WO2006098466A1 - Composition de monomere de chlorure de vinyle - Google Patents

Composition de monomere de chlorure de vinyle Download PDF

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Publication number
WO2006098466A1
WO2006098466A1 PCT/JP2006/305484 JP2006305484W WO2006098466A1 WO 2006098466 A1 WO2006098466 A1 WO 2006098466A1 JP 2006305484 W JP2006305484 W JP 2006305484W WO 2006098466 A1 WO2006098466 A1 WO 2006098466A1
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WO
WIPO (PCT)
Prior art keywords
vinyl chloride
chloride monomer
chloride
mass
vinyl
Prior art date
Application number
PCT/JP2006/305484
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English (en)
Japanese (ja)
Inventor
Masayuki Moriwaki
Shinobu Masaki
Masafumi Masuda
Original Assignee
Tokuyama Corporation
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Tokuyama Corporation filed Critical Tokuyama Corporation
Priority to JP2007508243A priority Critical patent/JPWO2006098466A1/ja
Publication of WO2006098466A1 publication Critical patent/WO2006098466A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C21/00—Acyclic unsaturated compounds containing halogen atoms
    • C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
    • C07C21/04—Chloro-alkenes
    • C07C21/06—Vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/38—Separation; Purification; Stabilisation; Use of additives
    • C07C17/392—Separation; Purification; Stabilisation; Use of additives by crystallisation; Purification or separation of the crystals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/38—Separation; Purification; Stabilisation; Use of additives
    • C07C17/42—Use of additives, e.g. for stabilisation

