JP6188238B2 - Halogen removing agent and method for producing ethylene-α-olefin copolymer or ethylene-propylene-nonconjugated diene copolymer - Google Patents

Description

  The present invention relates to a halogen removing agent and a method for producing an ethylene-α-olefin copolymer or an ethylene-propylene-nonconjugated diene copolymer.

Synthetic rubbers such as ethylene-α-olefin copolymers and ethylene-propylene-nonconjugated diene copolymers (hereinafter collectively referred to as “rubber-like polymers”) are transition metal compounds and organoaluminum compounds. In general, a raw material monomer is polymerized using a so-called Ziegler-based catalyst, a solvent is removed by steam stripping, and the polymer is recovered.
In the steam stripping, the solvent is removed by gasification with water vapor. At this time, a part of the catalyst residue soluble in water is removed from the polymer by transferring to water. However, much of the catalyst residue is recovered together with the polymer without being removed.

  The catalyst residue causes coloring and deterioration of the rubber-like polymer. Further, if the rubber-like polymer contains a large amount of halogen (especially chlorine) among the catalyst residues, the metal that comes into contact with the molded body when the rubber-like polymer molded body is used in various metal devices or instruments. It can also cause corrosion of materials (eg, iron, iron alloys, aluminum, etc.).

Therefore, as a method for producing a rubber-like polymer with little catalyst residue, at least selected from an alkyl ester derivative of polyethylene glycol, a cyclic ester compound, and a pentaerythritol tetraester as a polymerization terminator after a polymerization reaction using a Ziegler catalyst. A method using one kind of compound has been proposed (see, for example, Patent Document 1). According to this method, the original action as a polymerization terminator, that is, the progress of the polymerization is stopped, and the increase in the molecular weight of the polymer (prevention of gel generation) is performed, and at the same time, in the resulting rubbery polymer The catalyst residue can be reduced.
Patent Document 1 discloses that the amount of residual chlorine is higher when pentaerythritol diester or pentaerythritol triester is added than when water is added after the polymerization reaction (that is, pentaerythritol diester or pentaerythritol). Triesters show that the effect of reducing chlorine cannot be sufficiently obtained).

JP 59-74101 A

However, from the viewpoint of suppressing the coloring and deterioration of the rubbery polymer and extending the life by preventing the corrosion of metal equipment and instruments, it cannot be said that the halogen concentration of the rubbery polymer is still sufficient, and further improvement is required. ing.
In addition, alkyl ester derivatives of polyethylene glycol and pentaerythritol tetraester tend to have high viscosity and poor low temperature fluidity. For this reason, it takes time and effort to adjust the viscosity to an appropriate level before use, or to heat it up to melt from a solid to a liquid. There was a problem.
Furthermore, cyclic ester compounds such as γ-butyrolactone have a low flash point and poor handleability. In addition, the odor was strong, and there was concern about residual odor in the work environment and products.
Thus, the alkyl ester derivative of polyethylene glycol, the cyclic ester compound, and the pentaerythritol tetraester have a problem in handleability.

  The present invention has been made in view of the above circumstances, and a halogen removing agent capable of producing an ethylene-α-olefin copolymer or an ethylene-propylene-nonconjugated diene copolymer having a further reduced halogen concentration, and ethylene- It is an object of the present invention to provide a method for producing an α-olefin copolymer or an ethylene-propylene-nonconjugated diene copolymer.

The present invention has the following aspects.
[1] A halogen remover used for producing an ethylene-α-olefin copolymer or an ethylene-propylene-nonconjugated diene copolymer using a halogen-containing polymerization catalyst, which is described below as a pentaerythritol fatty acid ester. (A) component, (B) component, and (C) component, and the mass ratio represented by (A) component / ((A) component + (B) component + (C) component) is 0. A halogen remover that is 48 to 0.85.
(A) component: pentaerythritol tetrafatty acid ester (B) component: pentaerythritol trifatty acid ester (C) component: pentaerythritol difatty acid ester [2] The following (D) component is further contained as pentaerythritol fatty acid ester, and The halogen remover according to [1], wherein a mass ratio represented by (D) component / ((A) component + (B) component + (C) component + (D) component) is 0.02 or less.
Component (D): Pentaerythritol monofatty acid ester [3] The halogen remover according to [1] or [2], wherein the fatty acid moiety of the pentaerythritol fatty acid ester has 8 to 10 carbon atoms.

[4] A method for producing an ethylene-α-olefin copolymer or an ethylene-propylene-nonconjugated diene copolymer using a halogen-containing polymerization catalyst, and after polymerizing a raw material monomer, as a pentaerythritol fatty acid ester The following (A) component, (B) component, and (C) component are expressed as (A) component / ((A) component + (B) component + (C) component), and the mass ratio is 0.48. A method for producing an ethylene-α-olefin copolymer or an ethylene-propylene-nonconjugated diene copolymer, which is added to the polymerization reaction solution so as to be ˜0.85.
(A) Component: Pentaerythritol tetrafatty acid ester (B) Component: Pentaerythritol trifatty acid ester (C) Component: Pentaerythritol difatty acid ester [5] The fatty acid portion of the pentaerythritol fatty acid ester has 8 to 10 carbon atoms. [4] The manufacturing method of the ethylene-alpha-olefin copolymer or ethylene-propylene-nonconjugated diene copolymer as described in [4].

  According to the present invention, a halogen removing agent capable of producing an ethylene-α-olefin copolymer or ethylene-propylene-nonconjugated diene copolymer having a further reduced halogen concentration, and an ethylene-α-olefin copolymer or ethylene A method for producing a propylene-nonconjugated diene copolymer can be provided.

"Halogen remover"
The halogen remover of the present invention uses an ethylene-α-olefin copolymer or ethylene-propylene-nonconjugated diene copolymer (hereinafter collectively referred to as “rubber polymer”) using a halogen-containing polymerization catalyst. Is used when manufacturing.
The halogen removing agent of the present invention contains the following pentaerythritol fatty acid ester.

<Pentaerythritol fatty acid ester>
The halogen removing agent of the present invention contains the following component (A), component (B), and component (C) as pentaerythritol fatty acid ester. Moreover, you may further contain the following (D) components as a pentaerythritol fatty acid ester. The halogen remover may be a one-component type in which the component (A), the component (B), the component (C), and the component (D) as necessary are mixed, or the component (A), (B) The component, the component (C), and, if necessary, the component (D) may be prepared separately. However, the halogen remover is preferably a one-component type because it is easy to handle and can use a pentaerythritol fatty acid ester in which at least the components (A), (B), and (C) are mixed. .
(A) Component: Pentaerythritol tetrafatty acid ester (B) Component: Pentaerythritol trifatty acid ester (C) Component: Pentaerythritol difatty acid ester (D) Component: Pentaerythritol monofatty acid ester

Pentaerythritol fatty acid ester is an esterified product of pentaerythritol which is one kind of polyol and fatty acid.
Common polyols include, for example, ethylene glycol, trimethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 2 such as 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 1,16-hexadecanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, etc. Trihydric alcohols such as glycerin and trimethylolpropane; tetrahydric alcohols such as erythritol, sorbitan, mannitan, pentaerythritol, and diglycerin; pentahydric alcohols such as arabit and xylit Sorbitol, mannitol, Garakuchitto, such as hexavalent alcohol of dipentaerythritol and the like are known.
Among these polyols, mono-fatty acid esters and di-fatty acid esters obtained using dihydric alcohols and trihydric alcohols have a low flash point and are inferior in removing halogens such as chlorine. In addition, fatty acid esters obtained using a polyhydric alcohol having a valence of 5 or more have a high melting point and are difficult to use at room temperature. Moreover, although mentioned later in detail, there exists a fault that it is inferior to the solubility to the reaction solvent used for a polymerization reaction.
Among the tetrahydric alcohols, fatty acid esters obtained using pentaerythritol are excellent in balance between handling properties such as low-temperature fluidity and viscosity and halogen removability.

  The method for producing pentaerythritol is not particularly limited and is generally obtained by condensing one molecule of acetaldehyde and four molecules of formaldehyde with an alkali catalyst such as sodium hydroxide or calcium hydroxide. As a commercial product of pentaerythritol, a trade name “Pentalit” manufactured by Guangei Chemical Industry Co., Ltd. is preferable.

  The carbon number of the fatty acid moiety of the pentaerythritol fatty acid ester is preferably 6 to 14, more preferably 8 to 12, and particularly preferably 8 to 10 for any of the components (A) to (D). If the number of carbon atoms in the fatty acid moiety is 6 or more, the halogen removing property of the resulting halogen removing agent is further improved. On the other hand, when the halogen removing agent is a one-pack type, if the number of carbon atoms in the fatty acid portion is 14 or less, a halogen removing agent having a low viscosity is easily obtained, and handling properties are further improved.

