JPS6215248A - Additive for chlorine-containing resin and production thereof - Google Patents

Abstract

PURPOSE:To obtain the titled additive having high affinity to resins, and effective to synergetically prevent the discoloration of the resin when used in combination with a metal salt stabilizer, by adjusting the composition of the half-ester, etc., in an ester composition of malic acid and ethylene glycol. CONSTITUTION:An ester composition of malic acid and ethylene glycol and having liquid phase at normal temperature. The content of the half-ester in the composition is <=20wt% excluding the residual unreacted ethylene glycol, and the content of the malic acid (diethylene glycol) ester is 3-75wt%. The ester can be produced by esterifying 1mol of malic acid with 1.3-2.5mol of ethylene glycol in the presence of an acid catalyst (0.5-5wt% based on malic acid) while distilling out the produced water. The reaction is carried out at 70-120 deg.C.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to an additive for chlorine-containing resins comprising an ester composition of malic acid and ethylene glycol. The present invention relates to additives that can be used as chemical additives to prevent and stabilize coloring, particularly due to the so-called zinc burning phenomenon, and a method for producing the same.

Vinyl chloride polymers undergo dehydrochlorination due to the effects of heat and light when subjected to thermoforming processes such as calendering and extrusion processing, or during use, and the inherent properties of the resin gradually deteriorate. Therefore, in order to prevent this and stabilize it, stabilizers mainly consisting of various metal salt stabilizers have been conventionally added and blended. Such conventional metal salt stabilizers (so-called metal soaps) include a suitable combination of organic acid salts such as cadmium, lead, barium, etc., or an organic stabilizing auxiliary agent is used in combination therewith as necessary.

(Prior art) In recent years, the toxicity of cadmium and lead has become a problem, and processed products made from vinyl chloride resin containing them have been subject to problems such as leaching of cadmium and lead compounds and migration into food, as well as the waste of these compounds. Many problems arose, including restrictions on the processing of Therefore, attempts have been made to use suitable stabilizing aids in barium and zinc, barium and magnesium and zinc, or calcium and zinc based metal salt stabilizers without using cadmium and lead based stabilizers.

However, this zinc-based stabilizer has the disadvantage of causing the so-called zinc burning phenomenon, in which the resin turns black. In order to prevent this zinc burning, it is important to develop a so-called stabilizing agent, which prevents this phenomenon by capturing zinc chloride generated from zinc-based stabilizers and hydrogen chloride.

Polyols such as pentaerythritol are widely known as such auxiliaries, but recently a method has been developed in which an ester of malic acid and ethylene glycol is used together with a zinc-based metal soap stabilizer as a stabilizing auxiliary agent in vinyl chloride resin. It has been reported (“PVC and Polymers” Vol. 24 No. 2 No. 1)
~5 pages).

(Problem to be solved by the invention) However, as reported in the above literature,
The conventional ester of malic acid and ethylene glycol is
It is colored, its composition and molecular weight are undetermined, and there are problems in that it has not yet been developed into a practical technology as a stabilizing aid.

The object of the present invention is to provide a novel additive for chlorine-containing resins comprising an ester composition with toethylene glycol malate, which can solve the above-mentioned conventional problems, and a method for producing the same.

(Means for Solving the Problems) As a result of intensive studies to achieve the above object, the present inventors found that by controlling the composition of the ester composition of malic acid and ethylene glycol, the compatibility with the resin was improved. It has been found that this method improves the stability and also provides an excellent stabilizing effect.

In addition, regarding its production method, for example, since inorganic acid catalysts such as sulfuric acid cause coloration, in the presence of an organic acid catalyst, malic acid, which is different from the large excess of ethylene glycol described in the above-mentioned literature, is used. The inventors have discovered that it is possible to produce an ester composition that is easy to post-process, is colorless, and has an effect that meets the objectives of the present invention by using approximately 2 times the mole of ethylene glycol, and has completed the present invention. did.

