GB2285983A - Inhibiting polymerization of vinyl compounds - Google Patents
Inhibiting polymerization of vinyl compounds Download PDFInfo
- Publication number
- GB2285983A GB2285983A GB9501046A GB9501046A GB2285983A GB 2285983 A GB2285983 A GB 2285983A GB 9501046 A GB9501046 A GB 9501046A GB 9501046 A GB9501046 A GB 9501046A GB 2285983 A GB2285983 A GB 2285983A
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- GB
- United Kingdom
- Prior art keywords
- metal
- acrylic acid
- vinyl compound
- compound
- distillation
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/50—Use of additives, e.g. for stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B63/00—Purification; Separation; Stabilisation; Use of additives
- C07B63/04—Use of additives
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The present invention provides a method of inhibiting polymerization of a vinyl compound during distillation, which comprises adding to the vinyl compound to be distilled: (1) phenothiazine, hydroquinone, p-methoxyphenol, cresol, phenol, tert-butyl catechol, diphenylamine, or methylene blue; (2) a copper dithiocarbamate compound; and (3) a metal, an alloy containing the metal (at least 90% by weight), an acetate of the metal, or an oxide of the metal, wherein the metal is chromium, magnesium, titanium, and cobalt. The present invention also provides a polymerization inhibitor comprising components (1), (2) and (3).
Description
A METED OF INHIT.TTNG POLYDERIZATION OF VINYL COMP4"ND AND
POLYMERIZATION INHIBITOR USED THEREIN
BACKGROUND OF THE INVENTION
Field of the Invention
The present invention relates to a system of inhibiting polymerization of a vinyl compound. More specifically, the invention relates to a method of inhibiting polymerization of a vinyl compound, for example, acrylic acid or methacrylic acid, which is applicable to distillation for obtaining purified vinyl compound, and also relates to a polymerization inhibitor used therein.
Related State of the Art
Vinyl compounds such as acrylic acid and methacrylic acid are readily polymerized by application of light or heat.
Especially in the process of distillation or concentration, the polymerized vinyl compounds often cause serious problems.
For example, such polymerized vinyl compounds in distillation are stuck to heat transfer surface in a reboiler of a distillation column, thereby decreasing the heat transfer performance thereof. In addition, the polymer can choke the distillation column and degrade the ability thereof.
A method utilizing hydroquinone, p-methoxyphenol, or copper dimethyl dtiocarbamate is well known as a Method of inhibiting polymerization of the vinyl compounds. Several methods have also been proposed to inhibit polymerization of vinyl compounds. These conventional methods include; one utilizing at least one compound selected from the group consisting of hydroquinone, p-methoxyphenol, cresol, phenol, tert-butyl catechol, diphenylamine, phenothiazine, and methylene blue in combination with at least one compound selected from the group consisting of copper dimethyl dithiocarbamate, copper diethyl dithiocarbamate, copper dibutyl dithiocar bamate, and copper salicylate (JAPANESE EXAMINED PATENT PUBLI
CATION No. 52-34606); one utilizing a manganese salt, such as manganese acetate, alone or in combination with hydroquinone and/or p-methoxyphenol (JAPANESE PATENT KOKAI PUBLICATION No.
51-98211); and one utilizing manganese dithiocarbamate or thiurams (JAPANESE PATENT KOKAI PUBLICATION No. 5-51403).
These known methods of inhibiting polymerization are, however, not applicable to distillation of vinyl compounds of relatively high concentrations under a high temperature condition.
Acrylic acid, one of the vinyl compounds, is used as a material for water-absorbing gels and thus required to have sufficiently high purity. As a high purity acrylic acid, the total content of aldehydes, including acrolein, furfural, benzaldehyde, and salicylaldehyde, contained in the acrylic acid is required at most several ppm.
A simple and still reliable method of aldehyde elimination is distillation of the crude or distilled acrylic acid in the presence of an aldehyde treatment agent. The aldehyde treatment agents include, for example, hydrazine hydrate, phenylhydrazine, and m-phenylenediamine. This method, however, accelerates polymerization of the vinyl compounds, especially acrylic acid.
