JPH02248402A - Agent and method for inhibiting polymerization of acrylic ester - Google Patents
Agent and method for inhibiting polymerization of acrylic esterInfo
- Publication number
- JPH02248402A JPH02248402A JP6988489A JP6988489A JPH02248402A JP H02248402 A JPH02248402 A JP H02248402A JP 6988489 A JP6988489 A JP 6988489A JP 6988489 A JP6988489 A JP 6988489A JP H02248402 A JPH02248402 A JP H02248402A
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- polymerization inhibitor
- acrylic ester
- hydrocarbon group
- present
- 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
- 238000000034 method Methods 0.000 title claims description 8
- 230000002401 inhibitory effect Effects 0.000 title claims description 6
- -1 acrylic ester Chemical class 0.000 title abstract description 6
- 239000003112 inhibitor Substances 0.000 claims abstract description 27
- 238000004821 distillation Methods 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims abstract description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 abstract description 7
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 abstract description 3
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 abstract description 3
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- 150000002430 hydrocarbons Chemical group 0.000 abstract 1
- 231100000331 toxic Toxicity 0.000 abstract 1
- 230000002588 toxic effect Effects 0.000 abstract 1
- 239000000178 monomer Substances 0.000 description 9
- 125000005396 acrylic acid ester group Chemical group 0.000 description 7
- 230000020169 heat generation Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-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
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 229950000688 phenothiazine Drugs 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 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
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- YXYJVFYWCLAXHO-UHFFFAOYSA-N 2-methoxyethyl 2-methylprop-2-enoate Chemical compound COCCOC(=O)C(C)=C YXYJVFYWCLAXHO-UHFFFAOYSA-N 0.000 description 1
- PMTVEXBJLIRTEJ-UHFFFAOYSA-N 2-methyl-4-nitrosophenol Chemical compound CC1=CC(N=O)=CC=C1O PMTVEXBJLIRTEJ-UHFFFAOYSA-N 0.000 description 1
- UXKQNCDDHDBAPD-UHFFFAOYSA-N 4-n,4-n-diphenylbenzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 UXKQNCDDHDBAPD-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- RBXVOQPAMPBADW-UHFFFAOYSA-N nitrous acid;phenol Chemical class ON=O.OC1=CC=CC=C1 RBXVOQPAMPBADW-UHFFFAOYSA-N 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 150000004989 p-phenylenediamines Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、アクリル酸エステルモノマー類の重合禁止剤
及びそれを用いた重合禁止方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a polymerization inhibitor for acrylic acid ester monomers and a method for inhibiting polymerization using the same.
［従来の技術］
アクリル酸エステルモノマー類は、極めて重合しやすく
、製造工程や、貯蔵輸送中に、熱、光、その他の要因に
よって、しばしば重合することが知られている。従来か
ら、アクリル酸エステルモノマー用の重合禁止剤として
、キノン類、ハイドロキノン類及びその誘導体、ニトロ
ソ類、フェニレンジアミン等のアミン類、ニトロフェノ
ール類、フェノチアジン、金属キレート化合物等が知ら
れている。[Prior Art] Acrylic acid ester monomers are extremely easy to polymerize, and it is known that they often polymerize due to heat, light, and other factors during the manufacturing process and during storage and transportation. Conventionally, quinones, hydroquinones and their derivatives, nitrosos, amines such as phenylenediamine, nitrophenols, phenothiazine, metal chelate compounds, and the like have been known as polymerization inhibitors for acrylic acid ester monomers.
［発明が解決しようとする課題］
しかしながら、これらの化合物は、重合禁止能力が充分
でなかったり、高価であったり、毒性が高い等の問題を
有していた。さらに貯蔵安定性のために添加した場合に
は、従来の重合禁止剤では、蒸留等の操作によってのみ
、重合禁止剤の除去が可能であり、その除去は容易でな
かった。[Problems to be Solved by the Invention] However, these compounds have problems such as insufficient polymerization inhibition ability, high cost, and high toxicity. Furthermore, when added for storage stability, conventional polymerization inhibitors can only be removed by operations such as distillation, and removal is not easy.
