JPH0335006A - Polymerization initiator and polymerization of vinyl chloride - Google Patents

Abstract

PURPOSE:To obtain a polymer having excellent heat stability and coloring properties in high yield by using a polymerization initiator containing a peracid ester having a specific structural formula. CONSTITUTION:For example, a polymerization initiator containing a peracid ester shown by the formula (R is 1-7C alkyl, etc., when n=1 or ethylene when n=2) prepared by a hydroperoxide such as t-butylhydroperoxide with a propanoic acid chloride such as 2(1,2-dimethylpropyl)-2-(2,2-dimethylpropyl) propanoic acid chloride in the presence of sodium hydroxide as a catalyst is used and a vinyl monomer, especially vinyl chloride is (co)polymerized (preferably 0.01-1 pt.wt. peracid ester is used based on 100 pts.wt. vinyl monomer) to give a (co)polymer having excellent physical properties.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a polymerization initiator for vinyl monomers consisting of a novel peracid ester, and more particularly to vinyl monomers, especially vinyl chloride monomers or vinyl chloride monomers. By using a specific polymerization initiator when polymerizing monomers copolymerizable with this monomer (hereinafter abbreviated as vinyl chloride monomers), a polymer with good physical properties can be obtained in high yield. This invention relates to a method for polymerizing vinyl chloride.

[Conventional technology]

Conventionally, t-butylperoxyneodecanoate (hereinafter abbreviated as BND) and bis(2-ethylhexyl) have been used as polymerization initiators when polymerizing vinyl chloride monomers.
Peroxydicarbonate (hereinafter abbreviated as opp)
, 3,5.5-trimethylhexanoyl peroxide (
Hereinafter, it is already known that information such as INFO (hereinafter abbreviated as INFO) is used. The temperature at which the half-life of a 0.1 molar solution in benzene is 10 hours (hereinafter abbreviated as 10-hour half-life temperature) is within the range of 40 to 65°C. Therefore, these require a relatively high polymerization temperature and have a major economical problem in that the polymerization is not completed unless they are used in a considerably large amount. In order to improve this point and to shorten the polymerization cycle and increase productivity, lower temperature active polymerization initiators such as diisobutyryl peroxide (hereinafter abbreviated as 1BPO) have been developed, which can be used alone or in conventional polymerization. It is used in combination with an initiator. Specifically, such low-temperature active polymerization initiators include I
BPO and acetylcyclohexylsulfonyl peroxide (hereinafter abbreviated as AC3P) (Japanese Patent Publication No. 40-16
No. 795), etc., the temperature in the 10 o'clock time range was 40°C.
These are as follows. On the other hand, Japanese Patent Publication No. 59-14481 describes a method for polymerizing vinyl monomers using tertiary alkyl peroxy esters. In this case, the acyl group side has 12 carbon atoms
a tertiary carboxyl group having up to 7 alkyl groups, of which at most one is a methyl group, and a tertiary alkyl peroxide whose alkyl peroxy side is an alkyl group or phenyl group having up to 7 carbon atoms; Examples thereof include BND and ξruberoxyneodecanoate (hereinafter abbreviated as CND). [Problems to be Solved by the Invention] However, the activity of conventional low-temperature active polymerization initiators was not sufficient, and the effect of shortening the polymerization time was small. From this point of view, a polymerization initiator that is more active at lower temperatures is desired. Also,
At the same time as such productivity improvement, emphasis has recently been placed on the quality of polymers, and a polymerization initiator that not only has high activity but also improves the quality of polymers is desired. As described above, conventional low-temperature active polymerization initiators each have problems in terms of productivity improvement and polymer quality improvement. That is, IBPO does not have long-lasting polymerization activity, and AC3
P had problems with hygiene due to decomposition products and poor thermal stability, such as coloring of the obtained polymer. In addition, special public authorities represented by BND and CND