The known polymerization inhibitors are not applicable to distillation of the vinyl compounds in the presence of the aldehyde treatment agent.
SUMMARY OF THE INVENTION
One object of the present invention is to provide a method of inhibiting polymerization of vinyl compounds, which is applicable to distillation of the vinyl compounds of relatively high concentrations under a high temperature condition or in the presence of an aldehyde treatment agent.
Another object of the present invention is to provide a polymerization inhibitor, which is preferably applied to distillation of the vinyl compounds of relatively high concentrations under a high temperature condition or in the presence of the aldehyde treatment agent.
These and other objects will become apparent frcri the following description.
The present inventors made a study on developing a novel method of inhibiting polymerization and a novel polymerization inhibitor applicable to distillation of vinyl compounds, and found that the above objects can be achieved by combining a specific metal or metal compound with a copper dithiocarbamate compound and a compound like phenothiazine, hydroquinone, or p-methoxyphenol.
The present invention provides a method of inhibiting polymerization of a vinyl compound during distillation, which comprises distilling the vinyl compound in the presence of the following components:
(1) phenothiazine, hydroquinone, p-methoxyphenol, cresol, phenol, tert-butyl catechol, diphenylamine, or methylene blue;
(2) a copper dithiocarbamate compound; and
(3) a metal, an alloy containing at east-90% by weight of the metal, an acetate of the metal, or an oxide of the metal, wherein the metal is selected from the group consisting of chromium, magnesium, titanium, or cobalt.
The present invention also provides a polymerization inhibitor for the inhibition of polymerization during distillation of a vinyl compound, which comprises the above components (1), (2) and (3).
DETAILED DESCRIPTION Or THE INVENTION
The present invention is hereinafter described in detail.
Examples of the vinyl compounds in the present invention include acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters, acrylonitrile, and styrene.
Preferred acrylic acid esters or methacrylic acid esters are
C1-C4 alkyl esters of acrylic acid or Cl-C4 alkyl esters of methacrylic acid.
Copper dithiocarbamate compound is, for example, represented by the general formula Cu[R(R2)NCSSi2 in which R1 and R2 may be the same or different, and each represent alkyl, preferably of l to 6 carbon atoms, or R1 and
R2 together represent an alkylene group, preferably of 2 to 6 carbon atoms attached to the nitrogen atom, one of the carbon atoms optionally being replaced by oxygen such as oxydiethylene group, which has the structure of -(CH2)2-O-(CH2)2-.
Specific examples of the copper dithiocarbamate compounds include copper dialkyl dithiocarbamates such as copper dimethyl dithiocarbamate, copper diethyl dithiocarbamate, copper dipropyl dithiocarbamate and copper dibutyl dithiocarbamate; copper cyclic alkylene dithiocarbamates such as copper ethylene dithiocarbamate, copper trimethylene dithiocarbonate, copper tetramethylene dithiocarbamate, copper pentamethylene dithiocarbamate and copper hexamethylene dithiocarbamate; and copper cyclic oxydialkylene dithiocarbamates such as copper oxydiethylene dithiocarbamate.
The content of the at least one compound selected from the group consisting of phenothiazine, hydroquinone, p-methoxyphenol, cresol, phenol, tert-butyl catechol, diphenylamine, and methylene blue depends upon the type of vinyl compound to be distilled, the temperature, and the like, but is generally about 10 to 10,000 ppm by weight, preferably about 20 to 5,000 ppm by weight of the vinyl compound The content of less than 10 ppm by weight may result in insufficient effects of polymerization inhibition. In the present invention, 'at least one compound selected from the group consisting of phenothiazine, hydroqulnone, p-methoxyphenol, cresol, phenol, tert-butyl catechol, diphenylamine, and methylene blue' may hereinafter be referred to simply as the 'component (1)'.
The content of the copper dithiocarbamate compound also depends upon the type of vinyl compound to be distilled, the temperature, and the like, but is generally about 1 to 500 ppm by weight, preferably about 5 to 100 ppm by weight of the vinyl compound. Sufficient inhibition of polymerization may not be achieved by the content of less than 1 ppm by weight.
