JPH02160809A - Polymerization inhibitor for dialkylaminoalkyl (meth) acrylate - Google Patents
Polymerization inhibitor for dialkylaminoalkyl (meth) acrylateInfo
- Publication number
- JPH02160809A JPH02160809A JP31369788A JP31369788A JPH02160809A JP H02160809 A JPH02160809 A JP H02160809A JP 31369788 A JP31369788 A JP 31369788A JP 31369788 A JP31369788 A JP 31369788A JP H02160809 A JPH02160809 A JP H02160809A
- Authority
- JP
- Japan
- Prior art keywords
- acrylate
- dialkylaminoalkyl
- meth
- polymerization
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 41
- 239000003112 inhibitor Substances 0.000 title claims abstract description 28
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title abstract description 28
- 125000004985 dialkyl amino alkyl group Chemical group 0.000 title abstract description 25
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 10
- 239000010452 phosphate Substances 0.000 claims abstract description 10
- -1 dialkylaminoalkyl acrylate Chemical compound 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- 238000004821 distillation Methods 0.000 abstract description 17
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 238000005809 transesterification reaction Methods 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 abstract description 5
- 230000002401 inhibitory effect Effects 0.000 abstract description 4
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 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
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 4
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229950000688 phenothiazine Drugs 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 4
- 229940048086 sodium pyrophosphate Drugs 0.000 description 4
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005194 fractionation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- UZDXAQLLVAUBQD-UHFFFAOYSA-N ethyl prop-2-enoate;n-methylmethanamine Chemical compound CNC.CCOC(=O)C=C UZDXAQLLVAUBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- AODAQIOEZVDQLS-UHFFFAOYSA-N 3,4-ditert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1C(C)(C)C AODAQIOEZVDQLS-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Natural products CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 235000001465 calcium Nutrition 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-M crotonate Chemical compound C\C=C\C([O-])=O LDHQCZJRKDOVOX-NSCUHMNNSA-M 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- DLAPQHBZCAAVPQ-UHFFFAOYSA-N iron;pentane-2,4-dione Chemical compound [Fe].CC(=O)CC(C)=O DLAPQHBZCAAVPQ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-UHFFFAOYSA-N 0.000 description 1
- 229960003505 mequinol Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000002832 nitroso derivatives Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- GCKZNUDNTDWGFM-UHFFFAOYSA-N pentane-2,4-dione;tin Chemical class [Sn].CC(=O)CC(C)=O GCKZNUDNTDWGFM-UHFFFAOYSA-N 0.000 description 1
- WATYAKBWIQTPDE-UHFFFAOYSA-N pentane-2,4-dione;zinc Chemical compound [Zn].CC(=O)CC(C)=O WATYAKBWIQTPDE-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 150000003866 tertiary ammonium salts Chemical class 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
Abstract
Description
【発明の詳細な説明】
イ１発明の目的
［産業上の利用分野］
本発明はジアルキルアミノアルキルアクリレト又はジア
ルキルアミノアルキルメタクリレート（本明細書では両
者を併せてジアルキルアミノアルキル（メタ）アクリレ
ートという）用の重合防止剤に関するものであり、特に
エステル交換反応によるジアルキルアミノアルキル（メ
タ）アクリレートの合成工程、合成後の蒸留工程におい
て有効な重合防止剤に関するものである。Detailed Description of the Invention 1.Object of the Invention [Industrial Application Field] The present invention relates to dialkylaminoalkyl acrylate or dialkylaminoalkyl methacrylate (both herein referred to as dialkylaminoalkyl (meth)acrylate). The present invention relates to a polymerization inhibitor that is effective in the process of synthesizing dialkylaminoalkyl (meth)acrylate by transesterification reaction, and in the distillation process after synthesis.
