JPH04169559A - Preservation of n,n-dialkylaminoalkyl acrylate - Google Patents
Preservation of n,n-dialkylaminoalkyl acrylateInfo
- Publication number
- JPH04169559A JPH04169559A JP29401790A JP29401790A JPH04169559A JP H04169559 A JPH04169559 A JP H04169559A JP 29401790 A JP29401790 A JP 29401790A JP 29401790 A JP29401790 A JP 29401790A JP H04169559 A JPH04169559 A JP H04169559A
- Authority
- JP
- Japan
- Prior art keywords
- oxygen concentration
- dialkylaminoalkyl acrylate
- dissolved oxygen
- acrylate
- coloring
- 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
- 238000004321 preservation Methods 0.000 title abstract 2
- 239000001301 oxygen Substances 0.000 claims abstract description 68
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 67
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 238000003860 storage Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- -1 dialkylaminoalkyl acrylate Chemical compound 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 1
- 238000004040 coloring Methods 0.000 abstract description 19
- 238000006116 polymerization reaction Methods 0.000 abstract description 15
- 239000007789 gas Substances 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 238000002845 discoloration Methods 0.000 description 6
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- NFTVTXIQFYRSHF-UHFFFAOYSA-N 1-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)C(C)OC(=O)C=C NFTVTXIQFYRSHF-UHFFFAOYSA-N 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229950000688 phenothiazine Drugs 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 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
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- UOZJCRSVUOQDNJ-UHFFFAOYSA-N 2-(dibutylamino)ethyl prop-2-enoate Chemical compound CCCCN(CCCC)CCOC(=O)C=C UOZJCRSVUOQDNJ-UHFFFAOYSA-N 0.000 description 1
- HPGIOSOCXHTQGW-UHFFFAOYSA-N 2-(dipropylamino)ethyl prop-2-enoate Chemical compound CCCN(CCC)CCOC(=O)C=C HPGIOSOCXHTQGW-UHFFFAOYSA-N 0.000 description 1
- BDKSYBXVYUGXIG-UHFFFAOYSA-N 2-(ethylamino)ethyl prop-2-enoate Chemical compound CCNCCOC(=O)C=C BDKSYBXVYUGXIG-UHFFFAOYSA-N 0.000 description 1
- XUYDVDHTTIQNMB-UHFFFAOYSA-N 3-(diethylamino)propyl prop-2-enoate Chemical compound CCN(CC)CCCOC(=O)C=C XUYDVDHTTIQNMB-UHFFFAOYSA-N 0.000 description 1
- UFQHFMGRRVQFNA-UHFFFAOYSA-N 3-(dimethylamino)propyl prop-2-enoate Chemical compound CN(C)CCCOC(=O)C=C UFQHFMGRRVQFNA-UHFFFAOYSA-N 0.000 description 1
- CPQWVOLUENESHH-UHFFFAOYSA-N 3-(dipropylamino)propyl prop-2-enoate Chemical compound CCCN(CCC)CCCOC(=O)C=C CPQWVOLUENESHH-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は一般式（１）
％式％
（式中、Ｒ１は炭素数１〜４の直鎖又は分岐鎖のアルキ
レン基を示し、Ｒ２およびＲ３は各々独立して炭素数１
〜４のアルキル基を示す）で示されるＮ、 Ｎ−ジア
ルキルアミノアルキルアクリレートの貯蔵時における重
合を抑制しながら着色の進行をも抑制する方法に関する
ものである。Detailed Description of the Invention (Industrial Application Field) The present invention is based on the general formula (1) % formula % (wherein R1 represents a straight or branched alkylene group having 1 to 4 carbon atoms, R2 and R3 each independently has 1 carbon number
The present invention relates to a method for suppressing the progress of coloring while suppressing the polymerization of N,N-dialkylaminoalkyl acrylate represented by the alkyl group (-4) during storage.