Although the greater content of the copper dithiocarbamate compound exerts the better effects, an excessive amount of the copper dithiocarbamate compound is not preferable because of its corrosibility.
The metal which is chromium, magnesium, titanium or cobalt may be added as a elementary metal, an alloy containing the metal(at least 90% by weight), an acetate of the metal, or an oxide of the metal. In the present invention, 'a metal, an alloy containing at least 906 by weight of the metal, an acetate of the metal, or an oxide of the metal, wherein the metal is chromium, magnesium, titanium, or cobalt' may hereinafter be referred to simply as the 'metal or metal compound'. Among the metals, chromium, titanium and cobalt are preferred, and titanium is more preferred Any alloys containing chromium, magnesium, titanium, or cobalt it least 90% by weight) can be utilized as the alloy in the present invention. Examples of the acetate of the metal include chromium acetate, magnesium acetate, titanium acetate, and cobalt acetate whereas those of the oxide of the metal include chromium oxide, magnesium oxide, titanium oxide, and cobalt oxide. Among the metals or metal compounds, titanium metal and titanium oxide are preferred for their efficacy.
Both the copper dithiocarbamate compound and the component (1) may be added directly to the vinyl compound in the form of solid or powder, or alternatively their solution dissolved in an appropriate organic solvent.
The content of the metal or metal compound added in the form of powder or granules depends upon the type of vinyl compound to be distilled, the temperature, and the like, but is generally about 0.001 to 500 ppm by weight, preferably about 0.005 to 100 ppm by weight of the vinyl compound. The content less than 0.001 ppm by weight may result in insufficient inhibition of polymerization. The metal or metal compound, the copper dithiocarbamate compound and component (1) may be added to the vinyl compound separately or after being mixed together.
The powdery or granular metal or metal compound, copper dithiocarbamate compound and the component (1) may be added to the vinyl compound at any timing. For example, these components may be added to a solution of vinyl compound to be distilled or to a refluxed solution in the process of distillation.
Although it is generally assumed that granular or powdery form is preferable for the metal or metal compound, pieces or plates of the metal or metal compound have the same effects as the powdery or granular metal or metal compound in the present invention. According to one embodiment of the present invention, the metal or metal compound may be formed as an element of the distillation apparatus, which is contacted with the vinyl compound to be distilled. According to another embodiment of the present invention, an element of the distillation apparatus contacted with the vinyl compound to be distilled may be filled with the metal or metal compound of various shapes and forms, for example, net-shape, ring-shape, and porous bodies. Such embodiments described above are also aspects of the addition of the metal or metal compound in the present invention. To use the metal or metal compound as the element or the filler of the distillation apparatus is especially preferred in the industrial level. The surface area and the quantity of the metal or metal compound used as the element or the filler of the distillation apparatus are so determined as to preferably keep the content of the metal or metal compound in the vinyl compound to be distilled not less than 0.001 ppm by weight of the vinyl compound after consideration of the type of vinyl compound to be distilled, the temperature of distillation, and the like. Titanium metal is especially preferred for the element or the filler of the distillation apparatus.
Another polymerization inhibitor, for example, a manganese salt or thiuram, may be used toyeLlez wiLh the polymerization inhibitor of the present invention.
The conditions applied to distillation of a vinyl compound, such as the heating temperature, the pressure, and the residence time, are selected appropriately according to the type and quantity of vinyl compound to be distilled, the distillation apparatus, and the like. The distillation is carried out in the atmosphere of, for example, molecular oxygen or nitrogen.
Examples of the aldehyde treatment agents used for distillation of acrylic acid for higher purity include hydrazine compounds, such as hydrazine hydrate, phenylhydrazine, hydrazine sulfate and hydrazine hydrochloride, phenylenediamines, such as m-phenylenediamine, and their mixture of at least two kind.
The conditions applied to distillation of acrylic acid are also selected appropriately according to the distillation apparatus, the quantity of acrylic acid to be distilled, and the like, but the heating temperature of not more than 100"C is preferred.
