JPH04139165A - 1-cyclohexyl-1-methylethylperoxyneoalkanoate and its use - Google Patents

Abstract

NEW MATERIAL:A compound expressed by the formula (R1 to R3 are 1-9C alkyl and total of carbon number of R1 to R3 is 3-11). EXAMPLE:1-Cyclohexyl-1-methylethylperoxypyvalate. USE:A polymer initiator of vinyl-based monomer, capable of enhancing polymerization rate because of short half-life period and enabling shortening of polymerization cycle time and increase of production volume. The obtained polymer is free from coloring and smell. PREPARATION:For example, a carboxylic acid chloride is reacted with 1- cyclohexyl-1-methylethylhydroperoxide using sodium hydroxide, potassium hydroxide or an amine such as pyridine as a catalyst to provide the compound expressed by the formula.

Description

[Detailed description of the invention]

[0001]

[Industrial application field]

The present invention relates to a novel peroxyester, 1-cyclohexyl-1-methylethyl peroxyneoalkanoate, which is a novel peroxyester, and is based on a vinyl monomer such as M
It relates to use as a polymerization initiator for (meth)acrylic esters such as MA, vinyl chloride, vinyl acetate, etc. [0002]

[Conventional technology]

Conventionally, when polymerizing a vinyl monomer alone or a mixture with a vinyl monomer copolymerizable with it, various organic peroxides and azoisobutyronitrile (hereinafter abbreviated as AIBN) have been used as polymerization initiators. A method using an azo compound such as [0003] For example, in the polymerization of vinyl chloride monomers, diisobutyryl peroxide (hereinafter referred to as I
BPO) and acetylcyclohexylsulfonyl peroxide (hereinafter abbreviated as AC3P) described in Japanese Patent Publication No. 40-16795, etc.
Cumylperoxyneodecanoate (hereinafter abbreviated as CND) described in Publication No. 8-120611, and paramental peroxyneodecanoate (hereinafter referred to as PM
Compounds such as peracid esters (abbreviated as ND) in which the alpha carbon of the carboxylic acid is tertiary have been known. [0004] In addition, t-butylperoxypivalate (hereinafter referred to as B
It has been known to use paramenthane peroxypivalate (hereinafter abbreviated as PMPV) or AIBN for the polymerization of vinyl acetate monomers. [0005]

[Problem to be solved by the invention]

However, the methods for polymerizing vinyl chloride monomers using IBP◯, AC3P, CND and PMND as polymerization initiators each have their own problems. That is, IBPO is very unstable in water and decomposes when it comes into contact with water, so its polymerization activity is not sustainable, and as a result, the yield of the polymer is low. Furthermore, AC3P had problems regarding hygiene due to decomposition products and poor thermal stability, such as coloring of the obtained polymer. CND had the disadvantage that the polymer had a characteristic odor due to decomposition products caused by cumyl peroxy groups. Furthermore, P
MND had the disadvantage that the polymer had a terpene odor. [0006] In addition, in a method for polymerizing vinyl acetate monomers using AIBN as a polymerization initiator, polyvinyl acetate with a high degree of polymerization can be obtained, but the resulting polymer has poor thermal stability such as coloring. Ta. In the polymerization of (meth)acrylic acid ester monomers using BPV as a polymerization initiator, there are almost no problems with the physical properties of the resulting polymer, but the drawbacks are that the polymerization activity is somewhat low and the yield of the polymer is low. was there. Furthermore, when PMPV was used as a polymerization initiator, there was a problem in that the polymer had a terpene odor. Moreover, in the polymer industry, it is desired to increase the productivity of polymers for economic reasons, and active polymerization initiators continue to be required to shorten reaction times and increase production capacity. . An object of the present invention is to provide a polymerization initiator that is free from polymer discoloration and odor, and has a high yield. [0007]

[Means to solve the problem]

The present invention was proposed to solve these objects, and the first aspect of the present invention is to solve the following general formula (1).