一般式（１）で示されるＮ、 Ｎ−ジアルキルアミノ
アルキルアクリレートは、繊維の染色性改良剤、プラス
チックの帯電防止剤、塗料における顔料分散剋 紫外線
硬化助剤として有用であり、またアミノ基を４級化する
などして各種の誘導体として用いら札 あるいは単独重
合または他の不飽和化合物との共重合により生じた重合
体は繊維処理舷 トナーバインダー、塗料、潤滑油添加
舷紙力増強舷 接着舷 イオン交換樹脂ざらにはカチオ
ン性高分子凝集剤などとして用いられるものであって、
輻広い分野で有用である。N,N-dialkylaminoalkyl acrylate represented by the general formula (1) is useful as a dyeability improver for fibers, an antistatic agent for plastics, a pigment dispersion agent in paints, and an ultraviolet curing aid, and is also useful as Polymers produced by homopolymerization or copolymerization with other unsaturated compounds are fiber-treated ships, toner binders, paints, and lubricating oils, paper strength reinforcement ships, adhesive ships. Ion exchange resin particles are used as cationic polymer flocculants, etc.
It is useful in a wide range of fields.
（従来の技術）
工業的なＮ、 Ｎ−ジアルキルアミノアルキルアクリ
レート製品としては重合物が少ないことはもちろんであ
るが、用途によっては、着色がハーゼン色数（ＡＰＨＡ
）１００以下程度の品質が要求される。しかし、Ｎ、
Ｎ−ジアルキルアミノアルキルアクリレートは貯蔵時
における着色の進行が著しく、製造設備から得られたば
かりの製品も貯蔵している間に次第に着色し、特に貯蔵
時の外気温が高くなる夏期には着色の進行が著しくて１
〜２週間でＡＰＨＡ１００以上となり品質の保持が困難
となっていた。着色したＮ、 Ｎ−ジアルキルアミノ
アルキルアクリレートを原料として各種の誘導体や重合
物にすると、得られる二次製品自体も着色したものとな
る。そして例えば、高分子凝集剤として使用する場合に
高分子量の物が得られない、凝集剤としての性能が劣る
、ゲル物が生じ易いといった問題も生じる。(Prior art) Although it goes without saying that industrial N,N-dialkylaminoalkyl acrylate products contain only a small amount of polymer, depending on the application, the coloring may be at a Hazen color number (APHA).
)100 or less quality is required. However, N.
N-dialkylaminoalkyl acrylate undergoes significant discoloration during storage, and even products freshly obtained from manufacturing equipment gradually become discolored during storage, especially in the summer when the outside temperature is high during storage. is remarkable and 1
After ~2 weeks, the APHA value reached 100 or more, making it difficult to maintain quality. When colored N,N-dialkylaminoalkyl acrylate is used as a raw material to produce various derivatives and polymers, the resulting secondary products themselves are also colored. For example, when used as a polymer flocculant, there are problems such as not being able to obtain a product with a high molecular weight, poor performance as a flocculant, and a tendency to form a gel.
Ｎ、 Ｎ−ジアルキルアミノアルキルアクリレートの
貯蔵方法については安定剤の添加が種々検討されてきた
が、これは重合防止を目的としたもので着色防止に効果
を示すものは少ない。重合防止と着色防止とを目的とし
たもので、Ｎ、 Ｎ−ジメチルアミノエチルアクリレ
ートをフェノチアジンを用いて保存する方法が開示され
ている（特開昭５３−１４４５２１号）。しかしこれも
、重合防止と着色防止の両面で効果が十分とはいえず、
実用的なものは見出されていない。Regarding the storage method of N,N-dialkylaminoalkyl acrylate, various studies have been made on the addition of stabilizers, but these are aimed at preventing polymerization, and few have been shown to be effective in preventing discoloration. A method for preserving N,N-dimethylaminoethyl acrylate using phenothiazine is disclosed for the purpose of preventing polymerization and discoloration (Japanese Patent Application Laid-open No. 144521/1983). However, this method cannot be said to be sufficiently effective in both preventing polymerization and preventing discoloration.
Nothing practical has been found.
Ｎ、 Ｎ−ジアルキルアミノアルキルアクリレートの
一般的な貯蔵方法としては冷暗所保存が行われており、
本発明者らの知見によれば５℃以下で貯蔵した場合には
２ケ月経過した後でもごく僅かしか着色が進行しない。The general storage method for N,N-dialkylaminoalkyl acrylate is to store it in a cool and dark place.
According to the findings of the present inventors, when stored at 5° C. or lower, coloring progresses only slightly even after 2 months.
しかしこの方法は保冷設備が必要となり、設備投資、運
転維持の点からみて費用が極めて高くなるという欠点を
有している。However, this method requires cold storage equipment, and has the disadvantage that the cost is extremely high in terms of equipment investment and operation and maintenance.