The tertiary alkyl peroxy esters disclosed in Publication No. 481 are satisfactory in terms of thermal stability of the obtained polymers, but they are not sufficient in terms of low temperature activity compared to AC3P etc. It is desired that the polymer be active and have high polymerization efficiency. [Means for Solving the Problems] As a result of long-term research into the problems of the conventional low-temperature active polymerization initiators, the present inventors have found that by using a specific polymerization initiator, polymerization can be achieved with higher yields. The present invention was completed by confirming that coalescence was obtained and that the obtained polymer was excellent in thermal stability, particularly in colorability. That is, the present invention relates to the general formula (I), and - formula (II), (where n is 1, R is a linear or branched alkyl group having 1 to 7 carbon atoms, a phenyl group, a carbon number Represents a phenyl group substituted with 1 to 4 alkyl groups, and n is 2
In the case of R is ethylene group, ethynylene group, m- or p-
It relates to a polymerization initiator for vinyl monomers containing filtrate esters represented by the formulas (I) and (It), each alone or in a mixture, represented by the formulas (I) and (It). This is a polymerization method in which an organic peroxide, including one or a mixture thereof, is used as a polymerization initiator when polymerizing a vinyl chloride monomer. That is, the peracid ester of the present invention has a structure in which two branched alkyl groups having 5 carbon atoms are attached to the carbon (α-carbon) in contact with a carbonyl group, as shown in the above-mentioned formula (I), Or, as shown in formula (n) above, it has a structure in which a branched alkyl group having 4 and 6 carbon atoms is attached to the α-carbon, and the total number of carbon atoms including the carbonyl carbon is 13. It is a peroxyester of tertiary fatty acid, and is a new compound that has not been described in any literature. The present inventors have discovered that this peroxyester is extremely active at low temperatures compared to already known tertiary alkyl peroxyesters. That is, the 10-hour half-life temperature of the t-butylperoxy derivative is 38°C. In contrast, t-butylperoxy derivatives such as neooctanoate and neodecanoate have a 10-hour half-life temperature of 46-47°C. Therefore, the polymerization initiator of the present invention is
Consistent with the purpose of improving the productivity of polyvinyl chloride mentioned above,
It is a practically extremely effective polymerization initiator. Other vinyl monomers copolymerizable with the vinyl chloride monomer used in the present invention include, for example, ethylene, vinyl acetate, hnylidene chloride, styrene, acrylic esters,
These include methacrylic acid esters. The polymerization initiator used in the present invention is a peracid ester represented by the general formula (■) and the general formula (). Here, when n is l, R represents a linear or branched alkyl group having 1 to 7 carbon atoms, a phenyl group, or a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, and when n is 2, In this case, R represents an ethylene group, an ethynylene group, an m- or p-phenylene group. When n is 1, specific examples include t-butyl, t-aryl, t-hexyl, 1,1.3.3-tetramethylbutyl (hereinafter referred to as
(abbreviated as t-octyl), risal, p-methylcumyl, m-isopropyl cumyl, etc. When n is 2, specifically, 1,1,4.4-tetramethylbutylene , 1,1,4.4-tetramethyl-2-butynylene, α, α, α', α'-tetramethyl-m-xylylidene, α, α, α', α'-tetramethyl-p-xylylidene, etc. . Specific examples of peracid esters include t-butylperoxy-2-(I゜2-dimethylpropyl)-2-(2,2-dimethylpropyl)propanoate and t-hexyl from the general formula (I). Peroxy-2-(I,2-dimethylpropyl)-2-(2,2-dimethylpropyl)propanoate, t-octylperoxy-2-(I,2
-dimethylpropyl)-2-(2,2-dimethylpropyl)propanoate, mainly ruberoxy-2-(I゜2
-dimethylpropyl)-2-(2,2-dimethylpropyl)propanoate, α-(2-(I゜2-dimethylpropyl)-2-(2,2-dimethylpropyl)propanoyl)isopropyl-4-methylbenzene, α-(2-