[2] 1-cyclohexyl-1-methyl represented by Concerning ethyl peroxy neoalkanoates, the second aspect of the invention concerns the use of these peroxy esters in the polymerization of vinyl monomers. Note that the upper limit of the number of carbon atoms for R1 to R3 of the peroxyester represented by the first general formula (1) of the present invention is determined in consideration of practicality. Usually R1, R2 and R3 are each an alkyl group having up to 9 carbon atoms, and the total of R1, R2 and R3 is 1
Up to 1. [0008] Specific examples of the peroxyester of the present invention include 1
-Cyclohexyl-1-methylethylperoxypivalate, 1-cyclohexyl-1-methylethylperoxyneohexanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, 1-cyclohexyl -1-methylethylperoxyneodecanoate,
1-cyclohexyl-1-methylethyl peroxyneohexanoate and the like. The peroxyester of the present invention can be obtained according to conventional methods, for example, as follows. That is, carboxylic acid chloride and 1-cyclohexyl-
1-Methyl ethyl hydroperoxide is obtained using sodium hydroxide or potassium hydroxide or amines such as pyridine as a catalyst under reaction conditions similar to those for conventional peroxyesters [0009] That is, aromatic hydrocarbons, e.g. , toluene, ethylbenzene, or aliphatic hydrocarbons such as pentane, hexane, octane, petroleum naphtha, mineral spirits, or isoparaffin-based aliphatic hydrocarbons (for example, trade name "Shellzol"; manufactured by Shell Chemical Company)
It can be synthesized using the following methods or diluted after synthesis. Note that the reaction temperature is about -10°C to 30°C. The carboxylic acid chloride used in the present invention can be prepared by reacting a carboxylic acid with a chlorinating agent such as PCl, POCl, SOCl2, etc., and then isolating the acid chloride product from the reaction mixture. [0010] Specific examples of the carboxylic acid used in the present invention include pivalic acid, neoheptanoic acid, neooctanoic acid, neononanoic acid,
Neodecanoic acid, neotridecanoic acid (the latter five acids are carboxylic acids generally referred to as "neo acids" in which the α-carbon atom of the carboxylic acid is completely replaced by an alkyl group, each with a total number of carbon atoms of 7) .8.910.13 is an isomer mixture of carboxylic acids). 1-Cyclohexyl-1-methylethyl hydroperoxide used in the present invention can be prepared using a strong acid catalyst such as sulfuric acid,
Sunic acid, perchloric acid, acid form of ion exchange resin or p-
1 In the presence of luenesulfonic acid, hexahydro-
It can be made by treating alpha-cumyl alcohol with excess hydrogen peroxide. [0011] The second aspect of the present invention is that when polymerizing a (meth)acrylic acid ester such as MMA, a vinyl monomer such as vinyl chloride, vinyl acetate, etc. alone or a mixture thereof, the above general formula is used as a polymerization initiator. The specific peroxyester shown in (1) is used alone, or the temperature at which the half-life is 10 hours in a 0.1 molar solution in benzene is 30 to
