JPH02104535A - Dehydration and drying of reactive monomers - Google Patents
Dehydration and drying of reactive monomersInfo
- Publication number
- JPH02104535A JPH02104535A JP25788688A JP25788688A JPH02104535A JP H02104535 A JPH02104535 A JP H02104535A JP 25788688 A JP25788688 A JP 25788688A JP 25788688 A JP25788688 A JP 25788688A JP H02104535 A JPH02104535 A JP H02104535A
- Authority
- JP
- Japan
- Prior art keywords
- meth
- drying
- dehydration
- acrylate
- dry air
- 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
- 239000000178 monomer Substances 0.000 title claims abstract description 44
- 238000001035 drying Methods 0.000 title claims abstract description 39
- 230000018044 dehydration Effects 0.000 title claims abstract description 33
- 238000006297 dehydration reaction Methods 0.000 title claims abstract description 33
- -1 (meth)acryloxy group Chemical group 0.000 claims abstract description 24
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 22
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000003085 diluting agent Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 8
- 238000006116 polymerization reaction Methods 0.000 abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 238000007865 diluting Methods 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 230000005587 bubbling Effects 0.000 abstract description 2
- 239000007921 spray Substances 0.000 abstract description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 35
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 24
- 239000001294 propane Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 8
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 7
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- CHUGKEQJSLOLHL-UHFFFAOYSA-N 2,2-Bis(bromomethyl)propane-1,3-diol Chemical compound OCC(CO)(CBr)CBr CHUGKEQJSLOLHL-UHFFFAOYSA-N 0.000 description 2
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- YMOONIIMQBGTDU-VOTSOKGWSA-N [(e)-2-bromoethenyl]benzene Chemical compound Br\C=C\C1=CC=CC=C1 YMOONIIMQBGTDU-VOTSOKGWSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CISIJYCKDJSTMX-UHFFFAOYSA-N 2,2-dichloroethenylbenzene Chemical compound ClC(Cl)=CC1=CC=CC=C1 CISIJYCKDJSTMX-UHFFFAOYSA-N 0.000 description 1
- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- OZPOYKXYJOHGCW-UHFFFAOYSA-N 2-iodoethenylbenzene Chemical compound IC=CC1=CC=CC=C1 OZPOYKXYJOHGCW-UHFFFAOYSA-N 0.000 description 1
- VOZYDWQACVASLF-UHFFFAOYSA-N 4-(1-bromoethenyl)phenol Chemical compound OC1=CC=C(C(Br)=C)C=C1 VOZYDWQACVASLF-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- KBEBGUQPQBELIU-CMDGGOBGSA-N Ethyl cinnamate Chemical compound CCOC(=O)\C=C\C1=CC=CC=C1 KBEBGUQPQBELIU-CMDGGOBGSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical class ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- KBEBGUQPQBELIU-UHFFFAOYSA-N cinnamic acid ethyl ester Natural products CCOC(=O)C=CC1=CC=CC=C1 KBEBGUQPQBELIU-UHFFFAOYSA-N 0.000 description 1
- CCRCUPLGCSFEDV-UHFFFAOYSA-N cinnamic acid methyl ester Natural products COC(=O)C=CC1=CC=CC=C1 CCRCUPLGCSFEDV-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- CCRCUPLGCSFEDV-BQYQJAHWSA-N methyl trans-cinnamate Chemical compound COC(=O)\C=C\C1=CC=CC=C1 CCRCUPLGCSFEDV-BQYQJAHWSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-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、ビニル基、アクリロキシ基、メタクリロキシ
基、水酸基、ウレタン結合又はアロハネート結合を有す
るビニルモノマー類、又はそれらの混合物、又はそれら
を稀釈剤で稀釈した溶液の脱水乾燥方法に関するもので
ある。Detailed Description of the Invention "Industrial Application Field" The present invention relates to vinyl monomers having a vinyl group, an acryloxy group, a methacryloxy group, a hydroxyl group, a urethane bond or an allophanate bond, or a mixture thereof, or a diluent containing them. This relates to a method for dehydrating and drying a solution diluted with
「従来の技術」
従来の一般的な反応性モノマー類の脱水乾燥方法として
は１例えばモレキュラシープ、無水芒硝等の水分吸着剤
による吸着脱水乾燥−減圧脱水乾燥；乾燥窒素ガス、乾
燥二酸化炭素のような乾燥した不活性ガスを用いた気液
接触による脱水乾燥等が一般的に用いられている。``Prior art'' Conventional general dehydration and drying methods for reactive monomers include 1. Adsorption and dehydration drying using a moisture adsorbent such as molecular sheep and anhydrous sodium sulfate - vacuum dehydration drying; dry nitrogen gas, dry carbon dioxide, etc. Dehydration and drying by gas-liquid contact using a dry inert gas, etc., is generally used.