（発明が解決しようとする問題点）
本発明はＮ、 Ｎ−ジアルキルアミノアルキルアクリ
レートの貯蔵に際し、保冷設備を必要とせずにＮ、
Ｎ−ジアルキルアミノアルキルアクリレートの重合を抑
制しながら着色の進行をも抑制することを目的としたも
のである。(Problems to be Solved by the Invention) The present invention can store N,N-dialkylaminoalkyl acrylate without requiring cold storage equipment.
The purpose is to suppress the progress of coloring while suppressing the polymerization of N-dialkylaminoalkyl acrylate.
（問題点を解決するための手段）−
本発明者らは、まず着色の原因が何であるかを調査研究
したところ酸素の作用であることが明らかとなった。し
かし、酸素はＮ、 Ｎ−ジアルキルアミノアルキルア
クリレートの重合を抑制するうえで重要な役割を果たす
ものであり、酸素がない状態で貯蔵すると不溶性の重合
物が発生し、ついにはゲル化して製品としての品質を著
しく損なう。(Means for Solving the Problems) - The inventors of the present invention first investigated and researched the cause of coloring and found that it was the action of oxygen. However, oxygen plays an important role in inhibiting the polymerization of N,N-dialkylaminoalkyl acrylate, and when stored in the absence of oxygen, insoluble polymers are generated, which eventually gel and become unusable as a product. significantly impairs the quality of the product.
即ち、酸素の存在は重合抑制の面では有効な一方、着色
の面では不都合な作用をするという、相反する作用をな
す。本発明者らはこの点について着目し検討を進めた結
果、Ｎ、 Ｎ−ジアルキルアミノアルキルアクリレー
トを特定の溶存酸素濃度範囲にて貯蔵することにより着
色を著しく抑制でき、かつ重合も防止できることを見出
し、本発明を完成きせるに至った。即ち本発明は、一般
式（１）で示されるＮ、 Ｎ−ジアルキルアミノアル
キルアクリレートを貯蔵するに際し、Ｎ、 Ｎ−ジア
ルキルアミノアルキルアクリレートに空気を吹き込んで
酸素を飽和状態まで溶解きせた状態の溶存酸素濃度を１
００％として、Ｎ、 Ｎ−ジアルキルアミノアルキル
アクリレートを０．５％以上１０％以下の範囲内の溶存
酸素濃度で貯蔵するこ゛とを主旨とするＮ、 Ｎ−ジ
アルキルアミノアルキルアクリレートの貯蔵方法である
。That is, while the presence of oxygen is effective in inhibiting polymerization, it has a disadvantageous effect in terms of coloring, which is a contradictory effect. The inventors of the present invention have focused on this point and have conducted studies and found that by storing N,N-dialkylaminoalkyl acrylate within a specific dissolved oxygen concentration range, discoloration can be significantly suppressed and polymerization can also be prevented. , we have completed the present invention. That is, the present invention, when storing the N,N-dialkylaminoalkyl acrylate represented by the general formula (1), blows air into the N,N-dialkylaminoalkyl acrylate to dissolve oxygen to a saturated state. Oxygen concentration 1
This is a method for storing N,N-dialkylaminoalkyl acrylate whose main purpose is to store N,N-dialkylaminoalkyl acrylate at a dissolved oxygen concentration within the range of 0.5% to 10%.
本発明における一般式（１）で示されるＮ、 Ｎ−ジ
アルキルアミノアルキルアクリレトとしては、例えばＮ
、 Ｎ−ジメチルアミノエチルアクリレ−）−１Ｎ、
Ｎ−ジエチルアミノエチルアクリレート、Ｎ、
Ｎ−ジプロピルアミノエチルアクリレート、Ｎ、 Ｎ
−ジメチルアミノプロピルアクリレート、Ｎ、 Ｎ−
ジエチルアミノプロビルアクリレート、Ｎ、 Ｎ−ジ
プロピルアミノプロピルアクリレート、Ｎ、 Ｎ−ジ
ブチルアミノエチルアクリレート、Ｎ−メチル、Ｎ−エ
チルアミノエチルアクリレート等が挙げられる。The N,N-dialkylaminoalkylacrylate represented by the general formula (1) in the present invention includes, for example, N
, N-dimethylaminoethyl acrylate)-1N,
N-diethylaminoethyl acrylate, N,
N-dipropylaminoethyl acrylate, N, N
-dimethylaminopropyl acrylate, N, N-
Examples include diethylaminopropyl acrylate, N,N-dipropylaminopropyl acrylate, N,N-dibutylaminoethyl acrylate, N-methyl, N-ethylaminoethyl acrylate, and the like.