This is a method for polymerizing vinyl monomers, which is characterized in that it is used in combination with a polymerization initiator consisting of at least one of peroxyesters, diacyl peroxides, and peroxydicarbonates in the range of 65°C. [0012] Vinyl monomers for which the polymerization initiator of the present invention is used include, for example, vinyl chloride, ethylene, vinyl acetate, vinylidene chloride, styrene, methacrylic acid, acrylic acid, methyl methacrylate, methyl acrylate, These include methacrylic acid amide and acryl amide. The amount of the polymerization initiator used in the present invention is generally 0 parts by weight based on 100 parts by weight of the vinyl monomer.
．． 001 to 1 part by weight, preferably 0.01 to 0.001 to 1 part by weight.
5 parts by weight. If the amount is less than 0.001 part by weight, the polymerization rate tends to be slow. Moreover, if it exceeds 1 part by weight, it becomes difficult to control the polymerization reaction and the physical properties of the resulting polymer tend to deteriorate, which is not preferable. [0013] The polymerization initiator used in combination in the present invention is at least one of peroxyesters, diacyl peroxides, and peroxydicarbonates having a 10-hour half-life temperature of 30 to 65°C. Specific peroxyesters include t-butyl peroxypivalate (55℃), END (46.5℃)
, CND (36,6°C), diacyl peroxides such as IBP○ (32,5°C), 3,5.5-)limethylhexanoyl peroxide (59,5°C), lauroyl peroxide (62°C), octa Noyl peroxide (62°C), etc., and peroxydicarbonate includes di(2-ethylhexyl) peroxydicarbonate (hereinafter abbreviated as ○PP) (434°C).
n-propyl peroxydicarbonate (40.5°C)
Diisopropyl peroxydicarbonate (40,5
℃) etc. [0014] The amount of these polymerization initiators added may be selected as appropriate, and is usually 174 to 4 times the amount of 1-cyclohexyl-1-methylethyl peroxyneoalkanoate added. The polymerization methods used in the present invention include suspension polymerization, solution polymerization, and emulsion polymerization, but there are no problems with ordinary formulations except for the use of the polymerization initiator according to the present invention. The polymerization temperature is generally 10-75°C, preferably 30°C.
The temperature range is ~60°C. If the polymerization temperature is less than 10°C, the polymerization time tends to be long, whereas if it exceeds 75°C, the life of the polymerization initiator will be shortened and it will be difficult to reach a high polymerization conversion rate, which is not preferable. However, in order to reduce the amount of residual vinyl monomer as much as possible, there are some formulations in which post-polymerization is carried out by polymerizing at 10 to 75 degrees Celsius and then raising the temperature to about 120 degrees Celsius. It is also possible to carry out the polymerization by raising the temperature to about 120° C. at the same time as starting the polymerization. [0015]

