ．重合実施例 実施例１〜４ 水分の測定には、三菱化成工業（株）製、ＭＣＩディジ
タル微量水分測定装置ＣＡ−０２型（クーロメトリー、
カール・フィッシャー滴定法）を使用して行った。得ら
れたポリマーのタクチシチーの測定には、日本電子
（株）製、プロトン核磁気共鳴スペクトルＪＮＭ−ＧＸ
−２７０を使用して、５５℃重クロロホルム溶媒中でフ
ーリエ変換ＮＭＲ測定法を採用した。C. Polymerization Examples Examples 1 to 4 MCI digital trace moisture analyzer CA-02 type (coulometry, manufactured by Mitsubishi Kasei Co., Ltd.) was used to measure moisture.
Karl Fisher titration method). The tacticity of the obtained polymer was measured by JEOL Ltd., Proton Nuclear Magnetic Resonance spectrum JNM-GX.
-270 was used to employ Fourier Transform NMR measurements in 55 ° C. deuterated chloroform solvent.
【００２３】５０ｍｌ容積の三方コック付きガラス製ア
ンプル管を乾燥窒素で満たした後、別途前記調製例にし
たがって調製したメタクリル酸メチルおよびトルエンを
表１に示した通り加えた。この溶液に水を通した窒素で
所定時間バブリングし水を添加し、溶液中の水分を測定
した。これを−４７℃まで冷却し、これに別途前記調製
例にしたがって調製したｔｅｒｔ−ブチルマグネシウム
ブロマイドのジエチルエーテル溶液を表１に示した量
で、アンプルを攪拌しながら加え、重合を開始した。３
時間経過した後、２Ｎ塩酸−メタノールを添加して重合
を停止させた重合液を約１０倍容量のメタノールに漬
け、１日放置し、ポリマーを粉砕してこれを濾別し、約
５０℃で真空乾燥して評価試料とした。A glass ampoule tube with a three-way cock having a volume of 50 ml was filled with dry nitrogen, and then methyl methacrylate and toluene separately prepared according to the above-mentioned preparation example were added as shown in Table 1. Water was added to this solution by bubbling nitrogen through water for a predetermined time, and the water content in the solution was measured. This was cooled to −47 ° C., and a solution of tert-butylmagnesium bromide in diethyl ether prepared separately according to the above Preparation Example was added in an amount shown in Table 1 with stirring an ampoule to initiate polymerization. Three
After a lapse of time, 2N hydrochloric acid-methanol was added to terminate the polymerization, and the polymerization solution was immersed in about 10 times the volume of methanol and allowed to stand for 1 day. The polymer was crushed, filtered and filtered at about 50 ° C. It was vacuum dried to obtain an evaluation sample.
【００２４】実施例５ アニオン重合開始剤に１−ナフチルマグネシウムブロマ
イドのジエチルエーテル溶液を用いて実施例１〜４と同
様の方法でメタクリル酸メチルの重合を行った。ただし
重合温度は−１５℃とした。結果は表１に示す。Example 5 Methyl methacrylate was polymerized in the same manner as in Examples 1 to 4 using a diethyl ether solution of 1-naphthylmagnesium bromide as an anionic polymerization initiator. However, the polymerization temperature was -15 ° C. The results are shown in Table 1.
【００２５】比較例１、２ メタクリル酸メチルの重合を、実施例１〜４と同様の方
法で水を添加せずに行った。結果は表１に示す。Comparative Examples 1 and 2 Methyl methacrylate was polymerized in the same manner as in Examples 1 to 4 without adding water. The results are shown in Table 1.
【００２６】比較例３ メタクリル酸メチルの重合を、実施例５と同様の方法で
水を添加せずに行った。結果は表１に示す。表１の結果
より、重合系内の水が共存した実施例は、水のほとんど
が存在しない比較例と比べて、メタクリル酸メチル重合
体の収率は低下するが、得られたメタクリル酸メチル重
合体のイソタクチシチーは上昇することがわかる。この
ことは溶媒量を変えても同じである。また、得られたメ
タクリル酸メチルの重合体のイソタクチシチーは、共存
する水の量の絶対量に依存するものではなく、水と重合
開始剤であるグリニャール試薬のマグネシウムイオンと
のモル比に依存するものであることがわかる。Comparative Example 3 Polymerization of methyl methacrylate was carried out in the same manner as in Example 5 without adding water. The results are shown in Table 1. From the results shown in Table 1, in the example in which water in the polymerization system coexists, the yield of the methyl methacrylate polymer decreases as compared with the comparative example in which most of the water does not exist. It can be seen that the combined isotacticity increases. This is the same even if the amount of solvent is changed. Further, the isotacticity of the obtained polymer of methyl methacrylate does not depend on the absolute amount of coexisting water, but depends on the molar ratio of water to magnesium ion of the Grignard reagent which is a polymerization initiator. It turns out that it does.
【００２７】[0027]
【表１】 [Table 1]
【００２８】[0028]
【発明の効果】アニオン重合開始剤にグリニャール試薬
を用いてメタクリル酸メチルをアニオン重合させ高度に
イソタクチックなメタクリル酸メチル重合体を製造する
方法において、用いるメタクリル酸メチル単量体および
溶媒の精製を簡略化できるとともに、重合系内の水分を
抑制することにより生成されるメタクリル酸メチル重合
体のイソタクチシチーを容易に制御することができる。INDUSTRIAL APPLICABILITY In the method for producing a highly isotactic methyl methacrylate polymer by anionic polymerization of methyl methacrylate using a Grignard reagent as an anionic polymerization initiator, the purification of methyl methacrylate monomer and solvent used is simplified. In addition, the isotacticity of the methyl methacrylate polymer produced by suppressing the water content in the polymerization system can be easily controlled.
Claims (1)
タクチックなポリメタクリル酸メチルをアニオン重合に
より製造する方法において、重合開始剤であるグリニャ
ール試薬のマグネシウムイオンに対して、重合系内に水
をモル量で０．３倍以上共存させることを特徴とする立
体規則性メタクリル酸メチル重合体の製造方法。1. A method for producing highly isotactic polymethylmethacrylate by anionic polymerization using methylmethacrylate, wherein in the polymerization system, a molar amount of water is used with respect to magnesium ion of a Grignard reagent which is a polymerization initiator. The method for producing a stereoregular methyl methacrylate polymer is characterized in that it is allowed to coexist at 0.3 times or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19771792A JP3227209B2 (en) | 1992-07-01 | 1992-07-01 | Method for producing stereoregular methyl methacrylate polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19771792A JP3227209B2 (en) | 1992-07-01 | 1992-07-01 | Method for producing stereoregular methyl methacrylate polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0616726A true JPH0616726A (en) | 1994-01-25 |
| JP3227209B2 JP3227209B2 (en) | 2001-11-12 |
Family
ID=16379186
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19771792A Expired - Fee Related JP3227209B2 (en) | 1992-07-01 | 1992-07-01 | Method for producing stereoregular methyl methacrylate polymer |
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| Country | Link |
|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11279419B2 (en) | 2019-03-29 | 2022-03-22 | Sumitomo Chemical Company, Limited | Member for automobile roof and method for producing member for automobile roof |
-
1992
- 1992-07-01 JP JP19771792A patent/JP3227209B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11279419B2 (en) | 2019-03-29 | 2022-03-22 | Sumitomo Chemical Company, Limited | Member for automobile roof and method for producing member for automobile roof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3227209B2 (en) | 2001-11-12 |
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