JP2010121116A - Method for producing vinyl chloride polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a vinyl chloride polymer having excellent thermal stability without sacrificing productivity. <P>SOLUTION: The method for producing the vinyl chloride polymer is carried out by polymerizing a vinyl chloride monomer in the presence of at least one vanadium compound (A) expressed by the formula: V<SP>i</SP>(=O)<SB>j</SB>Z<SB>k</SB>, and at least one aluminum compound (B). In the formula i is the oxidation number of the vanadium atom and is an integer of 2-5; j is 0 or 1; Z is a ligand, more particular, an organic ligand capable of bonding to vanadium through a heteroatom, a halogen ligand, an optionally substituted monocyclic hydrocarbon ligand or an optionally substituted polycyclic hydrocarbon ligand, where a plurality of Zs are the same as or different from each other, and at least two Zs may bond to form a ring with the vanadium atom in the formula as a constituent; and k is the number of ligands and is an integer of 1-5. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a novel production method capable of producing a vinyl chloride polymer excellent in thermal stability with high productivity using a specific vanadium compound and a specific aluminum compound.

  Conventionally, a vinyl chloride polymer is generally produced by a suspension polymerization method using a radical polymerization initiator, and is inexpensive and has excellent physical and mechanical properties as a thermoplastic plastic in various fields. Widely used. However, the vinyl chloride polymer obtained by the general method as described above contains an abnormal structure such as a head-to-head bond or a branched structure, and the thermal stability of the vinyl chloride polymer from which these factors are obtained. Is significantly reduced.

  In order to eliminate the above disadvantages, for example, a polymerization method using a half titanocene compound has been proposed (Non-patent Document 1). However, the vinyl chloride polymer obtained by the polymerization method has improved thermal stability than the vinyl chloride polymer obtained by general radical polymerization, but the polymerization rate, catalytic activity and yield are high. Low and productivity is not good. In addition, this polymerization system is economically disadvantageous because it requires more expensive methylaluminoxane than vanadium compounds.

Polymer, 49 (2008) 1180-1184

  The present invention has been made in view of the above problems of the prior art, and it is an object of the present invention to provide a method capable of producing a vinyl chloride polymer having excellent thermal stability without sacrificing productivity. And

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have produced a vinyl chloride polymer excellent in thermal stability with high productivity by using a specific vanadium compound and a specific aluminum compound. As a result, the present invention has been completed.

That is, the general formula V ⁱ (= O) _j Z _k
(Wherein i represents the oxidation number of the vanadium atom and is an integer of 2 to 5. j is 0 or 1. Z is a ligand, and an organic compound capable of binding to vanadium at a hetero atom. A ligand, a halogen ligand, an optionally substituted monocyclic hydrocarbon ligand, or an optionally substituted polycyclic hydrocarbon ligand, wherein a plurality of Z are the same or different Or two or more Z's may combine to form a ring with the vanadium atom in the formula as a member.k represents the number of ligands and is an integer of 1 to 5.)
Production of a vinyl chloride polymer, wherein a vinyl chloride monomer is polymerized in the presence of at least one vanadium compound (A) and at least one aluminum compound (B). Provide a method.

According to the production method of the present invention, a vinyl chloride polymer having extremely excellent thermal stability can be efficiently produced, so that its industrial value is very high. Moreover, according to this method, the amount of aluminoxane used is significantly less than that of the prior art.

・ Vanadium compounds:
The vanadium compound used in the present invention is a vanadium compound represented by the general formula (1). These compounds may be used alone or in combination of two or more.

  In the organic ligand that can be bonded to vanadium by the hetero atom represented by the ligand Z in the general formula (1), examples of the hetero atom include an oxygen atom, a sulfur atom, and a nitrogen atom. Examples of organic ligands that can be bonded to vanadium through a heteroatom include methoxy ligands, ethoxy ligands, n-propoxy ligands, isopropoxy ligands, n-butoxy ligands, isobutoxy ligands. Alkoxy ligands such as ligands, aryloxy ligands such as phenoxy ligands and naphthoxy ligands, acetylacetone ligands, carboxylate ligands, salicylaldoimine ligands, salen ligands, porphyrins A ligand etc. are mentioned, These may be substituted. Among these, an alkoxy ligand, an aryloxy ligand, a salicylaldoimine ligand, and a salen ligand are preferable, and these may be substituted.