本発明においては、Ｎ、 Ｎ−ジアルキルアミノアル
キルアクリレート中の溶存酸素濃度が、ＮｌＮ−ジアル
キルアミノアルキルアクリレートに空気を吹き込んで酸
素を溶解させて飽和させた状態の溶存酸素濃度を１００
％とした場合に、０．５％以上１０％以下、好ましくは
１％以上５％以下の範囲内で貯蔵する。上記範囲よりも
低い濃度においてはポリマーの発生が起こり易く、また
逆に上記範囲よりも高い濃度では着色防止効果が不十分
となる。In the present invention, the dissolved oxygen concentration in the N,N-dialkylaminoalkyl acrylate is 100
When expressed as %, it is stored within the range of 0.5% or more and 10% or less, preferably 1% or more and 5% or less. At a concentration lower than the above range, polymer generation tends to occur, and conversely, at a concentration higher than the above range, the coloring prevention effect becomes insufficient.
通常、Ｎ、 Ｎ−ジアルキルアミノアルキルアクリレ
ート製品は重合防止のために酸素の存在下に精製して得
られる。従って、製造当初の製品は溶存酸素濃度が高い
状態である。この上うなＮ、 Ｎ−ジアルキルアミノ
アルキルアクリレートを本発明に従って貯蔵するには、
溶存酸素濃度を本発明が特定する範囲内に調節しなけれ
ばならない。具体的には、例えば、窒素又はヘリウム、
アルゴン等の不活性ガスか、これらの不活性ガスと空気
又は酸素とを混合して酸素濃度を調製したガスを、Ｎ、
Ｎ−ジアルキルアミノアルキルアクリレート中に吹
き込むか、あるいは気相部分のガスを酸素濃度を調製し
たガスで置換することにより実施できる。溶存酸素濃度
が飽和状態になるまでＮ、 Ｎ−ジアルキルアミノア
ルキルアクリレート中にガスを吹き込む場合に、吹き込
むガス中の酸素濃度と調製後のＮ、 Ｎ−ジアルキル
アミノアルキルアクリレート中の溶存酸素濃度との間に
は相関性がある。従って、このような方法によりＮ、
Ｎ−ジアルキルアミノアルキルアクリレート中の溶存
酸素濃度を容易に所定の濃度に調製することができる。Usually, N,N-dialkylaminoalkyl acrylate products are obtained by purification in the presence of oxygen to prevent polymerization. Therefore, the product at the time of manufacture has a high concentration of dissolved oxygen. Furthermore, to store N,N-dialkylaminoalkyl acrylate according to the present invention,
The dissolved oxygen concentration must be adjusted within the range specified by the present invention. Specifically, for example, nitrogen or helium,
Inert gas such as argon, or gas whose oxygen concentration is adjusted by mixing these inert gases with air or oxygen, is
This can be carried out by blowing into the N-dialkylaminoalkyl acrylate or by replacing the gas in the gas phase with a gas whose oxygen concentration has been adjusted. When gas is blown into the N,N-dialkylaminoalkyl acrylate until the dissolved oxygen concentration reaches a saturated state, the difference between the oxygen concentration in the blown gas and the dissolved oxygen concentration in the prepared N,N-dialkylaminoalkyl acrylate is There is a correlation between them. Therefore, by such a method, N,
The dissolved oxygen concentration in N-dialkylaminoalkyl acrylate can be easily adjusted to a predetermined concentration.
また、実際の操作では、製品タンクに貯蔵するような場
合に、貯蔵容器内の空間部の酸素がＮ。In addition, in actual operations, when storing products in tanks, the oxygen in the space inside the storage container is N.
Ｎ−ジアルキルアミノアルキルアクリレート中に溶解し
て溶存酸素濃度が１０％を越え、着色が進むことがある
。これを防ぐには空間部の酸素濃度を低く抑えることが
有効であり、具体的には２゜０％以下に保つことが望ま
しい。When dissolved in N-dialkylaminoalkyl acrylate, the dissolved oxygen concentration may exceed 10% and coloration may progress. To prevent this, it is effective to keep the oxygen concentration in the space low, and specifically, it is desirable to keep it below 2.0%.