【Example】

Hereinafter, the present invention will be specifically explained with reference to Examples. Example 1 283 g of a 35% aqueous potassium hydroxide solution was placed in 14 200 m Lof flasks equipped with a stirrer, and the temperature of the solution was adjusted to 20°C while stirring.
17.9 g of 95% 1-cyclohexyl-1-methylethyl hydroperoxide and 10 g of hexane while maintaining
A mixture of was added. Furthermore, 19.1 g of neodecanoyl chloride was added dropwise over 10 minutes while stirring and maintaining the liquid temperature at 20°C. After stirring was continued for 3 hours while maintaining the liquid temperature at 20° C., 20 g of cold water was added and further stirred for 5 minutes. The aqueous phase was separated, washed with 20 g of a 5% aqueous sodium hydroxide solution, and then washed three times with water. After drying this solution over anhydrous magnesium sulfate, hexane was removed under vacuum to obtain 24.1 g of the desired product as a colorless liquid. The amount of active oxygen is 4.83%, and the purity is 9 by calculation.
The yield was 4.3%, and the yield was 73 mol%. The identity of this material was confirmed by IR and NMR spectra. The results are shown in (Table 1). [0016] [0017] Furthermore, the thermal decomposition rate was measured using benzene as a solvent. (Concentration: 0.1 mol/1). As a result, the 10-hour half-life temperature (Tlo) of this peroxyester was 41°4°C. [0018] Example 2 (Synthesis of 1-cyclohexyl-1-methylethyl peroxypivalate) Synthesis was carried out in the same manner as in Example 1 except that pivalic acid chloride was used as the carboxylic acid chloride. I got something. The identity of this material was confirmed by IR and NMR spectra. The results are shown in (Table 1). Furthermore, the thermal decomposition rate was measured in the same manner as in Example 1. As a result, the 10-hour half-life temperature of this peroxyester was 49.1°C. Example 3 (Synthesis of 1-cyclohexyl-1-methylethyl peroxyneohexanoate) Synthesis was carried out in the same manner as in Example 1 except that neohexanoyl chloride was used as the carboxylic acid chloride, and the target product as a colorless liquid was obtained. Obtained. The identity of this material was confirmed by MR and NMR spectra. The results are shown in (Table 1). Furthermore, the thermal decomposition rate was measured in the same manner as in Example 1. As a result, the 10-hour half-life temperature of this peroxyester was 46.2°C. [0019] Example 4 (Synthesis of 1-cyclohexyl-1-methylethylheloxyneononanoate The synthesis was carried out in the same manner as in Example 1, except that neononanoyl chloride obtained by The thermal decomposition rate was measured by the method.As a result, the 10-hour half-life temperature of this peroxyester was 40.5°C.Example 5 (1-cyclohexyl-1-methylethylperoxyneoalkanoate Synthesis) Synthesis was carried out in the same manner as in Example 1, except that neotridecanoic acid chloride obtained by chlorinating neotridecanoic acid (fatty acid manufactured by Idemitsu Petrochemical Co., Ltd., trade name "Efuacid 13") was used as the carboxylic acid chloride. The target product as a colorless liquid was obtained. The results are shown in Table 1. [00201] Furthermore, the thermal decomposition rate was measured in the same manner as in Example 1. As a result, the 10-hour half-life of this peroxyester was The temperature was 40.9° C. From this result, the 1-cyclohexyl-1-methylethyl peroxyneoalkanoate of the present invention was found to be more effective than the prior art t-alkyl peresters derived from the same carboxylic acid. [0021] (Polymerization of vinyl chloride) Example 6 In a stainless steel autoclave with a volume of 400 ml, 200 ml of ion-exchanged water and 0.1 part by weight of polyvinyl alcohol were placed and dissolved. Next, 1-cyclohexyl-1-methylethyl peroxyneodecanoate (hereinafter abbreviated as CMEND) obtained in Example 1 was converted to 0.0 in terms of pure product.
After adding 7 parts by weight, the mixture was cooled to -80°C or lower, and 100 parts by weight of vinyl chloride monomer 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 maintained at 45° 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 to remove unreacted vinyl chloride monomer, and the resulting white powder was washed twice with 100 ml of water and then dried in vacuo. The yield of vinyl chloride polymer was 84% based on weight, and the average degree of polymerization was 2020. The obtained vinyl chloride polymer was tested for thermal stability, and the coloring test shown below was conducted, and at the same time, the odor was also investigated. The respective results are shown in (Table 2). [0022]