According to the present invention, polymerization of vinyl compound during distillation can effectively be inhibited even under readily polymerizable conditions.
When a vinyl compound, especially in the case of acrylic acid, is distilled for higher purity thereof in the presence of an aldehyde treatment agent, the total amount of polymers produced can significantly be reduced according to the present invention. For the above advantage, long time operation of the distillation, such as continuous distillation, can be carried out, and the ratio of distillate to the raw vinyl compound can be increased, thereby the raw material can effectively be utilized.
The present invention is hereinafter described in more detail by way of Examples. However, the present invention is not restricted to these Examples.
In the Examples and Comparative Examples below, ppm and % mean ppm by weight and % by weight respectively.
Examples 1 to 5
In each of examples 1 to 5, 100 ppm of p-methoxyphenol, 200 ppm of phenothiazine, and 10 to 30 ppm of copper dibutyl dithiocarbamate, and a metal or metal compound specified in
Table 1 were added to 20 kg of a distilled acrylic acid solution containing 200 ppm of furfural and 100 ppm of benzaldehyde, and 0.1 percent by weight of 60% hydrazine hydrate was then added to the acrylic acid solution to make a mixture.
The mixture was subjected to vacuum distillation using a rotary evaporator under the air supply condition to get higher purity acrylic acid as a distillate, at a teirperature of 83 to 85 C, at a pressure of 35 mmHg, and for 10 hours. The distillation was stopped when the concentrate in the flask reached approximately 130 g (concentration ratio of the mixture is approximately 150), and the total amount of polymers depositing in the flask was measured. The results are shown in Table 1.
Table 1
Examples Amount Type of Amount Total amount
No. of CU'1 Metal of Metal of polymers
added added produced
Example 1 10 ppm Titanium 0.1 g 0.1 g
powder
Example 2 10 ppm Magnesium 10 ppm 1 g
ribbon
Example 3 10 ppm Magnesium 25 ppm 1 g
Acetate
powder
Example 4 30 ppm Titanium 2 pieces 0.01 g
Metal
piece 2
Example 5 30 ppm Titanium 30 ppm 0.01 g
Oxide
powder *l: Copper dibutyl dithiocarbamate *2: Each piece having a surface area of 20cm2 was placed in gas phase and liquid phase.
Examples 6 to 8: Comparative Examples 1 and 2
A 300 ml flask having a packed portion of 30mm diame ter(Q) x 300 mm height (H) (filled with metal nets of SU$316L previously washed with hot water) was used as a distillation column. An acrylic acid solution containing 100 ppm of p-methoxyphenol, 50 ppm of phenothiazine, and 10 ppm of copper dibutyl dithiocarbamate (and 10 ppm of manganese dibutyl dithiocarbamate in Comparative Example 2) was supplied to the distillation system at a rate of 150 g/hr. Acrylic acid was continuously distilled and collected from the top of the distillation column while the metal or metal compound was added to the acrylic acid solution and the air flow was supplied at a rate of 10 ml/min.. The conditions of distillation were 250 torr in pressure, the interior and column top temperature at approximately llO"C and the temperature of the bath at 120 to 1300C. The operation of the distillation was stopped after three hours, and the total amount of polymers in the packed portion and in the residual solution in the flask was measured. The results are shown in Table 2.
Table 2
Amount Type of Amount Total amount
of CU'3 Metal of Metal of polymers
added added produced
Example 6 O Titanium Metal 2 pieces 0.4 g piece*' Example 7 0 Chromium 0.02 g 0.2 g
powder
Example 8 0 Cobalt 0.02 g 0.2 g
powder
Compara. 0 None 0 4 g
Exp.l
Compara. 10 ppm None 0 4 g
Exp.2 *3: Manganese dibutyl dithiocarbamate *4: Each piece having a surface area of 20cm2 was placed in gas phase and liquid phase.