本発明者らは、前記の問題点を克服すべく、アクリル酸
エステルモノマー類に有効で安価かつ、低毒性であり、
添加後の除去が容易な重合禁止剤及びそれを用いる重合
禁止方法について鋭意検討した結果、本発明に到達した
。In order to overcome the above problems, the present inventors have discovered that acrylic acid ester monomers are effective, inexpensive, and have low toxicity.
As a result of extensive research into polymerization inhibitors that are easy to remove after addition and methods for inhibiting polymerization using the same, the present invention was achieved.
［課題を解決するための手段］
即ち、本発明は、下式（１）で示されるアクリル酸エス
テル類の重合禁止剤、
（式中、Ａｒは炭素数６〜１６の芳香族炭化水素基、Ｒ
は炭素数１〜１６の炭化水素基を表わす。）及び、アク
リル酸エステル類の蒸留時に、酸素の存在下、前記式で
示される重合禁止剤を用いることを特徴とするアクリル
酸エステル類の重合禁止方法を提供するものである。[Means for Solving the Problems] That is, the present invention provides a polymerization inhibitor for acrylic esters represented by the following formula (1), (wherein Ar is an aromatic hydrocarbon group having 6 to 16 carbon atoms, R
represents a hydrocarbon group having 1 to 16 carbon atoms. ) and a method for inhibiting polymerization of acrylic esters, which comprises using a polymerization inhibitor represented by the above formula in the presence of oxygen during distillation of acrylic esters.
本発明に用いられるアクリル酸エステル類とは、次式で
示される（メタ）アクリル酸エステルモノマー類である
。The acrylic esters used in the present invention are (meth)acrylic ester monomers represented by the following formula.
ＣＨ２＝Ｃ−Ｃ−０Ｒ”
（式中、Ｒ１は水素又はメチル基、Ｒ２は炭素数１〜１
８のアルキル基又はアルコキシアルキル基を表わす。）
具体的には、メチルアクリレート、ブチルアクリレート
、２−エチル−ヘキシルアクリレート、ドデシルアクリ
レート、メチルメタクリレート、イソプロピルメタクリ
レート、オクチルメタクリレート、メトキシエチルメタ
クリレート等が挙げられる。CH2=C-C-0R" (wherein, R1 is hydrogen or a methyl group, R2 has 1 to 1 carbon atoms
8 represents an alkyl group or an alkoxyalkyl group. ) Specific examples include methyl acrylate, butyl acrylate, 2-ethyl-hexyl acrylate, dodecyl acrylate, methyl methacrylate, isopropyl methacrylate, octyl methacrylate, and methoxyethyl methacrylate.
本発明においては、前記式（１）で示される化合物をア
クリル酸エステル類の重合禁止剤として用いる。In the present invention, the compound represented by the formula (1) is used as a polymerization inhibitor for acrylic esters.
Ａｒの芳香族炭化水素基としては、フェニル基又はナフ
チル基が好ましく、具体例としては、Ｎ。The aromatic hydrocarbon group of Ar is preferably a phenyl group or a naphthyl group, and a specific example is N.
Ｎ′−ジフェニル−Ｐ−フェニレンジアミン、Ｎフェニ
ル−Ｎ′−アルキル−Ｐ−フェニレンジアミン、などを
挙げることができる。Examples include N'-diphenyl-P-phenylenediamine, Nphenyl-N'-alkyl-P-phenylenediamine, and the like.
本発明の重合禁止剤の使用量は、特に制限はないが、ア
クリル酸エステルモノマーに対して、０．００１〜１重
量％であり、好ましくは、０．０１〜０．１重量％であ
る。本重合禁止剤は、単独で用いることも、従来品との
混合系で用いることもできる。また、蒸留時等の高温で
使用する場合には、その蒸留条件に応じて、製品への混
入のない高沸点を有するものを選定するのが好ましい。The amount of the polymerization inhibitor used in the present invention is not particularly limited, but is 0.001 to 1% by weight, preferably 0.01 to 0.1% by weight, based on the acrylic acid ester monomer. This polymerization inhibitor can be used alone or in a mixed system with conventional products. In addition, when using at high temperatures such as during distillation, it is preferable to select one that has a high boiling point and does not mix into the product, depending on the distillation conditions.