ジメチルアミンエチルアクリレート、ジメチルアミノエ
チルメタクリレート、ジエチルアミノエチルメタクリレ
ート等のジアルキルアミノアルキル（メタ）アクリレー
トは、そのまま、またはアミノ基を３級もしくは４級ア
ンモニウム塩としたのちに、単独重合または他の不飽和
化合物と共重合することにより重合体を生成し、該重合
体は繊維処理剤、塗料、潤滑油添加剤、紙力増強剤、接
着剤、イオン交換樹脂さらには高分子凝集剤などとして
用いられるものであって、幅広い分野で使用されている
。従って、それらの薬剤を利用する分野で、本願発明は
有効に活用されるものである。Dimethylamine ethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate and other dialkylaminoalkyl (meth)acrylates can be used as they are, or after converting the amino group into a tertiary or quaternary ammonium salt, they can be homopolymerized or converted into other unsaturated compounds. A polymer is produced by copolymerizing with the polymer, and the polymer is used as a fiber treatment agent, paint, lubricating oil additive, paper strength enhancer, adhesive, ion exchange resin, and polymer flocculant. It is used in a wide range of fields. Therefore, the present invention can be effectively utilized in fields that utilize these drugs.
［従来の技術１
ジアルキルアミノアルキル（メタ）アクリレートは重合
し易い化合物であり、特にジアルキルアミノアルキル（
メタ）アクリレートの最も汎用的製造方法である、エス
テル交換反応によるジアルキルアミノアルキル（メタ）
アクリレートを製造において、その合成工程、特に合成
後の蒸留工程においては著しく重合し易く、その重合を
防止するために、此れまでも各種の重合防止剤、例えば
、ジアルキルヒドロキシルアミン、クロベン、芳香族ニ
トロソ化合物、Ｎ−へテロ環化合物、芳香族ニトロ化合
物、キノン類等の多くの重合防止剤が提案されてきてい
る。[Prior art 1 Dialkylaminoalkyl (meth)acrylate is a compound that easily polymerizes, especially dialkylaminoalkyl (meth)acrylate.
Dialkylaminoalkyl (meth) by transesterification, which is the most widely used method for producing meth)acrylate.
In the production of acrylate, it is extremely easy to polymerize during the synthesis process, especially the distillation process after synthesis, and in order to prevent the polymerization, various polymerization inhibitors have been used, such as dialkyl hydroxylamine, chloroben, aromatic Many polymerization inhibitors have been proposed, such as nitroso compounds, N-heterocyclic compounds, aromatic nitro compounds, and quinones.
［発明が解決しようとする問題点］
汎用的製造方法である前記エステル交換反応によるジア
ルキルアミノアルキル（メタ）アクリレートの製造方法
における、反応温度は一般に７０〜１２０°Ｃであり、
この程度の温度であれば、ジアルキルアミノアルキルメ
タクリレートの重合は従来の重合防止剤でも防止可能で
あるが、それより温度が高すぎると重合を防止すること
ができなくなり、またジアルキルアミノアルキルアルコ
ールは上記の反応温度においてさえ、その重合を従来の
重合防止剤で防止することは不可能である。[Problems to be Solved by the Invention] In the method for producing dialkylaminoalkyl (meth)acrylate by the transesterification reaction, which is a general-purpose production method, the reaction temperature is generally 70 to 120°C,
At this temperature, the polymerization of dialkylaminoalkyl methacrylate can be prevented using conventional polymerization inhibitors, but if the temperature is too high, polymerization cannot be prevented, and dialkylaminoalkyl alcohol Even at reaction temperatures of , it is impossible to prevent the polymerization with conventional polymerization inhibitors.
さらに、反応終了後、反応混合物より目的のジアルキル
アミノアルキル（メタ）アクリレートを蒸留により単離
する際は、ジアルキルアミノアルキル（メタ）アクリレ
ートを前記反応温度よりもかなりの高温に曝さざるを得
す、その様な高温下では従来の重合防止剤では満足に重
合を防止することができないばかりか、重合防止剤の蒸
気圧、昇華性及び安定性等に問題があり、さらには蒸留
後の製品中に、これら重合防止剤が残存混入して製品価
値を低下させるものもあるという問題点を有しているも
のである。Furthermore, when the desired dialkylaminoalkyl (meth)acrylate is isolated from the reaction mixture by distillation after the reaction is completed, the dialkylaminoalkyl (meth)acrylate must be exposed to a considerably higher temperature than the reaction temperature, Under such high temperatures, conventional polymerization inhibitors are not only unable to satisfactorily prevent polymerization, but also have problems with the vapor pressure, sublimation, and stability of polymerization inhibitors, and furthermore, they may cause problems in the product after distillation. However, there are problems in that some of these polymerization inhibitors may remain mixed in and reduce the product value.