反対にＮ、 Ｎ−ジアルキルアミノアルキルアクリレ
ートを貯蔵している間に時間の経過と共に徐々にではあ
るが溶存酸素が減少することもある。Conversely, while N,N-dialkylaminoalkyl acrylate is stored, dissolved oxygen may gradually decrease over time.
これは溶存酸素がＮ、 Ｎ−シアル′キルアミノアル
キルアクリレートと反応するために起こると考えられる
。従って長期の保存においては適宜酸素を供給してこの
濃度範囲に保つことも有効である。This is believed to occur because dissolved oxygen reacts with the N,N-sial'kylaminoalkyl acrylate. Therefore, for long-term storage, it is also effective to maintain the concentration within this range by supplying oxygen as appropriate.
溶存酸素濃度を調節する方法は、例えば、溶存酸素の減
少に応じて、酸素濃度を調製したガスをＮ。A method for adjusting the dissolved oxygen concentration is, for example, by adding nitrogen to a gas whose oxygen concentration has been adjusted according to the decrease in dissolved oxygen.
Ｎ−ジアルキルアミノアルキルアクリレート中に吹き込
むか気相部分のガスを酸素濃度を調製したガスで置換す
ることにより実施できる。This can be carried out by blowing into the N-dialkylaminoalkyl acrylate or by replacing the gas in the gas phase with a gas whose oxygen concentration has been adjusted.
貯蔵する温度は低温はど着色の速度は小きくなるが、必
要以上に下げると保冷設備が必要となる。The lower the storage temperature, the slower the rate of coloring, but if the temperature is lowered more than necessary, cold storage equipment will be required.
温度が高すぎると重合が起こりやすくなる。好ましい貯
蔵温度は５℃〜５０℃の範囲内、より好ましくは１５℃
〜４０℃の範囲内である。If the temperature is too high, polymerization tends to occur. Preferred storage temperature is within the range of 5°C to 50°C, more preferably 15°C
It is within the range of ~40°C.
また重合防止を確実にする為にハイドロキノンモノメチ
ルエーテル、ハイドロキノン、フェノチアジン、ジ−ｔ
−ブチルカテコール、ｐ−フェニレンジアミン、クペロ
ン等、従来公知の重合禁止剤を添加することも有効であ
る。In addition, to ensure the prevention of polymerization, hydroquinone monomethyl ether, hydroquinone, phenothiazine, di-t
It is also effective to add conventionally known polymerization inhibitors such as -butylcatechol, p-phenylenediamine, and cuperone.
保存する容器の材質に鉄、ステンレス、ニッケル、クロ
ム、コバルト等の金属を用いた場合には、ガラス、プラ
スチックを用いたものに比べ着色を促進きせる傾向があ
る。しかし本発明の条件下ではこれら金属容器中の貯蔵
も可能であり、その適用範囲が広く有用である。When the storage container is made of metal such as iron, stainless steel, nickel, chromium, or cobalt, it tends to accelerate discoloration compared to containers made of glass or plastic. However, under the conditions of the present invention, storage in these metal containers is also possible and is useful over a wide range of applications.
（実施例）
次に実施例をもって本発明を更に具体的に説明するが、
貯蔵の方法、条件はこれらの実施例に限定されるもので
はない。(Example) Next, the present invention will be explained in more detail with reference to Examples.
The storage method and conditions are not limited to these examples.
なお、Ｎ、 Ｎ−ジアルキルアミノアルキルアクリレ
ート中の溶存酸素濃度、着色度、ポリマー分および貯蔵
中のＮ、 Ｎ−ジアルキルアミノアルキルアクリレー
トの空間部の酸素濃度の測定は下記の方法によって行っ
た。The dissolved oxygen concentration, degree of coloration, polymer content in the N,N-dialkylaminoalkyl acrylate, and oxygen concentration in the space of the N,N-dialkylaminoalkyl acrylate during storage were measured by the following method.
・溶存酸素濃度：ポーラログラフ式酸素計を用いて、Ｎ
、 Ｎ−ジアルキルアミノアルキルアクリレートに空
気を吹き込んで酸素を溶解させて飽和させた状態の溶存
酸素濃度を１００％として校正した後、試料の溶存酸素
濃度を測定した。・Dissolved oxygen concentration: Using a polarographic oxygen meter,
After calibrating the dissolved oxygen concentration in a state where air was blown into N-dialkylaminoalkyl acrylate to dissolve oxygen and saturate it as 100%, the dissolved oxygen concentration of the sample was measured.