ｒ発明が解決しようとする課題」
しかしながら、このような従来の一般的な乾燥方法にあ
っては。"Problems to be Solved by the Invention" However, in such a conventional general drying method.
■吸着脱水乾燥法では水分吸着剤への反応性モノマー類
の吸着による法肩りの低下がさけられず、また反応性モ
ノマー類等と水分吸着剤との分離、水分吸着剤の除去と
いったａ￥雑な作業をともなう、
■減圧脱水乾燥法では脱水温度および真空度の管理が難
かしく、低沸点の反応性モノマーや稀釈剤の反応系外へ
の留出が起こる危険性がある、
■乾燥した不活性ガスによる脱水乾燥では、脱水を効率
よく行うために脱水温度を高くしたときに反応性モノマ
ーの重合が起こることがある
等の問題点が認られる場合が、少なくない。■In the adsorption/dehydration drying method, a reduction in the stiffness due to the adsorption of reactive monomers to the moisture adsorbent cannot be avoided, and a - In the vacuum dehydration drying method, it is difficult to control the dehydration temperature and degree of vacuum, and there is a risk that low-boiling point reactive monomers and diluents may distill out of the reaction system. Dehydration drying using an inert gas often presents problems such as polymerization of reactive monomers when the dehydration temperature is raised to ensure efficient dehydration.
そこで本発明が解決しようとする課題は、反応性モノマ
ー類の脱水乾燥時において、法肩りの低下がなく２反応
性モノマーや稀釈剤の反応系外への留出や１反応性モノ
マーの重合が起こらず、かつ繁雑な作業をともなうこと
なく作業性に優れた脱水乾燥方法を提供することにある
。Therefore, the problem to be solved by the present invention is to prevent the distillation of two-reactive monomers and diluents from the reaction system and the polymerization of one-reactive monomers without reducing the stiffness during dehydration and drying of reactive monomers. To provide a dehydrating and drying method which does not occur and has excellent workability without involving complicated work.
「課題を解決するための手段」
本発明の脱水乾燥方法は、ビニル基、アクリロキシ基、
メタクリロキシ基、水醜基、ウレタン結合又はアロハネ
ート結合を有するビニルモノマー類、又はそれらの混合
物、又はそれらを稀釈剤で稀釈した溶液（以下、反応性
モノマー類と称す）を脱水乾燥するに際し、乾燥空気を
用いた気液接触によって行なうことを要旨とするもので
ある。"Means for Solving the Problems" The dehydration drying method of the present invention includes vinyl groups, acryloxy groups,
When dehydrating and drying vinyl monomers having methacryloxy groups, water-ugly groups, urethane bonds, or allophanate bonds, or mixtures thereof, or solutions obtained by diluting them with a diluent (hereinafter referred to as reactive monomers), dry air is used. The gist of this method is to carry out gas-liquid contact using
［手段を構成する要件］
（乾燥空気）
本発明に使用する乾燥空気は、大気中の空気又は酸素ガ
スと窒素ガスとの混合物等であるが、それらの気体の露
点が一５℃以下、より好ましくは一１０℃以下のものが
、脱水乾燥の目的から好適である。[Requirements constituting the means] (Dry air) The dry air used in the present invention is atmospheric air or a mixture of oxygen gas and nitrogen gas, and the dew point of these gases is 15°C or less, or more. Preferably, temperatures below -10°C are suitable for the purpose of dehydration and drying.
さらに１反応性モノマーの重合を防止する意味から、か
かる乾燥空気は酸素／窒素の混合比が。Furthermore, in order to prevent the polymerization of monoreactive monomers, the dry air has an oxygen/nitrogen mixing ratio.
（同一圧力下の換算で、かつ容量）０．０５／９９．９
５〜ｌ ＯＯｌｏの範囲にあることが盛装であるが、５
／９５〜９０／ｌｏの範囲にあるものがより好適である
。(Converted under the same pressure and capacity) 0.05/99.9
It is appropriate to be in the range of 5 to l OOlo, but 5
A range of /95 to 90/lo is more preferable.