蒸留温度は、対象となるアクリル酸エステルモノマー類
の種類によって異なるが、一般に、７０°Ｃ以上、１５
０°Ｃ以下程度の温度レベルである。The distillation temperature varies depending on the type of acrylic acid ester monomer, but generally it is 70°C or higher and 15°C or higher.
The temperature level is about 0°C or less.
この観点から考えると、Ｎ−イソプロピル−Ｎ′フェニ
ル−Ｐ−フェニレンジアミン等のＮ−アルキル置換−Ｎ
′−フェニル置換型のＰ−フェニレンジアミン誘導体の
高沸点化合物が好ましい。Considering from this point of view, N-alkyl-substituted -N such as N-isopropyl-N'phenyl-P-phenylenediamine
'-Phenyl-substituted P-phenylenediamine derivatives with high boiling points are preferred.
また、本発明の重合禁止剤の使用雰囲気は、窒素等の不
活性ガス下でも有効であるが、アクリル酸エステル類の
蒸留等においては、酸素の存在下で使用する方が、後述
する様により有効である。Furthermore, although the polymerization inhibitor of the present invention is effectively used in an atmosphere under an inert gas such as nitrogen, it is better to use it in the presence of oxygen in distillation of acrylic esters, etc., as will be described later. It is valid.
酸素量としては、特に制限はなく、重合禁止剤の濃度に
も依るが、重合禁止剤の１０倍モル以上の濃度で存在す
ることが好ましい。係る酸素の供給方法としては、蒸留
系の場合、蒸留塔下部よりの空気バブリング方式が具体
例として挙げられる。The amount of oxygen is not particularly limited and depends on the concentration of the polymerization inhibitor, but it is preferably present at a concentration of 10 times the mole or more of the polymerization inhibitor. In the case of a distillation system, a specific example of such a method for supplying oxygen is an air bubbling method from the bottom of the distillation column.
さらに、本発明の重合禁止剤は、基本的に芳香族アミン
であることから、貯蔵安定剤として、アクリル酸エステ
ルモノマー類に添加しても、酸水溶液でこれら、アクリ
ルモノマー類を洗浄することにより、また、酸性のイオ
ン交換樹脂等を充填したカラムに流通させるだけでも容
易に除去することができる。即ち、従来の禁止剤が蒸留
等の操作を必要とし、この除去操作途中に加熱によって
重合が生じてしまうのに比較して、本発明の禁止剤の除
去は、酸洗浄及び吸着という低温の操作によって可能で
あり、重合の問題がまったく無い。Furthermore, since the polymerization inhibitor of the present invention is basically an aromatic amine, it can be added to acrylic acid ester monomers as a storage stabilizer by washing these acrylic monomers with an acid aqueous solution. Moreover, it can be easily removed simply by passing it through a column filled with acidic ion exchange resin or the like. That is, compared to conventional inhibitors that require operations such as distillation, and polymerization occurs due to heating during the removal operation, the removal of the inhibitor of the present invention requires low-temperature operations such as acid washing and adsorption. is possible, and there is no problem of polymerization.
また実施例で示す様に、本発明の禁止剤の禁止能力は、
従来のものより格段に優れており、貯蔵安定剤として用
いる場合では、１ ｐｐｍ以下の低濃度でも有用である
ため、除去はさらに容易となる。Further, as shown in the examples, the inhibitory ability of the inhibitor of the present invention is as follows:
It is much superior to conventional products, and when used as a storage stabilizer, it is useful even at a low concentration of 1 ppm or less, making it easier to remove.
また、本発明の重合禁止剤は、従来のニトロソ類や、重
金属キレート類と比較して低毒性であり、また、重金属
を含有しない化合物であるため、環境汚染の問題もない
。Furthermore, the polymerization inhibitor of the present invention has lower toxicity than conventional nitrosos and heavy metal chelates, and since it is a compound that does not contain heavy metals, there is no problem of environmental pollution.