The fatty acid may be a saturated fatty acid or an unsaturated fatty acid, but a saturated fatty acid is preferable in terms of enhancing stability against oxygen and heat. The fatty acid may be linear or branched.
Examples of fatty acids include caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, 4-isocaproic acid, 2-ethylhexanoic acid, 3,5,5-trimethyl. Examples include hexanoic acid, 4-ethylpentanoic acid, hexenoic acid, octenoic acid, noneic acid, caproleic acid, myristolein and the like. Among these, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, 4-isocaproic acid, 2-ethylhexanoic acid, 3,5,5-trimethylhexanoic acid, 4-ethylpentanoic acid are preferable, and caprylic acid Pelargonic acid, capric acid, 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid are particularly preferred.
These fatty acids can be used alone or in combination of two or more.

  Examples of the pentaerythritol tetrafatty acid ester as component (A) include tetracaproic acid pentaerythritol ester, tetraenanthic acid pentaerythritol ester, tetracaprylic acid pentaerythritol ester, tetrapelargonic acid pentaerythritol ester, tetracapric acid pentaerythritol ester, Tetraundecanoic acid pentaerythritol ester, tetralauric acid pentaerythritol ester, tetratridecanoic acid pentaerythritol ester, tetramyristic acid pentaerythritol ester, tetra 4-isocaproic acid pentaerythritol ester, tetra 2-ethylhexanoic acid pentaerythritol ester, tetra 3 , 5,5-Trimethylhexanoic acid pentaerythritol ester , Tetra4-ethylpentanoic acid pentaerythritol ester, tetrahexenoic acid pentaerythritol ester, tetraoctenoic acid pentaerythritol ester, tetranonenoic acid pentaerythritol ester, tetracaproleic acid pentaerythritol ester, tetramyristoleic acid pentaerythritol ester It is done.

Among these, an esterified product of saturated fatty acid and pentaerythritol is more preferable from the viewpoint of excellent chemical stability against oxygen and heat, and specifically, tetracaprylic acid pentaerythritol ester, tetrapelargonic acid pentaerythritol ester, tetracapric acid. Pentaerythritol ester, tetraundecanoic acid pentaerythritol ester, tetralauric acid pentaerythritol ester, tetra-2-ethylhexanoic acid pentaerythritol ester, tetra-3,5,5-trimethylhexanoic acid pentaerythritol ester are preferred. Furthermore, since the halogen removability is further improved and the halogen remover is a one-component type, the viscosity is lower and the low temperature fluidity is superior, so that tetracaprylic acid pentaerythritol ester, tetrapelargonic acid pentaerythritol ester, tetra Capric acid pentaerythritol ester, tetra-2-ethylhexanoic acid pentaerythritol ester, and tetra 3,5,5-trimethylhexanoic acid pentaerythritol ester are particularly preferred.
These components (A) can be used alone or in combination of two or more.

  Examples of the pentaerythritol trifatty acid ester which is component (B) include tricaproic acid pentaerythritol ester, trienanthic acid pentaerythritol ester, tricaprylic acid pentaerythritol ester, triperargonic acid pentaerythritol ester, tricapric acid pentaerythritol ester, triundecanoic acid penta Erythritol ester, Trilauric acid pentaerythritol ester, Tritridecanoic acid pentaerythritol ester, Trimyristic acid pentaerythritol ester, Tri-4-isocaproic acid pentaerythritol ester, Tri-2-ethylhexanoic acid pentaerythritol ester, Tri 3,5,5-trimethyl Hexanoic acid pentaerythritol ester, tri-4-ethylpenta Acid pentaerythritol ester, Torihekisen acid pentaerythritol ester, Toriokuten acid pentaerythritol ester, Torinonen acid pentaerythritol ester, tricaprate pro maleic acid pentaerythritol ester, tri myristoleic pentaerythritol esters.

Among these, an esterified product of saturated fatty acid and pentaerythritol is more preferable from the viewpoint of excellent chemical stability against oxygen and heat, and specifically, tricaprylic acid pentaerythritol ester, triperargonic acid pentaerythritol ester, and tricapric acid pentaerythritol. Ester, triundecanoic acid pentaerythritol ester, trilauric acid pentaerythritol ester, tri-2-ethylhexanoic acid pentaerythritol ester, tri-3,5,5-trimethylhexanoic acid pentaerythritol ester are preferred. Furthermore, the halogen removability is further improved, and when the halogen remover is a one-component type, the viscosity is lower and the low temperature fluidity is superior, so that tricaprylic acid pentaerythritol ester, triperargonic acid pentaerythritol ester, tricapric acid Particularly preferred are pentaerythritol ester, tri-2-ethylhexanoic acid pentaerythritol ester, and tri-3,5,5-trimethylhexanoic acid pentaerythritol ester.
These (B) components can be used individually by 1 type or in mixture of 2 or more types.

  Examples of the component (C) pentaerythritol difatty acid ester include dicaproic acid pentaerythritol ester, dienanthic acid pentaerythritol ester, dicaprylic acid pentaerythritol ester, dipelargonic acid pentaerythritol ester, dicapric acid pentaerythritol ester, diundecanoic acid pentaerythritol ester. , Dilauric acid pentaerythritol ester, ditridecanoic acid pentaerythritol ester, dimyristic acid pentaerythritol ester, di-4-isocaproic acid pentaerythritol ester, di2-ethylhexanoic acid pentaerythritol ester, di3,5,5-trimethylhexanoic acid penta Erythritol ester, pentaerythritol di-4-ethylpentanoate Le, Jihekisen acid pentaerythritol ester, Jiokuten acid pentaerythritol ester, Jinonen acid pentaerythritol ester, Jikapurorein acid pentaerythritol esters, such as dimyristoyl maleic acid pentaerythritol ester.

Among these, an esterified product of saturated fatty acid and pentaerythritol is more preferable from the viewpoint of excellent chemical stability against oxygen and heat, specifically, dicaprylic acid pentaerythritol ester, dipelargonic acid pentaerythritol ester, dicapric acid pentaerythritol ester. , Diundecanoic acid pentaerythritol ester, dilauric acid pentaerythritol ester, di-2-ethylhexanoic acid pentaerythritol ester, di3,5,5-trimethylhexanoic acid pentaerythritol ester are preferred. Further, the halogen removability is further improved, and when the halogen remover is a one-component type, the viscosity is lower, and the low temperature fluidity is superior, so that dicaprylic acid pentaerythritol ester, dipelargonic acid pentaerythritol ester, dicapric acid penta Particularly preferred are erythritol ester, di-2-ethylhexanoic acid pentaerythritol ester, and di3,5,5-trimethylhexanoic acid pentaerythritol ester.
These components (C) can be used alone or in combination of two or more.

  Examples of the component (D) pentaerythritol monofatty acid ester include monocaproic acid pentaerythritol ester, monoenanthic acid pentaerythritol ester, monocaprylic acid pentaerythritol ester, monopelargonic acid pentaerythritol ester, monocapric acid pentaerythritol ester, monoundecane Acid pentaerythritol ester, monolauric acid pentaerythritol ester, monomonodecanoic acid pentaerythritol ester, monomyristic acid pentaerythritol ester, mono 4-isocaproic acid pentaerythritol ester, mono 2-ethylhexanoic acid pentaerythritol ester, mono 3, 5, 5 -Trimethylhexanoic acid pentaerythritol ester, mono-4-ethylpenta Acid pentaerythritol ester, Monohekisen acid pentaerythritol ester, Monookuten acid pentaerythritol ester, Monononen acid pentaerythritol ester, mono capric Lorraine acid pentaerythritol esters, such as mono myristoleic pentaerythritol esters.

Among these, an esterified product of saturated fatty acid and pentaerythritol is more preferable from the viewpoint of excellent chemical stability against oxygen and heat, and specifically, monocaprylic acid pentaerythritol ester, monopelargonic acid pentaerythritol ester, monocapric acid. Pentaerythritol ester, monoundecanoic acid pentaerythritol ester, monolauric acid pentaerythritol ester, mono-2-ethylhexanoic acid pentaerythritol ester, mono-3,5,5-trimethylhexanoic acid pentaerythritol ester are preferred. Furthermore, since the halogen removability is further improved and the halogen remover is a one-component type, the viscosity is lower and the low temperature fluidity is superior, so that monocaprylic acid pentaerythritol ester, monopelargonic acid pentaerythritol ester, mono Capric acid pentaerythritol ester, mono-2-ethylhexanoic acid pentaerythritol ester, and mono-3,5,5-trimethylhexanoic acid pentaerythritol ester are particularly preferred.
These components (D) can be used alone or in combination of two or more.