Example 9: Comparative Examples 3 and 4
A mixture was prepared by adding 210 ppm of hydroquinone, 1 ppm of phenothiazine, and 120 ppm of p-methoxyphenol to a solution containing 50% of methacrylic acid, 27% of methyl methacrylate, 10% of water, and 13t of a solvent. The mixture was supplied to the distillation system used in Example 6 at the rate of 150 g/hr. Methacrylic acid solution was continuously distilled and collected while the air flow was supplied at the rate of 10 ml/mn.. The bath was heated to gradually increase the temperature from the initial value of 110 C to 135"C. After the three-hour operation at a pressure of 200 mmHg and the interior and column top temperature of approximately 1200C, the total amount of polymers found in the packed portion and in the residual solution was measured. The results are shown in Table 3.
Table 3
Amount Type of Amount Total amount
of CU'1 Metal of Metal of polymers
added added produced
Example 9 50 ppm Titanium Metal'5 2 pieces 0.001 g
piece
Compara. 0 ppm Titanium Metal 1 piece
Exp.3 piece 0.01 g
Titanium Metal 0.2 g sponge*7 Compara. 10 ppm None 0 0.01 g
Exp.4 *1: Copper dibutyl dithiocarbamate *5: Each piece having a surface area of 20cm7 was placed in gas phase and liquid phase.
*6: The piece having a surface area of 20cm2 was placed in gas phase.
*7: The sponge was placed in liquid phase.
Examples 10 and 11: Comparative Example 5
The distillation of acrylic acid containing the polymerization inhibitor described in Table 4 was carried out under the same conditions and distillation system as in Example 6. Pieces of titanium metal were used as the metal or metal compound. The results are shown in Table 4.
TABLE 4 Mop'8 PT9 CU*10 Titanium Amount of Amount of
Metal polymers polymers
piece produced produced port ion'11 in packed in liquid
Phase
Example 200 50 10 Used 0.4 g None
10
Example 200 50 50 Used 0.2 g None
11
Compara. 200 50 10 Not 3.5 g Slightly Exp,S used found *8: p-methoxyphenol *9: Phenothiazine *10: Copper dibutyl dithiocarbamate *11: Each piece having a surface area of 20cm2 was placed in gas phase and liquid phase.
Claims (12)
1. A method of inhibiting polymerization of a vinyl compound during distillation, which comprises distilling the vinyl compound in the presence of the following components:
(1) phenothiazine, hydroquinone, p-methoxyphenol, cresol, phenol, tert-butyl catechol, diphenylamine, or methylene blue;
(2) a copper dithiocarbamate compound; and
(3) a metal an alloy containing at least 90% by weight of the metal, an acetate ot thetai, - or an oxide of the metal, wherein the metal is chraium, magnesi, titanium, or cobalt.
2. A method according to Claim 1, wherein component (3) is a powder, granules, a metal net, a block, or a moulded shape.
3. A method according to Claim 1, wherein component (3) comprises part of the distillation apparatus in contact with the vinyl compound to be distilled.
4. A method according to Claim 1, 2 or 3, wherein component (3) is titanium metal.
5, A method according to any one of Claims 1 to 4, wherein the vinyl compound comprises acrylic acid, methacrylic A acid, acrylic acid ester, methacrylic acid ester, acrylonitrile, or styrene.
6. A method according to Claim 5, wherein the vinyl
compound comprises acrylic acid, methacrylic acid, C1-C4 alkyl
ester of acrylic acid, or C1-C alkyl ester of methacrylic
acid.
7. A method according to any one of Claims 1 to 4,
wherein the vinyl compound is acrylic acid or acrylic acid
ester, and distillation of acrylic acid or acrylic acid ester
is carried out in the presence of an aldehyde treatment agent.
8. A method according to Claim 7, wherein the aldehyde
treatment agent is a hydrazine compound.
9. A polymerization inhibitor for the inhibition of
polymerization during distillation of a vinyl compound, which
comprises:
(1) phenothiazine, hydroquinone, p-methoxyphenol, cresol,
phenol, tert-butyl catechol, diphenylamine, or methylene blue:
(2) a copper dithiocarbamate; and
(3) a metal, an alloy containing at least 90% by weight oz tne metal, an acetate of the metal, or an oxide of-the metal,
wherein the metal is chromium, magnesium, titanium, or cobalt.
