JPH02269708A - Production of vinyl chloride copolymer - Google Patents

Abstract

PURPOSE:To produce a vinyl chloride copolymer excellent in heat resistance, impact resistance and moldability by copolymerizing a vinyl chloride monomer with a phenylmethyl fumarate. CONSTITUTION:A vinyl chloride copolymer is produced by copolymerizing 99-1wt.% vinyl chloride monomer (A) with 1-99wt.% phenylmethyl fumarate (B) of the formula [wherein R<1>-R<2> are each H or a (nucleus-substituted) phenylmethyl, and at least either of them is a (nucleus-substituted) phenylmethyl], e.g. monomethylphenylmethyl fumarate or di(2- methylphenylmethyl) fumarate. The obtained copolymer has a good balance between thermal property and mechanical property, is remarkably improved in heat resistance, impact resistance and moldability as compared with a conventional vinyl chloride resin, and is useful as the materials for piping materials, valves, automobile members, pipes, sheets, weak-current machine members, etc., which have been problematic in heat resistance, impact resistance and moldability.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Field of Application> The present invention relates to a method for producing a vinyl chloride copolymer that has excellent heat resistance, impact resistance, and moldability.

<Object of the Invention> Vinyl chloride resin (PVC) is an inexpensive resin that is excellent in mechanical properties such as rigidity and tensile strength, as well as chemical resistance, oil resistance, and flame retardance.

However, it has a fatal drawback of poor thermal stability and low heat resistance, so its use is currently limited.

Therefore, various attempts have been made to improve the heat resistance of PVC, including (1) blending it with a highly heat-resistant polymer;

■Method of chlorination.

■Method of copolymerizing with rigid monomers.

and so on.

■ In the method of blending with a highly heat-resistant polymer, P
Due to the low thermal stability of VC, it is not possible to raise the processing temperature extremely, and it is difficult to mix the polymer with PVC. In addition, good compatibility between the polymer and PVC is required. It is not easy to develop a resin that can satisfy these conditions, and at present no resin with a high heat distortion temperature has been developed by this method.

In addition, as a method for improving the heat resistance of PVC that has been well known for a long time, there is a method (2) of improving heat resistance by chlorinating PVC. Chlorinated PV produced by the method
The heat distortion temperature of C (C-PVC) varies depending on the degree of chlorination of PVC, but for example, at a degree of chlorination of 70% by weight,
Heat-resistant PVC with a glass transition temperature of 95° C. and high heat resistance has been obtained.

However, the disadvantages of c-pvc are that it has significantly poorer moldability than PvC and is subject to severe thermal decomposition during molding. In particular, c-
In the case of PVC, severe thermal decomposition occurs during melt processing during molding. Therefore, in order to prevent this, the molding temperature cannot be raised, causing significant difficulty in molding the resin.

Regarding the method of (ii) improving heat resistance by copolymerizing with a rigid monomer, British Patent No. 1062872 describes a method of producing PvC with excellent heat resistance by copolymerizing vinyl chloride monomer and N-phenylmaleimide. is disclosed. Also, in Special Publication No. 44-12433,
A method for copolymerizing vinyl chloride monomer and N-siglohexylmaleimide is disclosed. however,
In any of these methods, although the heat resistance is improved by copolymerization with an imide compound, the impact resistance is reduced, so there is a problem that the uses of the resin are extremely limited.

In this way, none of the methods has been able to provide a satisfactory heat-resistant PVC with well-balanced thermal properties and mechanical properties, and it is difficult to obtain heat-resistant PVC with such well-balanced physical properties.
The emergence of this is now desired.

Thus, an object of the present invention is to provide a method for producing a vinyl chloride-based composite having excellent heat resistance, FFJ impact resistance, and moldability.

<Means and effects for solving the problems> As a result of intensive studies to improve the shortcomings of these conventional vinyl chloride resins (PVC), the present inventors discovered that vinyl chloride monomer and fumaric acid phenylmethyl ester with a specific structure By copolymerizing PVC, not only can the heat distortion temperature be significantly improved compared to PVC, but it also has good resistance! ! i
They discovered that it is possible to obtain a resin that has both impact resistance and moldability, and has excellent thermal and mechanical properties, leading to the completion of the present invention.