蒸留時にジアルキルアミノアルキル（メタ）アクリレー
トが重合するということは、単にその収量が低下するだ
けでなく、重合物が反応器や配管に付着し、閉塞等の原
因となり、操業に際し、危険をもたらすおそれがあり、
又、釜残の抜き出し、蒸留塔内の掃除等の作業にも重大
な支障をもたらすものである。Polymerization of dialkylaminoalkyl (meth)acrylate during distillation not only reduces the yield, but also poses a risk that the polymer may adhere to reactors and piping, causing blockages and other dangers during operation. There is,
In addition, this poses a serious problem in operations such as removing the residue from the pot and cleaning the inside of the distillation column.
口１発明の構成
Ｅ問題点を解決するための手段］
本発明者らは、従来の重合防止剤よりも優れた効果を発
揮する重合防止剤、特に、アルキルアクリレート又はア
ルキルメタクリレート（本明細書では両者を併せて（メ
タ）アルキルアクリレートという）とジアルキルアミノ
アルキルアルコールを触媒存在下エステル交換反応させ
、反応後反応液を蒸留して目的生成物であるジアルキル
アミノアルキル（メタ）アクリレートを製造するときに
有効な重合防止剤について鋭意検討し、縮合リン酸塩が
従来の重合防止剤よりも優れた効果を発揮するものであ
ることを見出して本発明を完成するに到った。1. Structure E of the Invention Means for Solving Problems] The present inventors have discovered a polymerization inhibitor that exhibits a superior effect to conventional polymerization inhibitors, particularly alkyl acrylate or alkyl methacrylate (herein referred to as When the desired product, dialkylaminoalkyl (meth)acrylate, is produced by transesterifying the two (together referred to as (meth)alkyl acrylate) and dialkylaminoalkyl alcohol in the presence of a catalyst, and distilling the reaction solution after the reaction. After extensive research into effective polymerization inhibitors, the present invention was completed by discovering that condensed phosphate salts exhibit superior effects to conventional polymerization inhibitors.
即ち、本発明は、縮合リン酸塩からなることを特徴とす
るジアルキルアミノアルキル（メタ）アクリレート用重
合防止剤に関するものである。That is, the present invention relates to a polymerization inhibitor for dialkylaminoalkyl (meth)acrylate characterized by comprising a condensed phosphate.
本発明の重合防止剤は、ジアルキルアミノアルキル（メ
タ）アクリレート用の重合を防止するためのものである
が、特にジアルキルアミノアルキル（メタ）アクリレー
トをエステル交換反応により製造する際の重合を防止す
ることに優れた効果を発揮するものである。The polymerization inhibitor of the present invention is for preventing polymerization for dialkylaminoalkyl (meth)acrylate, and is particularly useful for preventing polymerization when dialkylaminoalkyl (meth)acrylate is produced by transesterification. It exhibits excellent effects.
本発明におけるジアルキルアミノアルキル（メタ）アク
リレートとは、下記一般式で表せる化合物である。The dialkylaminoalkyl (meth)acrylate in the present invention is a compound represented by the following general formula.
＼
本発明の重合防止剤を適用するに好ましい化合物は、上
記一般式において、Ｒ１が水素またはメチル基であり、
Ｒ２が炭素数４以下のアルキレン基、Ｒ３、Ｒ４がお互
いに同一でも異なっていてもよい炭素数８以下のアルキ
ル基のものである。＼ Preferred compounds to which the polymerization inhibitor of the present invention is applied are those in the above general formula in which R1 is hydrogen or a methyl group,
R2 is an alkylene group having 4 or less carbon atoms, and R3 and R4 are an alkyl group having 8 or less carbon atoms, which may be the same or different.
