JPS63284146A - Production of (meth)acrylic acid ester - Google Patents
Production of (meth)acrylic acid esterInfo
- Publication number
- JPS63284146A JPS63284146A JP62118029A JP11802987A JPS63284146A JP S63284146 A JPS63284146 A JP S63284146A JP 62118029 A JP62118029 A JP 62118029A JP 11802987 A JP11802987 A JP 11802987A JP S63284146 A JPS63284146 A JP S63284146A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- activated clay
- meth
- addition reaction
- clay
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 title claims description 5
- 239000004927 clay Substances 0.000 claims abstract description 16
- 238000007259 addition reaction Methods 0.000 claims abstract description 12
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 3
- QUSSPXNPULRXKG-UHFFFAOYSA-N (+)-Galeon Chemical compound O1C(=CC=2)C(OC)=CC=2CCCCC(=O)CCC2=CC=C(O)C1=C2 QUSSPXNPULRXKG-UHFFFAOYSA-N 0.000 abstract description 10
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 abstract description 10
- -1 flocculant Substances 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 5
- 238000001914 filtration Methods 0.000 abstract description 5
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 abstract description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002270 dispersing agent Substances 0.000 abstract description 2
- 239000007789 gas Substances 0.000 abstract description 2
- 239000011261 inert gas Substances 0.000 abstract description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 abstract 2
- 238000010306 acid treatment Methods 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- 239000002202 Polyethylene glycol Substances 0.000 description 13
- 229920001223 polyethylene glycol Polymers 0.000 description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 7
- 229920001515 polyalkylene glycol Polymers 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000011109 contamination Methods 0.000 description 3
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012974 tin catalyst Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000010814 metallic waste Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical group CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- AOGDNNLIBAUIIX-UHFFFAOYSA-N 1-n,4-n-dinaphthalen-1-ylbenzene-1,4-diamine Chemical compound C1=CC=C2C(NC=3C=CC(NC=4C5=CC=CC=C5C=CC=4)=CC=3)=CC=CC2=C1 AOGDNNLIBAUIIX-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920005651 polypropylene glycol dimethacrylate Polymers 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、（メタ）アクリル酸エステルの製造法に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing (meth)acrylic acid ester.
従来、触媒として四塩化スズを使ってポリアルキレング
リコールモノ（メタ）アクリレートを製造する技術があ
る（例えば、特公昭５２−３０４８９号公報）。Conventionally, there is a technique for producing polyalkylene glycol mono(meth)acrylate using tin tetrachloride as a catalyst (for example, Japanese Patent Publication No. 52-30489).
しかしながらこの方法は、スズ触媒を用いるので、廃棄
物の重金属汚染がある。すなわち、このスズ触媒を中和
、炉別除去した時、濾過ケーキ中のスズ含量が大きくな
り、廃棄物処理に問題がある。However, since this method uses a tin catalyst, there is heavy metal contamination of the waste. That is, when this tin catalyst is neutralized and removed by furnace, the tin content in the filter cake becomes large, which poses a problem in waste treatment.
不発明者らは、重金属廃棄物汚染のないポリアルキレン
グリコールモノ（メタ）アクリレートの製造法について
鋭意検討した結果、本発明に到達した。The inventors of the present invention have arrived at the present invention as a result of intensive studies on a method for producing polyalkylene glycol mono(meth)acrylate that is free from heavy metal waste contamination.
すなわち本発明は一般式
％式％（１）
（式中、ＲはＨま１こはＣＨ，、Ａ、は炭素数２〜４の
アルキレン基である。）
で示される化合物に活性白土の存在下、アルキレンオキ
シドを付加反応させて一般式
％式％（２）
〔式中、ＲとＡ、は一般式（１）の場合と同様。That is, the present invention provides the presence of activated clay in a compound represented by the general formula % (1) (wherein, R is H, CH is CH, and A is an alkylene group having 2 to 4 carbon atoms). Below, an alkylene oxide is subjected to an addition reaction to obtain the general formula % formula % (2) [wherein R and A are the same as in the case of general formula (1).
Ａ、は炭素数２〜４のアルキレン基、ｎは２〜２０の整
数である。〕
で示される化合物を得ることを特徴とする（メタ）アク
リル酸エステルの製造である。A is an alkylene group having 2 to 4 carbon atoms, and n is an integer of 2 to 20. ] This is the production of a (meth)acrylic acid ester, characterized by obtaining a compound represented by the following.