以上の本発明の効果を要約すると、
（ア）従来の重合禁止剤よりも重合禁止能力が極めて高
い。（添加濃度が低くても、禁止できる）（イ）特に酸
素との共存在下では、重合禁止能力が大幅に向上する。To summarize the above effects of the present invention, (a) The polymerization inhibition ability is extremely higher than that of conventional polymerization inhibitors. (Polymerization can be inhibited even at a low addition concentration.) (a) Especially in the co-existence of oxygen, the ability to inhibit polymerization is greatly improved.
（つ）重合禁止剤の除去が酸水溶液での洗浄などにより
容易である。(1) The polymerization inhibitor can be easily removed by washing with an acid aqueous solution.
（１）重金属を含有しない禁止剤である。(1) It is an inhibitor that does not contain heavy metals.
（才）低毒性化合物である。It is a low toxicity compound.
となる。本発明を実施することにより、従来技術の欠点
を解決することが可能となり、その工業的意義は大きい
ものと思われる。becomes. By carrying out the present invention, it becomes possible to solve the drawbacks of the prior art, and it is believed to have great industrial significance.
［実施例］
次に実施例によって本発明をより、具体的に説明するが
、これらは、本特許を限定するものではない。尚、以下
の例において、部及び％は、特に限定しない限り、重量
部及び重量％を示すものである。[Examples] Next, the present invention will be explained in more detail with reference to Examples, but these are not intended to limit this patent. In the following examples, parts and % indicate parts by weight and % by weight unless otherwise specified.
［実験手法］
アクリル酸２−エチルヘキシルエステル（ＡＥ−Ｈと略
）１０ｇを計量し、これを小型反応管に仕込み、空気を
１５〜２０ｍ１／ｌｌｌ１ｎの流量で流通させ、この小
型反応管を１５０°Ｃのオイルバス中に浸して、ＡＥ−
Ｈの重合による発熱を観測、この重合による発熱が生じ
るまでの時間を、重合誘導期（ＩＰ）と定め、重合禁止
活性の指標とした。[Experimental method] Weighed 10 g of acrylic acid 2-ethylhexyl ester (abbreviated as AE-H), charged it into a small reaction tube, passed air through it at a flow rate of 15 to 20 ml/lll1n, and heated the small reaction tube at 150°. AE-
Heat generation due to polymerization of H was observed, and the time until heat generation occurred due to polymerization was defined as the polymerization induction period (IP), and was used as an index of polymerization inhibition activity.
本実験で用いたＡＨ−Ｈには、ＭＱ（ハイドロキノンモ
ノメチルエーテル）、１５ｐｐｍが存在していたが、本
条件下では、約２５０°Ｃの発熱がピークとして明確に
観測された。Although 15 ppm of MQ (hydroquinone monomethyl ether) was present in AH-H used in this experiment, under the present conditions, an exothermic peak of about 250°C was clearly observed.
本実験方法での再現性は極めて良好で重合禁止剤を存在
させないブランクのＩＰは、１５０ ’Ｃで１９分であ
った。The reproducibility of this experimental method was extremely good, and the blank IP in which no polymerization inhibitor was present was 19 minutes at 150'C.
［・実施例−１］
Ｎ−イソプロピル−Ｎ′−フェニル−Ｐ−フェニレンジ
アミンを１１００ｐｐ添加し、実験手法の項で述べた方
法によってＩＰ−’！測測定たところ、９００分を経過
しても、重合による発熱は見られず、またＡＨ−Ｈの粘
度上昇も無かった。[Example-1] 1100 pp of N-isopropyl-N'-phenyl-P-phenylenediamine was added, and IP-'! was obtained by the method described in the experimental method section. As a result of measurement, no heat generation due to polymerization was observed even after 900 minutes, and no increase in the viscosity of AH-H was observed.
添加濃度を１０ｐｐｎ＋ 、 ｉｐｐｍとした場合の
ＩＰは、２４０分、４５分であった。When the added concentration was 10 ppn+ and ippm, the IP was 240 minutes and 45 minutes.