なお、上記ジアルキルアミノアルキル（メタ）アクリレ
ートの製造において、使用されるアルキル（メタ）アク
リレートとしては、炭素数４以下のアルキル基を有する
ものが、反応性の点、副成するアルコールの除去の点等
から好ましく、具体的には、例えばメチルアクリレート
、メチルメタクリレート、エチルアクリレート、エチル
メタクリレート、ｎ−プロピルアクリレート、ｎ−プロ
ピルメタクリレート、ｎ−ブチルアクリレート、ｎ−ブ
チルメタクリレート、５ｅｃ−ブチルアクリレート、５
ｅｃ−ブチルメタクリレート、ｔ−ブチルアクリレート
、ｔ−ブチルメタクリレートが挙げられる。特に好まし
いものとしては、メチルアクリレート、メチルメタクリ
レート、エチルアクリレート、エチルメタクリレート等
を、反応による副成アルコールの除去のし易さ、反応混
合物の均一性、コストの面から挙げることが出来る。In the production of the above-mentioned dialkylaminoalkyl (meth)acrylate, the alkyl (meth)acrylate used is one having an alkyl group of 4 or less carbon atoms in terms of reactivity and removal of by-produced alcohol. Preferred examples include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 5ec-butyl acrylate, 5ec-butyl acrylate, etc.
Examples include ec-butyl methacrylate, t-butyl acrylate, and t-butyl methacrylate. Particularly preferred are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, etc. from the viewpoints of ease of removal of by-product alcohol by reaction, uniformity of the reaction mixture, and cost.
また、使用されるジアルキルアミノアルキルアルコール
ジメチルアミノエチル（メタ）アクリレートを目的とす
るときはジメチルアミノエチルアルコールが用いられ、
ジエチルアミンエチル（メタ）アクリレートを目的とす
るときはジエチルアミノエチルアルコールが用いられる
。その他に用いられるジアルキルアミノアルキルアルコ
ールとしては、ジロープロピルアミノエチルアルコール
、ジ−ｎ−ブチルアミノエチルアルコール、ジエチルア
ミノ−ｎプロピルアルコール、ジベンジルアミノエチル
アルコール等を挙げることができる。In addition, when the purpose is to use dialkylaminoalkyl alcohol dimethylaminoethyl (meth)acrylate, dimethylaminoethyl alcohol is used.
When the purpose is diethylamine ethyl (meth)acrylate, diethylaminoethyl alcohol is used. Other dialkylaminoalkyl alcohols that can be used include diropropylaminoethyl alcohol, di-n-butylaminoethyl alcohol, diethylamino-npropyl alcohol, and dibenzylaminoethyl alcohol.
本発明の重合防止剤は、縮合リン酸塩からなるものであ
るが、縮合リン酸塩の具体例としては、ピロリン酸カリ
ウム、ピロリン酸ナトリウム、ビロリン酸カルシウム、
トリポリリン酸ナトリウム、トリポリリン酸カリウム等
を挙げることができる。The polymerization inhibitor of the present invention is composed of a condensed phosphate, and specific examples of the condensed phosphate include potassium pyrophosphate, sodium pyrophosphate, calcium birophosphate,
Examples include sodium tripolyphosphate and potassium tripolyphosphate.
これらのなかでもピロリン酸カリウムの重合防止効果は
格別に優れている。Among these, potassium pyrophosphate is particularly effective in preventing polymerization.
これら重合防止剤の使用量としては、ジアルキルアミノ
アルキル（メタ）アクリレートに対して、好ましくは０
．０１〜２．０％であり、さらに好ましくは０．０５〜
１．０％である。The amount of these polymerization inhibitors used is preferably 0 to dialkylaminoalkyl (meth)acrylate.
．． 01 to 2.0%, more preferably 0.05 to 2.0%
It is 1.0%.