[Table 2] (Colorability test and odor) 100 parts by weight of vinyl chloride polymer, 2.5 parts by weight of dibutyl tin maleate, 80 parts by weight of dioctyl phthalate as a plasticizer
Parts by weight were mixed, kneaded for 10 minutes on a roll at 160°C, a 1 mm thick sheet was taken out, and the degree of coloring of the sheet was visually observed using G2. At the same time, the odor of the sheet was examined when it was taken out. Example 7.8 Polymerization of vinyl chloride monomer was carried out in the same manner as in Example 6 except that the amount of the polymerization initiator CMEND and the polymerization temperature were changed.The results are shown in Table 1. 2). Example 9 In Example 6, CMENDo, 07 was used as a polymerization initiator.
Change in weight part ECMENDo, 03 weight part and ○PP0
．． Polymerization of vinyl chloride monomer was carried out in accordance with Example 6 except that 03 parts by weight was used. These results are shown in (Table 2). Example 10 In Example 9, IB was used instead of ○PP as a polymerization initiator.
Polymerization of vinyl chloride monomer was carried out in accordance with Example 9, except that 0.03 parts by weight of PO was added to 03 parts by weight of CMENDo. These results are shown in Table 2. [0024] Example 11 In Example 6, 90 parts by weight of vinyl chloride monomer and 10 parts by weight of vinyl acetate monomer were used instead of 100 parts by weight of vinyl chloride monomer.
Polymerization was carried out according to Imaginary Example 6, except that the polymerization temperature was 50°C.These results are shown in Table 2.
Shown below. Comparative Example 1 CMENDo, 07 was used as a polymerization initiator in Example 6.
The vinyl chloride monomer was polymerized according to Example 6, except that 0.07 parts by weight of IBPO was used instead of 0.07 parts by weight. These results are shown in (Table 2). Comparative Example 2.3.4 CMENDo, 07 as a polymerization initiator in Example 6
Polymerization of vinyl chloride monomer was carried out in the same manner as in Example 6, except that 0.07 parts by weight of each of AC3P, CND, and PMND was used instead of 0.07 parts by weight. These results are shown in Table 2. As is clear from the above (Table 2), compared to the method using a conventional polymerization initiator as a polymerization initiator, the method using the polymerization initiator of the present invention yields a polymer with good physical properties in higher yield. Example 12 CMENDo, 07 as a polymerization initiator in Example 6
1-cyclohexyl-1 obtained in Example 2 by changing to parts by weight
-Methyl ethyl peroxypivalate (CMEP)
Vinyl chloride monomer was polymerized according to Example 6, except that 0.03 parts by weight (abbreviated as V) and 03 parts by weight of ENDo, and the polymerization temperature was 52°C. As a result, the yield of polyvinyl chloride was 83%. [0025] Comparative Example 5 For comparison, CM was used as the polymerization initiator in Example 12.
Polymerization of vinyl chloride monomer was carried out in accordance with Example 12, except that 0.03 parts by weight of cumyl peroxypivalate was added to BNDo, 03 parts by weight instead of EPVo, 03 parts by weight. As a result, the yield of polyvinyl chloride was 79%.
Met. Example 13 CMENDo, 07 as a polymerization initiator in Example 6
1-Cyclohexyl-1 obtained in Example 3 by changing to parts by weight
-Methyl ethyl peroxyneohexanoate (hereinafter referred to as
(abbreviated as CMENH) 0.03 parts by weight and BNDo, 0
Polymerization of vinyl chloride monomer was carried out according to Example 6 except that 3 parts by weight was used and the polymerization temperature was 50°C. As a result, the yield of polyvinyl chloride was 82%. [0026] Example 14 CMENDo, 07 as a polymerization initiator in Example 6
1-Cyclohexyl-1 obtained in Example 4 by changing to parts by weight
-Methyl ethylheloxyneononanoate (hereinafter referred to as C
The vinyl chloride monomer was polymerized at a polymerization temperature of 45°C in the same manner as in Example 6, except that 0.07 parts by weight (abbreviated as MENN) was used. As a result, the yield of polyvinyl chloride was 8
6%, and a polymer without odor and coloring was obtained. Comparative Example 6 For comparison, CM was used as the polymerization initiator in Example 14.
ENN and cumyl peroxy neononanoate 0.
Polymerization of vinyl chloride monomer was carried out in accordance with Example 14 except that 0.07 parts by weight was used. As a result, the yield of polyvinyl chloride was 80%. As a result of investigating the odor of this polymer, it was found that there was a device similar to acetophenone [0027] Example 15 In Example 14, CMEN No. 0 was used as a polymerization initiator.
Change to 7 parts by weight, CMEN No., 03 parts by weight and ○PP0