・着色度： ハーゼン標準液との比色により測定した（
ＪＩＳ Ｋ４１０１に準拠）。・Coloring degree: Measured by color comparison with Hazen standard solution (
Based on JIS K4101).
・ボυマー分：試料４ｍｌをアセトン３０ｍ１にて希釈
し、水浴冷却下、濃塩酸５ｍｌを加え４級塩とし、３０
分静置した後、濁りの程度を透過光濁度（カオリン標準
液基準、 ＪＩＳ ＫＯＩＯＩに準じる方法）で測定
し、ポリマー分とした。・Bomber portion: Dilute 4ml of sample with 30ml of acetone, add 5ml of concentrated hydrochloric acid under cooling in a water bath to make a quaternary salt,
After standing for a minute, the degree of turbidity was measured by transmitted light turbidity (based on kaolin standard solution, method according to JIS KOIOI) and determined as the polymer content.
・空間部の酸素濃度：ポーラログラフ式酸素計を用いて
、空気中の酸素濃度を２１％として校正した後、測定し
た。- Oxygen concentration in the space: Measured using a polarographic oxygen meter after calibrating the oxygen concentration in the air to 21%.
また、以下の各実施例および比較例に用いたＮ。Also, N used in each of the following Examples and Comparative Examples.
Ｎ−ジメチルアミノエチルアクリレートは製造設備から
採取したものを用いた。このＮ、 Ｎ−ジメチルアミ
ノエチルアクリレートはハイドロキノンモノメチルエー
テル２０００ ｐｐｍを含ｈ’ｃのＡＰＨＡは５、溶存
酸素濃度は２０％であった。N-dimethylaminoethyl acrylate was collected from the manufacturing facility. This N,N-dimethylaminoethyl acrylate contained 2000 ppm of hydroquinone monomethyl ether, had an h'c APHA of 5, and a dissolved oxygen concentration of 20%.
実施例 １
酸素濃度０． ６％の酸素と窒素の混合ガスを満たした
５００慕ｌの５ＵＳ３０４容器に上記のＮ。Example 1 Oxygen concentration 0. Add the above N to a 500 μL 5US304 container filled with a 6% oxygen and nitrogen gas mixture.
Ｎ−ジメチルアミノエチルアクリレ−）２５０ｍｌを入
へ 酸素濃度０．６％の酸素と窒素の混合ガスを溶存酸
素濃度が飽和状態になるまで吹き込んだ。このときの溶
存酸素濃度は１．５％であった。A mixed gas of oxygen and nitrogen with an oxygen concentration of 0.6% was blown into the solution until the dissolved oxygen concentration became saturated. The dissolved oxygen concentration at this time was 1.5%.
容器内の空間部を酸素濃度０．６％の酸素と窒素の混合
ガスで置換した後密封し、３０℃の恒温槽にて貯蔵した
。貯蔵中、約１週間毎に溶存酸素濃度を測定し、溶存酸
素濃度が１．０％以上３．０％以下の範囲になるように
酸素濃度０．６％のガスを適宜補給し酸素を補った。２
力月後に色を測定したところ、ＡＰＨＡ５０で着色の進
行は明らかに抑制きれており本方法が十分効果を示して
いることが確かめられた。またポリマー分ばＯで検出さ
れなかフた。After replacing the space inside the container with a mixed gas of oxygen and nitrogen having an oxygen concentration of 0.6%, the container was sealed and stored in a constant temperature bath at 30°C. During storage, the dissolved oxygen concentration was measured approximately every week, and oxygen was supplemented by appropriately replenishing gas with an oxygen concentration of 0.6% so that the dissolved oxygen concentration was within the range of 1.0% to 3.0%. Ta. 2
When the color was measured after a month, it was confirmed that the progress of coloring was clearly suppressed with APHA50, and it was confirmed that this method was sufficiently effective. In addition, the polymer component was not detected in O.
比較例 Ｉ
Ｎ、 Ｎ−ジメチルアミノエチルアクリレート中の溶
存酸素濃度の調節を全く行わず、かつ空気雰囲気下にし
た以外は実施例１と同様にして貯蔵した。その結果、２
力月後のＡＰＨＡは４００にまで着色が進行し、品質の
大きな低下を招いた。Comparative Example I N,N-Dimethylaminoethyl acrylate was stored in the same manner as in Example 1, except that the dissolved oxygen concentration in N-dimethylaminoethyl acrylate was not adjusted at all and the product was kept under an air atmosphere. As a result, 2
The coloration of APHA after heating progressed to 400, resulting in a significant drop in quality.