  Moreover, as a halogen ligand represented by the ligand Z in General formula (1), a fluorine ligand, a chlorine ligand, a bromine ligand etc. are mentioned, for example.

  Furthermore, examples of the monocyclic hydrocarbon ligand or polycyclic hydrocarbon ligand which may be substituted represented by the ligand Z in the general formula (1) include, for example, a cyclopentadienyl ligand. , Indenyl ligand, and fluorenyl ligand. In view of enhancing the catalytic activity, k is preferably 4 or 5.

  Here, the catalytic activity means the activity of the vanadium compound as a catalyst, and is defined as the mass of the vinyl chloride polymer produced from 1 mol of the vanadium compound per unit time.

  Among the vanadium compounds, vanadium (V) oxytrialkoxide such as vanadium (V) oxytriethoxide, vanadium (V) oxysalen, and vanadium (IV) oxysalen are preferable, and they may be substituted.

  The concentration of the organic vanadium compound in the polymerization system in the present invention is not particularly limited, but the vanadium metal concentration is 0.01 to 100 mmol / L, preferably 1 to 10 mmol / L. If this concentration is too low, the yield tends to decrease. On the other hand, if it is too high, the effect of increasing the polymerization activity, polymerization rate and polymerization yield is saturated, and it cannot be said that the productivity is good.

Aluminum compound:
The aluminum compound in the present invention is preferably represented by the general formula AlX ₃ (wherein X is independently a halogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted alkoxy). Group or an aryloxy group which may be substituted.), An aluminum compound represented by the general formula {-Al (R ¹ ) O—} _p (wherein R ¹ is an alkyl which may be independently substituted) A cyclic aluminoxane having a structure represented by the general formula R ² {—Al (R ² ) O—} _q AlR ² ₂ (wherein R ² represents An alkyl group which may be independently substituted, q represents an integer of 1 or more) at least one aluminization selected from the group consisting of linear aluminoxanes having the structure Thing is.

Here, specific examples of the aluminum compound represented by the general formula AlX ₃ include trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum.

Then, having the general formula ^{-Al (R 1) _O-} cyclic aluminoxane having the structure represented by _p and the general formula _{^{R 2 {-Al (R 2)}} O-} structure represented by q ^AlR _{2 2} Specific examples of R ¹ and R ² in the linear aluminoxane include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl and neopentyl. p and q are integers of 1 or more, preferably 1 to 40. More preferably, R ¹ and R ² are methyl, ethyl, propyl, isobutyl, and p and q are integers of 3-20. However, since aluminoxane is relatively easy to cut and form the Al—O—Al bond constituting the main chain, the cyclic structure becomes a linear structure or the linear structure is changed with the passage of time or heat. It is easy to change to a cyclic structure, and p and q in the above formula are also likely to change. Accordingly, aluminoxane usually exists in a mixture of a cyclic structure and a linear structure having various chain lengths, and it is difficult to clearly identify the structure.

Among the aluminoxanes, methylaluminoxane, in which R ¹ or R ² is methyl, is particularly preferable. The methylaluminoxane is usually a mixture of a methylaluminoxane having a cyclic structure and a methylaluminoxane having a linear structure.

  Moreover, as the concentration of the aluminum compound, considering the catalytic activity, the molar ratio of the aluminum atom / vanadium atom is 0.1-100, preferably 0.5- The range is 10. If this molar ratio is too small or too large, the yield and catalytic activity tend to decrease.

  The production method of the present invention can be carried out by a general polymerization method such as a bulk polymerization method or a solution polymerization method. And there is no restriction | limiting in particular as a solvent at the time of performing solution polymerization, For example, alkanes, such as n-pentane, n-hexane, n-heptane, n-octane, n-isooctane, cyclohexane, methylcyclohexane, etc. Or alkyl aromatic hydrocarbons such as cycloalkane, toluene, xylene, ethylbenzene, mono- or dialkylnaphthalene, chloromethane, methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, chloronaphthalene, orthodichlorobenzene, etc. Examples include halogenated hydrocarbons, hydrogenated aromatic hydrocarbons such as tetrahydronaphthalene and decahydronaphthalene, high molecular weight liquid paraffin, or mixtures thereof. Among them, halogenated hydrocarbons can increase yield and catalytic efficiency. preferable.