(I,2-dimethylpropyl)-2-(2,2-dimethylpropyl)propanoyl)-p-diisopropylbenzene, α,α'-bis(2-(I,2-dimethylpropyl)-2-(2, Examples include 2-dimethylpropyl)-propanoyl)-m-diisopropylbenzene. Furthermore, from the general formula (■), t-butylperoxy-
2-(2-methylpropyl)-2-(I゜2.2-)limethylpropyl)propanoate, t-amylberoxy-2-(2-methylpropyl)-2-(I,2,2-
)limethylpropyl)propanoate, t-octylperoxy-2=(2-methylpropyl)-2-(I,
2,2-1-limethylpropyl)propanoate, 2-(2-methylpropyl)-2-(I
゜2.2-)limethylpropyl)propanoate, α-
(2-(2-methylpropyl)-2-(I゜2.2-trimethylpropyl)propanoyl)m-diisopropylbenzene, α,α'-bis(2-(2-methylpropyl')-2-(I , 2,2-trimethylpropyl)-propanoyl)-p-diisopropylbenzene, and the like. These can be obtained, for example, as follows. That is, t-butyl hydroperoxide, t-arhydroperoxide, t-hexyl hydroperoxide, t-
- octyl hydroperoxide, cumyl hydroperoxide, meta- and para-diisopropylbenzene monohydroperoxides, each alone or a mixture of two thereof, meta- and para-diisopropylbenzene dihydroperoxide, each alone or a mixture of two thereof; a hydroperoxide selected from 2- (I゜2-
dimethylpropyl)-2-(2,2-dimethylpropyl)propanoyl chloride or 2-(2-methylpropyl)-2-(I,2,2-)dimethylpropylpropanoyl chloride alone or in a mixture thereof. It is obtained under the same reaction conditions as conventional peroxy esters using sodium hydroxide, potassium hydroxide, or a main group such as pyridine as a catalyst. That is, aromatic hydrocarbons (e.g., toluene, ethylbenzene) or aliphatic hydrocarbons (e.g., hexane,
Octane, petroleum naphtha, mineral spirits, product name:
It can be used by diluting it after synthesis, or by diluting it after synthesis. Incidentally, the reaction temperature is approximately 0°C to 30°C. 2-(I,2-dimethylpropyl)-2 used in the present invention
-(2,2-dimethylpropyl)propanoyl chloride or 2-(2-methylpropyl)-2-(I,2,2-
) Dimethylpropylpropanoyl chloride is 2-
(I,2-dimethylpropyl)-2-(2,2-dimethylpropyl)propanoic acid or 2-(2-methylpropyl)-2-(I,2,2-)dimethylpropyl)propanoic acid with a chlorinating agent , for example, P, C13, POC13, S. The acid chloride product can be made by isolating the acid chloride product from the reaction mixture after reacting C12, phosgene, etc. Here, the raw material 2-(I,2-dimethylpropyl)-2
-(2,2-dimethylpropyl)propanoic acid or 2-(
2-Methylpropyl)-2-(I2,2-)dimethylpropyl)propanoic acid is available under the trade name “Equasisod 13”.
You may use the one manufactured by Idemitsu Petrochemical Company. The amount of the polymerization initiator represented by the above-mentioned formula used in the present invention is generally from o, oot to 2 parts by weight in terms of pure product, based on 100 parts by weight of the vinyl chloride monomer.
Preferably it is 0.01-1 part by weight. The amount is o, o
If the amount is less than oi parts by weight, the polymerization rate tends to be slow. Moreover, if it exceeds 2 parts by weight, it becomes difficult to control the polymerization reaction and the physical properties of the obtained polymer tend to deteriorate, which is not preferable. The specific polymerization initiators of the present invention may be used alone or as a mixture for polymerization at relatively low temperatures to obtain polyvinyl chloride with a high degree of polymerization. For polymerization at relatively high temperatures for the purpose of improving
It can also be used in combination with other conventionally used peroxyesters, peroxydicarbonates, diacyl peroxides, and azobis-based polymerization initiators. Specifically, the peroxyesters include BND,
Examples include t-butylperoxyneohexanoate, t-butylperoxypivalate, t-hexylperoxypivalate, t-octylperoxyneodecanoate, etc. Peroxydicarbonates include OPP
, di(2-ethoxyethyl) peroxydicarbonate, di-n-propylperoxydicarbonate, diisopropylperoxydicarbonate, etc., and diacyl peroxides include IBPo, INPO, lauroyl peroxide, octanoyl peroxide, etc. . Furthermore, specific examples of azobis-based polymerization initiators include azobisisobutyronitrile and the like. The polymerization method used in the present invention is usually a suspension polymerization method, but there is no problem with ordinary formulations other than the use of the polymerization initiator in the present invention. The polymerization temperature is generally 10-75°C, preferably 30-75°C.