実施例 ２
恒温槽の温度を１５℃にした以外は実施例１と同様にし
て貯蔵した。２力月間後のＡＦ）’ＨＡは３０、ポリマ
ー分もＯであり、良好な結果を示した。Example 2 It was stored in the same manner as in Example 1 except that the temperature of the constant temperature bath was 15°C. After 2 months, the AF)'HA was 30 and the polymer content was O, showing good results.
比較例 ２
Ｎ、 Ｎ−ジメチルアミノエチルアクリレート中の溶
存酸素濃度の調節を全く行わず、かつ空気雰囲気下にし
た以外は実施例１と同様にして貯蔵した。その結果、２
力月後のＡＰＨＡは２００にまで着色が進行した。Comparative Example 2 N,N-Dimethylaminoethyl acrylate was stored in the same manner as in Example 1, except that the dissolved oxygen concentration in N,N-dimethylaminoethyl acrylate was not adjusted at all and the product was kept under an air atmosphere. As a result, 2
After the month, coloring progressed to APHA of 200.
実施例 ３〜６ 及び 比較例 ３〜６溶存酸素濃度、
容器空間部の酸素濃度、容器の材質を表１に示した条件
に変え、ガラス容器の場合は遮光を施した以外は実施例
１と同様にして貯蔵し、表１に示した結果を得た。Examples 3 to 6 and Comparative Examples 3 to 6 dissolved oxygen concentration,
The oxygen concentration in the container space and the material of the container were changed to the conditions shown in Table 1, and in the case of a glass container, the containers were stored in the same manner as in Example 1, except that they were shielded from light, and the results shown in Table 1 were obtained. .
（発明の効果）
表１の結果より溶存酸素濃度が低くなると共に着色の進
行も抑制されていることがわかる。また、貯蔵容器にＳ
ＵＳ材質を用いた場合ガラス容器に比べて着色が促進さ
れるが、酸素濃度の選択により十分着色が抑制できてい
る。比較例３に示きれるように無酸素状態では着色防止
は問題ないが、重合によるポリマー分の発生が起こり好
ましくないことがわかる。(Effects of the Invention) From the results in Table 1, it can be seen that the dissolved oxygen concentration is lowered and the progress of coloring is also suppressed. Also, put S in the storage container.
When US material is used, coloring is promoted compared to glass containers, but coloring can be sufficiently suppressed by selecting the oxygen concentration. As shown in Comparative Example 3, there is no problem in preventing coloring in an oxygen-free state, but it is understood that polymer components are generated due to polymerization, which is not preferable.
以上の結果より溶存酸素濃度と着色の進行との相関は顕
著であり、酸素濃度を調節する本発明の貯蔵方法の有効
性は明らかである。From the above results, the correlation between the dissolved oxygen concentration and the progress of coloring is significant, and the effectiveness of the storage method of the present invention for adjusting the oxygen concentration is clear.
本発明の貯蔵方法により、着色の少ない高品質のＮ、
Ｎ−ジアルキルアミノアルキルアクリレートを容易に
安定して供給することができ、高品質のポリマーの製造
が円滑にできるようになった。By the storage method of the present invention, high quality N with little coloring,
N-dialkylaminoalkyl acrylate can now be easily and stably supplied, making it possible to smoothly produce high-quality polymers.