10. A polymerization inhibitor according to Claim 9,
wherein component (3) is titanium metal.
11. A method according to Claim 1 substantially as
hereinbefore described in any one of Examples 1 to 11.
12. A polymerization inhibitor according to Claim 9 substantially as hereinbefore described in any of Examples 1 to 11.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP646594 | 1994-01-25 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB9501046D0 GB9501046D0 (en) | 1995-03-08 |
| GB2285983A true GB2285983A (en) | 1995-08-02 |
| GB2285983B GB2285983B (en) | 1997-10-29 |
Family
ID=11639205
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB9501046A Expired - Fee Related GB2285983B (en) | 1994-01-25 | 1995-01-19 | A method of inhibiting polymerization of vinyl compound and polymerization inhibitor used therein |
Country Status (5)
| Country | Link |
|---|---|
| KR (1) | KR100337100B1 (en) |
| CN (1) | CN1051986C (en) |
| GB (1) | GB2285983B (en) |
| SG (1) | SG49028A1 (en) |
| TW (1) | TW287170B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0810196A1 (en) * | 1996-05-27 | 1997-12-03 | Mitsubishi Chemical Corporation | Method for inhibiting polymerization of (meth) acrylic acid or esters thereof |
| WO2002051784A1 (en) * | 2000-12-22 | 2002-07-04 | Basf Aktiengesellschaft | Method for producing acrylic acid |
| US6583281B2 (en) | 2000-05-22 | 2003-06-24 | Basf Aktiengesellschaft | Stabilized N-alkenyllactam |
| US6870066B2 (en) * | 2002-04-25 | 2005-03-22 | Nippon Shokubai Co., Ltd | Method for decomposition of Michael type adduct |
| FR2877003A1 (en) * | 2004-10-26 | 2006-04-28 | Arkema Sa | IMPROVED PROCESS FOR THE MANUFACTURE OF (METH) ACRYLIC ANHYDRIDE |
| EP2000451A2 (en) * | 2006-03-24 | 2008-12-10 | Hakuto Co., Ltd | Method of inhibiting polymerization of aromatic vinyl compound |
| US10173960B2 (en) | 2015-04-09 | 2019-01-08 | Daikin Industries, Ltd. | Composition |
| US10766848B2 (en) | 2015-09-07 | 2020-09-08 | Rhodia Operations | Use of polymerization inhibitor compositions |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1082499C (en) * | 1996-06-05 | 2002-04-10 | Basf公司 | Mixture containing monomers and stabilizers |
| CN100441551C (en) * | 2000-10-16 | 2008-12-10 | 尤尼罗亚尔化学公司 | C-nitrosoaniline compounds and their blends as polymerization inhibitors |
| US6685823B2 (en) * | 2000-10-16 | 2004-02-03 | Uniroyal Chemical Company, Inc. | C-nitrosoaniline compounds and their blends as polymerization inhibitors |
| MY135762A (en) * | 2002-01-09 | 2008-06-30 | Basf Ag | Method for producing acrylic acid |
| US6960279B2 (en) * | 2002-05-06 | 2005-11-01 | Fina Technology, Inc. | Method for stabilizing vinyl aromatic monomers using selected polymerization inhibitors and polymers prepared therewith |
| JP5759073B2 (en) * | 2011-08-26 | 2015-08-05 | ドルフ ケタール ケミカルズ（インド）プライベート リミテッドＤｏｒｆ Ｋｅｔａｌ Ｃｈｅｍｉｃａｌｓ（Ｉｎｄｉａ） Ｐｒｉｖａｔｅ Ｌｉｍｉｔｅｄ | Additive composition for inhibiting and inhibiting polymerization of styrene, production method and use thereof |
| CN103360200B (en) * | 2012-03-30 | 2016-01-13 | 中国石油化工股份有限公司 | A kind of double solvents of recycling vinyl benzene with abstraction distillation from hydrocarbon mixture and method |
| US20170158621A1 (en) * | 2015-12-04 | 2017-06-08 | Baker Hughes Incorporated | Substituted phenol derivatives for mitigating fouling |