．． The vinyl chloride monomer was polymerized at a polymerization temperature of 45°C in the same manner as in Example 14, except that 03 parts by weight was used. As a result, the yield of polyvinyl chloride was 85%, and a polymer free of odor and coloration was obtained. Example 16 In Example 14, CMEN No. 0 was used as a polymerization initiator.
Change to 7 parts by weight, CMEN No., 03 parts by weight and BNDo.
Polymerization of vinyl chloride monomer was carried out at a polymerization temperature of 45°C in the same manner as in Example 14, except that 03 parts by weight of 0.03 parts by weight were used. As a result, the yield of polyvinyl chloride was 85%, and a polymer free of odor and coloration was obtained. [0028] (Polymerization of MMA) Example 17 Capacity 50 equipped with stirrer, thermometer, gas introduction tube, and cooler
200 ml of ion-exchanged water and 0.1 part by weight of polyvinyl alcohol were placed in a 0 ml four-bottle flask and dissolved therein. Then 200 parts by weight of methyl methacrylate and CMEP
5 parts by weight of Vo and 0.1 part by weight of n-octylmercaptan were added. After the space in the flask was sufficiently replaced with nitrogen gas, polymerization was carried out at 60° C. for 8 hours. After polymerization, the mixture was cooled and filtered to obtain a colorless and transparent bead-shaped polymer. The polymerization conversion rate was 99.7% as determined by quantifying the residual monomer using gas chromatography. Also GP
C had a number average molecular weight of 270,000 and a weight average molecular weight of 530,000. Comparative Example 7 For comparison, CM was used as the polymerization initiator in Example 17.
Changed to EPV, t-butylperoxypivalet) 0.0
MMA was polymerized according to Example 17 except that 7 parts by weight was used. As a result, the polymerization conversion rate was 90.3%. Also, the number average molecular weight was 250,000 by GPC,
The weight average molecular weight was 515,000 [0029] Example 18 99 parts by weight of methyl methacrylate, 1 part by weight of methyl acrylate, 0.5 parts by weight of CMEPVO, 0.1 part by weight of n-dodecylmercaptan and 0.0 parts by weight of triphenylphosphine. 1 part by weight was mixed, poured into a mold made using two glass plates, heated in a constant temperature bath at 50°C for 5 hours, then raised to 80°C and heated for 2 hours to complete polymerization. Ta. After cooling, it was peeled off from the glass plate to obtain a 3 mm transparent plate. The resulting board was completely colorless and odorless. Comparative Example 8 For comparison, CM was used as the polymerization initiator in Example 18.
Polymerization was carried out in the same manner as in Example 18, except that 05 parts by weight of PMPVo was used instead of EPV. The resulting board was colorless but had a terpene odor. [0030] (Polymerization of vinyl acetate) Example 19 100 parts by weight of vinyl acetate monomer was dissolved in 50 parts by weight of methanol, and while stirring under reflux, 05 parts by weight of CMEPVo was added and polymerization was carried out for 5 hours. . As a result, polyvinyl acetate with a degree of polymerization of 741 was obtained. The polymerization conversion rate at this time was 69.8%. Moreover, the obtained polymer was completely colorless. Comparative Example 9 For comparison, CM was used as the polymerization initiator in Example 19.
Vinyl acetate was polymerized according to Example 19, except that 10 parts by weight of AIBNo was used instead of EPV. As a result, polyvinyl acetate with a degree of polymerization of 765 was obtained. The polymerization conversion rate at this time was 70.3%. Moreover, the obtained polymer was colored pale yellow. [0031]

【Effect of the invention】

1-cyclohexyl- of the present invention represented by general formula (1)
1-Methyl ethyl peroxy neoalkanoate is a new compound characterized by a shorter half-life for degradation than prior art t-alkyl peresters derived from the same carboxylic acid. Therefore, the polymerization rate can be increased by using the peroxyester of the present invention alone as a polymerization initiator in conventional polymerization, or by using it in combination with a specific polymerization initiator. Therefore, polymerization cycle time can be shortened and production capacity can be increased. The polymers obtained at the same time are odorless, thermally stable and, in particular, colorless.

Claims (2)

[Claims] [Claim 1] General formula (1) [Chemical formula 1] ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (1) (In the formula, R_1, R_2 and R_3 each represent an alkyl group having 1 to 9 carbon atoms, and R_1 , R_2 and R_
The sum of 3 is 3-11. ) 1-Cyclohexyl-1-methylethylperoxyneoalkanoate. Claim 2: 1-cyclohexyl-1- according to claim 1
A polymerization initiator for vinyl monomers containing methyl ethyl peroxy neoalkanoate as an active ingredient.