（気液接触方法）
本発明において、乾燥空気と反応性モノマー類との気液
接触を行う方法としては、例えば、噴霧塔内での気液接
触方法あるいは、反応性モノマー類中に直接バブリング
することによる気液接触方法等が挙げられるが、その他
のどのような方法でもかまわない。(Gas-liquid contact method) In the present invention, the method of bringing dry air into gas-liquid contact with the reactive monomers includes, for example, a gas-liquid contact method in a spray tower, or direct bubbling into the reactive monomers. For example, a gas-liquid contact method may be used, but any other method may be used.
（反応性モノマー類）
本発明に使用する反応性モノマー類としては、次の様な
ものが挙げられる。(Reactive Monomers) Examples of the reactive monomers used in the present invention include the following.
ビニル基を有するビニルモノマー類；
例エバスチレン、クロロスチレン、ジクロロスチレン、
ブロモスチレン、ジプロモスチレン、ヨードスチレン、
ジビニルベンゼン、Ｎ−ビニルカルバゾール等である。Vinyl monomers having a vinyl group; Examples: evastyrene, chlorostyrene, dichlorostyrene,
Bromostyrene, dipromostyrene, iodostyrene,
These include divinylbenzene and N-vinylcarbazole.
アクリロキシ基又はメタクリロキシ基を有するビニルモ
ノマー類：
例えばポリオキシアルキレングリコールのジ（メタ）ア
クリレート、トリメチロールプロパンのトリ（メタ）ア
クリレート、ネオペンチルグリコールのジ（メタ）アク
リレート、フェニル（メタ）アクリレート、フェノキシ
エトキシエチル（メタ）アクリレート、ポリオキシアル
キレン化フェノールの（メタ）アクリレート、フェノキ
シエチル（メタ）アクリレート、１．４−ジ（メタ）７
クリロキシベンゼン、１．４−ジ（メタ）アクロキシエ
トキシベンゼン、１．４−ジ（メタ）アクロキシナフタ
レン、１．４−ジ（メタ）アクリロキシエトキシナフタ
レン、２．２−ビス〔４−（メタ）アクリロキシフェニ
ル〕プロパン、２．２−ビス（４−（メタ）アクリロキ
シエトキシフェニル〕プロパン、ポリオキシアルキレン
化ビスフェノールＡのジ（メタ）アクリレート、桂皮酸
メチル、桂皮酸エチル、ベンジル（メタ）アクリレート
、ジブロモネオペンチルグリコールのジ（メタ）アクリ
レート、モノブロモフェニル（メタ）クリレート、トリ
ブロモフェニル（メタ）クリレート、モノクロロフェノ
キシエチル（メタ）クリレート、トリクロロフェノキシ
エチル（メタ）クリレート、ペンタブロモフェノキシエ
チル（メタ）クリレート、モノブロモフェノキシエトキ
シエチル（メタ）アクリレート、トリブロモフェノキシ
エトキシエチル（メタ）アクリレート、ポリオキシアル
キレン化テトラブロモフェノールの（メタ）アクリレー
ト、１．４−ジ（メタ）アクリロキシ−２，３，５，６
−チトラクロロベンゼン、１．４−ジ（メタ）アクリロ
キシエトキシ−２，３，５，６−チトラプロモベンゼン
、１．４−ジ（メタ）アクリロキシエトキシ−２，３，
５，６−チトラクロロナフタレン、テトラブロモフター
ル酸−ジ〔２−（メタ）アクリロキシエチル）、２．２
−ビス〔４−（メタ）アクリロキシ−３，５−ジブロモ
フェニル〕プロパン、２．２−ビス（４−（メタ）アク
リロキシエトキシ−３，５−ジブロモフェニル〕プロパ
ン、ポリオキシアルキレン化テトラブロモビスフェノー
ルＡのジ（メタ）アクリレート、１．５−ジ（メタ）ア
クリロキシエトキシ−２，４，６，８−テトラブロモナ
フタレン等である。Vinyl monomers having an acryloxy or methacryloxy group: For example, polyoxyalkylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, phenyl(meth)acrylate, phenoxy Ethoxyethyl (meth)acrylate, (meth)acrylate of polyoxyalkylenated phenol, phenoxyethyl (meth)acrylate, 1,4-di(meth)7