| CN106187768A (en) * | 2016-07-12 | 2016-12-07 | 中国石油化工股份有限公司 | For the collaborative suppressing method that vinyl acetate polymerization is out of control |
| WO2021022550A1 (en) * | 2019-08-08 | 2021-02-11 | Rhodia Operations | Polymerization inhibitor compositions and uses thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6211735A (en) * | 1985-05-30 | 1987-01-20 | コンパ−ジツト デイベロツプメントリミテツド | Reinforced resin material and its production |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4021310A (en) * | 1972-12-22 | 1977-05-03 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Method for inhibiting the polymerization of acrylic acid or its esters |
| JPS5198211A (en) * | 1975-02-19 | 1976-08-30 | Arufua beetafuhowakarubonsanno jugoboshihoho |
-
1995
- 1995-01-19 SG SG1996005322A patent/SG49028A1/en unknown
- 1995-01-19 GB GB9501046A patent/GB2285983B/en not_active Expired - Fee Related
- 1995-01-24 KR KR1019950001141A patent/KR100337100B1/en not_active IP Right Cessation
- 1995-01-24 TW TW084100592A patent/TW287170B/zh not_active IP Right Cessation
- 1995-01-25 CN CN95101459A patent/CN1051986C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6211735A (en) * | 1985-05-30 | 1987-01-20 | コンパ−ジツト デイベロツプメントリミテツド | Reinforced resin material and its production |
Non-Patent Citations (1)
| Title |
|---|
| WPI Abstract Accession No. 94-283299/35 & JP 62 011 735 A * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0810196A1 (en) * | 1996-05-27 | 1997-12-03 | Mitsubishi Chemical Corporation | Method for inhibiting polymerization of (meth) acrylic acid or esters thereof |
| US5856562A (en) * | 1996-05-27 | 1999-01-05 | Mitsubishi Chemical Corporation | Method for inhibiting polymerization of (meth) acrylic acid or esters thereof |
| US6583281B2 (en) | 2000-05-22 | 2003-06-24 | Basf Aktiengesellschaft | Stabilized N-alkenyllactam |
| WO2002051784A1 (en) * | 2000-12-22 | 2002-07-04 | Basf Aktiengesellschaft | Method for producing acrylic acid |
| US6870066B2 (en) * | 2002-04-25 | 2005-03-22 | Nippon Shokubai Co., Ltd | Method for decomposition of Michael type adduct |
| FR2877003A1 (en) * | 2004-10-26 | 2006-04-28 | Arkema Sa | IMPROVED PROCESS FOR THE MANUFACTURE OF (METH) ACRYLIC ANHYDRIDE |
| WO2006045919A1 (en) * | 2004-10-26 | 2006-05-04 | Arkema France | Improved method for the production of (meth)acrylic anhydride |
| EP2000451A2 (en) * | 2006-03-24 | 2008-12-10 | Hakuto Co., Ltd | Method of inhibiting polymerization of aromatic vinyl compound |
| EP2000451A4 (en) * | 2006-03-24 | 2014-07-09 | Hakuto Kk | Method of inhibiting polymerization of aromatic vinyl compound |
| US10173960B2 (en) | 2015-04-09 | 2019-01-08 | Daikin Industries, Ltd. | Composition |
| RU2721964C2 (en) * | 2015-04-09 | 2020-05-25 | Дайкин Индастриз, Лтд. | Composition |
| US10766848B2 (en) | 2015-09-07 | 2020-09-08 | Rhodia Operations | Use of polymerization inhibitor compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| TW287170B (en) | 1996-10-01 |
| KR100337100B1 (en) | 2002-11-23 |
| CN1051986C (en) | 2000-05-03 |
| GB9501046D0 (en) | 1995-03-08 |
| KR950032023A (en) | 1995-12-20 |
| CN1111605A (en) | 1995-11-15 |
| SG49028A1 (en) | 1998-05-18 |
| GB2285983B (en) | 1997-10-29 |
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