The temperature range is 60°C. If the polymerization temperature is less than 10°C, the polymerization time tends to be long, and if it exceeds 75°C, the life of the polymerization initiator will be shortened, making it difficult to reach a high polymerization conversion rate, which is not preferred.

【Example】

Hereinafter, the present invention will be specifically explained with reference to Examples. Synthesis Example 1 (2-(I,2-dimethylpropyl)-2-(2゜2-
dimethylpropyl)propanoyl chloride and 2-(2
-Methylpropyl)-2-(I,2゜2-trinotylpropyl)propanoyl chloride mixture) In a 300 m 14-day round bottom flask equipped with a thermometer and a cooling tube with a drying tube, a Multi-branched saturated tertiary fatty acid with a total of 13 carbon atoms [Product name: E-acid 13J
, 2-(I,2-dimethylpropyl')-2-(2,
Add 214.4 g of a mixture of 2-dimethylpropyl)propanoic acid and 2-(2-methylpropyl)-2-(I,2,2-trinotylpropyl)propanoic acid, and heat to room temperature while stirring with a magnetic stirrer. Phosphorus trichloride 54.9
g was added. Further, while stirring, the liquid temperature was raised to 75°C to reflux the phosphorus trichloride, and this was maintained for 2 hours. Thereafter, heating was stopped and the mixture was cooled to room temperature. After separating the phosphoric acid, the remaining phosphorus trichloride was distilled off under reduced pressure to obtain 230.5 g of acid chloride. The amount of chlorine in the obtained acid chloride was 15.2%, and the calculated purity was 99.8%. This product was used as an acid chloride in the following synthesis of peracid ester. Hereinafter, the chloride of this mixed acid ("Efuacid 13") will be simply abbreviated as neotridecanoic acid chloride, and the filtered acid ester derived from this chloride will be abbreviated as peroxyneotridecanoate. Synthesis Example 2 (Synthesis of t-butylperoxyneotridecanoate) 35% potassium hydroxide water was added to a 200m 14th flask equipped with a stirrer. 48.1 g of liquid g was added thereto, and 20.1 g of 98.4% t-butyl hydroperoxide was added while stirring and maintaining the liquid temperature at 15°C. Further, 46.7 g of neotridecanoic acid chloride obtained in Synthesis Example 1 (obtained by chlorinating the above "Efuacid 13") was added dropwise over 8 minutes while stirring and keeping the liquid temperature at 20°C. After raising the liquid temperature to 25° C. and continuing stirring for 1 hour, 70 g of cold water was added and stirring was further continued for 5 minutes. The aqueous phase was separated, washed with 50 g of a 5% aqueous sodium hydroxide solution, and then washed three times with water. This solution was dried over anhydrous magnesium sulfate. As a result, 45.2 g of a product was obtained as a colorless transparent liquid. The amount of active oxygen was 5.39%, the purity was calculated to be 96.5%, and the yield was 76.1 mol%. Synthesis Example 3 (Synthesis of other perneotridecanoate esters) Synthesis was carried out in the same manner as in Synthesis Example 1, except that various hydroperoxides of Jl were used instead of t-butyl hydroperoxide. An ester was obtained. All the obtained substances were colorless liquids. t-Hexylperoxyneotridecanoate purity 95
．． 7%, yield 75.9% t-octylperoxyneotridecanoate purity 94
．． 1%, yield $78.0% Reperoxy neotridecanoate purity 94.4%
, yield 74.7% α-(neotridecanoylperoxy)-diisopropylbenzene (mixture of 45% meta form and 55% para form) Purity 93.9%, yield 70.8% α,α′-bis (Neotridecanoylperoxy)-diisopropylbenzene (mixture of 37% meta form and 63% para form) Purity 95.2%, yield 73.3% Example 1 In a stainless steel autoclave with a capacity of 400 m1, 200 m1 of ion-exchanged water was placed. and 0.1 part by weight of polyvinyl alcohol were added and melted. Next, after adding 0.05 parts by weight of t-butylperoxyneotridecanoate (hereinafter abbreviated as BNT) obtained in Synthesis Example 2 in terms of pure product, -