Acryloxybenzene, 1.4-di(meth)acryloxyethoxybenzene, 1.4-di(meth)acryloxynaphthalene, 1.4-di(meth)acryloxyethoxynaphthalene, 2.2-bis[4- (meth)acryloxyphenyl]propane, 2,2-bis(4-(meth)acryloxyethoxyphenyl)propane, di(meth)acrylate of polyoxyalkylenated bisphenol A, methyl cinnamate, ethyl cinnamate, benzyl ( meth)acrylate, di(meth)acrylate of dibromoneopentyl glycol, monobromophenyl(meth)acrylate, tribromophenyl(meth)acrylate, monochlorophenoxyethyl(meth)acrylate, trichlorophenoxyethyl(meth)acrylate, pentabromophenoxy Ethyl (meth)acrylate, monobromophenoxyethoxyethyl (meth)acrylate, tribromophenoxyethoxyethyl (meth)acrylate, (meth)acrylate of polyoxyalkylenated tetrabromophenol, 1,4-di(meth)acryloxy-2 ,3,5,6
-Titrachlorobenzene, 1,4-di(meth)acryloxyethoxy-2,3,5,6-titrabromobenzene, 1,4-di(meth)acryloxyethoxy-2,3,
5,6-Titrachloronaphthalene, di[2-(meth)acryloxyethyl) tetrabromophthalate, 2.2
-Bis[4-(meth)acryloxy-3,5-dibromophenyl]propane, 2,2-bis(4-(meth)acryloxyethoxy-3,5-dibromophenyl)propane, polyoxyalkylenated tetrabromobisphenol These include di(meth)acrylate of A, 1,5-di(meth)acryloxyethoxy-2,4,6,8-tetrabromonaphthalene, and the like.
水酸基を有するビニルモノマー類；
例えばポリオキシアルキレングリコールのモノ（メタ）
アクリレート、トリメチロールプロパンのモノ（メタ）
アクリレート、ネオペンチルグリコールのモノ（メタ）
アクリレート、トリメチロールプロパンのジ（メタ）ア
クリレート、４−ヒドロキシフェニル（メタ）アクリレ
ート、４−ヒドロキシエトキシフェニル（メタ）アクリ
レート、４−ヒドロキシスチレン、４−ヒドロキシエト
キシスチレン、３−フェノキシ−２−ヒドロキシプロピ
ル（メタ）アクリレート、２−（４−ヒドロキシフェニ
ル）−２−（４−（メタ）アクリロキシフェニル〕プロ
パン、２−（４−ヒドロキシエトキシフェニル）−２−
（４−（メタ）アクリロキシエトキシフェニル〕プロパ
ン、 ２− （４−ヒドロキシジェトキシフェニル）
−２−（４−（メタ）アクリロキシジェトキシフェニル
〕プロパン、ポリオキシアルキレン化ビスフェノールＡ
のモノ（メタ）アクリレート、２ 、２−ヒス（４−（
３−（メタ）アクリロキシ−２−ヒドロキシプロポキシ
）フェニル〕プロパン、ジブロモネオペンチルグリコー
ルのモノ（メタ）アクリレート、４−ヒドロキシモノブ
ロモフェニル（メタ）アクリレート、４−ヒドロキシＩ
・ジブロモフェニル（メタ）アクリレート、４−ヒドロ
キシテトラブロモフェニル（メタ）アクリレート、４−
ヒドロキシエトキシトリブロモフェニル（メタ）アクリ
レート、４−ヒドロキシテトラブロモフェニル（メタ）
アクリレート、４−ヒドロキシエトキシテトラブロモフ
ェニル（メタ）アクリレート、４−ヒドロキシモノブロ
モスチレン、４−ヒドロキシテトラブロモスチレン、４
−ヒドロキシエトキシテトラブロモスチレン、３−（２
，４，６−）リプロモフェノキシ）−２−ヒドロキシプ
ロピル（メタ）アクリレート、２．２−ビス（４−３−
（メタ）アクリロキシ−２−ヒドロキシプロポキシ）−
３，５−ジブロモフェニル）プロパン、２−（４−ヒド
ロキシ−３，５−ジブロモフェニル）−２−（４−（メ
タ）アクリロキシ−３，５−ジブロモフェニル）プロパ
ン、２−（４−ヒドロキシエトキシ−３，５−ジブロモ
フェニル）−２−（４−（メタ）アクリロキシエトキシ
−３゜５−ジブロモフェニル）プロパン、２−（４−１
＝ドロキシジェトキシ−３，５−ジブロモフェニル）−
２−（４−（メタ）アクリロキシジェトキシ−３，５−
ジブロモフェニル〕プロパン等である。Vinyl monomers having hydroxyl groups; e.g. polyoxyalkylene glycol mono(meth)
Acrylate, trimethylolpropane mono (meth)
Acrylate, neopentyl glycol mono (meth)
Acrylate, di(meth)acrylate of trimethylolpropane, 4-hydroxyphenyl(meth)acrylate, 4-hydroxyethoxyphenyl(meth)acrylate, 4-hydroxystyrene, 4-hydroxyethoxystyrene, 3-phenoxy-2-hydroxypropyl (meth)acrylate, 2-(4-hydroxyphenyl)-2-(4-(meth)acryloxyphenyl]propane, 2-(4-hydroxyethoxyphenyl)-2-
(4-(meth)acryloxyethoxyphenyl]propane, 2-(4-hydroxyjethoxyphenyl)
-2-(4-(meth)acryloxyjethoxyphenyl]propane, polyoxyalkylenated bisphenol A