That is, in the present invention, the amount of malic acid is 200% by weight or less, and the content of ester (malic acid and ethylene glycol) is 20% by weight or less.
An additive for chlorine-containing resins, characterized in that it is a composition of malic acid di(ethylene glycol) ester in a proportion of not less than 75% by weight, and 1.3 to Z5 times the mole of malic acid and malic acid. The gist of this invention is a method for producing an additive for chlorine-containing resins, which is characterized by reacting ethylene glycol with ethylene glycol in the presence of an acid catalyst and esterifying the reaction water while distilling off the reaction water.

In the present invention, the chlorine-containing resin may be a homopolymer of vinyl chloride (so-called homopolymer) or other monomers copolymerizable with it, such as vinylidene chloride, vinyl acetate, alkyl vinyl ether, maleic acid, or fumaric acid. It may also be a copolymer with diester, acrylic acid, acrylic ester, methacrylic acid, methacrylic ester, ethylene, propylene, butylene, isobutylene, butadiene, styrene, acrylonitrile, or the like.

(Function) The ester composition of phosphorus-4 and ethylene glycol constituting the additive for chlorine-containing resins of the present invention preferably contains 5% by weight or less of di(ethylene glycol) as a plasticizer for chlorine-containing resins. ) The content of ester is 20% by weight or more, preferably 3 to 75% by weight, more preferably 20 to 75% by weight, particularly preferably 30 to 6% by weight, and the other components are mostly higher-order esters, It is necessary that the composition is composed of so-called oligomers and is liquid at room temperature. The viscosity of the ester composition is 20
100,000cP or less at °C, especially about 15,0OO
cP or less is preferable.

Note that even if a certain amount of ethylene glycol remains in the ester composition, the effects of the present invention are not impaired. That is, if the ester composition contains a large amount of half ester component, the effect of preventing zinc burning will be reduced;
The effect of dialkyl ester components of malic acid and hymalic acid alone is even smaller.

The amount of the additive of the present invention added to the chlorine-containing resin is, for example, 0.05 to 1 part by weight per 100 parts by weight of the vinyl chloride polymer.
0 parts by weight, preferably 0.1 to 1.0 parts by weight. Since the additive of the present invention has good compatibility with chlorine-containing resins, the amount added can be varied over a wide range, but even if the amount added is smaller than conventional products, it can be particularly effective as a stabilizing aid. From an economic point of view, it is not desirable to add more than necessary.

However, it is advantageous in that it is possible to adjust the amount used within a wide range depending on the application, thereby achieving a particularly suitable effect for each application.

Low-toxicity or non-toxic metal salt stabilizers used in combination with the additives of the present invention include salts of zinc, barium, magnesium, calcium and the like, although combinations thereof are usually used. For example, barium-zinc, barium-zinc-magnesium, and calcium-zinc salts are commonly used.

Among these salts, hydrochloride, diacetate, ethylhexanoate, octanoate, stearate, oleate,
Mention may be made of laurate, palmitate, myristate, ricinoleate, benzoate and phthalate. The amount of these metal salts added is generally 0.1 to 5% by weight based on 100 parts by weight of the vinyl chloride polymer.

In addition, at least one of an organic phosphite, a phenol compound, or an epoxy compound can be used in combination with the additive of the present invention, if necessary. For example, organic phosphites include triphenyl phosphite, trioctyl phosphite, tridecyl phosphite, diphenyldecyl phosphite, diphenyldecyl phosphite, etc.; phenols include carbolic acid, cresol, p-
t-butylphenol, p-octylphenol, nonylphenol, etc.; as the epoxy compound, epoxidized unsaturated oils and fats, epoxidized unsaturated fatty acid esters, epoxycyclohexane derivatives, epichlorohydrin derivatives, etc. are used in combination.

In addition to the effect as a stabilizing aid, the additive of the present invention has a plasticizing effect, an antioxidant effect, an anti-coloration effect, etc., but depending on the final use of the chlorine-containing resin, for example, Agents, resin reinforcing agents, pigments, antioxidants, antistatic agents, antifogging agents, plate-out inhibitors, lubricants, flame retardants, other processing aids, and the like can be added and used in combination.

The method for producing the ester composition of malic acid and ethylene glycol, which is the most effective stabilizing aid constituting the additive of the present invention, is as follows.