That is, the present invention comprises (A) 99 to 1% by weight of vinyl chloride monomer, and (8)
The following general formula (wherein R1 and R2 are the same or different groups and represent hydrogen or a phenylmethyl group which may be substituted with a nucleus, and at least one is a phenylmethyl group which may be substituted with a nucleus. ) The present invention relates to a method for producing a vinyl chloride copolymer characterized by copolymerizing 1 to 99% by weight of a fumaric acid phenylmethyl ester represented by (A) a vinyl chloride monomer of 99 to 99% by weight. 1 layer pass%, (
B) The following general formula (wherein R1 and R2 are the same or different groups and represent hydrogen or a phenylmethyl group which may be substituted with a nucleus, and at least one is a phenylmethyl group which may be substituted with a nucleus. 1 to 99% by weight of fumaric acid phenylmethyl esters represented by The total amount of C) is 101ff1
%. This invention relates to a method for producing a vinyl chloride copolymer, which comprises copolymerizing a vinyl chloride copolymer.

The present invention will be explained in more detail below.

The fumaric acid phenylmethyl esters (B) used in the present invention are represented by the above general formula, and specific examples include monophenylmethyl fumarate,
Mono(2-chlorophenylmethyl) fumarate, mono(
4-chlorophenylmethyl) fumarate, mono(2-methylphenylmethyl) fumarate, mono(4-methylphenylmethyl) fumarate, mono(2-methoxyphenylmethyl) fumarate, mono(4-methoxyphenylmethyl) fumarate, mono(2-methoxyphenylmethyl) fumarate, -Fluorophenylmethyl) fumarate, mono(2,4,6-difluorophenylmethyl) fumarate 1-, mono(3-nitrophenylmethyl) fumarate, di(phenylmethyl) fumarate, di(2-chlorophenylmethyl) fumarate , di(4-chlorophenylmethyl) fumarate, di(2-methylphenylmethyl) fumarate, di(4-methylphenylmethyl) fumarate, di(2-methoxyphenylmethyl) fumarate, di(4-methoxyphenylmethyl) fumarate, Di(2-fluorophenylmethyl) fumarate, di(2,4,6-dolifluorophenylmethyl) fumarate, di(3-nitrophenylmethyl) fumarate, phenylmethyl(2-chlorophenylmethyl) fumarate,
Phenylmethyl (4-chlorophenylmethyl) fumarate, phenylmethyl (2-methylphenylmethyl) fumarate, phenylmethyl (4-methylphenylmethyl)
Fumarate, Phenylmethyl (2-methoxyphenylmethyl) fumarate, Phenylmethyl (4-methoxyphenylmethyl) fumarate, Phenylmethyl (2-fluorophenylmethyl) fumarate, Phenylmethyl (2,
Examples include 4,6-drifluoro-phenylmethyl) fumarate.

Further, other vinyl monomers (C) copolymerizable with vinyl chloride monomer (A) and fumaric acid phenylmethyl esters (B) include, for example, vinyl acetate, vinylidene chloride, vinyl ethers, maleic anhydride, and vinyl esters. , allyl esters, acrylamide, N-alkylacrylamide, N.

N'-dialkyl acrylamide, acrylonitrile,
Examples include isobutylene, 1,3-butadiene, isoprene, acrylic acid and methacrylic esters, styrene, nuclear alkyl-substituted styrenes, and nuclear halogen-substituted styrenes.

The usage ω of each monomer used in the present invention is 99 to 1% by weight of the vinyl chloride monomer (A), preferably 95 to 1% by weight.
50% by weight, fumaric acid phenylmethyl esters (B)
The proportion is 1 to 99% by weight, preferably 5 to 50% by weight, and when using other vinyl monomers (C), the upper limit of the usage amount of the monomer (C) is 40% by weight. If the amount of vinyl chloride monomer (A) used is less than 1% by weight, the inherent moldability and economic efficiency of the vinyl chloride resin will be impaired.