mono(meth)acrylate, 2,2-His(4-(
3-(meth)acryloxy-2-hydroxypropoxy)phenyl]propane, mono(meth)acrylate of dibromoneopentyl glycol, 4-hydroxymonobromophenyl(meth)acrylate, 4-hydroxy I
・Dibromophenyl (meth)acrylate, 4-hydroxytetrabromophenyl (meth)acrylate, 4-
Hydroxyethoxytribromophenyl (meth)acrylate, 4-hydroxytetrabromophenyl (meth)
Acrylate, 4-hydroxyethoxytetrabromophenyl (meth)acrylate, 4-hydroxymonobromostyrene, 4-hydroxytetrabromostyrene, 4
-Hydroxyethoxytetrabromostyrene, 3-(2
, 4,6-)lipromophenoxy)-2-hydroxypropyl (meth)acrylate, 2,2-bis(4-3-
(meth)acryloxy-2-hydroxypropoxy)-
3,5-dibromophenyl)propane, 2-(4-hydroxy-3,5-dibromophenyl)-2-(4-(meth)acryloxy-3,5-dibromophenyl)propane, 2-(4-hydroxyethoxy) -3,5-dibromophenyl)-2-(4-(meth)acryloxyethoxy-3゜5-dibromophenyl)propane, 2-(4-1
=Droxyjethoxy-3,5-dibromophenyl)-
2-(4-(meth)acryloxyjethoxy-3,5-
dibromophenyl]propane, etc.
ウレタン結合又はアロハネート結合を有するビニルモノ
マー類；
例えば前記水酸基を有するビニルモノマー類と脂肪族イ
ンシアネート、脂環族インシアネート又は芳香族インシ
アネート等のインシアネート類との反応生成物等である
。Vinyl monomers having a urethane bond or allophanate bond; for example, reaction products of the vinyl monomers having a hydroxyl group and incyanates such as aliphatic incyanate, alicyclic incyanate, or aromatic incyanate.
かかるインシアネート類としては、例えばヘキサメチレ
ンジイソシアネート、インホロンジイソシアネート、２
，２．４−）リメチルへキサメチレンジイソシアネート
、ジシクロヘキシルメタンジイソシアネート、リジンジ
イソシアネートメチルエステル、キシレンジイソシアネ
ート、ビス（インシアネートメチル）シクロヘキサン、
トリレンジイソシアネート、４．４゛−ジフェニルメタ
ンジインシアネート、ヘキサメチレンジイソシアネート
のビウレット化反応生成物、ヘキサメチレンジイソシア
ネートとトリメチロールプロパンとの反応アダクト体、
ヘキサメチレンジイソシアネートのインシアヌレート変
性体、２−インシアネートエチル−２，６−ジイツシア
ネートヘキサノエー）、ｌ、６．ｉｆ−ウンデカントリ
インシアネート、イソホロンジイソシアネートとトリメ
チロールプロパンとの反応アダクト体、キシレンジイソ
シアネートとトリメチロールプロパントノ反応アダクト
体、ビス（インシアネートメチル）シクロヘキサンとト
リメチロールプロパンとの反応アダクト体等が挙げられ
る。Examples of such incyanates include hexamethylene diisocyanate, inphorone diisocyanate, 2
, 2.4-)limethylhexamethylene diisocyanate, dicyclohexylmethane diisocyanate, lysine diisocyanate methyl ester, xylene diisocyanate, bis(incyanate methyl)cyclohexane,
Tolylene diisocyanate, 4.4'-diphenylmethane diincyanate, biuretization reaction product of hexamethylene diisocyanate, reaction adduct of hexamethylene diisocyanate and trimethylolpropane,
Incyanurate modified product of hexamethylene diisocyanate, 2-incyanate ethyl-2,6-ditucyanate hexanoate), 1, 6. If-undecane triincyanate, a reaction adduct of isophorone diisocyanate and trimethylolpropane, a reaction adduct of xylene diisocyanate and trimethylolpropane, a reaction adduct of bis(incyanate methyl)cyclohexane and trimethylolpropane, etc. .