Definitions

  • the present invention relates to a novel vinyl chloride monomer composition excellent in storage stability and polymerizability.
  • Polyvinyl chloride resin has excellent weather resistance and has been used for various purposes (typically piping materials) for a long time. Since the vinyl chloride monomer, which is a raw material for producing such a polyvinyl chloride resin, is easily polymerized particularly by heat, moisture, and light, it needs to be sufficiently managed when stored in a tank or the like.
  • vinyl chloride monomer is produced by the direct chlorination of ethylene or by the oxidation-reaction reaction with oxygen and hydrogen chloride to produce 1,2-dichloroethane, which is pyrolyzed (dehydrochlorinated). It is manufactured by.
  • the vinyl chloride monomer produced in this way (hereinafter sometimes referred to as crude vinyl chloride monomer) contains various organic impurities in addition to unreacted ethylene and 1,2-dichloroethane.
  • organic impurities include chlorinated saturated hydrocarbons such as methyl chloride and acetyl chloride, acetylene, butyne, 1,3-butadiene and vinylacetylene.
  • 1,3-butadiene-vinylacetylene causes polymerization inhibition in the polymerization process, resulting in a vinyl chloride resin. It has been known for a long time that it is a substance that deteriorates the quality of raw materials. For this reason, crude vinyl chloride monomer is subjected to purification operations by distillation, and 1,3-butadiene and The content of vinyl acetylene, which has a higher boiling point than vinyl monomers, is reduced.
  • organic impurities such as ethylene, acetylene and methyl chloride, which have a lower boiling point than 1,3-butadiene, vinyl acetylene Impurities such as chloro chloride, butyne, and 1,2-dichloroethane, which have higher boiling points, were also removed with a very high degree of vinyl chloride monomer.
  • a vinyl chloride monomer is produced by the oxycyclination reaction described above and subsequent thermal decomposition, a large amount of unreacted 1,2-dichloroethane is present in the crude vinyl chloride monomer (same as the vinyl chloride monomer).
  • the total amount of 1,3-butadiene and vinylacetylene is about 20 mass ppm, and the total amount of saturated hydrocarbons other than chlorinated 1,2-dichloroethane (methyl chloride and acetyl chloride) is 40.
  • Such crude vinyl chloride monomer was added to a tower top temperature of 42 to 37 ° C, a pressure of 0.665 to 0.7 OMP a G, a tower bottom temperature of 65 to 70 ° C, and a pressure of 0.70 to 0.775 MPa.
  • a low-boiling distillation column controlled to G and a top temperature of 37 to 42 ° C,
  • the vinyl chloride monomer purified by the above method has high polymerizability due to the removal of polymerization inhibitory substances, but it has poor stability in storage and the liquid becomes cloudy in a short period of time. Problems arise.
  • a method of adding a polymerization inhibitor such as phenol, hydroquinone, and tertiary butyl catechol has been proposed for storing vinyl chloride monomer.
  • a polymerization inhibitor such as phenol, hydroquinone, and tertiary butyl catechol
  • purification equipment such as distillation equipment is required, leading to an increase in the cost of manufacturing polyvinyl chloride resin.
  • a method of improving the stability by cooling the storage tank or the like using a cooling medium such as water or a refrigerant can be considered.
  • a specific method there is a method of cooling the storage device using water, a refrigerant or the like.
  • electricity costs for cooling, cooling equipment, etc. lead to a cost increase in the production of polyvinyl chloride resin.
  • vinyl monomers particularly those targeting acrylonitrile, can be used with nitrogen containing a specific amount of oxygen or other inert gas.
  • a method for preventing abnormal polymerization by sealing the surface has also been proposed.
  • an object of the present invention is to provide a vinyl chloride that is excellent in polymerizability when producing polyvinyl chloride and at the same time is stably prevented from being polymerized during storage and can be stably stored for a long period of time. It is to provide a monomer composition.
  • the present inventors have continued an arbitrary study to solve the above problems. As a result, such a purpose can be achieved by allowing a certain percentage of chlorinated saturated hydrocarbons to be present in the chlorinated vinyl monomer after removal of the polymerization inhibitor 1,3-butadiene, vinylacetylene, etc. As a result, the present invention has been completed.
  • a vinyl chloride monomer composition comprising a vinyl chloride monomer containing a chlorinated saturated hydrocarbon at a concentration of 45 to 200 mass ppm.
  • the chlorinated saturated hydrocarbon is a chlorinated saturated hydrocarbon having 1 to 3 carbon atoms
  • the chlorinated saturated hydrocarbon is at least one selected from the group consisting of methyl chloride, methylene chloride and ethyl chloride;
  • chlorinated saturated hydrocarbon is added so as to have a concentration of 45 to 200 mass m.
  • a method for producing a vinyl chloride monomer composition is provided.
  • the vinyl chloride monomer composition of the present invention by adding a chlorinated saturated hydrocarbon to the vinyl chloride monomer, even when stored in a storage tank or the like for a long period of time, white turbidity due to polymerization is prevented and stable. Can be stored.
  • a polymerization initiator without removing the chlorinated saturated hydrocarbon during use, it is possible to produce a vinyl chloride resin with excellent quality by stable polymerization without causing polymerization inhibition. can do.
  • the present invention can be carried out by an extremely simple means of adding a predetermined amount of chlorinated saturated hydrocarbon to purified vinyl chloride monomer, and can store and handle vinyl chloride monomer extremely stably. And its industrial value is extremely high.
  • the crude vinyl chloride monomer is produced by a method known per se, for example, produced by direct chlorination of ethylene or by an oxidation-reduction reaction using ethylene, hydrogen chloride or oxygen.
  • 2-Dichloroethane is produced, which is then produced by pyrolysis. It can also be produced by the carbide acetylene method produced from acetylene and hydrogen chloride.
  • the crude vinyl chloride monomer produced by these methods contains various organic impurities, such as ethylene, acetylene, chloride, as organic impurities having a lower boiling point than vinyl chloride monomer.
  • organic impurities such as ethylene, acetylene, chloride
  • Methyl, 1,3-butadiene, etc. are included, and high-boiling organic impurities include vinyl acetylene, chloro chloride, butyne, 1,2-dichloroethane and the like.
  • Such crude vinyl chloride monomer is subjected to a purification treatment, and among the above impurities, in particular, 1,3-butadiene and vinylacetylene, which are polymerization inhibitors, are removed, and the total concentration is 17%. It is adjusted so that the mass is less than ppm, in particular, 15 mass ppm or less.
  • Such purification treatment may be carried out by a normal distillation operation by appropriately adjusting the reflux ratio, the heating amount, the supply position, and the like.
  • the greatest characteristic of the vinyl chloride monomer composition of the present invention is that the crude vinyl chloride is as described above. Chlorinated saturated hydrocarbons are added after purifying the monomer, and the concentration of chlorinated saturated hydrocarbons is adjusted to 45 to 200 ppm, especially 50 to 160 ppm. . When the concentration of the chlorinated saturated hydrocarbon is lower than the above range, the polymerization inhibitory effect of the vinyl chloride monomer is not sufficient, and when it is higher than the above range, the polymerization characteristics after storage are deteriorated.
  • the chlorinated saturated hydrocarbon is not particularly limited, but a saturated hydrocarbon compound having 1 to 3 carbon atoms in which hydrogen bonded to carbon is replaced with chlorine, such as methyl chloride, methyl chloride, chloroform, carbon tetrachloride, Chloride chloride, dichloride chloride, trichloride chloride, tetrachloride chloride, pentachloride chloride, hexachloride chloride, propyl chloride, propane dichloride, propane trichloride, propane tetrachloride, propane pentachloride, hexachloride Propane, chloropentachloromethane, and propaneoctachloride are preferably used. These can be used alone or in combination of two or more.