(Composition ratio of pentaerythritol fatty acid ester)
The mass ratio represented by (A) component / ((A) component + (B) component + (C) component) is 0.48 to 0.85, preferably 0.55 to 0.82. 61-0.75 is more preferable. When the mass ratio represented by (A) component / ((A) component + (B) component + (C) component) is within the above range, a halogen remover excellent in halogen removability can be obtained. In addition, when the halogen removing agent is a one-component type, the handleability is also improved. Specifically, the viscosity is lowered, the low temperature fluidity is improved, the flash point is increased, and the odor is reduced. When the mass ratio is less than 0.48, the halogen removability of the halogen removing agent is lowered. On the other hand, when the mass ratio exceeds 0.85, the halogen removability of the halogen removing agent decreases. In addition, when the halogen removing agent is a one-component type, low temperature fluidity is lowered.

When the halogen remover contains the component (D), the mass ratio represented by (D) component / ((A) component + (B) component + (C) component + (D) component) is 0.00. 02 or less is preferable, 0.016 or less is more preferable, and 0.008 or less is particularly preferable.
(D) component is a component which improves the low temperature fluidity | liquidity of a one-component type halogen removal agent. Therefore, as the proportion of the component (D) increases, the low temperature fluidity improves, but on the other hand, suspended matters and precipitates are likely to be generated, and the transparency of the halogen removing agent also tends to decrease. In particular, when a halogen removing agent in which precipitates are generated is used in the production of an ethylene-α-olefin copolymer or an ethylene-propylene-nonconjugated diene copolymer, the precipitates are likely to accumulate in a reaction vessel (tank) or piping. . Therefore, it takes time to remove the halogen remover by washing after the production of these rubbery polymers.
If the mass ratio represented by (D) component / ((A) component + (B) component + (C) component + (D) component) is within the above range, the transparency of the one-component halogen remover The low temperature fluidity can be further increased while maintaining the above. Therefore, workability when used for the production of an ethylene-α-olefin copolymer or an ethylene-propylene-nonconjugated diene copolymer is enhanced, and the washability after the production of these rubbery polymers is also improved.
The lower limit of the mass ratio represented by (D) component / ((A) component + (B) component + (C) component + (D) component) is not particularly limited, but is preferably 0.001 or more, 0 0.003 or more is more preferable.

(Method for producing pentaerythritol fatty acid ester)
Pentaerythritol fatty acid ester can be produced by a known esterification method. Pentaerythritol fatty acid ester produced by the esterification method is a partial ester (full ester (component (A))) in which fatty acid groups are bonded to all hydroxyl groups of pentaerythritol, and a partial ester showing a structure in which a part of hydroxyl groups remains ( (B) component, (C) component, (D) component), and a mixture of full ester and partial ester.
In the present invention, the pentaerythritol fatty acid ester obtained in the form of a mixture containing at least the component (A), the component (B), and the component (C) is also referred to as “pentaerythritol fatty acid ester composition”.

The ratio (composition ratio) of the (A) component, the (B) component, the (C) component, and the (D) component in the pentaerythritol fatty acid ester composition, which will be described in detail later, can be controlled by production conditions, It can be easily measured by chromatographic analysis.
Therefore, a one-component halogen remover can be easily obtained by producing pentaerythritol fatty acid ester so that the ratio of each component is the above-described mass ratio.

Examples of the method for producing pentaerythritol fatty acid ester include the following methods (1) to (3).
(1) A method in which a fatty acid and pentaerythritol are esterified by reacting them in the presence of an acid, an alkali, or an organometallic catalyst.
(2) A method of transesterifying by reacting a fatty acid ester such as a fatty acid alkyl ester with pentaerythritol in the presence of an acid, alkali or organometallic catalyst.
(3) A method of subjecting vegetable oil such as palm oil, soybean oil, palm oil, palm kernel oil and the like to pentaerythritol in the presence of an acid, alkali or organometallic catalyst to transesterify, followed by fractionation by distillation or the like.

When producing a pentaerythritol fatty acid ester by the method (2), for example, it is carried out as follows.
First, the fatty acid alkyl ester and pentaerythritol are charged into the reaction vessel so that the fatty acid alkyl ester becomes an excessive amount. Next, in the presence of an acid catalyst, alkali catalyst or organometallic catalyst in a nitrogen atmosphere, the fatty acid alkyl ester is refluxed under the prescribed temperature and pressure conditions, and at the same time, the by-produced alkyl alcohol is distilled out of the system. The synthesis reaction of the pentaerythritol fatty acid ester is performed until the ratio (composition) of the components (A), (B), (C), and (D) in the reaction product is within a desired range. Thereafter, the unreacted fatty acid alkyl ester is removed from the system by topping under reduced pressure. Further, when a solid catalyst is used, the catalyst is removed by filtration, or when a homogeneous catalyst is used, the catalyst is appropriately removed or inactivated by neutralizing or adsorbing the catalyst. When pentaerythritol, which is an unreacted solid raw material, remains in the reaction product, the pentaerythritol is appropriately removed by filtration. In this way, a pentaerythritol fatty acid ester composition having a desired composition is obtained.

As the reaction vessel, a reaction vessel made of glass, glass lining, or stainless steel equipped with a reflux tube can be used.
6-14 are preferable, as for carbon number of the fatty-acid part of fatty-acid alkylester, 8-12 are more preferable, and 8-10 are especially preferable. On the other hand, 1-8 are preferable, as for carbon number of an alkyl part, 1-4 are more preferable, and 1-2 are especially preferable.

The amount of fatty acid alkyl ester charged is 1.00 to 1.30 times equivalent of the molar amount of fatty acid alkyl ester necessary for producing full ester (component (A)) with respect to the number of moles of hydroxyl group of pentaerythritol. It is preferable that If the amount of fatty acid alkyl ester charged is less than 1.00 times equivalent, the reaction may not proceed sufficiently. On the other hand, when the amount of the fatty acid alkyl ester charged is more than 1.30 times equivalent, the reaction may proceed so much that it may be difficult to obtain a pentaerythritol fatty acid ester composition having a desired composition. Moreover, since the ratio of the unreacted fatty acid alkyl ester increases, the amount of the unreacted fatty acid alkyl ester removed by the topping operation increases, and the load on the manufacturing process increases.
As the amount of fatty acid alkyl ester charged decreases, the proportion of full ester (component (A)) decreases and the proportion of partial esters (component (B), component (C), component (D)) increases. There is a tendency to increase.

As an acid catalyst, an alkali catalyst, and an organometallic catalyst, a catalyst used in a normal transesterification reaction can be used. Among these, an alkali catalyst is preferable.
Examples of the alkali catalyst include potassium carbonate, sodium carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate if they are solid catalysts, and examples include sodium methylate if they are homogeneous catalysts. A solid catalyst is preferable because it can be easily removed after the reaction, and sodium hydrogen carbonate is particularly preferable.
The addition amount of the catalyst is preferably 0.05 to 5.0 parts by mass when the total amount of the fatty acid alkyl ester and pentaerythritol used as raw materials is 100 parts by mass. If the addition amount of the catalyst is less than 0.05 parts by mass, the reaction may not proceed sufficiently. On the other hand, when the addition amount of the catalyst is more than 5.0 parts by mass, the amount of the catalyst to be filtered or neutralized increases, and the load on the manufacturing process increases.

The transesterification reaction is performed under a nitrogen atmosphere, but may be performed under reduced pressure or under a nitrogen gas flow at normal pressure. Conditions under which the by-produced alkyl alcohol can be efficiently distilled off are preferred.
When the transesterification reaction is carried out under reduced pressure, the degree of reduced pressure is preferably 133 Pa (1 torr) to 53320 Pa (400 torr), more preferably 133 Pa to 33325 Pa (250 torr). The transesterification reaction may be performed at a certain degree of reduced pressure, or may be performed under conditions that increase the degree of reduced pressure stepwise.
On the other hand, when the transesterification reaction is performed under a normal pressure nitrogen gas flow, the gas flow rate is preferably about 0.01 to 50 L / min.

The reaction temperature may be a temperature at which a normal transesterification reaction proceeds, preferably 50 to 250 ° C, more preferably 100 to 230 ° C. If the reaction temperature is lower than 50 ° C, the reaction may not proceed sufficiently. On the other hand, when the reaction temperature is higher than 250 ° C., the color tone of the reaction product may deteriorate or the odor may deteriorate.
The reaction time is a time until the production amount of the full ester (component (A)) reaches a predetermined amount due to the progress of the transesterification reaction, but is usually 1 to 20 hours.
As the reaction temperature is lowered and the reaction time is shortened, the proportion of full ester (component (A)) decreases, and partial esters (component (B), component (C), (D ) Component) tends to increase.