尚、本発明の重合防止剤は、公知の重合防止剤と併用で
きることは当然で、併用できる公知の重合防止剤として
は、ハイドロキノン、ハイドロキノン千ツメチルエーテ
ル、ジｔｅｒｔ−プチルカテコル、フェノチアジン、バ
ラフェニレンジアミン等を挙げることができ、その使用
量は反応液総重量に対し、好ましくは１０〜５， ０
０ ０ｐｐｍ 、さらに好ましくは５０〜３， Ｏ Ｏ
Ｏｐｐｍである。It goes without saying that the polymerization inhibitor of the present invention can be used in combination with known polymerization inhibitors. Examples of known polymerization inhibitors that can be used in combination include hydroquinone, hydroquinone methyl ether, di-tert-butylcatechol, phenothiazine, paraphenylenediamine, etc. The amount used is preferably 10-5.0% based on the total weight of the reaction solution.
00ppm, more preferably 50~3,00ppm
It is Oppm.
ジアルキルアミノアルキル（メタ）アクリレートの製造
は、従来公知のエステルとアルコールのエステル交換反
応により行われる。即ち、前記ジアルキル（メタ）アク
リレート、前記ジアルキルアミノアルキルアルコール、
縮合リン酸塩、従来公知の触媒、必要に応じ副成アルコ
ールとの共沸剤、従来公知の重合防止剤等を混合し、７
０〜１２０°Ｃに加熱し、副成アルコールを抜き出しな
がら反応を進め得られた合成液を減圧蒸留し目的物を得
るという方法で行われる。The dialkylaminoalkyl (meth)acrylate is produced by a conventionally known transesterification reaction between an ester and an alcohol. That is, the dialkyl (meth)acrylate, the dialkylaminoalkyl alcohol,
A condensed phosphate, a conventionally known catalyst, an azeotropic agent with a by-product alcohol if necessary, a conventionally known polymerization inhibitor, etc. are mixed, and 7
The reaction is carried out by heating to 0 to 120° C., removing the by-product alcohol, and distilling the resulting synthetic liquid under reduced pressure to obtain the desired product.
本発明の重合防止剤である縮合リン酸塩は、前記した様
に、ジアルキルアミノアルキル（メタ）アクリレートの
製造に際して用いられるときは、反応原料と共に仕込む
ことが好ましい。As described above, when the condensed phosphate which is the polymerization inhibitor of the present invention is used in the production of dialkylaminoalkyl (meth)acrylate, it is preferably added together with the reaction raw materials.
ジアルキルアミノアルキル（メタ）アクリレートの製造
のための触媒としては、公知のアルカリ金属アルコラー
ド、マグネシウムアルコラード、チタンアルコラード、
ジブチルスズオキサイド等の有機スズ化合物、アセチル
アセトン鉄、アセチルアセトンニッケル等のアセチルア
セトン金属錯化合物等の他に本発明者等が提案したアセ
チルアセトンスズ化合物（特願昭６３−１２５９７１）
、アセチルアセトン亜鉛化合物（特願昭６３−１６４８
７４）及びアセチルアセトフコハル＋−化合ｈ（特願昭
６３−２０８２２１）も好ましく用いられる。Catalysts for the production of dialkylaminoalkyl (meth)acrylates include known alkali metal alcoholades, magnesium alcoholades, titanium alcoholades,
In addition to organic tin compounds such as dibutyltin oxide, acetylacetone metal complex compounds such as iron acetylacetone and nickel acetylacetonate, tin acetylacetone compounds proposed by the present inventors (Japanese Patent Application No. 125971/1983)
, acetylacetone zinc compound (patent application 1648/1986)
74) and acetylacetofucohal+-compound h (Japanese Patent Application No. 63-208221) are also preferably used.
［作用］
本発明に用いられる縮合リン酸塩は高，昌でも極めて安
定であり、分解等のおそれもなく、且つ合成触媒に対し
ても不活性であるため、ジアルキルアミノアルキル（メ
タ）アクリレ一トの合成工程及び反応後の蒸留工程のい
ずれにも同等支障なく用いることができるうえ、重合防
止効果は従来公知の重合防止剤に比較して非常に優れた
作用を示すものである。[Function] The condensed phosphate used in the present invention is extremely stable even under high temperatures and conditions, has no risk of decomposition, and is inert to synthesis catalysts. It can be used equally well in both the synthesis step and the post-reaction distillation step, and it exhibits a much superior polymerization inhibitory effect compared to conventionally known polymerization inhibitors.