一般式（１）においてんの炭素数２Ａ−４のアルキレン
基としてはエチレン基、プロピレン基、ｎ−まｔこはし
一ブチレン基があげられ、好ましくは、エチレン基およ
びプロピレン基である。Examples of the alkylene group having 2A-4 carbon atoms in general formula (1) include ethylene group, propylene group, and n-butylene group, with ethylene group and propylene group being preferred.
一般式（１）で示される化合物としては、２−ヒドロキ
シエチル（メタ）アクリレート、２−ヒドロキシプロピ
ル（メタ）アクリレート、２−ヒドロキシブチル（メタ
）アクリレート、２−ヒドロキシ−１−メチルプロピル
（メタ）アクリレート、２−ヒドロキシ−２−メチルプ
ロピル（メタ）アクリレートなどがあげられる。Examples of the compound represented by general formula (1) include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 2-hydroxy-1-methylpropyl (meth)acrylate. Examples include acrylate, 2-hydroxy-2-methylpropyl (meth)acrylate, and the like.
アルキレンオキサイド（以下ＡＯと略記）としては、エ
チレンオキサイド（以下ＥＯと略記）、プロピレンオキ
サイド（以下ＰＯと略記）、１．２−１２．３−１１．
３−１１．４−ブチレンオキサイドおよびこれらの２種
以上併用系があげられる。これらの好ましいのはＥＯ，
ＰＯおよびＰＯとＥＯの併用である。Examples of alkylene oxide (hereinafter abbreviated as AO) include ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), 1.2-12.3-11.
Examples include 3-11.4-butylene oxide and a combination system of two or more thereof. Preferable among these are EO,
PO and combination of PO and EO.
本発明における活性白土としては、モンモリロナイト属
粘土を主成分とする原料上を酸処理したものがあげられ
る。活性白土の化学組成は、通常１．珪酸（Ｓｉｎ、）
６０〜９０％、好ましくは７０〜８０％、アルミナ（
ＡＩ、Ｏ，） ５〜２５％、好ましくは９〜１３％、酸
化鉄（Ｆｅ！０．）１〜１０％、好ましくは４〜６％、
苦土（ＭｇＱ）０．１〜５％、好ましくは１〜２％、石
灰（ＣａＯ）０．１〜５％、好ましくは１〜２％である
。具体的にはガレオンアース（水澤化学（株）製）など
がある・
一般式（１）の化合物にＡＵ付加させるに際して使用す
る活性白土の量は、一般式（１）の化合物の重量に基づ
いて、通常０．１〜１０％、好ましくは２〜６％である
。０．１％未満では触媒効果が少なく、１０％を越えて
も触媒効果が向上しない。Examples of the activated clay in the present invention include acid-treated raw materials containing montmorillonite clay as a main component. The chemical composition of activated clay is usually 1. Silicic acid (Sin)
60-90%, preferably 70-80%, alumina (
AI, O,) 5-25%, preferably 9-13%, iron oxide (Fe!0.) 1-10%, preferably 4-6%,
Magnesium (MgQ) is 0.1 to 5%, preferably 1 to 2%, and lime (CaO) is 0.1 to 5%, preferably 1 to 2%. Specifically, there is Galleon Earth (manufactured by Mizusawa Chemical Co., Ltd.). The amount of activated clay used when adding AU to the compound of general formula (1) is based on the weight of the compound of general formula (1). , usually 0.1 to 10%, preferably 2 to 6%. If it is less than 0.1%, the catalytic effect will be low, and if it exceeds 10%, the catalytic effect will not improve.
一般式（１）の化合物に付加させるＡＯのモル数は通常
１〜２０、好ましくは１〜１０である。The number of moles of AO added to the compound of general formula (1) is usually 1 to 20, preferably 1 to 10.
ＡＵを付加する場合、反応温度は通常２０〜９０℃、好
ましくは３０〜６０℃である。When adding AU, the reaction temperature is usually 20 to 90°C, preferably 30 to 60°C.
反応時変は通常１〜２０時間である。The reaction time is usually 1 to 20 hours.
反応は常圧でも加圧でも行うことができる。The reaction can be carried out at normal pressure or under elevated pressure.
まｔこ反応は不活性ガス（Ｎｔガスなど）雰囲気中で通
常行われる。The Matoko reaction is usually carried out in an inert gas (such as Nt gas) atmosphere.