After completion of the reaction, topping is performed to remove unreacted fatty acid alkyl ester out of the system. At this time, it is preferable to perform topping until the ratio of the unreacted fatty acid alkyl ester in the reaction product is 1% by mass or less. When the proportion of the unreacted fatty acid alkyl ester is 1% by mass or less, a one-component halogen remover having a lower odor and a higher flash point can be obtained. The ratio of the unreacted fatty acid alkyl ester in the reaction product is more preferably 0.5% by mass or less, and particularly preferably 0.1% by mass or less.
The degree of vacuum during topping is preferably 1330 Pa (10 torr) or less. The higher the degree of vacuum, the shorter the time for removing the unreacted fatty acid alkyl ester.
The topping time is preferably 0.5 to 6 hours.

It is preferable to remove or deactivate the catalyst after the topping.
When a solid catalyst is used, the catalyst is preferably removed by filtration using a leaf filter or a filter press. At this time, in order to perform filtration efficiently, an aggregation accelerator may be added or a precoat treatment may be performed.
On the other hand, when a homogeneous catalyst is used, the catalyst is preferably neutralized or adsorbed. For example, when a homogeneous alkali catalyst is used, the neutralization treatment neutralizes the alkali catalyst by adding an acidic compound. Examples of the acidic compound include hydrochloric acid, sulfuric acid, acetic acid, citric acid, p-toluenesulfonic acid, methanesulfonic acid and the like. On the other hand, in the adsorption treatment, an adsorption treatment agent is added and the catalyst is adsorbed by ion exchange. Examples of the adsorption treatment agent include Kyowa Kagaku Kogyo Co., Ltd. trade name “KYOWARD” series. Adsorption treatment is preferred because the metal content can be reduced.

When the pentaerythritol fatty acid ester is produced by the method (1), it is carried out in the same manner as in the method (2) except that a fatty acid is used instead of the fatty acid alkyl ester. However, since fatty acids have a higher boiling point than fatty acid alkyl esters, it is difficult to sufficiently remove fatty acids in the topping process. Therefore, 1 mass% or more of unreacted fatty acids may remain in the reaction product. If a large amount of fatty acid remains, the acid value of the resulting pentaerythritol fatty acid ester becomes high, and there is a concern that the quality stability is lowered. In such a case, after the topping step, an alkali compound (for example, sodium hydroxide, sodium hydrogen carbonate, sodium carbonate, potassium hydroxide, potassium hydrogen carbonate, potassium carbonate, etc.) is added to neutralize or ion It is preferable to reduce the acid value by performing adsorption treatment by exchange. In particular, it is preferable to reduce the acid value by an adsorption treatment, and specifically, the adsorption treatment is preferably performed until the acid value becomes 0.05 mgKOH / g or less, preferably 0.02 mgKOH / g or less.
When a homogeneous catalyst is used, the adsorption treatment and the acid value can be reduced simultaneously by performing the adsorption treatment after the topping step.

As the adsorption treatment agent used for the adsorption treatment, an inorganic synthetic adsorbent mainly composed of magnesium (Mg), aluminum (Al), silicon (Si) or the like is preferable. For example, a trade name “KYOWARD” manufactured by Kyowa Chemical Industry Co., Ltd. "Series (KYOWARD 100, 200, 300, 400, 500, 600, 700, 1000, 2000, etc.); Trade name" Tmiter AD "series (Tomita AD100, 500, 600, 700, etc.) manufactured by Tomita Pharmaceutical Co., Ltd. Is mentioned.
The addition amount of the adsorption treatment agent is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the reaction product (esterified product).
The treatment temperature is preferably 20 to 160 ° C., and the treatment time is preferably 10 minutes to 10 hours.
Further, the neutralization treatment may be performed in the air, may be performed in an inert gas atmosphere such as nitrogen or argon, or may be performed under reduced pressure conditions.

The pentaerythritol fatty acid ester obtained by the methods (1) to (3) is preferably degassed to remove moisture and air. Specifically, after nitrogen replacement, preferably 20 to Distill off under reduced pressure at 160 ° C. for 10 minutes to 10 hours under a vacuum degree of 0.1 to 80 kPa. In this case, azeotropic distillation may be performed by adding about 0.1 to 3 mol of a compound that azeotropes with water, such as toluene, kerosene, isopropyl alcohol, ethanol, or pyridine, with respect to the water in the pentaerythritol fatty acid ester. By these operations, the water content in the pentaerythritol fatty acid ester is reduced to 0.1 to 200 ppm, preferably 0.1 to 100 ppm. As a result, decomposition such as hydrolysis can be suppressed, and the quality stability of the halogen removing agent can be reduced. Can be increased. In addition, when there is much content of water, in part, superposition | polymerization will be stopped using water, and it may affect the halogen removability of a halogen removal agent.
After the deaeration treatment, it is preferable to store in a nitrogen atmosphere or in dry air so that the pentaerythritol fatty acid ester does not absorb moisture again. Further, a dehydrating agent such as Molecular Sieves 4A (manufactured by Junsei Co., Ltd.) may be added and stored in an amount of 0.1 to 30 parts by mass with respect to 100 parts by mass of pentaerythritol fatty acid ester. Due to the action of a dehydrating agent such as Molecular Sieves 4A, it is possible to maintain a state where the water content in the pentaerythritol fatty acid ester is 0.1 to 100 ppm for a long period of time.

<Optional component>
The halogen remover may contain a component (optional component) other than pentaerythritol fatty acid ester, if necessary, for the purpose of further improving durability.
Examples of optional components include antioxidants and other additives.
Examples of the antioxidant include phenolic antioxidants such as dibutylhydroxytoluene (BHT) and butylhydroxyanisole (BHA); amine antioxidants such as dioctyldiphenylamine and phenyl-α-naphthylamine; ascorbic acid (vitamin C) And tocopherol (vitamin E). Among these, a phenolic antioxidant and tocopherol are preferable, and BHT, BHA, and tocopherol are more preferable.
Examples of other additives include extreme pressure agents, detergent dispersants, pour point depressants, rust inhibitors, and antifoaming agents.

<Effect>
Since the halogen removing agent of the present invention described above contains the above-described components (A), (B), and (C) at a specific mass ratio, the halogen removing agent is excellent. Therefore, when the ethylene-α-olefin copolymer or the ethylene-propylene-nonconjugated diene copolymer is produced using a halogen-containing polymerization catalyst, the halogen remover of the present invention is used after polymerizing the raw material monomers ( Specifically, when used as a polymerization terminator), the halogen (eg, chlorine) derived from the polymerization catalyst is removed by the halogen removing agent of the present invention, so that the ethylene-α-olefin copolymer is further reduced in halogen concentration. A coalescence or ethylene-propylene-nonconjugated diene copolymer is obtained.

  In addition, when the halogen removing agent is a one-pack type, it is excellent in handleability. Specifically, the pour point tends to be less than −5 ° C. (preferably less than −10 ° C., more preferably less than −15 ° C.), and the low temperature fluidity is excellent. Further, the flash point tends to be 250 ° C. or higher (preferably 260 ° C. or higher). In addition, the viscosity is low and the odor is reduced.

"Method for producing ethylene-α-olefin copolymer or ethylene-propylene-nonconjugated diene copolymer"
The present invention produces an ethylene-α-olefin copolymer such as an ethylene-propylene copolymer (EPM) or an ethylene-propylene-nonconjugated diene copolymer (EPDM) using a polymerization catalyst containing halogen. Is the method.

When producing an ethylene-α-olefin copolymer, ethylene and α-olefin are used as raw material monomers.
Examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene and the like.
90 / 10-30 / 70 is preferable and, as for mass ratio (ethylene / alpha-olefin) of ethylene and alpha-olefin in a copolymer, 85 / 15-40 / 60 is more preferable.

When producing an ethylene-propylene-nonconjugated diene copolymer, ethylene, propylene and a nonconjugated diene are used as raw material monomers.
Non-conjugated dienes include, for example, 5-alkylidene-2-norbornene (5-ethylidene-2-norbornene, 5-isopropenyl-2-norbornene, 5-propenyl-2-norbornene, etc.), 2,5-norbornadiene, 2- Methylenenorbornene, 2-ethylnorbornene, 5-methylenenorbornene, 5- (2-butenyl) -2-norbornene, dicyclopentadiene, 1,4-hexadiene, bicyclo [3,2,0] heptadiene, tetrahydroindene, alkyltetrahydro Examples include indene, dialkyltetrahydroindene, 9,10-dihydro-dicyclopentadiene, 11-ethyl-1,11-tridecadiene, 6-methyl-1,5-heptadiene, 1,5-hexadiene, and the like.
The proportion of non-conjugated diene units in the copolymer is preferably from 0.1 to 8 mol%.