［実施例］
以下、実施例及び比較例を用いて、本発明を更に詳細に
説明する。[Examples] Hereinafter, the present invention will be explained in more detail using Examples and Comparative Examples.
実施例１
攪拌機、温度計、充填塔、冷却器及びＨ管を備えた三ロ
フラスコにメチルメタクリレート１５０ｇ （ １ ５
ｍｏｌ）、ジメチルアミノエチルアルコール６ ６ ９
ｇ（７． ５ ｍｏｌ．）、マグネシウムエチラート
８．６ｇ （０，０８ｍｏｌ）、ｎ−ヘキサン１２９ｇ
（６ｗｔ％）、フェノチアジン２．１ｇ（１０００ｐｐ
ｍ ） 、ピロリン酸カリウム１．１ｇ（５００ρＰｉ
ｌ＋）、を加え加熱を開始した。Example 1 150 g of methyl methacrylate (15
mol), dimethylaminoethyl alcohol 6 6 9
g (7.5 mol.), magnesium ethylate 8.6 g (0.08 mol), n-hexane 129 g
(6wt%), phenothiazine 2.1g (1000pp
m ), 1.1 g of potassium pyrophosphate (500ρPi
l+), and heating was started.
還流比１で充填塔塔頂温度を６３〜６８°Ｃに維持して
、メタノール／ｎ−ヘキサン共沸混合物を４時間留出さ
せた。このときガスクロマトグラフィーによって、内容
物の分析を行ったところ、ジメチルアミノエチルアルコ
ールの転化率は９５％であり、ジメチルアミノエチルメ
タクリレートの収率は９２％であった。The methanol/n-hexane azeotrope was distilled out for 4 hours by maintaining the top temperature of the packed column at 63 to 68°C at a reflux ratio of 1. At this time, the contents were analyzed by gas chromatography, and the conversion rate of dimethylaminoethyl alcohol was 95%, and the yield of dimethylaminoethyl methacrylate was 92%.
次いでこの反応液を１００ Ｔｏｒｒの減圧下でメチル
メタクリレートを留去し、さらに１００Ｔｏｒｒの減圧
下で分留塔塔頂温度１２０〜１２５°Ｃでジメチルアミ
ノエチルメタクリレートを留出させ、ジメチルアミノエ
チルメタクリレ−）１０３５ｇ（収率８８％）を得た。Next, methyl methacrylate was distilled off from this reaction solution under a reduced pressure of 100 Torr, and dimethylaminoethyl methacrylate was further distilled off under a reduced pressure of 100 Torr at a fractionation column top temperature of 120 to 125°C. -) 1035g (yield 88%) was obtained.
蒸留残渣は室温下でも充分流動性を有していた。The distillation residue had sufficient fluidity even at room temperature.
比較例１
ピロリン酸カリウムを用いなかった以外は実施例１と同
様の装置、条件で反応及び蒸留を実施した。その結果ジ
メチルアミノエチルメタクリレ−）９６５ｇ（収率８３
％）が得られた。蒸留残渣はかなりの高粘度状態であっ
た。Comparative Example 1 Reaction and distillation were carried out using the same apparatus and conditions as in Example 1, except that potassium pyrophosphate was not used. As a result, 965 g of dimethylaminoethyl methacrylate (yield: 83
%)was gotten. The distillation residue was in a considerably highly viscous state.