［実施例−２］
Ｎ−（１，４−ジメチルペンチル）−Ｎ′−フェニル−
Ｐ−フェニレンジアミンを１００ ｐｐｍ 添加し、同
様にＩＰを測定したところ、９００分を経過しても、重
合による発熱が見られず、粘度上昇もなかった。[Example-2] N-(1,4-dimethylpentyl)-N'-phenyl-
When 100 ppm of P-phenylenediamine was added and IP was measured in the same manner, no heat generation due to polymerization was observed even after 900 minutes, and no increase in viscosity was observed.
添加濃度を１０ｐｐｍとした場合のＩＰは、１５０分で
あった。IP was 150 minutes when the added concentration was 10 ppm.
［実施例−３，４］
窒素ガス流量１５〜２０ｍ１／ｗｉｎの流速下で、Ｎ−
イソプロピル−Ｎ′−フェニル−Ｐ−フェニレンジアミ
ン及び、Ｎ−（１，４−ジメチルペンチル）−Ｎ’−フ
ェニル−Ｐ−フェニレンジアミンを各々１００ｐｐ＋ａ
添加してＩＰを測定した。いずれも、６００分を経過し
ても、重合による発熱はなかった。[Example-3, 4] At a nitrogen gas flow rate of 15 to 20 m1/win, N-
100 pp+a each of isopropyl-N'-phenyl-P-phenylenediamine and N-(1,4-dimethylpentyl)-N'-phenyl-P-phenylenediamine
was added and the IP was measured. In either case, no heat generation due to polymerization occurred even after 600 minutes.
［実施例−５，６］
実施例３，４で、添加濃度を各々、１０ｐｐｍとした結
果ＩＰは、夫々９０．９５分であった。[Examples 5 and 6] In Examples 3 and 4, when the additive concentration was set to 10 ppm, the IP was 90.95 minutes.
［比較例１〜９］
実施例１と同様にして、ハイドロキノン、ハイドロキノ
ンモノメチルエーテル、フェノチアジン、４−ニトロソ
−オルソクレゾール、ジブチルジチオカルバミン酸銅塩
、４．６−シニトロオルソフレゾール、Ｐ−フェニレン
ジアミン、トリエチレンジアミン、０−フェニレンジア
モンの９化合物を各々、１１００ｐｐ添加して、ＩＰを
測定した。[Comparative Examples 1 to 9] In the same manner as in Example 1, hydroquinone, hydroquinone monomethyl ether, phenothiazine, 4-nitroso-orthocresol, dibutyldithiocarbamic acid copper salt, 4,6-cinitroorthofresol, P-phenylenediamine , triethylene diamine, and 0-phenylene diamone were added at 1100 pp each, and the IP was measured.
空気１５〜２０Ｉｌｌｌ／１ＩＩｉｎ流通下、禁止剤１
１００ｐｐ添加の結果を表−１にまとめて記す。Under air flow of 15-20Ill/1IIin, inhibitor 1
The results of adding 100 pp are summarized in Table 1.