The polymerization catalyst used in the present invention contains halogen. Examples of such a polymerization catalyst include a Ziegler-Natta catalyst containing a transition metal compound and an organoaluminum compound.
As transition metal compounds, compounds such as nickel (Ni), cobalt (Co), vanadium (V), niobium (Nb), lanthanum (La), and the like are known. Examples of the vanadium compound include vanadium oxytrichloride (VOCl ₃ ), vanadium trichloride (VCl ₃ ), vanadium tetrachloride (VCl ₄ ), vanadium trisacetylacetonate (V (AcAc) ₃ ), and the like. Among these, the vanadium oxytrichloride, the vanadium tetrachloride, or a soluble vanadium compound that is a modified product of these alcohols (having 1 to 12 carbon atoms) is preferable. Here, “AcAc” represents acetylacetonate.

  Examples of the organoaluminum compound include trialkylaluminum, dialkylaluminum chloride, alkylaluminum sesquichloride, alkylaluminum dichloride, and alkylaluminum halide. Specific examples include triethylaluminum, trimethylaluminum, triisopropylaluminum, triisobutylaluminum, diethylaluminum chloride, dimethylaluminum chloride, ethylaluminum dichloride, methylaluminum dichloride, and ethylaluminum sesquichloride. Among these, trialkylaluminum such as ethylaluminum sesquichloride, diethylaluminum chloride, ethylaluminum dichloride, triethylaluminum, or a mixture thereof is preferable.

  The combination of the transition metal compound and the organoaluminum compound is not particularly limited, but a combination of a vanadium compound and an organoaluminum compound is preferable. However, it is assumed that halogen is contained in at least one of the transition metal compound and the organoaluminum compound.

  The amount of the polymerization catalyst used is preferably an amount such that the transition metal compound is 0.05 to 0.1 mol and the organoaluminum compound is 0.4 to 1.6 mol with respect to 1 mol of the raw material monomer. An amount is preferred.

An activator may be used for the polymerization of the raw material monomer using the polymerization catalyst.
Examples of the activator include alkyl monohalogenomalonates such as ethyl monochloromalonate, methylmonochloromalonate, ethylmonobromomalonate, and methylmonobromomalonate; ethyldichloromalonate, methyldichloromalonate, ethyldibromomalonate And alkyl dihalogenomalonates such as methyl dibromomalonate.
The addition amount of the activator is preferably 0.05 to 150 mol with respect to 1 mol of the transition metal compound. When the addition amount of the activator is 0.05 mol or more, the effect of adding the activator is sufficiently obtained, and the yield of the rubbery polymer is improved. On the other hand, if the addition amount of the activator is 150 mol or less, the activator can suppress the deactivation of the active site during the polymerization reaction.

Moreover, you may use a chain transfer agent for the superposition | polymerization of the raw material monomer using a polymerization catalyst as needed.
Examples of the chain transfer agent include dialkyl zinc and hydrogen.

  Examples of the reaction solvent used for the polymerization reaction include aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, ethers, ketones, esters, and the like. Specifically, n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, cycloheptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, styrene Methyl ethyl ketone, diethyl ether, dipropyl ether, ethyl acetate, acetic acid, chloroform, tetrachloroethane and the like. Among these, aliphatic hydrocarbons, aromatic hydrocarbons, and halogenated hydrocarbons are preferable, and n-hexane, n-heptane, and n-octane are particularly preferable.

The polymerization temperature is preferably from -30 to 90 ° C, more preferably from 10 to 60 ° C. The polymerization pressure is preferably 0.1 MPa (0 kg G / cm ² ) to ² MPa (20 kg G / cm ² ).

In the method for producing an ethylene-α-olefin copolymer or ethylene-propylene-nonconjugated diene copolymer of the present invention, after the raw material monomer is polymerized (that is, after the polymerization reaction solution reaches a predetermined polymer concentration). The (A) component, the (B) component, and the (C) component described above as pentaerythritol fatty acid ester are represented by (A) component / ((A) component + (B) component + (C) component). It adds to a polymerization reaction liquid so that mass ratio may be 0.48-0.85. Further, the mass ratio represented by (D) component / ((A) component + (B) component + (C) component + (D) component) is 0.02 or less. It is preferable to add to. If the mass ratio of each component in the polymerization reaction solution is within the above range, each component may be added to the polymerization reaction solution separately. Addition to the polymerization reaction solution is preferable because it can be added to the polymerization reaction solution so that the mass ratio of each component is within the above range by one addition.
A halogen (for example, chlorine) can be removed by adding a halogen remover to the polymerization reaction solution. Further, since the halogen removing agent of the present invention also serves as a polymerization terminator, the polymerization is stopped by adding the halogen removing agent to the polymerization reaction solution.
The addition amount of the halogen removing agent is preferably 0.01 to 5 parts by mass and more preferably 0.1 to 1 part by mass with respect to 100 parts by mass of the resulting rubbery polymer.

  After adding the halogen removing agent to the polymerization reaction liquid, 0.05 to 0.4 parts by mass of water, preferably 0.1 to 0.3 parts by mass of water is added to 1 part by mass of the polymerization reaction liquid, It is preferable to emulsify with stirring. The temperature during addition and stirring is preferably -10 to 60 ° C. The pH of the polymerization reaction solution after adding water is preferably 4.0 to 12. As long as the pH falls within the above range, various aqueous solutions such as an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, and an aqueous ammonia solution may be used instead of water. If pH is 4.0 or more, a polymerization apparatus will not corrode easily. On the other hand, if the pH is 12 or less, catalyst residues such as halogen are easily dissolved in water.

Further, a surfactant may be added to water added to the polymerization reaction solution.
Examples of the surfactant include nonionic surface activity such as polyoxyethylene alkyl ether type, polyoxyethylene alkyl phenol ether type, sorbitan ester type, polyoxyethylene sorbitan ester type, polyethylene glycol, polypropylene glycol, polyoxyethylene fatty acid ester type, etc. Agents and the like.
The amount of the surfactant added is preferably 0.005 to 0.3 parts by mass, more preferably 0.01 to 0.1 parts by mass with respect to 100 parts by mass of water.
Water containing a surfactant is added to the polymerization reaction liquid, and after sufficiently stirring and emulsifying, 0.2 to 2.0 parts by mass of water is further added to 1 part by mass of the polymerization reaction liquid, It is preferable to separate water from the polymerization reaction solution after stirring and phase inversion.

  When the polymerization reaction solution thus obtained is subjected to steam stripping according to a conventional method, the reaction solvent is gasified and removed by water vapor. The reaction product, a rubbery polymer, dissolves in the reaction solvent, but hardly dissolves in water, and thus precipitates when the reaction solvent is removed. On the other hand, the halogen present in the polymerization reaction solution is dissolved in water by the action of pentaerythritol fatty acid ester. In addition, the polymerization catalyst and the pentaerythritol fatty acid ester itself are dissolved in water. Therefore, by performing steam stripping, the rubber-like polymer can be separated from the polymerization catalyst, halogen and pentaerythritol fatty acid ester, and the rubber-like polymer from which halogen has been further removed can be recovered without increasing the molecular weight.

<Effect>
According to the method for producing the ethylene-α-olefin copolymer or ethylene-propylene-nonconjugated diene copolymer of the present invention described above, the above-described (A) component, (B) component, after polymerizing the raw material monomers, And (C) component is added to a polymerization reaction liquid by specific mass ratio. Therefore, it is possible to produce an ethylene-α-olefin copolymer or an ethylene-propylene-nonconjugated diene copolymer in which halogen is further reduced.
In particular, the one-component halogen remover of the present invention has low viscosity, excellent low-temperature fluidity, high flash point, and reduced odor, so that it is excellent in handleability. Therefore, if a one-component type halogen removing agent is used, halogen can be removed by a relatively simple operation, and the economy is excellent.

  The ethylene-α-olefin copolymer or ethylene-propylene-nonconjugated diene copolymer obtained according to the present invention is a non-corrosive synthetic rubber having a further reduced halogen content. Therefore, it is suitable as a raw material for rubber products that are used in contact with materials that are easily altered by halogen such as chlorine, such as metal materials.

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated in detail, this invention is not limited by the following description. In addition, the compounding quantity of the component used in each example is a pure conversion value unless there is particular notice.