反応には重合禁止剤を添加する。この重合禁止剤として
は、ヒドロキノン、Ｎ、Ｎ’−ジナフチル−パラフェニ
レンジアミン、ヒドロキノンモノメチルエーテル、亜硝
酸ソーダ、ベンゾキノンなどがあげられ、好ましくは、
ヒドロキノンおよびヒドロキノンモノメチルエーテルで
ある。A polymerization inhibitor is added to the reaction. Examples of the polymerization inhibitor include hydroquinone, N,N'-dinaphthyl-paraphenylenediamine, hydroquinone monomethyl ether, sodium nitrite, benzoquinone, etc., and preferably,
Hydroquinone and hydroquinone monomethyl ether.
重合禁止剤の添加量は、用途、付加モル数などによって
種々調整することができるが、一般式（１）と付加する
ＡＯの合計重量に基づいて通常１００〜１０００ ｐｐ
ｍである０重合禁止剤の添加は反応前に一般式（１）の
化合物および活性白土と同時に添加することによって行
われる。The amount of the polymerization inhibitor added can be adjusted in various ways depending on the use, the number of moles added, etc., but it is usually 100 to 1000 pp based on the total weight of general formula (1) and AO to be added.
The polymerization inhibitor m is added by simultaneously adding the compound of general formula (1) and activated clay before the reaction.
一般式（１）の化合物にＡＯを付加反応後、活性白土は
、濾過などの簡単な操作により生成物から容易に分離で
きる。このように分離回収した活性白土は再使用が可能
である。After the addition reaction of AO to the compound of general formula (1), activated clay can be easily separated from the product by simple operations such as filtration. The activated clay thus separated and recovered can be reused.
得られる（メタ）アクリル酸エステルは一般式 ％式％（２） （式中、Ｒ７とＡ１は一般式（１）の場合と同様。The resulting (meth)acrylic ester has the general formula % formula % (2) (In the formula, R7 and A1 are the same as in general formula (1).
Ａ、は炭素数２〜４のアルキレン基、ｎは１〜２０の整
数でｎ個のオキシアルキレン基は同じでも異っていても
よく、異っている場合はブロックでもランダムでも、ま
１こその併用結合でもよい）で示すことができる。ここ
でんとしては一般式（１）のＡ１と同様な基があげられ
る。ｎは好ましくは１〜１０である。A is an alkylene group having 2 to 4 carbon atoms, n is an integer of 1 to 20, and the n oxyalkylene groups may be the same or different, and if they are different, they may be block or random. It can also be shown as a combined combination of Examples of the group include the same groups as A1 in general formula (1). Preferably n is 1-10.
以下、実施例により本発明をさらに説明するが、本発明
はこれに限定されるものではない。The present invention will be further explained below with reference to Examples, but the present invention is not limited thereto.
実施例中の部は重量部である。Parts in the examples are parts by weight.
実施例１゜
２−ヒドロキシエチルメタクリレート３００部（２，３
モル）を加圧反応器に仕込み、ガレオンアース１３．４
部、およびヒドロキノンモノメチルエーテル０．３部（
４３０ｐｐｍ）を添加し、窒素置換後、５０部５℃で１
２時間を要してＢ１２Ｏ３部（９，２モル）を付加反応
させたのち、同温度で１時間熟成し、吸引濾過すること
で６９１部（収ｆ！９８．０％）のポリエチレングリコ
ールモノメタクリレートを得た。このメタクリレート中
のポリエチレングリコールジメタクリレート含量は、０
．２％（ガスクロマトグラフィー）であった、またポリ
エチレングリコールモノメタクリレートは９６．８％で
あつ１こ。Example 1 300 parts of 2-hydroxyethyl methacrylate (2,3
mol) into a pressurized reactor, Galleon Earth 13.4
parts, and 0.3 parts of hydroquinone monomethyl ether (
430 ppm), and after nitrogen substitution, 50 parts of 1
After 2 hours of addition reaction with 3 parts (9.2 mol) of B12O, 691 parts (yield: 98.0%) of polyethylene glycol monomethacrylate was obtained by aging at the same temperature for 1 hour and suction filtration. I got it. The polyethylene glycol dimethacrylate content in this methacrylate is 0
．． 2% (gas chromatography), and polyethylene glycol monomethacrylate was 96.8%.