  Here, the catalyst efficiency means the efficiency of the vanadium compound as a catalyst, and is defined as the number of moles of the vinyl chloride polymer produced from 1 mole of the vanadium compound.

  Although polymerization temperature is not specifically limited, For example, the range of -78 degreeC-100 degreeC can be selected. The polymerization reaction pressure is not particularly limited.

  The “vinyl chloride monomer” to be polymerized by the production method of the present invention is a vinyl chloride monomer alone or other vinyl copolymerizable with vinyl chloride monomer and vinyl chloride monomer. It may be a mixture of monomers. Examples of vinyl monomers copolymerizable with vinyl chloride monomer include olefin compounds such as ethylene and propylene, vinyl esters such as vinyl acetate and vinyl propionate, acrylic acid, and α-alkylacrylic acid. Unsaturated monocarboxylic acids or alkyl esters or amides thereof, unsaturated nitriles such as acrylonitrile, unsaturated dicarboxylic acids such as maleic acid or fumaric acid or alkyl esters thereof, anhydrides or N-substituted maleimides, vinyl methyl Ethers, vinyl alkyl ethers such as vinyl ethyl ether, vinylidene compounds such as vinylidene chloride, conjugated dienes such as butadiene and isoprene, non-conjugated dienes such as 1,5-hexadiene and 1,4-pentadiene, cyclohexene, norbornene Like cycloolefin Emissions, styrene, styrene derivatives, vinyl aromatic compounds such as N- vinyl carbazole, carbon oxides such as carbon monoxide and the like.

  In addition, as usual in the polymerization of vinyl chloride monomers, additives such as a heat stability improver, processability improver, and other modifiers may be appropriately added to the polymerization system.

  The vinyl chloride polymer obtained by the present invention can be used for conventional vinyl chloride polymer applications such as materials for molding into films, sheets and the like.

  EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Hereinafter, the measurement method and calculation method of the monomer etc. which were used by the Example and the comparative example, and a yield other characteristic are shown.

-Vinyl chloride monomer-
A commercially available product was used as the vinyl chloride monomer (hereinafter also abbreviated as VCM).

-Vanadium compounds-
Vanadium (V) oxytriethoxide was used without purifying a commercial product.

  V compound 1 (Example 9) was used after purifying a compound synthesized according to the document “Journal of the American Chemical Society, 108 (1986) 4088-4095”.

  V compound 2 (Example 10) was used after purifying a compound synthesized according to the document “Bulletin of the Chemical Society of Japan, 77 (2004) 1849-1854”.

-Aluminum compounds and radical initiators-
The aluminum compound / radical initiator was used without purifying a commercial product.

-Polymerization solvent-
The polymerization solvent was used after purification on calcium hydride.

-Yield of vinyl chloride polymer-
It calculated from the dry mass of the obtained vinyl chloride polymer.

-Calculation of catalyst efficiency-
Catalyst efficiency (%) = {[VCM (mol / L)] × (yield (%) ÷ 100) × 62.5} ÷ {[transition metal (mol / L)] × number average molecular weight (Mn)} × 100

-Calculation method of catalyst activity-
Catalytic activity (g-PVC / mol-transition metal · h) = {[VCM (mol / L)] ×
(Yield (%) ÷ 100) × 62.5} ÷ {[transition metal (mol / L)] × polymerization time (h)}

-Measurement of number average molecular weight and weight average molecular weight of vinyl chloride polymer-
The obtained vinyl chloride polymer was measured with a gel permeation chromatograph (manufactured by Tosoh Corporation) using tetrahydrofuran as a solvent and the number average molecular weight (Mn) and weight average molecular weight (Mw) in terms of polystyrene. did.

  Here, Mw / Mn was defined as molecular weight distribution.

-Thermal decomposition temperature of vinyl chloride polymer-
Using a thermobalance (trade name TG / DTA6200, manufactured by Seiko Denshi Co., Ltd.), the 5% mass reduction temperature measured at 10 ° C./min in a nitrogen stream was defined as the thermal decomposition temperature of the vinyl chloride polymer.