実施例２
実施例１と同様の装置に、メチルアクリレート１２９０
ｇ（１５ｍｏｌ）、ジメチルアミノエチルアルコール６
６９ ｇ（７，５ｍｏり、ニッケルビス（アセチルアセ
トネート）１８．１ｇ（０゜０４ｍｏｌ）、フェノチア
ジン２．１ｇ（１０００ｐｐ餠）、ピロリン酸ナトリウ
ム１．１ｇ（５００ｐｐｍ）、を加え加熱を開始した。Example 2 Methyl acrylate 1290 was added to the same apparatus as in Example 1.
g (15 mol), dimethylaminoethyl alcohol 6
69 g (7.5 mol), 18.1 g (0°04 mol) of nickel bis(acetylacetonate), 2.1 g (1000 ppm) of phenothiazine, and 1.1 g (500 ppm) of sodium pyrophosphate were added, and heating was started.
生成したメタノールとメチルアクリレートの共沸混合物
を３０分間全還流させた後、さらに充填塔塔頂温度を６
０〜６５°Ｃに維持して共沸混合物を系外に抜き出しな
がら６時間反応させた。ジメチルアミノエチルアクリレ
ートの収率は７０％であった。 次いでこの反応液を７
０Ｔｏｒｒの減圧下でメチルアクリレートを留去し、さ
らに７０Ｔ。After the resulting azeotropic mixture of methanol and methyl acrylate was completely refluxed for 30 minutes, the temperature at the top of the packed column was further increased to 6.
The reaction was carried out for 6 hours while maintaining the temperature at 0 to 65°C and extracting the azeotrope from the system. The yield of dimethylaminoethyl acrylate was 70%. Next, this reaction solution was
Methyl acrylate was distilled off under reduced pressure of 0 Torr, and the mixture was further heated to 70 T.
ｒｒの減圧下で分留塔塔頂温度１００〜１０５°Ｃでジ
メチルアミノエチルアクリレートを留出させ、ジメチル
アミンエチルアクリレート７０８ｇ（収率６６％）を得
た。蒸留残渣は室温下でも充分流動性を有していた。Dimethylaminoethyl acrylate was distilled out under reduced pressure of RR at a fractionation column top temperature of 100 to 105°C to obtain 708 g (yield: 66%) of dimethylamine ethyl acrylate. The distillation residue had sufficient fluidity even at room temperature.
比較例２
ピロリン酸ナトリウムを用いなかった以外は実施例２と
同様の装置、条件で反応及び蒸留を実施した。その結果
ジメチルアミノエチルアクリレート５９０ｇ（収率５５
％）が得られた。蒸留残渣はかなりの高粘度状態であっ
た。Comparative Example 2 Reaction and distillation were carried out using the same apparatus and conditions as in Example 2, except that sodium pyrophosphate was not used. As a result, 590 g of dimethylaminoethyl acrylate (yield: 55
%)was gotten. The distillation residue was in a considerably highly viscous state.
実施例３
実施例１と同様の装置に、メチルアクリレート１２９０
ｇ（１５ｍｏｌ）、ジメチルアミノエチルアルコール６
６９ ｇ（７，５ｍｏｌ）、モロ−ブチルチン（アセチ
ルアセトネー）） １６．２ ｇ （０，０４ｍｏｌ
）、ｎ−ヘキサン１２９ｇ（６ｗｔ％）、゛フェノチア
ジン２．１ｇ（１０００ｐｐｍ） 、ビロリン酸カリウ
ム１．１ｇ（５００ｐｐｍ）を加え加熱を開始した。充
填塔塔頂温度を４８〜５３°Ｃに維持して、メタノール
とｎ−ヘキサンの共沸混合物の一部を系外に抜き出しな
がら６時間反応させた。反応液をガスクロマトグラフィ
ーによって分析した之ころ、ジメチルアミノエチルアク
リレートの収率は９２％であった。さらにこの反応液を
７０Ｔｏｒｒの減圧下でメチルアクリレートを留去した
後、分留塔塔頂温度１００〜１０５°Ｃでジメチルアミ
ノエチルアクリレート９４４ｇ（収率８８％）を得た。Example 3 Methyl acrylate 1290 was added to the same apparatus as in Example 1.