Claims (1)
キレン基を示し、Ｒ＾２およびＲ＾３は各々独立して炭
素数１〜４のアルキル基を示す）で示されるＮ，Ｎ−ジ
アルキルアミノアルキルアクリレートを貯蔵するに際し
、Ｎ，Ｎ−ジアルキルアミノアルキルアクリレートに空
気を吹き込んで酸素を飽和状態まで溶解させた状態の溶
存酸素濃度を１００％として、Ｎ，Ｎ−ジアルキルアミ
ノアルキルアクリレートを０．５％以上１０％以下の範
囲内の溶存酸素濃度で貯蔵することを特徴とするＮ，Ｎ
−ジアルキルアミノアルキルアクリレートの貯蔵方法。 ２ 貯蔵中のＮ，Ｎ−ジアルキルアミノアルキルアクリ
レートの空間部の酸素濃度を２．０％以下に保つことを
特徴とする請求項１に記載のＮ，Ｎ−ジアルキルアミノ
アルキルアクリレートの貯蔵方法。 ３ ５℃以上５０℃以下の範囲内の温度で貯蔵すること
を特徴とする請求項１に記載のＮ，Ｎ−ジアルキルアミ
ノアルキルアクリレートの貯蔵方法。[Claims] 1 General formula (1) ▲There are numerical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1 represents a straight chain or branched alkylene group having 1 to 4 carbon atoms, and R^2 and R^3 each independently represent an alkyl group having 1 to 4 carbon atoms. The N,N-dialkylaminoalkyl acrylate is stored at a dissolved oxygen concentration in the range of 0.5% to 10%, assuming that the dissolved oxygen concentration in the state in which N is dissolved to a saturated state is 100%. ,N
- A method for storing dialkylaminoalkyl acrylate. 2. The method for storing N,N-dialkylaminoalkylacrylate according to claim 1, characterized in that the oxygen concentration in the space of the N,N-dialkylaminoalkylacrylate during storage is maintained at 2.0% or less. 3. The method for storing N,N-dialkylaminoalkyl acrylate according to claim 1, wherein the N,N-dialkylaminoalkyl acrylate is stored at a temperature within a range of 5°C or higher and 50°C or lower.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2294017A JP2536961B2 (en) | 1990-10-30 | 1990-10-30 | Method for storing N, N-dialkylaminoalkyl acrylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2294017A JP2536961B2 (en) | 1990-10-30 | 1990-10-30 | Method for storing N, N-dialkylaminoalkyl acrylate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04169559A true JPH04169559A (en) | 1992-06-17 |
| JP2536961B2 JP2536961B2 (en) | 1996-09-25 |
Family
ID=17802180
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2294017A Expired - Fee Related JP2536961B2 (en) | 1990-10-30 | 1990-10-30 | Method for storing N, N-dialkylaminoalkyl acrylate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2536961B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0850916A1 (en) * | 1996-12-27 | 1998-07-01 | Nippon Shokubai Co., Ltd. | Color-stabilized basic monomers, process for producing the same |
| WO2001092365A1 (en) * | 2000-05-31 | 2001-12-06 | Corning S.A. | Preparation of a stable composition of radically copolymerisable monomers which contains at least one monomer having urea function(s) |
| EP0982290A3 (en) * | 1998-08-24 | 2003-10-15 | Nippon Shokubai Co., Ltd. | Method for handling alkylamino (meth)acrylates |
| JP2011528008A (en) * | 2008-07-16 | 2011-11-10 | ワッカー ケミー アクチエンゲゼルシャフト | Method for inhibiting polymerization of unsaturated organosilicon compounds |
| CN115873171A (en) * | 2021-09-29 | 2023-03-31 | 爱森（中国）絮凝剂有限公司 | 2-dimethylaminoethyl acrylate polymer and preparation method thereof |
-
1990
- 1990-10-30 JP JP2294017A patent/JP2536961B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0850916A1 (en) * | 1996-12-27 | 1998-07-01 | Nippon Shokubai Co., Ltd. | Color-stabilized basic monomers, process for producing the same |
| US5912384A (en) * | 1996-12-27 | 1999-06-15 | Nippon Shokubai Co., Ltd. | Color-stabilized basic monomers, process for producing the same and method for handling the same |
| EP0982290A3 (en) * | 1998-08-24 | 2003-10-15 | Nippon Shokubai Co., Ltd. | Method for handling alkylamino (meth)acrylates |
| WO2001092365A1 (en) * | 2000-05-31 | 2001-12-06 | Corning S.A. | Preparation of a stable composition of radically copolymerisable monomers which contains at least one monomer having urea function(s) |
| US6528606B2 (en) | 2000-05-31 | 2003-03-04 | Corning S.A. | Preparation of a stable composition of radically copolymerisable monomers which contains at least one monomer having urea function(s) |
| JP2011528008A (en) * | 2008-07-16 | 2011-11-10 | ワッカー ケミー アクチエンゲゼルシャフト | Method for inhibiting polymerization of unsaturated organosilicon compounds |
| CN115873171A (en) * | 2021-09-29 | 2023-03-31 | 爱森（中国）絮凝剂有限公司 | 2-dimethylaminoethyl acrylate polymer and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2536961B2 (en) | 1996-09-25 |
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