実施例２゜
２−ヒドロキシエチルアクリレート３００部（２，６モ
ル）にガレオンアース１３．４部、およびヒドロキノン
モノメチルエーテル０．３ 部（３９６ｐｐｍ）を加え
、窒素置換後、５０部５℃で８時間要してＥＯ４５８部
（１０，４モル）付加反応させたのち、同温度で１時間
熟成し１こ。Example 2 13.4 parts of galleon earth and 0.3 parts (396 ppm) of hydroquinone monomethyl ether were added to 300 parts (2.6 moles) of 2-hydroxyethyl acrylate, and after purging with nitrogen, 50 parts were heated at 5°C for 8 hours. In total, 458 parts (10.4 mol) of EO was subjected to an addition reaction, and then aged at the same temperature for 1 hour.
反応終了後、生成物を吸引濾過することで、７５０部（
収量９９．０％）のポリエチレングリコールモノアクリ
レートを得１こ、このアクリレートのポリエチレングリ
コールジメクリレート含量は０．３％であった。ま１こ
ポリエチレングリコールモノアクリレートは９７．２％
であつ１こ。After the reaction is complete, the product is suction-filtered to yield 750 parts (
One piece of polyethylene glycol monoacrylate (yield: 99.0%) was obtained, and the content of polyethylene glycol dimecrylate in this acrylate was 0.3%. Ma1ko polyethylene glycol monoacrylate is 97.2%
And one.
実施例３゜
２−ヒドロキシプロピルメタアクリレート３００部（２
，１モル）にガレオンアース１０．０部およびヒドロキ
ノンモノメチルエーテル０．４部（５１１ｐｐｍ）加え
、窒素置換後、５０部５℃で５時間要してＰＯ４８３部
（８，３モル）を付加反応させＴコのち同温度で１時間
熟成した。生成物は吸引濾過することで７７１部（収量
９８゜５％）のポリプロピレングリコールモノメタクリ
レートを得１こ、このメタクリレートのポリプロピレン
グリコールジメタクリレート含量は０．３％であった。Example 3 300 parts of 2-hydroxypropyl methacrylate (2
, 1 mol) were added to 10.0 parts of Galleon Earth and 0.4 parts (511 ppm) of hydroquinone monomethyl ether, and after nitrogen substitution, 50 parts were subjected to an addition reaction with 483 parts (8.3 mol) of PO at 5°C for 5 hours. After that, it was aged for 1 hour at the same temperature. The product was filtered with suction to obtain 771 parts (yield: 98.5%) of polypropylene glycol monomethacrylate, and the polypropylene glycol dimethacrylate content of this methacrylate was 0.3%.
またポリプロピレングリコールモノメタクリレートは９
６．８％であつｔこ。Also, polypropylene glycol monomethacrylate is 9
At 6.8%.
実施例１〜３において、濾過後のガレオンアースは、そ
のまま廃棄処分し１こ。In Examples 1 to 3, the Galleon Earth after filtration was disposed of as is.
比較例１゜
触媒としてガレオンアースの代わりに四塩化スズ２．１
部を用いる以外は、実施例１と同様な条件でＥＯを付加
反応させ、ポリエチレングリコールモノメタクリレート
を得１こ、この生成物のポリエチレングリコールジメタ
クリレート含量は、１．３％であった。またポリエチレ
ングリコールモノメタクリレートは９０．３％であった
。Comparative Example 1゜Stannic tetrachloride 2.1 instead of Galleon Earth as a catalyst
Polyethylene glycol monomethacrylate was obtained by carrying out an addition reaction of EO under the same conditions as in Example 1, except that 1% of polyethylene glycol dimethacrylate was used.The content of polyethylene glycol dimethacrylate in this product was 1.3%. Moreover, the content of polyethylene glycol monomethacrylate was 90.3%.
このスズ触媒を中和戸別除去し１こ際重金属を含むν過
ケーキが発生しｒこ。When this tin catalyst is neutralized and removed, a filtration cake containing heavy metals is generated.
比較例２
触媒としてガレオンアースの代わりに、三フッ化ホウ素
ジエチルエーテル３．０部を用いる以外は、実施例１と
同様な条件でＥＯを付加反応させポリエチレングリコー
ルモノメタクリレートを得た。このメタクリレートのポ
リエチレングリコールジメタクリレート含量は、２１．
１％であつ１こ、ま１こポリエチレングリコールモノメ
タクリレートは６３．０％であつ１こ。Comparative Example 2 Polyethylene glycol monomethacrylate was obtained by carrying out an addition reaction with EO under the same conditions as in Example 1, except that 3.0 parts of boron trifluoride diethyl ether was used instead of Galleon Earth as a catalyst. The polyethylene glycol dimethacrylate content of this methacrylate is 21.