g (15 mol), dimethylaminoethyl alcohol 6
69 g (7.5 mol), Moro-butyltin (acetylacetonate) 16.2 g (0.04 mol)
), 129 g (6 wt%) of n-hexane, 2.1 g (1000 ppm) of phenothiazine, and 1.1 g (500 ppm) of potassium birophosphate were added, and heating was started. The temperature at the top of the packed column was maintained at 48 to 53°C, and the reaction was allowed to proceed for 6 hours while part of the azeotropic mixture of methanol and n-hexane was extracted from the system. When the reaction solution was analyzed by gas chromatography, the yield of dimethylaminoethyl acrylate was 92%. Furthermore, methyl acrylate was distilled off from this reaction solution under reduced pressure of 70 Torr, and 944 g (yield: 88%) of dimethylaminoethyl acrylate was obtained at a fractionation column top temperature of 100 to 105°C.
蒸留残渣は室温下でも充分流動性を有していた。The distillation residue had sufficient fluidity even at room temperature.
比較例３
重合防止剤ピロリン酸ナトリウムを用いなかった以外は
実施例３と同様の装置、条件で反応及び蒸留を実施した
。その結果ジメチルアミノエチルアクリレート８２６ｇ
（収率７７％）が得られた。Comparative Example 3 Reaction and distillation were carried out using the same equipment and conditions as in Example 3, except that the polymerization inhibitor sodium pyrophosphate was not used. As a result, 826g of dimethylaminoethyl acrylate
(yield 77%) was obtained.
蒸留残渣は流動性を示さず室温下では半固体状態であっ
た。The distillation residue showed no fluidity and was in a semi-solid state at room temperature.
ハ８発明の効果
本発明によれば、ジアルキルアミノアルキル（メタ）ア
クリレートを高純度、高収率で製造することができ、高
分子凝集剤、繊維処理剤等の製造に非常に好適な原料を
供給することができ、それらを使用する業界に寄与する
効果は多大なものである。C8 Effects of the Invention According to the present invention, dialkylaminoalkyl (meth)acrylate can be produced with high purity and high yield, and is a very suitable raw material for producing polymer flocculants, fiber treatment agents, etc. The benefits they can provide and contribute to the industries that use them are enormous.
Claims (1)
アミノアルキルアクリレート又はジアルキルアミノアル
キルメタクリレート用重合防止剤。1. A polymerization inhibitor for dialkylaminoalkyl acrylate or dialkylaminoalkyl methacrylate, characterized by comprising a condensed phosphate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31369788A JPH02160809A (en) | 1988-12-14 | 1988-12-14 | Polymerization inhibitor for dialkylaminoalkyl (meth) acrylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31369788A JPH02160809A (en) | 1988-12-14 | 1988-12-14 | Polymerization inhibitor for dialkylaminoalkyl (meth) acrylate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02160809A true JPH02160809A (en) | 1990-06-20 |
Family
ID=18044429
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31369788A Pending JPH02160809A (en) | 1988-12-14 | 1988-12-14 | Polymerization inhibitor for dialkylaminoalkyl (meth) acrylate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02160809A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130274094A1 (en) * | 2012-04-11 | 2013-10-17 | The Procter & Gamble Company | Catalysts For The Conversion Of Hydroxypropionic Acid Or Its Derivatives To Acrylic Acid Or Its Derivatives |
| CN106966913A (en) * | 2017-04-06 | 2017-07-21 | 青岛科技大学 | A kind of preparation method of improved methacrylic acid dialkylamino ethyl ester |
-
1988
- 1988-12-14 JP JP31369788A patent/JPH02160809A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130274094A1 (en) * | 2012-04-11 | 2013-10-17 | The Procter & Gamble Company | Catalysts For The Conversion Of Hydroxypropionic Acid Or Its Derivatives To Acrylic Acid Or Its Derivatives |
| US10106484B2 (en) * | 2012-04-11 | 2018-10-23 | The Procter & Gamble Company | Catalysts for the conversion of hydroxypropionic acid or its derivatives to acrylic acid or its derivatives |
| CN106966913A (en) * | 2017-04-06 | 2017-07-21 | 青岛科技大学 | A kind of preparation method of improved methacrylic acid dialkylamino ethyl ester |
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