Claims (2)
剤。 ▲数式、化学式、表等があります▼ （式中、Ａｒは炭素数６〜１６の芳香族炭化水素基、Ｒ
は炭素数１〜１６の炭化水素基を表わす。）(1) A polymerization inhibitor for acrylic esters represented by the following formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Ar is an aromatic hydrocarbon group having 6 to 16 carbon atoms, R
represents a hydrocarbon group having 1 to 16 carbon atoms. )
、次式で示される重合禁止剤を用いることを特徴とする
アクリル酸エステル類の重合禁止方法。 ▲数式、化学式、表等があります▼ （式中、Ａｒは炭素数６〜１６の芳香族炭化水素基、Ｒ
は炭素数１〜１６の炭化水素基を表わす。）(2) A method for inhibiting polymerization of acrylic esters, which comprises using a polymerization inhibitor represented by the following formula in the presence of oxygen during distillation of acrylic esters. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Ar is an aromatic hydrocarbon group having 6 to 16 carbon atoms, R
represents a hydrocarbon group having 1 to 16 carbon atoms. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6988489A JPH02248402A (en) | 1989-03-22 | 1989-03-22 | Agent and method for inhibiting polymerization of acrylic ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6988489A JPH02248402A (en) | 1989-03-22 | 1989-03-22 | Agent and method for inhibiting polymerization of acrylic ester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02248402A true JPH02248402A (en) | 1990-10-04 |
Family
ID=13415623
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6988489A Pending JPH02248402A (en) | 1989-03-22 | 1989-03-22 | Agent and method for inhibiting polymerization of acrylic ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02248402A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06298699A (en) * | 1993-03-09 | 1994-10-25 | Elf Atochem Sa | Preparation of halogenated ester of carboxylic acid or dicarboxylic acid |
| JP2005336082A (en) * | 2004-05-26 | 2005-12-08 | Mitsubishi Chemicals Corp | Polymerization inhibitor, composition containing the same, and method for producing easily polymerizable compound by using the polymerization inhibitor |
| JP2006509030A (en) * | 2002-12-04 | 2006-03-16 | ザ・スタンダード・オイル・カンパニー | Method for preventing polymerization during recovery and purification of unsaturated mononitriles |
| US7029556B1 (en) | 1999-11-24 | 2006-04-18 | Arkema | Method for purifying (meth)acrylic monomers by distillation |
| JP2016216437A (en) * | 2015-04-21 | 2016-12-22 | 三菱レイヨン株式会社 | Distillation method for unsaturated carboxylic acid silyl ester |
| WO2018221314A1 (en) * | 2017-05-31 | 2018-12-06 | 大阪有機化学工業株式会社 | Polymerization inhibitor and method for producing (meth)acrylic acid ester using said polymerization inhibitor, rectified product |
| WO2023204122A1 (en) * | 2022-04-18 | 2023-10-26 | 信越化学工業株式会社 | Method for purifying hydroxyl-group- and (meth)acryl-group-containing siloxane, and hydroxyl-group- and (meth)acryl-group-containing siloxane composition |
-
1989
- 1989-03-22 JP JP6988489A patent/JPH02248402A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06298699A (en) * | 1993-03-09 | 1994-10-25 | Elf Atochem Sa | Preparation of halogenated ester of carboxylic acid or dicarboxylic acid |
| US7029556B1 (en) | 1999-11-24 | 2006-04-18 | Arkema | Method for purifying (meth)acrylic monomers by distillation |
| JP2006509030A (en) * | 2002-12-04 | 2006-03-16 | ザ・スタンダード・オイル・カンパニー | Method for preventing polymerization during recovery and purification of unsaturated mononitriles |
| JP2005336082A (en) * | 2004-05-26 | 2005-12-08 | Mitsubishi Chemicals Corp | Polymerization inhibitor, composition containing the same, and method for producing easily polymerizable compound by using the polymerization inhibitor |
| JP4556491B2 (en) * | 2004-05-26 | 2010-10-06 | 三菱化学株式会社 | Polymerization inhibitor, composition containing the same, and method for producing easily polymerizable compound using the polymerization inhibitor |
| JP2016216437A (en) * | 2015-04-21 | 2016-12-22 | 三菱レイヨン株式会社 | Distillation method for unsaturated carboxylic acid silyl ester |
| WO2018221314A1 (en) * | 2017-05-31 | 2018-12-06 | 大阪有機化学工業株式会社 | Polymerization inhibitor and method for producing (meth)acrylic acid ester using said polymerization inhibitor, rectified product |
| JPWO2018221314A1 (en) * | 2017-05-31 | 2020-04-02 | 大阪有機化学工業株式会社 | Polymerization inhibitor, method for producing (meth) acrylate ester using the polymerization inhibitor, rectified product |
| WO2023204122A1 (en) * | 2022-04-18 | 2023-10-26 | 信越化学工業株式会社 | Method for purifying hydroxyl-group- and (meth)acryl-group-containing siloxane, and hydroxyl-group- and (meth)acryl-group-containing siloxane composition |
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