For example, para-toluenesulfonic acid (
Hereinafter, it will be abbreviated as PTS. ) at a reaction temperature of about 70 to about 120°C, preferably 80°C.
The reaction is carried out while distilling off the reaction water produced at ~100°C.

A method for distilling off the reaction water is a method of blowing an inert gas such as nitrogen into the reaction system under normal pressure and distilling off the reaction water, for example, at a reduced pressure of 5 to 200 fiHf, preferably 20 to 50 fiHf. Either a method of separating the reaction water by azeotropic dehydration using a solvent such as benzene or toluene, etc. can be adopted. Moreover, according to the method of distilling off under reduced pressure, almost no ethylene glycol exists after the reaction.

The reaction temperature needs to be carried out at a temperature of about 70°C to about 120°C for the majority of the reaction so as to eliminate at least unreacted malic acid, but if necessary, depending on the application, the temperature may be higher after the reaction is mostly completed. 120 to obtain the next ester
The temperature can also be raised to 150°C or higher, for example.

The esterification catalyst is preferably a catalyst that allows esterification to proceed easily at a reaction temperature of about 100° C. or lower, such as aromatic sulfonic acids such as PTS1 benzenesulfonic acid, naphthalenesulfonic acid, and xylene sulfonic acid;
Examples include aliphatic sulfonic acids such as methanesulfonic acid; halogenated fatty acids such as trichloroacetic acid and fluoroacetic acid; organic acid catalysts such as strongly acidic ion exchange resins, and inorganic acid catalysts such as sulfuric acid. If no catalyst is used, the ester composition that can constitute the additive of the present invention cannot be obtained, and if mineral acids such as sulfuric acid are used, the ester composition will be colored and a purification step will be required. Therefore, it is preferable to use an organic acid catalyst. It will be done. The amount used varies depending on the type of catalyst, but it is generally 0.1 to 0.1 to malic acid.
10% by weight, usually 0.5-5% by weight.

If the reaction temperature is low, the reaction rate is slow; if the reaction temperature is too high, condensation of ethylene glycol itself, dehydration and fumarization of malic acid, local polymerization of malic acid ester, etc. may occur, and stabilization aids may occur. Not only will the effect of the agent be reduced and the product will become a viscous substance that is difficult to handle, but if the reaction proceeds further, polymerization will progress too much and the compatibility or dispersibility with plasticizers and chlorine-containing resins will deteriorate.

If the amount of ethylene glycol used is small, the half-ester component will be large and the product will not be viscous. It produces a compound that cannot achieve the purpose of the invention and is not preferable as an additive for the present invention.
Furthermore, it is extremely difficult to remove residual ethylene glycol from an industrial perspective.

The ester composition thus produced can be used as it is as a stabilizing agent constituting the additive of the present invention, but depending on the use, the acid catalyst in the composition may be neutralized, for example, as a zinc salt and/or a calcium salt. You can also do it.

(Example) Next, the present invention will be explained in more detail with reference to Examples.

However, unless otherwise specified, "chi" and "bu" are used as "chi" and "bu".
"% by weight" and "parts by weight" are shown.

Example 1 134f of malic acid (1
mole) and ethylene glycol 124t (2 mok) and P
TSt and or were added and reacted at 100° C. for 6 hours while distilling off the generated water under a nitrogen gas flow, and the reaction water was collected by cooling. The obtained ester composition was a colorless viscous liquid that was fluid at room temperature, and its viscosity was about 200 cP at 20°C.

The composition of the obtained ester composition was as follows.

Ethylene glycol 1o thioligomer 2thiodiester 3o thioligomer - 55% fumaric acid ester 3ti Example 2 Malic acid 134F (1
mol) and ethylene glycol 124t (2 mol) and P
T S 1. Oy and 85℃, degree of vacuum 50
The reaction was allowed to proceed for 4 hours while distilling off the reaction water produced by waHt, and the reaction water was collected by cooling.

The obtained ester composition is a colorless viscous liquid that is fluid at room temperature, and its viscosity is s, o o at 20'C.
It was o cP.

The composition of the obtained ester composition was as follows.