The mixture was cooled to 80° C. or below, and 100 parts by weight of vinyl chloride i-mer was added. After the space in the autoclave was sufficiently replaced with nitrogen gas, it was sealed tightly. It was immersed in a constant temperature water bath kept at 50° C. for 8 hours to polymerize. Stirring was performed by rotating the autoclave in a water bath at 32 r, p, m. After polymerization, the mixture was cooled and unreacted vinyl chloride monomer was removed, and the resulting white powder was washed twice with 100 SO1 water and then dried in vacuo. The yield of vinyl chloride polymer was 83% based on weight. As a thermal stability test of the obtained vinyl chloride polymer, the following coloring test was conducted. The results are shown in Table-1. (Colorability test) 100 parts by weight of vinyl chloride polymer, 1 dioctyl utare
50 parts by weight and 2.5 parts by weight of dibutyltin malate were mixed and kneaded for 10 minutes on a roll at 160°C.
A thick sheet was taken out, and the degree of coloring of the sheet was visually observed. Example 2 Vinyl chloride monomer was polymerized in the same manner as in Example 1, except that the amount of BNT used as a polymerization initiator and the polymerization temperature were changed. The results are shown in Table-1. Example 3 Vinyl chloride monomers were prepared in the same manner as in Example 1, except that t-hexylperoxyneotridecanoate (hereinafter abbreviated as HNT) obtained in Synthesis Example 2 was used instead of BNT as a polymerization initiator. Polymerization was carried out. The results are shown in Table-1. Examples 4 to 7 As shown in Tables 1 and 2, t-octylperoxyneotridecanoate (hereinafter abbreviated as ○NT) obtained in Synthesis Example 3 was used instead of BNT as a polymerization initiator. Primarily luperoxyneotridecanoate (hereinafter abbreviated as CNT), α-(neotridecanoylperoxy)-diisopropylbenzene (mixture of meta and para forms) (hereinafter referred to as
Example 1 was carried out, except that α,α′-bis(neotridecanoylperoxy)-diisopropylbenzene (mixture of meta and para forms) (hereinafter abbreviated as DIBNT) was used. Polymerization of vinyl chloride monomer was carried out. These results are shown in Table-1 and Table-2. Example 8.9 Polymerization of vinyl chloride monomers was carried out in the same manner as in Example 1, except that the amount of DIBNT used as a polymerization initiator and the polymerization temperature were changed. These results are shown in Table 2. Examples 10-12 As shown in Table 3, 0NTO,
Polymerization of vinyl chloride monomer was carried out in accordance with Example 1, except that in addition to 0.03 parts by weight, conventionally used polymerization initiators BND, OPP, and INPO were each used in amounts of 0.03 parts by weight. The results are shown in Table 3. Example 13 As shown in Table 3, 0NTO,
Using 0 parts of Tffi, and 100 parts of vinyl chloride monomer
Polymerization was carried out according to Example 1, except that 90 parts by weight of vinyl chloride monomer and 10 parts by weight of vinyl acetate monomer were used instead of parts by weight. The results are shown in Table-3. Comparative Examples 1 to 3 Vinyl chloride was polymerized according to Example 1, except that conventionally used IBPO, AC3P, and CND were used instead of BNT as the polymerization initiator. These results are shown in Table-4. Comparative Examples 4 to 6 As shown in Table 4, ○PP0.