  • chlorinated saturated hydrocarbons that are most preferably used include methyl chloride, methylene chloride, and chlorinated chloride having a boiling point close to that of vinyl chloride monomer.
  • composition of the present invention it has not been confirmed that the effect produced by the chlorinated saturated hydrocarbon is clear, but the chlorine is probably surrounded by the vinyl chloride monomer or the initial polymer of the monomer. It is estimated that the saturated hydrocarbons are distributed, and as a result, the polymerization chain is reduced and the storage stability is improved.
  • the temperature at which the vinyl chloride monomer composition of the present invention is stored is not particularly limited, and the problem of cloudiness due to polymerization does not occur as long as it is stored at general conditions, for example, 0 to 10 ° C.
  • the vinyl chloride monomer composition of the present invention contains a chlorinated saturated hydrocarbon at a constant concentration as described above, and further includes a total content of 1,3-butadiene and vinyl acetylene which are polymerization inhibitors. Except for the point that is suppressed to a predetermined value or less, the content of other organic impurities may be the same as that of a known vinyl chloride monomer composition. For example, it may be suppressed to 5 mass ppm or less.
  • 1,2-Dichloroethane was obtained by the oxycycline method, and the crude vinyl chloride monomer obtained by thermally decomposing this 1,2-dichloroethane was mixed with a low-boiling distillation column and a high-boiling distillation column satisfying the following conditions. Then, the total amount of 1,3-butadiene and vinylacetylene was refined to 12 mass ppm and other impurities to 1 mass ppm or less.
  • the vinyl chloride monomer thus purified is charged as a liquid into a 150 ml SUS31 6 pressure vessel as a liquid.
  • a container filled with 0.9 mI of methyl chloride gas and a container filled with 1.1 mI of chloride chloride gas are connected to this pressure vessel, and methyl chloride and chloride chloride are mixed with vinyl chloride monomer.
  • a vinyl chloride composition containing components other than vinyl chloride in the following amounts was prepared.
  • the pressure vessel containing the vinyl chloride monomer obtained above was kept at 30 ° C, and the time until the hue matched with the reference solution (that is, the time until white turbidity) was measured was 140 ⁇ . .
  • the hue was measured by transferring to a 1 Om I pressure-resistant glass container and comparing with a reference solution.
  • a reference solution 0.2 g of Latex LX 852 manufactured by Nippon Zeon Co., Ltd., pure water And diluted to 2 liters.
  • suspension polymerization was carried out at a temperature of 58 ° C for 8 hours, and the average particle size was 150 Wm, and there was no reduction in particle size or delay in polymerization time. .
  • the period until white turbidity was produced in the same manner as in Example 1 was 200 days or more. Further, as in Example 1, suspension polymerization was carried out at a temperature of 58 ° C. for 8 hours. As a result, the average particle size was 150 / m, and neither the particle size was reduced nor the polymerization time was delayed.
  • Example 3-A vinyl chloride composition containing the following components other than vinyl chloride in the same manner as in Example 1 except that the amount of methyl chloride and acetyl chloride mixed with the vinyl chloride monomer after purification was changed. A product was prepared.
  • -Vinyl chloride composition :
  • Example 1 Total amount of butadiene and vinyl acetylene; 1 2 mass p pm Other impurities; 1 p pm or less
  • the period until white turbidity was produced in the same manner as in Example 1 was 200 days or more.
  • suspension polymerization was carried out at a temperature of 58 ° C. for 8 hours. As a result, the average particle size was 150 / m, and neither the particle size was reduced nor the polymerization time was delayed.
  • a vinyl chloride composition containing components other than vinyl chloride in the following amounts was prepared in the same manner as in Example 1 except that 80 mass ppm of acetyl chloride was mixed with the purified vinyl chloride monomer.
  • the period until white turbidity was produced in the same manner as in Example 1 was 200 days or more.
  • the average particle size was 150 jUm, and neither particle size refinement nor polymerization time delay occurred.
  • a vinyl chloride composition containing components other than vinyl chloride in the following amounts was prepared in the same manner as in Example 1, except that 80 mass ppm of methyl chloride was mixed with the purified vinyl chloride monomer.
  • Example 2 About the vinyl chloride composition obtained above, white turbidity was produced in the same manner as in Example 1. The measurement period was 200 days or more. Further, as in Example 1, suspension polymerization was carried out at a temperature of 58 ° C. for 8 hours. As a result, the average particle size was 150 jt / m, and no refinement of the particle size or delay of the polymerization time occurred.
  • a vinyl chloride composition containing components other than vinyl chloride in the following amounts was prepared in the same manner as in Example 1, except that 80 mass ppm of methylene chloride was mixed with the purified vinyl chloride monomer.
  • the period until white turbidity was produced in the same manner as in Example 1 was 200 days or more. Further, as in Example 1, suspension polymerization was carried out at a temperature of 58 ° C. for 8 hours. As a result, the average particle size was 150 im, and no refinement of the particle size or delay of the polymerization time occurred.
  • Example 1 Comparative Example 1- The composition of vinyl chloride containing the following components other than vinyl chloride in the same manner as in Example 1 except that the amounts of methyl chloride and acetyl chloride mixed in the purified vinyl chloride monomer were changed. A product was prepared.
  • Example 2 About the vinyl chloride composition obtained above, white turbidity was produced in the same manner as in Example 1. The measurement period was 70 days, and white turbidity was observed in a significantly shorter period than in Examples 1-6. Similarly to Example 1, when suspension polymerization was carried out at a temperature of 58 ° C. for 8 hours, the average particle size was 150 j «m, and no refinement of the particle size or delay of the polymerization time occurred.
  • a vinyl chloride composition containing components other than vinyl chloride in the following amounts was prepared in the same manner as in Example 1 except that the amounts of methyl chloride and acetyl chloride mixed with the purified vinyl chloride monomer were changed.
  • the period until white turbidity was produced in the same manner as in Example 1 was 200 mm or more. Further, as in Example 1, suspension polymerization was carried out at a temperature of 58 ° C. for 8 hours and 30 minutes. As a result, the average particle size was as small as 130 ⁇ m. In addition, although the polymerization time is long, the particles are miniaturized, indicating that the polymerization time is delayed.
  • Example 1 For the crude vinyl chloride monomer with a total amount of 1,3-butadiene and vinylacetylene of 50 mass p pm (other impurity content: 1 mass p pm or less) obtained by changing the production conditions, Example 1 and Similarly, the period until white turbidity was measured was 200 days or more. Further, as in Example 1, suspension polymerization was carried out at a temperature of 58 ° C. for 8 hours and 15 minutes. As a result, the average particle size was further refined to 125 jum. In addition, although the polymerization time is long, the particles are becoming finer. It can be seen that there is a delay.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L’invention concerne une composition de monomère de chlorure de vinyle, caractérisée en ce que le monomère de chlorure de vinyle contient un hydrocarbone chloré saturé en concentration massique de 45 à 200 ppm. La composition de monomère de chlorure de vinyle présente une excellente aptitude à la polymérisation pour la fabrication de chlorure de polyvinyle. De plus, la stabilité de la composition empêche sa polymérisation pendant le stockage et elle peut donc être stockée de façon stable pendant de longues périodes.
PCT/JP2006/305484 2005-03-15 2006-03-14 Composition de monomere de chlorure de vinyle WO2006098466A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2007508243A JPWO2006098466A1 (ja) 2005-03-15 2006-03-14 塩化ビニルモノマー組成物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2005-073830 2005-03-15
JP2005073830 2005-03-15