（希釈剤）
本発明において、ビニルモノマー類を希釈する希釈剤と
しては、ビニルモノマー類に反応活性を示さない溶剤が
挙げられる。具体的には、ベンゼン、トルエン、キシレ
ン、ジオキサン、メチルセロンルブ、エチルセロソルブ
、酢酸エチル等が好適に使用できる。(Diluent) In the present invention, examples of the diluent for diluting vinyl monomers include solvents that do not show any reaction activity toward vinyl monomers. Specifically, benzene, toluene, xylene, dioxane, methylcellosolve, ethylcellosolve, ethyl acetate, etc. can be suitably used.
さらにスチレン、ブロモスチレン、ジプロモスチレン、
ジビニルベンゼン等の液体のビニルモノマーも希釈剤と
して、他のビニルモノマー類に添加して使用することも
できる。Furthermore, styrene, bromostyrene, dipromostyrene,
Liquid vinyl monomers such as divinylbenzene can also be used as diluents by being added to other vinyl monomers.
「作用」
本発明の方法は、乾燥空気を使用することにより、反応
性モノマー類の有するビニル基、アクリロキシ基又はメ
タクリロキシ基等の重合が乾燥空気中の酸素によって防
止され。"Operation" In the method of the present invention, by using dry air, polymerization of vinyl groups, acryloxy groups, methacryloxy groups, etc. contained in reactive monomers is prevented by oxygen in the dry air.
さらに、乾燥空気と反応性モノマー類との気液接触によ
る脱水乾燥であることから、脱水乾燥時に法肩りの低下
がない、反応性モノマーや希釈剤の反応系外への留出が
ない等、さらに作業性に優れた反応性モノマー類の脱水
乾燥方法である。Furthermore, since dehydration and drying is carried out through gas-liquid contact between dry air and reactive monomers, there is no reduction in shoulder height during dehydration and drying, and there is no distillation of reactive monomers or diluents out of the reaction system. This is a method for dehydrating and drying reactive monomers that has excellent workability.
「実施例」
実施例１゜
還流冷却器を備えた２文官の四ツ目フラスコ中にジプロ
モスチレン１０００重量部を入れ、４０℃で攪拌しなが
らフラスコ下部から露１点−６０℃の乾燥空気（０２／
Ｎ ２ ＝ ５０ ／ ５０容琶比）を常圧下で毎分
４００ ｍ ｌの流量で３時間流し、気液接触による脱
水乾燥を行った。"Example" Example 1 1000 parts by weight of dipromostyrene was placed in a four-eye flask equipped with a reflux condenser, and while stirring at 40°C, one point of dew was poured from the bottom of the flask into dry air at -60°C. (02/
N2 = 50/50 volume ratio) was flowed under normal pressure at a flow rate of 400 ml per minute for 3 hours to perform dehydration and drying by gas-liquid contact.
この結果、脱水乾燥前に３５０ｐｐｍであった水分を１
２０ｐｐｍまで脱水乾燥できた。また、ジプロモスチレ
ンの重合は認められなかった。As a result, the water content, which was 350 ppm before dehydration and drying, was reduced to 1
It was possible to dehydrate and dry it to 20 ppm. Further, no polymerization of dipromostyrene was observed.
結果を表−１に示す。The results are shown in Table-1.
実施例２〜８゜
乾燥空気組成を一定にし、乾燥空気の露点を変えて実施
例１と同様に、表−１に示した条件下で脱水乾燥を行っ
た。結果を表−１に示す。Examples 2 to 8 Dehydration and drying were carried out under the conditions shown in Table 1 in the same manner as in Example 1, keeping the drying air composition constant and changing the dew point of the drying air. The results are shown in Table-1.