"Example 1"
<Production of halogen remover>
Capillic acid methyl ester (product name “Pastel M8” manufactured by Lion Co., Ltd., fatty acid methyl ester derived from a carbon number 8 fraction derived from palm kernel oil or palm oil) 1392 g (pentaerythritol) in a 2 L four-necked flask with a stirring blade Of pentaerythritol (produced by Guangei Chemical Co., Ltd., trade name) under normal pressure while flowing nitrogen gas at a rate of 10 mL / min into the reaction vessel under stirring. “Pentalite”) 272 g and 2.54 g of sodium hydrogen carbonate were further charged, and the temperature was raised from room temperature to 170 ° C. over 1 hour. After maintaining at 170 ° C. for 3 hours, the temperature was further raised to 200 ° C. After transesterification by holding at 200 ° C. for 6 hours, the mixture was cooled to 100 ° C., the pressure in the flask was reduced to 266 Pa (2 mmHg) or less with a vacuum pump, and the temperature was gradually raised to 200 ° C. It distilled off until the ratio of unreacted caprylic acid methyl ester was less than 0.1% by mass (topping step) to obtain a reaction product. To 1000 g of the reaction product, 2.5 g of a filter aid (manufactured by Celite Corporation, trade name “Hyflo Supercell”) (0.25 part by mass with respect to 100 parts by mass of the reaction product) was added and dispersed uniformly. Thereafter, pressure filtration was performed at 60 ° C. to remove the catalyst (sodium hydrogen carbonate) and unreacted pentaerythritol to obtain a pentaerythritol fatty acid ester. This was used as a halogen remover.

<Composition analysis of halogen remover>
Collect 1g of halogen remover, dilute with 20g of acetone to prepare a sample for composition analysis, perform gas chromatography (GC) analysis under the following conditions, and obtain component (A) (pentaerythritol tetrafatty acid) obtained by a conventional method. Ester), (B) component (pentaerythritol trifatty acid ester), (C) component (pentaerythritol difatty acid ester), (D) component (pentaerythritol monofatty acid ester), and unreacted raw material (fatty acid alkyl ester or fatty acid) ) GC area% was quantified by a calibration curve with an internal standard substance.
(Equipment etc.)
Gas chromatography apparatus: Product name “7890A” manufactured by Agilent Technologies, Inc.
Column: manufactured by Agilent Technologies, Inc., trade name “Agilent J & W GC Column DB-1 HT”, 15 m × 0.25 mm, film thickness 0.10 μm.
(Measurement condition)
Column temperature: 50 ° C. → temperature increase 10 ° C./min→370° C. (8 min)
・ Inlet temperature: 350 ℃
・ Outlet temperature: 350 ℃

The content or residual amount of each component in the halogen remover (X1) was calculated by substituting the quantitative value of each component obtained by GC into the following formulas.
Residual amount of unreacted raw material (mass%) = quantitative value of unreacted raw material / (quantitative value of unreacted raw material + quantitative value of component (A) + quantitative value of component (B) + (C) component Quantitative value + (D) Quantitative value of component) x 100
-(D) component content (% by mass) = (D) component quantitative value / (unreacted raw material quantitative value (A) component quantitative value + (B) component quantitative value + (C) component Quantitative value + (D) Quantitative value of component) x 100
-(C) component content (% by mass) = (C) component quantitative value / (unreacted raw material quantitative value + (A) component quantitative value + (B) component quantitative value + (C) component Quantitative value + (D) Quantitative value of component) x 100
Content of component (B) (% by mass) = quantitative value of component (B) / (quantitative value of unreacted raw material + quantitative value of component (A) + quantitative value of component (B) + (C) component Quantitative value + (D) Quantitative value of component) x 100
Content of component (A) (% by mass) = quantitative value of component (A) / (quantitative value of unreacted raw material + quantitative value of component (A) + quantitative value of component (B) + (C) component Quantitative value + (D) Quantitative value of component) x 100

  As a result of analyzing the composition of the halogen removing agent by gas chromatography, the content of monocaprylic acid pentaerythritol ester (pentaerythritol monocaprylic acid ester) as component (D) was 0% by mass, and dicaprylic acid as component (C) The content of pentaerythritol ester (pentaerythritol dicaprylate) is 1.2% by mass, the content of tricaprylic acid pentaerythritol ester (pentaerythritol tricaprylate) as component (B) is 18.4% by mass, ( The content of tetracaprylic acid pentaerythritol ester (pentaerythritol tetracaprylic acid ester) as component A) was 80.4% by mass. The results are shown in Table 1.

<Measurement / Evaluation>
Using the obtained halogen removing agent, the following measurements and evaluations were performed.

(1) Appearance evaluation After 70 mL of a halogen removing agent was put in a 100 mL lidded container and stored at 25 ° C. for 3 days, the appearance was visually confirmed, and the appearance of the halogen removing agent was evaluated according to the following evaluation criteria. . The results are shown in Table 1.
(Evaluation criteria)
A (good): A light yellow transparent liquid.
B (Applicable): Some white floats are observed, but no sedimentation has occurred.
C (difficult to apply): white sediment is observed.
D (difficult to apply): light yellow solid.

(2) Measurement of kinematic viscosity The kinematic viscosity (unit: mm ² / s) of the halogen remover was measured in accordance with JIS K 2283. Specifically, the halogen remover was collected in a Cannon Fenceke type kinematic viscosity tube and kept warm for 30 minutes or more in a thermostatic bath maintained at 40 ° C. Thereafter, the time when the sample was allowed to flow down from a certain height in the Canon Fenceke type kinematic viscosity tube was measured, and the kinematic viscosity (unit: mm ² / s) at 40 ° C. was obtained. The results are shown in Table 1.
In addition, the case where the kinematic viscosity is less than 45 mm ² / s is evaluated as “applicable”, and the case where the kinematic viscosity is 45 mm ² / s or more, or the case where it cannot be measured because it is solid at 40 ° C. is regarded as “difficult to apply”. evaluated.

(3) Evaluation of low temperature fluidity The pour point of the halogen remover was measured according to JIS K 2269 “Pour point of crude oil and petroleum products and cloud point test method of petroleum products”. The results are shown in Table 1.
When the pour point is less than −15 ° C., it is evaluated as “good”, when the pour point is −15 ° C. or more and less than −5 ° C., it is evaluated as “applicable”, and when the pour point is −5 ° C. or more. Was evaluated as “difficult to apply”.

(4) Measurement of flash point The flash point of the halogen removing agent was measured in accordance with JIS K 2265 "Flash point test (Cleveland open type)". The results are shown in Table 1.
In addition, the case where the flash point is 260 ° C. or higher is evaluated as “good”, the case where the flash point is 250 ° C. or higher and lower than 260 ° C. is evaluated as “applicable”, and the case where the flash point is lower than 250 ° C. is “difficult to apply”. It was evaluated.

(5) Evaluation of removability of halogen (chlorine) Normal hexane 3 L / h, vanadium oxytrichloride 2.0 mmol / h, ethylaluminum sesquichloride 9.1 mmol / h, 5-ethylidene-2-norbornene in a 5 L continuous polymerization vessel 26 g / h, ethylene 300 g / h, and propylene 860 g / h were continuously charged, and hydrogen was charged so that the hydrogen in the gas phase portion of the polymerization vessel was maintained at 20%. The reaction was carried out under conditions of 35 ° C. and 0.8 MPa (7.5 kgG / cm ³ ) so that the liquid residence time was 40 minutes. The concentration of the ethylene copolymer in the effluent was 98 g / L.
Next, 0.25 g of a halogen removing agent is added to 1 L of the polymerization reaction liquid to the polymerization reaction liquid (copolymer liquid) and stirred for 5 minutes, followed by steam stripping to form a rubbery polymer (ethylene-propylene-nonconjugated). Diene copolymer) was precipitated, collected, and dried, and then the residual chlorine concentration (Cl concentration (x)) of the obtained rubbery polymer was measured by fluorescent X-ray.

Separately, the residual chlorine concentration (Cl concentration (y)) of the rubbery polymer obtained by adding water instead of the halogen removing agent was measured in the same manner, and the residual chlorine rate was determined from the following formula.
Chlorine residual rate (%) = Cl concentration (x) / Cl concentration (y) × 100

From the chlorine residual rate, the chlorine removal property of the halogen removing agent was evaluated according to the following evaluation criteria. The results are shown in Table 1.
(Evaluation criteria)
AA (very good): Chlorine residual rate is less than 60%.
A (good): Chlorine residual rate is 60% or more and less than 80%.
B (Applicable): Chlorine residual rate is 80% or more and less than 100%.
C (difficult to apply): Chlorine residual rate of 100% or more

(6) Evaluation of Odor Sensory evaluation of the odor was conducted by 10 expert panelists on the halogen remover. Specifically, sensory evaluation was performed by scoring based on the following evaluation criteria. And the average score of sensory evaluation by 10 professional panelists was calculated. The results are shown in Table 3.
In addition, the case where the average score is 3.0 or more is evaluated as “A (good)”, and the case where the average score is 2.5 or more and less than 3.0 is evaluated as “B (applicable)”. The case where the average score was less than 2.5 was evaluated as “C (difficult to apply)”.
(Evaluation criteria)
1 point: Strong smell.
2 points: Slightly smelly.
3 points: Slightly weak smell.
4 points: The smell is weak.