Polyethylene glycol monomethacrylate has 1 ounce at 1%, and 1 ounce at 63.0%.
比較例３゜
触媒としてガレオンアースの代わりに水酸化カリウム７
．８部を用いる以外は、実施例１と同様な条件でＥＯを
付加反応させたが、反応器内の圧は全く下がらず反応し
なかった。Comparative Example 3゜Potassium hydroxide 7 instead of Galleon Earth as a catalyst
．． An addition reaction of EO was carried out under the same conditions as in Example 1 except that 8 parts of EO was used, but the pressure inside the reactor did not drop at all and no reaction occurred.
実施例１〜３、比較例１〜３の生成物の性質および組成
は、表１のとおりである。The properties and compositions of the products of Examples 1 to 3 and Comparative Examples 1 to 3 are shown in Table 1.
表１
〔発明の効果〕
（１）本発明は、重金属廃棄物汚染のない（メタ）アク
リル酸エステルの製造法である。Table 1 [Effects of the Invention] (1) The present invention is a method for producing (meth)acrylic acid ester without heavy metal waste contamination.
（２ン 本発明において用いた活性白土は濾過等の簡
単な操作により分離できる。また回収しＴこ活性白土は
再利用することもでき、あるいはそのまま廃棄処理でき
る。(2) The activated clay used in the present invention can be separated by simple operations such as filtration.Also, the recovered activated clay can be reused, or it can be disposed of as is.
（３）本発明は、高純度のポリアルキレングリコールモ
ノ（メタ）アクリレートを製造できる。(3) The present invention can produce highly pure polyalkylene glycol mono(meth)acrylate.
従来、ＡＯ付加物を製造する場合、硫酸、Ｐ−トルエン
スルホン酸などの強酸性触媒、三フッ化ホウ素等のルイ
ス酸触を用いるが、不純物としてポリアルキレングリコ
ールおよびポリアルキレングリコールジ（メタ）アクリ
レートが副生ずる。特にポリアルキレングリコールジ（
メタ）アクリレートの含有率が高いと他のモノマーと共
重合する場合、網目構造をとりゲル化現象が起り満足な
性能の共重合物が得られなかった１本発明によれば、副
生ポリアルキレングリコールジ（メタ）アクリレートの
含量の極めて少ないすぐれた製品が得られる。Conventionally, when producing AO adducts, strong acid catalysts such as sulfuric acid and P-toluenesulfonic acid, and Lewis acid catalysts such as boron trifluoride are used, but polyalkylene glycol and polyalkylene glycol di(meth)acrylate are used as impurities. is a by-product. Especially polyalkylene glycol di(
When the content of meth)acrylate is high, when it is copolymerized with other monomers, a network structure is formed and a gelation phenomenon occurs, making it impossible to obtain a copolymer with satisfactory performance.1 According to the present invention, by-product polyalkylene An excellent product with a very low content of glycol di(meth)acrylates is obtained.
上記効果を奏することから、本発明は、繊維改質剤、凝
集剤、分散剤等のモノマー組成に適しているポリアルキ
レングリコール（メタ）アクリレートが得られる。Since the above effects are achieved, the present invention provides polyalkylene glycol (meth)acrylate suitable for monomer compositions such as fiber modifiers, flocculants, and dispersants.
Claims (1)
のアルキレン基である。） で示される化合物に活性白土の存在下、アルキレンオキ
サイドを付加反応させて一般式 ▲数式、化学式、表等があります▼（２） 〔式中、ＲとＡ＿１は一般式（１）の場合と同様。 Ａ＿２は炭素数２〜４のアルキレン基、ｎは１〜２０の
整数である。〕 で示される化合物を得ることを特徴とする （メタ）アクリル酸エステルの製造法。 ２、活性白土の量が、一般式（１）で示される化合物の
重量に基いて０．１〜１０重量％である特許請求の範囲
第１項記載の製造法。[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (1) (In the formula, R is H or CH_3, A_1 has 2 to 4 carbon atoms.