比較例１〜４゜
露点０°Ｃの乾燥空気を使用した以外は、実施例１と同
様の条件で脱水乾燥を行った。Comparative Examples 1 to 4 Dehydration and drying were carried out under the same conditions as in Example 1, except that dry air with a dew point of 0°C was used.
結果を表−２に示す。The results are shown in Table-2.
実施例９゜
還流冷却器を備えた２文官の四ツ目フラスコ中ニスチレ
ン５ＧＯ［ｌｉ”３とジプロモスチレン５００ｍＩＩＥ
部よりなるビニルモノマーの混合溶液を入れ、４０°Ｃ
で攪拌しながらフラスコ下部から露点−６０℃の乾燥空
気（Ｏｚ ／ Ｎ ２ ＝ ９０７ ｌ Ｏ容量比）を
常圧下で毎分４００ｍＪｌの流量で４時間流し、気液接
触による脱水乾燥を行った。Example 9 Nistyrene 5GO [li”3 and dipromostyrene 500 mIIE in two civilian four-eye flasks equipped with reflux condensers
Add a mixed solution of vinyl monomers consisting of
Dry air (Oz/N2=907 lO volume ratio) with a dew point of -60°C was flowed from the bottom of the flask under normal pressure at a flow rate of 400 mJl per minute for 4 hours while stirring to perform dehydration and drying by gas-liquid contact.
この結果、脱水乾燥前に５００ｐｐｍであった水分を１
８０ｐｐｍまで脱水乾燥できた。As a result, the water content, which was 500 ppm before dehydration and drying, was reduced to 1
It was possible to dehydrate and dry it to 80 ppm.
また、このビニル千ツマー溶液の重合は認められなかっ
た。結果を表−３に示す。Further, no polymerization of this vinyl chloride solution was observed. The results are shown in Table-3.
実施例１ＯＮ１４゜
実施例９と同様の方法で、乾燥空気の組成、および露点
を変えて表−３に示した条件で脱水乾燥を行った。結果
を表−３に示す。Example 1 ON14° In the same manner as in Example 9, dehydration and drying was carried out under the conditions shown in Table 3 by changing the composition of the drying air and the dew point. The results are shown in Table-3.
比較例５〜７゜
乾燥空気に変えて窒素を使用した以外は実施例９と同様
の条件で脱水乾燥を行った。結果を表−４に示す。Comparative Examples 5-7° Dehydration and drying were carried out under the same conditions as in Example 9 except that nitrogen was used instead of dry air. The results are shown in Table 4.
実施例１５゜
還流冷却器を備えた２文官の四ツ目フラスコ中にジプロ
モスチレンｔｏｏｏ重量部を入れ、４００Ｃで攪拌しな
がらフラスコ下部から露点−６０℃の乾燥空気（０２／
Ｎ ２ ＝ ９０７１０容量比）を常圧下で毎分４０
０ｍ文の流量で３時間流し、気液接触による脱水乾燥を
行った。Example 1 Too many parts by weight of dipromostyrene were placed in a four-eye flask equipped with a reflux condenser, and while stirring at 400C, dry air with a dew point of -60℃ (02/
N2 = 90710 volume ratio) at 40% per minute under normal pressure.
It was run for 3 hours at a flow rate of 0m to perform dehydration and drying through gas-liquid contact.
この結果、脱水乾燥前に３５０ｐｐｍであった水分を１
３０ｐｐｍまで脱水乾燥できた。続いて、このジプロモ
スチレン約１００ｍ１を完全に密栓でき水分および空気
を遮断できるガラス容器に入れ、１６所で、４０℃３０
間放置して、保存安定性をテストした。As a result, the water content, which was 350 ppm before dehydration and drying, was reduced to 1
It was possible to dehydrate and dry it to 30 ppm. Next, about 100 ml of this dipromostyrene was placed in a glass container that can be completely sealed to shut out moisture and air, and heated at 40°C and 30°C in 16 places.
The storage stability was tested by leaving it for a while.
その結果、３日後においてもジプロモスチレンは透明溶
液の外観を保っており、ポリマーの生成によるゲルは認
められなかった。As a result, even after 3 days, dipromostyrene maintained the appearance of a transparent solution, and no gel was observed due to polymer formation.