"Example 2"
A halogen remover was obtained in the same manner as in Example 1 except that the holding time at 200 ° C. was changed to 4 hours in the transesterification.
As a result of analyzing the composition of the obtained halogen removing agent by gas chromatography, the content of monocaprylic acid pentaerythritol ester (D) component was 0% by mass, and the content of dicaprylic acid pentaerythritol ester (C) component was The amount of tricaprylic acid pentaerythritol ester as component (B) was 23.7% by mass, and the content of tetracaprylic acid pentaerythritol ester as component (A) was 72.3% by mass. It was. The results are shown in Table 1.
Further, the obtained halogen remover was subjected to the measurements and evaluations (1) to (5) in the same manner as in Example 1. The results are shown in Table 1.

"Example 3"
A halogen remover was obtained in the same manner as in Example 1 except that the holding time at 200 ° C. was changed to 2 hours in the transesterification.
As a result of analyzing the composition of the obtained halogen removing agent by gas chromatography, the content of the monocaprylic acid pentaerythritol ester (D) component was 0.8 mass%, and the dicaprylic acid pentaerythritol ester (C) component was The content of tricaprylic acid pentaerythritol ester as component (B) is 28.4% by mass, and the content of tetracaprylic acid pentaerythritol ester as component (A) is 64.1%. It was mass%. The results are shown in Table 1.
Further, the obtained halogen remover was subjected to the measurements and evaluations (1) to (5) in the same manner as in Example 1. The results are shown in Table 1.

Example 4
The same procedure as in Example 1 except that the amount of caprylic acid methyl ester charged was changed to 4.0 mol equivalent to 1 mol of pentaerythritol, and the holding time at 200 ° C. was changed to 3 hours in the transesterification. A halogen remover was obtained.
As a result of analyzing the composition of the obtained halogen removing agent by gas chromatography, the content of the monocaprylic acid pentaerythritol ester (D) component was 1.1% by mass, and the dicaprylic acid pentaerythritol ester (C) component was The content of tricaprylic acid pentaerythritol ester as component (B) is 30.9% by mass, and the content of tetracaprylic acid pentaerythritol ester as component (A) is 59.4%. It was mass%. The results are shown in Table 1.
Further, the obtained halogen remover was subjected to the measurements and evaluations (1) to (5) in the same manner as in Example 1. The results are shown in Table 1. Further, the evaluation of (6) was performed in the same manner as in Example 1. The results are shown in Table 3.

"Example 5"
The same procedure as in Example 1 except that the amount of caprylic acid methyl ester charged was changed to 4.0 mol equivalent to 1 mol of pentaerythritol, and the holding time at 200 ° C. was changed to 2 hours in the transesterification. A halogen remover was obtained.
As a result of analyzing the composition of the obtained halogen removing agent by gas chromatography, the content of the monocaprylic acid pentaerythritol ester (D) component was 1.6 mass%, and the dicaprylic acid pentaerythritol ester (C) component was The content of the tricaprylic acid pentaerythritol ester as the component (B) is 32.3 mass%, and the content of the tetracaprylic acid pentaerythritol ester as the component (A) is 57 mass%. Met. The results are shown in Table 1.
Further, the obtained halogen remover was subjected to the measurements and evaluations (1) to (5) in the same manner as in Example 1. The results are shown in Table 1.

"Example 6"
The same procedure as in Example 1 except that the amount of caprylic acid methyl ester charged was changed to 5.2 mol equivalent to 1 mol of pentaerythritol and the holding time at 200 ° C. was changed to 4 hours in transesterification. A halogen remover was obtained.
As a result of analyzing the composition of the obtained halogen removing agent by gas chromatography, the content of monocaprylic acid pentaerythritol ester (D) component was 0% by mass, and the content of dicaprylic acid pentaerythritol ester (C) component was The amount of tricaprylic acid pentaerythritol ester which is (B) component is 15.9% by mass, and the content of tetracaprylic acid pentaerythritol ester which is (A) component is 83.5% by mass. Met. The results are shown in Table 1.
Further, the obtained halogen remover was subjected to the measurements and evaluations (1) to (5) in the same manner as in Example 1. The results are shown in Table 1.

"Example 7"
<Production of halogen remover>
To a 2 L four-necked flask equipped with a stirring blade was charged 1152 g of 2-ethylhexanoic acid (trade name “octylic acid” manufactured by Toyo Gosei Kogyo Co., Ltd.) (equivalent to 4.0 mol per mol of pentaerythritol), Under stirring, nitrogen gas was allowed to flow into the reaction vessel at a rate of 10 ml / min, and under normal pressure, 272 g of pentaerythritol (manufactured by Guangei Chemical Industry Co., Ltd., trade name “Pentalit”) and p-toluenesulfonic acid (Kenanka Kogyo) Further, 1.42 g (trade name “PTS acid” manufactured by Co., Ltd.) was added, and the temperature was raised from room temperature to 150 ° C. over 1 hour. After maintaining at 150 ° C. for 3 hours, the temperature was further raised to 200 ° C. to carry out an esterification reaction. Then, after cooling to 100 degreeC and reducing the pressure in a flask to 266 Pa (2 mmHg) or less with a vacuum pump, it heated up gradually to 200 degreeC and the ratio of unreacted 2-ethylhexanoic acid is 0.00. It distilled off until it became less than 1 mass% (topping process), and obtained the reaction material. To 1000 g of the reaction product, 5.0 g of an adsorbent (trade name “KYOWARD 1000” manufactured by Kyowa Chemical Industry Co., Ltd.) was added and stirred at 80 ° C. for 1 hour. . Thereafter, 2.5 g of a filter aid (manufactured by Celite Corporation, trade name “Hyflo Supercell”) (0.25 part by mass with respect to 100 parts by mass of the reaction product) was added and dispersed uniformly, and then at 60 ° C. By performing pressure filtration, the catalyst (paratoluenesulfonic acid) and unreacted pentaerythritol were removed to obtain a pentaerythritol fatty acid ester. This was used as a halogen remover.

As a result of analyzing the composition of the obtained halogen removing agent by gas chromatography, the content of mono-2-ethylhexanoic acid pentaerythritol ester (pentaerythritol mono-2-ethylhexanoic acid ester) as component (D) was 0.5. % By mass, content of di-2-ethylhexanoic acid pentaerythritol ester (pentaerythritol di-2-ethylhexanoate) as component (C) is 7.5% by mass, and tri-2-ethylhexane as component (B) The content of acid pentaerythritol ester (pentaerythritol tri-2-ethylhexanoate) is 29% by mass, and the component (A) is tetra-ethylhexanoate pentaerythritol ester (pentaerythritol tetra-2-ethylhexanoate). The content was 63% by mass. The results are shown in Table 1.
Further, the obtained halogen remover was subjected to the measurements and evaluations (1) to (5) in the same manner as in Example 1. The results are shown in Table 1. Further, the evaluation of (6) was performed in the same manner as in Example 1. The results are shown in Table 3.

"Comparative Example 1"
A halogen remover was obtained in the same manner as in Example 1 except that the charged amount of caprylic acid methyl ester was changed to 5.6 mol equivalent to 1 mol of pentaerythritol.
As a result of analyzing the composition of the obtained halogen removing agent by gas chromatography, the content of monocaprylic acid pentaerythritol ester (D) component was 0% by mass, and the content of dicaprylic acid pentaerythritol ester (C) component was The amount of tricaprylic acid pentaerythritol ester as component (B) was 7.7% by mass, and the content of tetracaprylic acid pentaerythritol ester as component (A) was 92.3% by mass. It was. The results are shown in Table 2.
Further, the obtained halogen remover was subjected to the measurements and evaluations (1) to (5) in the same manner as in Example 1. The results are shown in Table 2.

"Comparative Example 2"
The same procedure as in Example 1 except that the amount of caprylic acid methyl ester charged was changed to 5.6 mol equivalent to 1 mol of pentaerythritol, and the holding time at 200 ° C. was changed to 16 hours in transesterification. A halogen remover was obtained.
As a result of analyzing the composition of the obtained halogen removing agent by gas chromatography, the content of monocaprylic acid pentaerythritol ester (D) component was 0% by mass, and the content of dicaprylic acid pentaerythritol ester (C) component was The amount of tricaprylic acid pentaerythritol ester as component (B) was 1.6% by mass, and the content of tetracaprylic acid pentaerythritol ester as component (A) was 98.4% by mass. It was. The results are shown in Table 2.
Further, the obtained halogen remover was subjected to the measurements and evaluations (1) to (5) in the same manner as in Example 1. The results are shown in Table 2.