is an alkylene group. ) In the presence of activated clay, the compound represented by alkylene oxide is subjected to an addition reaction to form the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (2) [In the formula, R and A_1 are the same as those in general formula (1). Same. A_2 is an alkylene group having 2 to 4 carbon atoms, and n is an integer of 1 to 20. ] A method for producing a (meth)acrylic acid ester, characterized by obtaining a compound represented by the following. 2. The manufacturing method according to claim 1, wherein the amount of activated clay is 0.1 to 10% by weight based on the weight of the compound represented by formula (1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62118029A JPH0710801B2 (en) | 1987-05-14 | 1987-05-14 | Method for producing (meth) acrylic acid ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62118029A JPH0710801B2 (en) | 1987-05-14 | 1987-05-14 | Method for producing (meth) acrylic acid ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63284146A true JPS63284146A (en) | 1988-11-21 |
| JPH0710801B2 JPH0710801B2 (en) | 1995-02-08 |
Family
ID=14726295
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62118029A Expired - Lifetime JPH0710801B2 (en) | 1987-05-14 | 1987-05-14 | Method for producing (meth) acrylic acid ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0710801B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1200506A1 (en) | 1999-07-09 | 2002-05-02 | The Dow Chemical Company | Polymerization of ethylene oxide using metal cyanide catalsyts |
| JP2015500848A (en) * | 2011-12-22 | 2015-01-08 | エボニック レーム ゲゼルシャフト ミット ベシュレンクテル ハフツングＥｖｏｎｉｋ Ｒｏｅｈｍ ＧｍｂＨ | Method for producing bicyclic or tricyclic (meth) acrylate |
| CN105622400A (en) * | 2014-10-28 | 2016-06-01 | 中国石油化工股份有限公司 | Acrylate synthesis method |
-
1987
- 1987-05-14 JP JP62118029A patent/JPH0710801B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1200506A1 (en) | 1999-07-09 | 2002-05-02 | The Dow Chemical Company | Polymerization of ethylene oxide using metal cyanide catalsyts |
| JP2015500848A (en) * | 2011-12-22 | 2015-01-08 | エボニック レーム ゲゼルシャフト ミット ベシュレンクテル ハフツングＥｖｏｎｉｋ Ｒｏｅｈｍ ＧｍｂＨ | Method for producing bicyclic or tricyclic (meth) acrylate |
| CN105622400A (en) * | 2014-10-28 | 2016-06-01 | 中国石油化工股份有限公司 | Acrylate synthesis method |
| CN105622400B (en) * | 2014-10-28 | 2018-06-15 | 中国石油化工股份有限公司 | A kind of synthetic method of acrylate |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0710801B2 (en) | 1995-02-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0279892B1 (en) | Polycarboxylic acids with small amount of residual monomer | |
| US4589995A (en) | Maleic acid copolymer, production thereof and scale-preventing agent containing the same | |
| WO2006104255A1 (en) | (meth)acrylic acid copolymer, method for producing the same, and application thereof | |
| KR20030032808A (en) | Process for preparing allyletherester monomer and cement dispersing agent | |
| WO2009080214A1 (en) | Defoamers | |
| JP2546124B2 (en) | Method for producing polyfunctional (meth) acrylate | |
| US3839393A (en) | Ammonium and alkali metal salts of sulfato-alkane acrylates and methacrylates | |
| JPS63284146A (en) | Production of (meth)acrylic acid ester | |
| JP4305908B2 (en) | Method for producing water-soluble (meth) acrylic acid polyalkylene glycol ester | |
| EP0641363B1 (en) | Detergent compositions containing copolymers | |
| CN110713438B (en) | Production process of ethylene glycol di (meth) acrylate | |
| JP2914075B2 (en) | Method for producing (meth) acrylic acid ester | |
| EP0683183B1 (en) | Michael adducts of n-vinylformamide and acrylic and methacrylic esters | |
| JP3084485B2 (en) | Production of macromonomer | |
| JP4609611B2 (en) | Method for producing high-purity adamantyl (meth) acrylates | |
| US6794473B2 (en) | Acrylic acid (salt) polymer, its production process and uses | |
| US5663253A (en) | Policarboxylic acids | |
| JP3044694B2 (en) | Purification method of glycidyl methacrylate | |
| JP3463876B2 (en) | Vinyl ether group-containing (meth) acrylate composition and method for producing the same | |
| JP2008201780A (en) | Method for producing hydroxyalkyl (meth)acrylate | |
| JP3550248B2 (en) | Purification method of nonionic surfactant | |
| US4987210A (en) | Polymerizable derivatives of 5-oxo-pyrrolidinecarboxylic acid | |
| US4946967A (en) | Polymerizable derivatives of 5-oxo-pyrrolidinecarboxylic acid | |
| JPWO2002088151A1 (en) | Polymerizable phosphate ester and method for producing the same | |
| EP0679665B1 (en) | Polymerization of acrylic acid and derivatives thereof |