実施例１６〜１７゜
実施例１５と同様の方法で、表−５に示した条件で脱水
乾燥後１反応性上ツマー類の保存安定性をテストした。Examples 16 to 17 In the same manner as in Example 15, the storage stability of the 1-reactive upper tumers was tested after dehydration and drying under the conditions shown in Table 5.
結果を表−５に示す。The results are shown in Table-5.
比較例８〜ｌＯ１
露点０℃の乾燥空気を使用した以外は実施例１５と同様
の条件で脱水乾燥を行い、反応性上ツマー類の保存安定
性をテストした。Comparative Example 8-lO1 Dehydration and drying was performed under the same conditions as in Example 15, except that dry air with a dew point of 0° C. was used, and storage stability of the reactivity and tsumars was tested.
結果を表−５に示す。The results are shown in Table-5.
「発明の効果」
以上説明した通り１本発明は反応性千ツマー類の脱水乾
燥に乾燥空気を使用する方法を提供しうろことにより、
反応性モノマー類の脱水乾燥時の組合防止、法肩り低下
の防止が図れ、さらに脱水乾燥後の反応性モノマー類の
保存安定性（保存時の反応性モノマー類の重合の有ｐＡ
）が極めて良好であり、かつ作業性の向上に貢献しうる
ちのである。"Effects of the Invention" As explained above, the present invention provides a method of using dry air for dehydration and drying of reactive chemicals.
It is possible to prevent the combination of reactive monomers during dehydration and drying, and to prevent the reduction of shoulder stiffness, and also to improve the storage stability of reactive monomers after dehydration and drying (polymerization of reactive monomers during storage).
) is extremely good and contributes to improved workability.
Claims (1)
水酸基、ウレタン結合又はアロハネート結合を有するビ
ニルモノマー類、又はそれらの混合物、又はそれらを稀
釈剤で稀釈した溶液（以下、反応性モノマー類と称す）
を脱水乾燥するに際し、乾燥空気を用いた気液接触によ
って行なうことを特徴とする反応性モノマー類の脱水乾
燥方法。(1) Vinyl group, acryloxy group, methacryloxy group,
Vinyl monomers having hydroxyl groups, urethane bonds or allophanate bonds, mixtures thereof, or solutions diluted with diluents (hereinafter referred to as reactive monomers)
1. A method for dehydrating and drying reactive monomers, characterized in that the dehydration and drying of reactive monomers is carried out through gas-liquid contact using dry air.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63257886A JPH0651645B2 (en) | 1988-10-13 | 1988-10-13 | Method for dehydrating and drying reactive monomers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63257886A JPH0651645B2 (en) | 1988-10-13 | 1988-10-13 | Method for dehydrating and drying reactive monomers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02104535A true JPH02104535A (en) | 1990-04-17 |
| JPH0651645B2 JPH0651645B2 (en) | 1994-07-06 |
Family
ID=17312550
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63257886A Expired - Fee Related JPH0651645B2 (en) | 1988-10-13 | 1988-10-13 | Method for dehydrating and drying reactive monomers |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0651645B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0426122A (en) * | 1990-05-22 | 1992-01-29 | Yoshihide Shibano | Method and apparatus for drying high integration work after washing |
| US5187335A (en) * | 1990-02-23 | 1993-02-16 | Kabushiki Kaisha Tokai Rika Denki Seisakusho | Switch with interlocked operators |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62186902A (en) * | 1986-02-12 | 1987-08-15 | Dai Ichi Kogyo Seiyaku Co Ltd | Method for removing organic solvent remaining in small amount |
| JPH026413A (en) * | 1988-06-27 | 1990-01-10 | Mitsubishi Rayon Co Ltd | Removal of dissolved oxygen in vinylic monomer |
-
1988
- 1988-10-13 JP JP63257886A patent/JPH0651645B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62186902A (en) * | 1986-02-12 | 1987-08-15 | Dai Ichi Kogyo Seiyaku Co Ltd | Method for removing organic solvent remaining in small amount |
| JPH026413A (en) * | 1988-06-27 | 1990-01-10 | Mitsubishi Rayon Co Ltd | Removal of dissolved oxygen in vinylic monomer |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5187335A (en) * | 1990-02-23 | 1993-02-16 | Kabushiki Kaisha Tokai Rika Denki Seisakusho | Switch with interlocked operators |
| JPH0426122A (en) * | 1990-05-22 | 1992-01-29 | Yoshihide Shibano | Method and apparatus for drying high integration work after washing |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0651645B2 (en) | 1994-07-06 |
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