JPS60155207A - Polymerization or copolymerization of vinyl chloride - Google Patents

Abstract

PURPOSE:To effect polymerization within a short time even at low temperature and to improve the heat stability, etc., of the polymer, by using diallyl peroxydicarbonate as a polymerization initiator in (co)polymerizing a vinyl chloride monomer. CONSTITUTION:About 0.001-0.4pt.wt. diallyl peroxydicarbonate as a polymerization initiator is added to 100pts.wt. vinyl chloride monomer or mixture of vinyl chloride monomer and copolymerizable monomers (e.g., vinyl acetate). The resulting mixture is polymerized at a temperature of about 20-60 deg.C, whereby the polymerization can be performed within a short time and an odorless polymer having excellent colorability can be obtained. Diallyl peroxydicarbonate can be produced by reacting allyl alcohol with phosgene and reacting the resulting allyl chloroformate with an aqueous solution of sodium peroxide in the presence of an aromatic hydrocarbon solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention involves the use of a specific polymerization initiator when polymerizing a vinyl chloride monomer or copolymerizing a cyclized vinyl monomer and a vinyl monomer copolymerizable therewith. By using 50
The present invention relates to a vinyl chloride vehicle chassis and a copolymerization method that allow a short polymerization time and a polymer with excellent thermal stability to be obtained even at a polymerization temperature of 0.degree. C. or lower.

Conventionally, in the method of polymerizing or copolymerizing vinyl chloride monomer or vinyl monomer copolymerizable with vinyl chloride monomer (hereinafter referred to as vinyl chloride polymerization method), when carrying out suspension polymerization, an oil-soluble polymerization initiation method is used. Agent C (hereinafter referred to as initiator) includes 8th-butylperoxypivalate, 8th-butylperoxyneodecanoate (END), bis(2-ethylhexyl)peroxydicarbonate (OPP), and diisopropyl. Peroxydicarbonates and the like have been used.

When these initiators were used at a polymerization temperature higher than 50°C, there were no problems with the polymerization time or the physical properties of the obtained polymer, but when used at a polymerization temperature lower than that, the polymerization time was If the amount of initiator added is increased to shorten the polymerization time, residual initiator or decomposition products of the initiator may deteriorate the physical properties of the resulting polymer. There were problems such as

On the other hand, initiators that are activated at lower temperatures than the above-mentioned initiators have also been developed. For example, diisobutyryl peroxide (more PO
), acetylcyclohexylsulfonyl peroxide (
hasP) (Special Publication No. 1974-1flri Q5) and cumyl peroxyneodecanoate raND) C% Kaisho 5
8-120611), these initiators are
It is used at polymerization temperatures of °C or lower. However, each of these initiators had their own problems. That is, IB
PO does not have long-lasting polymerization activity, AC8P has hygienic problems due to decomposition products, and the obtained polymer has poor thermal stability.Furthermore, OND is also a decomposition product and has a characteristic odor of polymers. There were some.

The present inventors conducted research on the problems of the above-mentioned conventional method, and found that by using a specific initiator, 50°
The present invention was completed after confirming that the polymerization time is short even at a polymerization temperature of C or lower, and that the resulting polymer has excellent thermal stability, particularly colorability, and is odorless.

That is, the present invention is a method for polymerizing vinyl chloride, which is characterized in that diallyl peroxydicarbonate is used as an initiator when polymerizing vinyl chloride monomers.

The amount of diallyl peroxydicarbonate, which is a specific initiator used in the present invention, can be selected as appropriate, but it is usually 0.001 to 0.00% in terms of pure product per 100 parts by weight of vinyl chloride monomer. The amount is about 4 parts by weight, preferably 0.08 to 0.2 parts by weight. The amount is Q, 90
If it is less than 1 part by weight, the polymerization rate will be slow. Moreover, if it exceeds 0.4 parts by weight, it becomes difficult to control the polymerization reaction and the physical properties of the resulting polymer deteriorate, which is not preferable.

The polymerization method used in the present invention may be a conventional suspension polymerization method, and the polymerization temperature is generally 20 to BO°C, preferably 30 to 50°C. If the polymerization temperature is less than 20°C, the polymerization time tends to be longer;
If it exceeds C, the life of the initiator will be shortened, which is disadvantageous.

Examples of other vinyl monomers copolymerizable with the vinyl chloride monomer used in the present invention include ethylene, vinyl acetate, vinylidene chloride, styrene, and acrylic esters.

The specific initiator used in the present invention can be obtained, for example, by pressing as follows.

That is, stoichiometric amounts of allyl chloroformate obtained by the reaction of allyl alcohol and phosgene and an aqueous solution of sodium peroxide are mixed in an aromatic hydrocarbon solvent (for example, toluene).
obtained by reacting in the presence of Note that the reaction temperature is about -10'C to 10C.

The specific initiator used in the present invention can be used alone or in combination with other conventionally used peroxydicarbonates, diacyl peroxides, peroxyesters, AO8P, azobis-based initiators, etc. It is also possible to use

The present invention using the above specific initiator has the following characteristics.

That is, the polymerization activity is higher and the polymerization rate is higher than in the method using a conventional initiator (for example, OPP%END). Therefore, it is excellent in terms of polymer collection. Furthermore, compared to methods using conventional initiators (for example, OND, AO8P), the obtained polymer has no odor and is superior in terms of thermal stability and, in particular, no coloration.