“Comparative Example 3”
The same procedure as in Example 1 was conducted except that the amount of caprylic acid methyl ester charged was changed to 3.8 mol equivalent to 1 mol of pentaerythritol and the holding time at 200 ° C. was changed to 2 hours in the transesterification. A halogen remover was obtained.
As a result of analyzing the composition of the obtained halogen removing agent by gas chromatography, the content of the monocaprylic acid pentaerythritol ester (D) component was 3.8% by mass, and the dicaprylic acid pentaerythritol ester (C) component was The content of tricaprylic acid pentaerythritol ester as component (B) is 34.1% by mass, and the content of tetracaprylic acid pentaerythritol ester as component (A) is 44% by mass. Met. The results are shown in Table 2.
Further, the obtained halogen remover was subjected to the measurements and evaluations (1) to (5) in the same manner as in Example 1. The results are shown in Table 2.

“Comparative Example 4”
To a 2 L four-necked flask equipped with a stirring blade, 1305 g of trimethylol (capillic acid methyl ester (trade name “Pastel M8”, manufactured by Lion Corporation, fatty acid methyl ester derived from palm kernel oil or palm oil with 8 carbon atoms)) Trimethylolpropane (manufactured by Mitsubishi Gas Chemical Co., Ltd.) under normal pressure while stirring and flowing nitrogen gas at a rate of 10 mL / min. 369 g of a trade name “TMP”) and 3.35 g of sodium hydrogen carbonate were further charged, and the temperature was raised from room temperature to 150 ° C. over 1 hour. After maintaining at 150 ° C. for 2 hours, the temperature was further raised to 200 ° C. over 2 hours. Further, the ester exchange was carried out by heating to 220 ° C. over 3 hours. Then, after cooling to 100 ° C. and reducing the pressure in the flask to 266 Pa (2 mmHg) or less with a vacuum pump, the temperature was gradually raised to 200 ° C., and the ratio of unreacted caprylic acid methyl ester was 0.1 It distilled off until it became less than the mass% (topping process), and obtained the reaction material. To 1000 g of the reaction product, 2.5 g of a filter aid (manufactured by Celite Corporation, trade name “Hyflo Supercell”) (0.25 part by mass with respect to 100 parts by mass of the reaction product) was added and dispersed uniformly. Thereafter, pressure filtration was performed at 60 ° C. to remove the catalyst (sodium hydrogen carbonate) and unreacted trimethylolpropane, thereby obtaining a trimethylolpropane fatty acid ester. This was used as a halogen remover.

As a result of analyzing the composition of the obtained halogen removal agent by gas chromatography, the content of monocaprylic acid trimethylolpropane ester (trimethylolpropane monocaprylic acid ester) was 1.7% by mass, dicaprylic acid trimethylolpropane ester ( The content of trimethylolpropane dicaprylate ester) was 14.7% by mass, and the content of tricaprylic acid trimethylolpropane ester (trimethylolpropane tricaprylate ester) was 83.6% by mass. The results are shown in Table 2. For convenience, the content of tricaprylic acid trimethylolpropane ester in the column of component (B) in Table 2 is described, the content of dicaprylic acid trimethylolpropane ester in the column of component (C), and (D ) In the column of the component, the content of monocaprylic acid trimethylolpropane ester is described.
Further, the obtained halogen remover was subjected to the measurements and evaluations (1) to (5) in the same manner as in Example 1. The results are shown in Table 2.

“Comparative Example 5”
Instead of caprylic acid methyl ester, stearic acid methyl ester (manufactured by Lion Corporation, trade name “Pastel M180”) was used, and the charge was changed to 5.6 moles per mole of pentaerythritol, and transesterification was performed. In Example 1, a halogen remover was obtained in the same manner as in Example 1 except that the holding time at 200 ° C. was changed to 16 hours.
As a result of analyzing the composition of the obtained halogen removing agent by gas chromatography, the content of monostearic acid pentaerythritol ester (pentaerythritol monostearic acid ester) as component (D) was 0% by mass, and component (C) The content of a certain distearic acid pentaerythritol ester (pentaerythritol distearic acid ester) is 0% by mass, the content of the (B) component tristearic acid pentaerythritol ester (pentaerythritol tristearic acid ester) is 1% by mass, ( The content of tetrastearic acid pentaerythritol ester (pentaerythritol tetrastearic acid ester) as component A) was 99% by mass. The results are shown in Table 2.
Further, the obtained halogen remover was subjected to the measurements and evaluations (1) to (5) in the same manner as in Example 1. The results are shown in Table 2.

“Test Example 1”
(6) was evaluated in the same manner as in Example 1 for γ-butyrolactone (manufactured by Junsei Chemical Co., Ltd., reagent special grade, flash point 98 ° C. (sealed container)). The results are shown in Table 3.

"Test Example 2"
2 parts by mass of caprylic acid methyl ester was added to 100 parts by mass of the halogen removing agent obtained in Example 1, and (6) was evaluated in the same manner as in Example 1. The results are shown in Table 3.
Test Example 2 is an example assuming a case where a large amount of unreacted fatty acid ester is contained in the pentaerythritol fatty acid ester.

As is apparent from Table 1, the halogen remover obtained in each example had a low kinematic viscosity and pour point and was excellent in handling properties. In addition, the halogen remover obtained in each example had a high flash point, a high residual chlorine ratio, and excellent chlorine removability.
Therefore, it was shown that the rubber-like polymer having a further reduced halogen concentration can be obtained by using the halogen remover of each example in the production of the rubber-like polymer.
On the other hand, as is clear from Table 2, the halogen remover obtained in each comparative example was inferior in chlorine removability as compared with the halogen remover of each example.
In addition, the halogen removers of Comparative Examples 1, 2, and 5 in which the mass ratio represented by (A) component / ((A) component + (B) component + (C) component) exceeds 0.85 The point was high and the low temperature fluidity was inferior. In particular, the halogen remover of Comparative Example 5 has a high pour point of 67.5 ° C., and the handling property at room temperature is very poor. After heating and dissolving at 80 ° C., it must be added quickly. It was confirmed here that there is a great difficulty in handling during production. Furthermore, it was inferior in transparency.
The halogen remover of Comparative Example 3 in which the mass ratio represented by (A) component / ((A) component + (B) component + (C) component) is less than 0.48 has high kinematic viscosity, and each of the implementations. The flash point was lower than that of the example halogen remover. Moreover, it was inferior to transparency.
The halogen remover of Comparative Example 4 composed of trimethylolpropane fatty acid ester had a lower flash point than the halogen remover of each Example.

Further, as apparent from Table 3, the halogen removers obtained in Examples 1, 4, and 7 had reduced odor.
On the other hand, from the results of Test Example 1, γ-butyrolactone (corresponding to the cyclic ester compound described in Patent Document 1) had a strong odor.
From the results of Test Example 2, it was found that when methyl caprylate was added to the halogen remover of Example 1, the odor of the halogen remover was increased. Therefore, from the viewpoint of further reducing odor, when producing pentaerythritol fatty acid ester, it is preferable to perform topping so that the ratio of unreacted fatty acid alkyl ester in the reaction product is 1% by mass or less. I can say that.

Claims (5)

A halogen remover for use in producing an ethylene-α-olefin copolymer or ethylene-propylene-nonconjugated diene copolymer using a halogen-containing polymerization catalyst,
It contains the following (A) component, (B) component, and (C) component as pentaerythritol fatty acid ester, and is represented by (A) component / ((A) component + (B) component + (C) component). The halogen removal agent whose mass ratio is 0.48-0.85.
(A) Component: Pentaerythritol tetrafatty acid ester (B) Component: Pentaerythritol trifatty acid ester (C) Component: Pentaerythritol difatty acid ester The following (D) component is further contained as a pentaerythritol fatty acid ester, and the mass ratio represented by (D) component / ((A) component + (B) component + (C) component + (D) component) The halogen removing agent according to claim 1, which is 0.02 or less.
Component (D): Pentaerythritol monofatty acid ester   The halogen remover according to claim 1 or 2, wherein the pentaerythritol fatty acid ester has 8 to 10 carbon atoms in the fatty acid moiety. A method for producing an ethylene-α-olefin copolymer or an ethylene-propylene-nonconjugated diene copolymer using a halogen-containing polymerization catalyst,
After polymerizing the raw material monomers, the following (A) component, (B) component, and (C) component as pentaerythritol fatty acid ester, (A) component / ((A) component + (B) component + (C) A method for producing an ethylene-α-olefin copolymer or an ethylene-propylene-nonconjugated diene copolymer, which is added to the polymerization reaction solution so that the mass ratio represented by (Component) is 0.48 to 0.85.
(A) Component: Pentaerythritol tetrafatty acid ester (B) Component: Pentaerythritol trifatty acid ester (C) Component: Pentaerythritol difatty acid ester   The manufacturing method of the ethylene-alpha-olefin copolymer or ethylene-propylene-nonconjugated diene copolymer of Claim 4 whose carbon number of the fatty acid part of the said pentaerythritol fatty acid ester is 8-10.