[Example 1]
Nitrogen-substituted glass reaction vessel was charged with 7 mL of vanadium (V) oxytriethoxide (14.3 mmol / L) diluted with n-hexane and 1 mL of trimethylaluminum (0.1 mol / L) diluted with n-hexane. It is. Thereafter, 2 mL (30 mmol) of vinyl chloride monomer obtained by vacuum distillation at −78 ° C. on calcium hydride was charged into the reaction vessel, and the reaction vessel was sealed under vacuum and adjusted to 50 ° C. The polymerization was started by dipping in a bath. When a reaction time of 24 hours passed, the vinyl chloride polymer was recovered by putting the polymerization reaction system into a large amount of methanol containing 5 vol% hydrochloric acid.

  Tables 1 and 2 show the polymerization conditions and the evaluation results of the obtained vinyl chloride polymer.

[Example 2]
The same procedure as in Example 1 was performed except that triethylaluminum was used instead of trimethylaluminum described in Example 1.

  Tables 1 and 2 show the polymerization conditions and the evaluation results of the obtained vinyl chloride polymer.

Example 3
The same procedure as in Example 1 was performed except that triisobutylaluminum was used instead of trimethylaluminum described in Example 1.

  Tables 1 and 2 show the polymerization conditions and the evaluation results of the obtained vinyl chloride polymer.

Example 4
In a glass reaction vessel purged with nitrogen, 7 mL of vanadium (V) oxytriethoxide (14.3 mmol / L) diluted with n-hexane and methylaluminoxane (PMAO) diluted with toluene (trade name: PMAO-S, Tosoh)・ Fine Chem Co., Ltd. (0.24 mol / L) 1 mL was charged. Thereafter, 2 mL (30 mmol) of vinyl chloride monomer obtained by vacuum distillation at −78 ° C. on calcium hydride was charged into the reaction vessel, and the reaction vessel was sealed under vacuum and adjusted to 50 ° C. The polymerization was started by dipping in a bath. When a reaction time of 24 hours passed, the vinyl chloride polymer was recovered by putting the polymerization reaction system into a large amount of methanol containing 5 vol% hydrochloric acid.

  Tables 1 and 2 show the polymerization conditions and the evaluation results of the obtained vinyl chloride polymer.

Example 5
The same procedure as in Example 3 was performed except that the dilute solvent of vanadium (V) oxytriethoxide was changed from n-hexane to toluene.

  Tables 1 and 2 show the polymerization conditions and the evaluation results of the obtained vinyl chloride polymer.

Example 6
The same procedure as in Example 3 was performed except that the diluting solvent for vanadium (V) oxytriethoxide was changed from n-hexane to carbon tetrachloride.

  Tables 1 and 2 show the polymerization conditions and the evaluation results of the obtained vinyl chloride polymer.

Example 7
A glass reaction vessel purged with nitrogen was charged with 7 mL of vanadium (V) oxytriethoxide (28.6 mmol / L) diluted with methylene chloride and 1 mL of triisobutylaluminum (0.1 mol / L) diluted with n-hexane. It is. Thereafter, 2 mL (30 mmol) of vinyl chloride monomer obtained by vacuum distillation at −78 ° C. on calcium hydride was charged into the reaction vessel, and the reaction vessel was sealed under vacuum and adjusted to 50 ° C. The polymerization was started by dipping in a bath. When a reaction time of 24 hours passed, the vinyl chloride polymer was recovered by putting the polymerization reaction system into a large amount of methanol containing 5 vol% hydrochloric acid.

  Tables 1 and 2 show the polymerization conditions and the evaluation results of the obtained vinyl chloride polymer.

Example 8
A glass reaction vessel purged with nitrogen was charged with 7 mL of vanadium (V) oxytriethoxide (14.3 mmol / L) diluted with methylene chloride and 1 mL of triisobutylaluminum (0.1 mol / L) diluted with n-hexane. It is. Thereafter, 2 mL (30 mmol) of vinyl chloride monomer obtained by vacuum distillation at −78 ° C. on calcium hydride was charged into the reaction vessel, and the reaction vessel was sealed under vacuum and adjusted to 50 ° C. The polymerization was started by dipping in a bath. When a reaction time of 24 hours passed, the vinyl chloride polymer was recovered by putting the polymerization reaction system into a large amount of methanol containing 5 vol% hydrochloric acid.

  Tables 1 and 2 show the polymerization conditions and the evaluation results of the obtained vinyl chloride polymer.