In addition to 03 parts by weight, conventionally used IBPO,
Polymerization of vinyl chloride monomers was carried out in the same manner as in Example 1, except that 0.03 parts by weight of each of AC3P and CND was used. These results are shown in Table-4. Table-1 Table-2 Table-3 Table-4 The abbreviations in Tables-1 to Table-4 above have the following meanings. (I): Pure product conversion value (parts by weight) (2): Polymerization time is 8 hours or more.As is clear from Tables 1 to 4, conventional polymerization initiators (IBP○, AC3P and C.N.
In the method using D), even when used alone or in combination with other polymerization initiators, the polymer yield is low or the heat resistance (coloring property) of the obtained polymer is poor. On the other hand, in the method using the polymerization initiator of the present invention, a polymer with good physical properties can be obtained in good yield. [Effects of the Invention] As detailed above, according to the present invention using a specific polymerization initiator, the virgin quality of the obtained polymer is better than that of a method using a conventional polymerization initiator (for example, AC3P). , it has an excellent effect in that it is not particularly colored. Also,
The persistence of polymerization activity is higher than that using conventional polymerization initiators (e.g., [BP○), and the polymerization rate is faster than that of methods using conventional polymerization initiators (e.g., CND). As a result, it has the advantage of increasing the polymer yield.

Claims (1)

[Claims] 1. There are the following general formulas (I), ▲mathematical formulas, chemical formulas, tables, etc.▼(I) (Here, when n is 1, R is a straight chain with 1 to 7 carbon atoms or represents a branched alkyl group, a phenyl group, a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms; when n is 2, R represents an ethylene group, an ethynylene group, an m- or p-phenylene group); A polymerization initiator for vinyl monomers containing the peracid ester shown. 2. The following general formula (II), ▲Mathematical formulas, chemical formulas, tables, etc.▼(II) (Here, when n is 1, R is a linear or branched alkyl group having 1 to 7 carbon atoms, Phenyl group, represents a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, and n is 2
In the case of R is ethylene group, ethynylene group, m- or p-
A polymerization initiator for vinyl monomers containing a peracid ester (representing a phenylene group). 3. General formula (I), ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) and General formula (II), ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) (Here, if n is 1 , R represents a linear or branched alkyl group having 1 to 7 carbon atoms, a phenyl group, or a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, and n is 2
In the case of R is ethylene group, ethynylene group, m- or p-
A polymerization initiator for vinyl monomers containing a mixture of peracid esters (representing a phenylene group). 4. When polymerizing vinyl chloride monomers or vinyl chloride monomers and monomers copolymerizable with them, the above general formula (I), ▲mathematical formula, chemical formula, table, etc. are available as polymerization initiators▼( I) (Here, when n is 1, R represents a linear or branched alkyl group having 1 to 7 carbon atoms, a phenyl group, or a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, and n is 2
In the case of R is ethylene group, ethynylene group, m- or p-
A method for polymerizing vinyl chloride, characterized by using an organic peroxide containing a peracid ester represented by (representing a phenylene group). 5. When polymerizing a vinyl chloride monomer or a vinyl chloride monomer and a monomer copolymerizable therewith, general formula (II)
, ▲Mathematical formulas, chemical formulas, tables, etc.▼(II) (Here, when n is 1, R is a linear or branched alkyl group with 1 to 7 carbon atoms, a phenyl group, or a phenyl group with 1 to 4 carbon atoms. Represents a phenyl group substituted by an alkyl group, where n is 2
In the case of R is ethylene group, ethynylene group, m- or p-
A method for polymerizing vinyl chloride, characterized by using an organic peroxide containing a peracid ester represented by (representing a phenylene group). 6. When polymerizing a vinyl chloride monomer or a vinyl chloride monomer and a monomer copolymerizable therewith, the general formula (I
), ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) and general formulas (II), ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) (Here, if n is 1, R is the number of carbon atoms 1 Represents a phenyl group substituted with a straight-chain or branched alkyl group of up to 7, a phenyl group, or an alkyl group having 1 to 4 carbon atoms, and n is 2
In the case of R is ethylene group, ethynylene group, m- or p-
A method for polymerizing vinyl chloride, which comprises using an organic peroxide containing a mixture of peracid esters represented by (representing a phenylene group).