Publications (1)

Publication Number Publication Date
WO2006098466A1 true WO2006098466A1 (fr) 2006-09-21

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PCT/JP2006/305484 WO2006098466A1 (fr) 2005-03-15 2006-03-14 Composition de monomere de chlorure de vinyle

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JP (1) JPWO2006098466A1 (fr)
KR (1) KR20070112241A (fr)
CN (1) CN101142159A (fr)
TW (1) TW200643081A (fr)
WO (1) WO2006098466A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007039377A (ja) * 2005-08-03 2007-02-15 Tokuyama Corp 塩化ビニルモノマーの貯蔵方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4951209A (fr) * 1972-07-19 1974-05-18
JPS49102605A (fr) * 1973-02-15 1974-09-27
JPS50106906A (fr) * 1974-01-21 1975-08-22
JPS61115034A (ja) * 1984-11-09 1986-06-02 ワツカー‐ケミー・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング １，２‐ジクロルエタンを熱分解のために処理する方法
JPS61209903A (ja) * 1985-03-08 1986-09-18 ワツカー‐ケミー・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング １，２―ジクロルエタンの熱分解からの塩化水素の精製法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4951209A (fr) * 1972-07-19 1974-05-18
JPS49102605A (fr) * 1973-02-15 1974-09-27
JPS50106906A (fr) * 1974-01-21 1975-08-22
JPS61115034A (ja) * 1984-11-09 1986-06-02 ワツカー‐ケミー・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング １，２‐ジクロルエタンを熱分解のために処理する方法
JPS61209903A (ja) * 1985-03-08 1986-09-18 ワツカー‐ケミー・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング １，２―ジクロルエタンの熱分解からの塩化水素の精製法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007039377A (ja) * 2005-08-03 2007-02-15 Tokuyama Corp 塩化ビニルモノマーの貯蔵方法

Also Published As

Publication number Publication date
KR20070112241A (ko) 2007-11-22
JPWO2006098466A1 (ja) 2008-08-28
CN101142159A (zh) 2008-03-12
TW200643081A (en) 2006-12-16

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