Ethylene glycol 2% Half ester 2% Diester 38% Oligomer 55% Fumaric acid ester Comparative example 1 (1) Malic acid 134 in a four-eyed 7-disco equipped with a stirrer
t (1 mol) and ethylene glycol 310f (5 mol)
and PTSL and Of were added thereto and reacted at 100° C. for 6 hours while water was distilled off under a nitrogen gas flow, and the reaction water was collected by cooling. The obtained ester composition was a colorless viscous liquid that was fluid at room temperature, and the residual amount of ethylene glycol in the obtained product was about 46%.

Due to the high content of ethylene glycol in the product,
In order to distill off excess ethylene glycol, the product was subjected to a vacuum of 2.5 degrees. ．． 5fiH? , heat at 64℃ for about 30 minutes,
Ethylene glycol --- is distilled off dfit, 9.-7p and y distillation f=.

The composition of the obtained ester composition was as follows.

Ethylene glycol 10% half ester 2 thiodiester 69 thioligomer-15 polyfumaric acid ester 4 thioligomer The viscosity was λs o cP at 20°C. The obtained ester composition was used in Comparative Example 1-( in Example 3).
1) was used as a sample of the stabilizing aid.

(2) In addition, when the above Comparative Example 1-(t) was carried out in the same manner except that the amount of ethylene glycol was increased by 1.25 times by mole, the half ester component in the reaction product was large and the viscosity was high. The fluidity was poor, and an ester composition that was practical as an additive for resins could not be obtained. Note that this reaction product was used as a stabilizing aid sample in Comparative Example 1-(2) in Example 3.

Example 3 Example 1, Example 2 and Comparative Example 1-(t) and -(2
) A thermal coloring test was conducted on vinyl chloride polymer (hereinafter abbreviated as PvC) using each of the ester compositions obtained as samples.

Each of the above ester compositions was used as a stabilizing agent sample from 0 to 6
．． 100 parts of PvC, 20 parts of dioctyl phthalate (hereinafter abbreviated as DOP) and 3 parts of metal soap (zinc stearate/calcium stearate =
2/1), stirred well in a beaker, and kneaded for 5 minutes with open rolls (4" x 8") adjusted to 150 ± 5°C. Got a sheet. This was pressed with a glass plate to make a sample sheet with a smooth surface, and cut out into 5 parts and 7 m long tanzak shapes.
Heated in gear open (160±5°C). During that time, each heated sample sheet was taken out every 15 minutes up to 120 minutes, and color changes were measured using a colorimeter.

The results are shown in Table 1 below.

Table 1 Note: ■Additional amount is parts by weight based on 100 parts by weight of resin.

In Table 0, O is almost colorless, . is almost black, Δ is partially black, and . is yellow.

(Effects of the Invention) As is clear from the above results, the additive for chlorine-containing resins comprising the ester composition of malic acid and ethylene glycol of the present invention can be used as a stabilizing agent, for example, as known in the art. It has better compatibility with resins than polyols such as pentaerythritol, and when used in combination with plasticizers and metal salt stabilizers such as zinc, it is extremely effective in preventing discoloration due to the zinc burning phenomenon. It can be prevented by plasticizers,
The function as a metal salt stabilizer and other additives is not diminished, but rather can be reinforced, which is a remarkable effect of industrial value.

Claims (3)

[Claims] (1) Consisting of an ester composition of malic acid and ethylene glycol, the half ester content calculated by excluding residual unreacted ethylene glycol in the ester composition is 2
An additive for chlorine-containing resins, characterized in that the content of malic acid di(ethylene glycol) ester is 0% by weight or less and 3% by weight or more and 75% by weight or less, and the composition is liquid at room temperature. (2) Chlorine characterized by reacting malic acid and ethylene glycol in an amount of 1.3 to 2.5 times the mole of malic acid in the presence of an acid catalyst, and esterifying while distilling off the reaction water. Method for producing additives for containing resins. (3) The production method according to claim 2, wherein the catalyst amount is 0.5 to 5% by weight based on malic acid, and the temperature conditions for most of the reaction are 70 to 120°C.