In addition, the amount of chloride and nil monomer (A) used is 99% by weight and 8%
If it exceeds this amount, a copolymer with excellent heat resistance and impact resistance cannot be obtained. Furthermore, if the other vinyl monomer (C) is used in a large amount exceeding 40% by weight, the heat resistance, impact resistance, or moldability of the resulting copolymer tends to decrease.

In the present invention, as the copolymerization method used, any method such as bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization can be adopted.

When producing a copolymer by emulsion polymerization, water, an emulsifier, and a polymerization initiator are charged into a reactor, and the atmosphere inside the reactor is replaced with an inert gas such as nitrogen, helium, argon, or carbon dioxide. Vinyl chloride monomer (A), fumaric acid phenylmethyl ester (8), and if necessary, other vinyl monomer (C) are added and polymerized with stirring.

Further, if necessary, both or one of these monomers may be added dropwise during polymerization. In this case, there are no particular restrictions on the emulsifier and polymerization initiator used, but sodium lauryl sulfate, sodium alkylbenzenesulfonate, sodium stearate, etc. are preferably used as the emulsifier. [The F combination temperature is usually 3
The temperature range is 0 to 100'C. The polymerization time varies depending on the polymerization initiator and polymerization temperature, but is usually 1 to 2 hours.
It is preferable to carry out the treatment for 4 hours. Post-treatment of the product obtained by emulsion polymerization is carried out by known methods such as salting out, filtration, and drying.

When producing a copolymer by a suspension polymerization method, vinyl chloride monomer (A), fumaric acid phenylmethyl ester (8) and other vinyl monomers (C) are added to water, and a dispersing agent is added. Polymerization may be carried out using a radical initiator while mechanically stirring and dispersing in the presence of the polymer. Also, in this case, if necessary, it is necessary to carry out polymerization while dropping 7-mer and replace the atmosphere in the reactor with an inert gas such as nitrogen, helium, argon, carbon dioxide, etc. is preferred. As the polymerization initiator, organic peroxides such as benzoyl peroxide, di-t-butyl peroxide, and lauroyl peroxide, and azo compounds such as azobisisobutyronitrile and azobiscyclohexane are preferably used. Furthermore, as a dispersant for stabilizing the suspension, methylcellulose, polyvinyl alcohol, gelatin, polyvinylpyrrolidone, etc. are used. The polymerization temperature varies depending on the polymerization initiator, but is preferably in the range of 30 to 100°C.

The polymerization time varies depending on the type of polymerization initiator and the polymerization temperature, but is suitably 1 to 24 hours. Post-treatment of the polymer obtained by the suspension polymerization method is carried out by known methods such as door-to-door treatment and drying.

<Effects of the invention> The vinyl chloride copolymer obtained by the method of the invention has the following properties:
It has well-balanced thermal and mechanical properties, and in particular, it has significantly improved heat resistance, impact resistance, and moldability compared to conventional vinyl chloride resins.

Therefore, the vinyl chloride copolymer obtained by the present invention can be used in piping materials, valves, automobile parts, window frames, etc., which have conventionally had problems in heat resistance, Ili impact resistance, and moldability.
It is particularly effective as a material for industrial boards, blow bottles, vibrators, film sheets, parts for light electrical equipment, etc.

EXAMPLES> The present invention will be specifically explained below with reference to Examples and Comparative Examples.

Example 1 1,900 d of distilled water, 5 g of sodium lauryl sulfate, and 3 Q of potassium persulfate were charged into an autoclave with a capacity of 51 equipped with a stirrer, a pressure gauge, and a thermometer. After degassing in a vacuum, the gas phase of the autoclave was purged with nitrogen. Replaced. The contents of the autoclave were heated to 50° C. over 15 minutes.

Next, 70g of vinyl chloride monomer was injected under stirring, and then 120g of di(phenylmethyl) fumarate was added to 300atl of methanol! The solution obtained by mixing with
The reaction was carried out with continuous addition at a rate of n. After addition,
After the reaction was continued for 150 minutes, the reaction solution was cooled to 40° C. to obtain a copolymer latex.