Example 9
In a glass reaction vessel purged with nitrogen, diluted with methylene chloride,

1,2-ethylenediamino-N, N′-bis (3 ′, 5′-di-tert-butylsalicylidene) oxovanadium (V) (abbreviated as V compound 1 in Table 1) (1 .43 mmol / L) and 7 mL of triethylaluminum (0.1 mol / L) diluted with n-hexane were charged. Thereafter, 2 mL (30 mmol) of vinyl chloride monomer obtained by vacuum distillation at −78 ° C. on calcium hydride was charged into the reaction vessel, and the reaction vessel was sealed under vacuum and adjusted to 50 ° C. The polymerization was started by dipping in a bath. When a reaction time of 24 hours passed, the vinyl chloride polymer was recovered by putting the polymerization reaction system into a large amount of methanol containing 5 vol% hydrochloric acid.

  Tables 1 and 2 show the polymerization conditions and the evaluation results of the obtained vinyl chloride polymer.

Example 10
In a glass reaction vessel purged with nitrogen, diluted with methylene chloride,

2-oxy-1,3-propanediamino-N, N′-bis (3 ′, 5′-di-tert-butylsalicylidene) oxovanadium (V) (in Table 1, V compound 2 and (Omitted) (1.43 mmol / L) 7 mL and triethylaluminum (0.1 mol / L) 1 mL diluted with n-hexane were charged. Thereafter, 2 mL (30 mmol) of vinyl chloride monomer obtained by vacuum distillation at −78 ° C. on calcium hydride was charged into the reaction vessel, and the reaction vessel was sealed under vacuum and adjusted to 50 ° C. The polymerization was started by dipping in a bath. When a reaction time of 24 hours passed, the vinyl chloride polymer was recovered by putting the polymerization reaction system into a large amount of methanol containing 5 vol% hydrochloric acid.

  Tables 1 and 2 show the polymerization conditions and the evaluation results of the obtained vinyl chloride polymer.

[Comparative Example 1]
A glass reactor substituted with nitrogen was charged with 8 mL of vanadium (V) oxytriethoxide (12.5 mmol / L) diluted with methylene chloride, and then the chloride obtained by vacuum distillation at −78 ° C. over calcium hydride. 2 mL (30 mmol) of vinyl monomer was charged into the reaction vessel, the reaction vessel was sealed under vacuum, and immersed in a thermostat adjusted to 50 ° C. to initiate polymerization. When the reaction had passed for 24 hours, the polymerization reaction system was put into a large amount of methanol containing 5 vol% hydrochloric acid.

  Tables 1 and 2 show the polymerization conditions and the evaluation results of the obtained vinyl chloride polymer.

[Comparative Example 2]
A glass reactor substituted with nitrogen was charged with 8 mL of triisobutylaluminum diluted with methylene chloride (12.5 mmol / L), and then 2 mL of vinyl chloride monomer obtained by vacuum distillation at −78 ° C. over calcium hydride. (30 mmol) was charged into the reactor, the reactor was sealed under high vacuum, and immersed in a thermostat adjusted to 50 ° C. to initiate polymerization. When the reaction had passed for 24 hours, the polymerization reaction system was put into a large amount of methanol containing 5 vol% hydrochloric acid.

  Tables 1 and 2 show the polymerization conditions and the evaluation results of the obtained vinyl chloride polymer.

[Comparative Example 3]
In a glass reaction vessel purged with nitrogen, 2 mL of triphenoxy (pentamethylcyclopentadienyl) titanium (15 mmol / L) diluted with toluene and methylaluminoxane (PMAO) diluted with toluene (trade name: PMAO-S, Tosoh 1 mL of Finechem Co., Ltd. (0.3 mol / L) was charged. After aging for 10 minutes at room temperature, toluene was removed under high vacuum. Thereafter, 8 mL of methylene chloride and 2 mL (30 mmol) of vinyl chloride monomer obtained by vacuum distillation at −78 ° C. over calcium hydride were charged into the reaction vessel, and the reaction vessel was sealed under vacuum at 50 ° C. The polymerization was started by immersing in a thermostat adjusted to 1. When the reaction time reached 48 hours, the vinyl chloride polymer was recovered by putting the polymerization reaction system into a large amount of methanol containing 5 vol% hydrochloric acid.

  Tables 1 and 2 show the polymerization conditions and the evaluation results of the obtained vinyl chloride polymer.