Hereinafter, the present invention will be specifically explained with reference to Examples.

First, diallyl peroxydicarbonate was synthesized according to the following reference example.

Reference Example Synthesis of Diallyl Beroxydicarbonate (APP) 448.9 (0, a mol) of a 5% by weight aqueous sodium hydroxide solution was placed in a 4-liter flask equipped with a stirrer, and the mixture was stirred. 50% by weight hydrogen peroxide solution 18.7 ty
(0,275 mol) was added. Next, add toluene to 80
．． 9 was added and the liquid temperature was kept at 0''C in an ice water bath.While stirring, allylchloroforme) 60.8.9 (0.5 mol) was added dropwise over 20 minutes while keeping the liquid temperature at o'c. did.

After continuing stirring for 1 hour, the aqueous phase was separated, and the oil phase was washed twice with 800 ml of 5"C water and dried over anhydrous magnesium sulfate. .5N was obtained.As a result of analyzing this solution by IR and NMR, it was confirmed that this solution was a toluene solution of diallyl peroxydicarbonate.As a result of measuring the amount of active oxygen in this solution, it was 4.46%. According to calculation, the purity was 56.44i% and the purity was 47.4% by mole.Toluene was added to this solution to adjust the purity to 50% by weight, and it was used as an initiator in the following examples.

Example 1 In a stainless steel autoclave with a volume IB of 400 ml, 200% of ion-exchanged water and 0.1% of polyvinyl alcohol were added.
parts by weight were added and dissolved. Next, diallyl peroxydicarbonate obtained in the reference example (APP with a purity of 50%)
0.2 parts by weight was added, the mixture was cooled to -80°C or lower, and 100 parts by weight of vinyl chloride monomer was added. The space in the autoclave was thoroughly filled with nitrogen gas and then sealed tightly. It was immersed in a constant temperature water bath maintained at 45° C. for 8 hours to polymerize. For stirring, use an autoclave with 9 parts: 82 r, p, m,
This was done by rotating it. After polymerization,
After cooling, unreacted vinyl chloride monomer was removed, and the resulting white powder was washed twice with 100 ml of water and then dried in vacuo. The yield of the cyclized vinyl polymer from the bamboo shoots was 8R%.

As a thermal stability test of the obtained vinyl chloride polymer, a coloring test was conducted using the method shown below, and at the same time, odor was also investigated. The results are shown in Table 2.

[Colorability test]

Vinyl chloride polymer i00 parts by weight, dibutyltin male)
Mix 2.5 parts by weight and 80 parts by weight of dioctyl phthalate as a plasticizer, knead for 10 minutes on a roll at 160'C, take out a 1 *** thick sheet, and visually check the degree of coloration of the sheet. Observed.

Examples 2 to 4 Vinyl chloride monomers were polymerized in the same manner as in Example 1, except that the amount of the initiator APP added and the polymerization temperature or polymerization time were changed as shown in Table 1.

The yield of each polymer at this time is shown in i-1.

A coloring test was also conducted in the same manner as in Example 1, and odor was also investigated. Table 2 shows these results.
Shown below.

Example 5 Copolymerization was carried out in the same manner as in Example 1, except that the vinyl chloride monomer was changed to 90 parts by weight of vinyl chloride single tile and 10 parts by weight of vinyl acetate single lid, and the polymerization time was shortened. I did it. Table 1 shows the collection of copolymers at this time. A coloring test was also conducted in the same manner as in Example 1, and odor was also investigated. These results are shown in Table-2.

Ratio inversion 1 to 4 As an initiator, bis(2-ethylhexyl) peroxydicarbonate (2-ethylhexyl) peroxydicarbonate, which has been conventionally used in place of APP,
oPP), 8th-butyl peroxy neodecanoate (BND), cumyl peroxy neo f-h/!
Except for using (OND) and acetylcyclohexylsulfonyl peroxide (AC8P),
Polymerization of vinyl chloride monomer was carried out according to Example 1 under the conditions shown in Table 1. Table 1 shows the yield of each polymer at this time.

A coloring test was also conducted in the same manner as in Example 1, and odor was also investigated. These results are shown in Figure 2.

Comparative Example 5 100 parts by weight of vinyl chloride monolayer and 90 parts by weight of vinyl chloride monomer
Copolymerization was carried out in the same manner as in Example 1 under the conditions shown in Table 1, except that parts by weight and parts of vinyl acetate monomer were changed to 10 s<10 s. Table 1 shows the results of the copolymer at this time. In addition, a colorability test was conducted in the same manner as in Example 1,
We also investigated odor. These results are shown in Table-2.

7/'/'/' / /' Table 2 As is clear from the above Tables 1 and 2, in the method using conventional initiators, the polymerization time is long or the obtained polymer is In contrast, the method of the present invention has problems such as poor heat resistance (coloring property) and odor, or low yield even if coloring property and odor are good. I am satisfied with all of them.

The absence of odor is favorable from the viewpoint of the production environment during molding and processing.

Patent applicant: Nippon Yushi Co., Ltd.

Claims (1)

[Claims] 1.) When polymerizing vinyl a monomer or copolymerizing vinyl chloride monomer with other vinyl monomers that can be copolymerized with vinyl chloride monomer, use diallylperoxydi as a polymerization initiator. A method for polymerizing and copolymerizing vinyl chloride, characterized by using carbonate.