A 15% aqueous calcium chloride solution was added to the obtained latex to solidify it, followed by filtration and drying to obtain copolymer (1) as a white powder.

Example 2 In Example 1, di(phenylmethyl) fumarate 1
100 g of di(2-methylphenylmethyl) fumarate instead of the solution obtained by mixing 20 g in 300 m of methanol.
Copolymer (2) as a white powder was obtained by carrying out the same operation as in Example 1, except that a solution obtained by mixing 1.

Example 3 2000#Le distilled water in which 2 g of polyvinyl alcohol was dissolved and 1 g of lauroyl peroxide were added to an 8I5 autoclave equipped with a stirrer, a pressure gauge, and a thermometer, and the autoclave was placed in a dry ice-methanol bath. ,
The atmosphere in the autoclave was replaced with nitrogen while cooling to -20°C.

Next, a solution obtained by mixing 700% of vinyl chloride monomer (1, 100% of di(2-methylphenylmethyl) fumarate (+) in 200% of methanol and 50% of vinyl acetate monomer () were charged, and the contents of the autoclave were heated to 100% of di(2-methylphenylmethyl) fumarate.
After raising the valve temperature to 60℃ for 5 minutes, keep it at the same temperature and heat it for 300 r.
, p, and m for 8 hours to carry out the reaction.

After the polymerization reaction is complete, return the temperature of the autoclave to room temperature,
The residual vinyl chloride monomer was removed from the autoclave using Persil, and the autoclave was then purged with nitrogen. The produced copolymer was washed with water, filtered, and dried to obtain a white powder copolymer (3).

Comparative Example 1 Exactly the same operation as in Example 2 was carried out, except that 100 N-cyclohexylmaleimide (J) was added in place of di(2-methylphenylmethyl) fumarate 100 (+) along with vinyl chloride hexamer. A white powder comparative copolymer (1) was obtained.

Example 4 Copolymer (1) obtained in Examples 1 to 3 and Comparative Example 1
-(3) and comparative copolymer (1), 3.0 parts by weight of a dibutyltin malate stabilizer and 0.3 parts by weight of butyl stearate as a lubricant were blended, and the surface temperature was 190°C. The mixture was kneaded for 4 minutes using two rolls. The obtained rolled sheet was press-molded at 190° C. for 5 minutes, and the sheet obtained was used as a test piece, and its physical properties were measured by the method shown below. The results are shown in Table 1.

Comparative Examples 2 and 3 in Table 1 are for comparison between commercially available chlorinated PVC (C-PVC) and general-purpose PVC with an average degree of polymerization of 1000.

The method used for the evaluation is as follows.

1) Softening temperature: JIS K 67402) I
ii Impact value: JIS K 7111
3) Molding processability: Evaluated by the flow rate measured using a Koka type flow tester.

Claims (1)

[Claims] 1. (A) 99 to 1% by weight of vinyl chloride monomer, and (B
) The following general formula ▲ Numerical formulas, chemical formulas, tables, etc. is a phenylmethyl group which may be substituted on the nucleus.) 1 to 99% by weight of fumaric acid phenylmethyl esters are copolymerized. 2. (B) The vinyl chloride system according to claim 1, wherein R^1 and R^2 in the general formula representing fumaric acid phenylmethyl esters are phenylmethyl groups which may be substituted with nuclear alkyl or nuclear halogen. Method for producing copolymer. 3. (A) 99-1% by weight of vinyl chloride monomer, (B)
The following general formula ▲ includes mathematical formulas, chemical formulas, tables, etc. 1 to 99% by weight of fumaric acid phenylmethyl esters (optionally substituted phenylmethyl group) and (C) more than 0 to 40% by weight of other copolymerizable vinyl monomers
% by weight or less (however, components (A), (B) and (C)
) is 100% by weight. ) A method for producing a vinyl chloride copolymer, comprising copolymerizing. 4. (B) The vinyl chloride system according to claim 3, wherein R^1 and R^2 in the general formula representing fumaric acid phenylmethyl esters are phenylmethyl groups which may be substituted with nuclear alkyl or nuclear halogen. Method for producing copolymer.