Example 11
In a glass reaction vessel substituted with nitrogen, 7 mL of vanadium (V) oxytriethoxide (14.3 mmol / L) diluted with n-hexane and 1 mL of triisobutylaluminum (0.1 mol / L) diluted with n-hexane were added. Prepared. Thereafter, 2 mL (30 mmol) of vinyl chloride monomer obtained by vacuum distillation at −78 ° C. over calcium hydride was charged into the reaction vessel, and the reaction vessel was sealed under vacuum to adjust to −25 ° C. The polymerization was initiated by immersion in a thermostatic bath. When a reaction time of 24 hours passed, the vinyl chloride polymer was recovered by putting the polymerization reaction system into a large amount of methanol containing 5 vol% hydrochloric acid.

  Tables 3 and 4 show the polymerization conditions and the evaluation results of the obtained vinyl chloride polymer.

[Comparative Example 4]
A nitrogen-substituted glass reaction vessel was charged with 0.379 mmol of lauroyl peroxide (LPO) (radical initiator) and 152 mmol of vinyl chloride monomer obtained by vacuum distillation at −78 ° C. over calcium hydride. The total volume was 10 mL. The reaction vessel was sealed under vacuum and immersed in a thermostat adjusted to 30 ° C. to initiate polymerization. When the reaction had passed for 12 hours, the polymerization reaction system was put into a large amount of methanol containing 5 vol% hydrochloric acid to recover the vinyl chloride polymer.

  Tables 3 and 4 show the polymerization conditions and the evaluation results of the obtained vinyl chloride polymer.

  The present invention is useful for producing a vinyl chloride polymer excellent in thermal stability with high productivity.

Claims (8)

General formula: V ⁱ (= O) _j Z _k
(Wherein i represents the oxidation number of the vanadium atom and is an integer of 2 to 5. j is 0 or 1. Z is a ligand, and an organic compound capable of binding to vanadium at a hetero atom. A ligand, a halogen ligand, an optionally substituted monocyclic hydrocarbon ligand, or an optionally substituted polycyclic hydrocarbon ligand, wherein a plurality of Z are the same or different Or two or more Z's may combine to form a ring with the vanadium atom in the formula as a member.k represents the number of ligands and is an integer of 1 to 5.)
Production of a vinyl chloride polymer, wherein a vinyl chloride monomer is polymerized in the presence of at least one vanadium compound (A) and at least one aluminum compound (B). Method.   Z of the vanadium compound (A) is at least one selected from the group consisting of an alkoxy ligand, an aryloxy ligand, a salicylaldoimine ligand, and a salen ligand, and they may be substituted. The method for producing a vinyl chloride polymer according to claim 1, which is good.   The vanadium compound (A) is at least one selected from the group consisting of vanadium (V) oxytrialkoxide, vanadium (V) oxysalen and vanadium (IV) oxysalen, which may be substituted. A method for producing a vinyl chloride polymer according to claim 1 or 2. The aluminum compound (B) has the general formula AlX ₃ (wherein X is independently a halogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxy group or a substituted group). An aryloxy group which may be substituted), an aluminum compound represented by the general formula {-Al (R ¹ ) O—} _p (wherein R ¹ independently represents an optionally substituted alkyl group). p represents an integer of 1 or more) and a general formula R ² {—Al (R ² ) O—} _q AlR ² ₂ (wherein R ² is independently substituted) 4 represents a good alkyl group, q represents an integer of 1 or more), and is at least one selected from the group consisting of linear aluminoxanes. Vinyl chloride Method of manufacturing a polymer.   The vinyl chloride heavy metal according to any one of claims 1 to 4, wherein the aluminum compound (B) is at least one selected from the group consisting of trimethylaluminum, triethylaluminum, triisobutylaluminum, and methylaluminoxane. Manufacturing method of coalescence.   The method for producing a vinyl chloride polymer according to any one of claims 1 to 5, wherein the polymerization is carried out in bulk or in a solvent.   The chlorination according to claims 1 to 6, wherein the polymerization is carried out in a solvent, and the solvent is at least one selected from the group consisting of toluene, n-hexane, methylene chloride, and carbon tetrachloride. A method for producing a vinyl polymer.   The method for producing a vinyl chloride polymer according to any one of claims 1 to 6, wherein the polymerization is performed in a solvent, and the solvent is a halogenated hydrocarbon.