JPS6045215B2 - Synthetic polymer modifier - Google Patents

Description

[Detailed description of the invention] The present invention relates to a modifier for synthetic resins.

In general, synthetic polymer materials are highly susceptible to static electricity.
Despite its many other advantages, its use may be a concern.

That is, collection, adsorption, and repulsion caused by electrostatic charges cause trouble in all aspects, from processing to products. Conventionally, antistatic agents include amine-based,
Cationic activators such as amide-based activators, or fatty acid esters such as zorbitan, glycerin, and polyoxyethylene glycol are generally used, but the former amine-based and amide-based cationic activators can be processed and molded at high temperatures of 1600C or higher. However, while the latter fatty acid esters have high temperature stability, they have disadvantages such as poor antistatic performance and significant bleeding.

In addition, natural fatty acids are used as the fatty acids in the fatty acid esters mentioned above, and there are problems with heat resistance and coloring properties.To solve these problems, hydrogenated fatty acids have higher melting points and bleed. There is a drawback that this becomes even more significant.

The present inventors have focused their studies on these problems, and have discovered that a synthetic fatty acid derivative consisting of a mixture of a saturated straight-chain fatty acid and a side-chain fatty acid synthesized from olefins by the oxo method has been developed. The present invention was achieved based on the discovery that it has superior antistatic properties and compatibility, and is excellent as a modifier for synthetic resins, compared to fatty acid derivatives made from natural oils and fats.

That is, the present invention deals with the general formula R1-CH2-COOH (1) (wherein R1 is an alkyl group having 8 to 20 carbon atoms) obtained by synthesis from olefin by the oxo method, and (wherein R2 is an alkyl group having 4 to 19 carbon atoms). Alkyl group, R3 has 1 carbon number
In the mixed fatty acids (1) and (2) represented by (~10 alkyl groups), (1) and (2) have a weight ratio of 30:
Aliphatic acid obtained by reacting an adduct obtained by adding 1 to 50 moles of ethylene oxide or propylene oxide to a synthetic fatty acid having a total carbon number of 10 to 22 in a ratio of 70 to 70:30, and an aliphatic dicarboxylic acid. By adding the reaction product obtained by adding epichlorohydrin or alkyl halohydrin to dicarboxylic acid monoester to vinyl chloride resin, it not only prevents static electricity damage but also improves hygroscopicity and improves plasticizer removal. Each characteristic, e.g.
Among non-migration properties, flexibility, compatibility, etc., compatibility can be particularly improved.

The saturated fatty acids used in the present invention have general formulas (1) and (2).
) in a weight ratio of 30:70 to 70:30,
Total carbon number 10-22, preferably total carbon number 12-19
It is a mixed fatty acid obtained by synthesizing olefins obtained from petroleum by the rioxo method, and of these, the one with the above-mentioned mixing ratio is used.

Synthetic fatty acids synthesized by the oxo method are characterized by being a mixture of saturated straight-chain fatty acids and side-chain fatty acids, and in addition, the mixed fatty acids have an odd total number of carbon atoms, which are hardly included in natural fat raw materials. Contains fatty acids. Due to such a composition, it has general properties such as a lower melting point, lower viscosity, and higher oxidation stability than natural fatty acids.
While considering the use of such synthetic fatty acids, we added ethylene oxide or propylene oxide to give them hydrophilicity, made the adduct a monoester of aliphatic dicarboxylic acid, and added epichlorohydrin to the terminal carboxyl group. Or Alkilha. The present invention was completed by adding stohydrin and using the resulting compound to improve the compatibility with vinyl chloride resin and impart antistatic properties and hygroscopic properties.
The aliphatic dicarboxylic acids used here include saturated dicarboxylic acids, and the unsaturated dicarboxylic acids include succinic anhydride,
Maleic anhydride, maleic acid, fumaric acid, itaconic acid,
Examples include citraconic acid, mesaconic acid, and glutaconic acid.

Further, examples of the alkyl halohydrin include ethylene chlorohydrin, ethylene bromohydrin, propylene chlorohydrin, and propylene bromohydrin. The method for producing the synthetic polymer modifier of the present invention is based on general formulas (1) and (2).
of mixed fatty acids, with an average molecular weight of 1 mole, and 1 to 1 mol of ethylene oxide or propylene oxide.
Add 50 moles. In the addition reaction, fatty acid is reacted with ethylene oxide or propylene oxide in the presence of an alkali catalyst such as caustic soda at 130 to 180° C. under normal pressure or increased pressure. Next, the reaction between the obtained product and aliphatic dicarboxylic acid occurs by heating and stirring both at 80 to 150°C when reacting with dicarboxylic anhydride, and when using dicarboxylic acid It is obtained by heating to 120-200°C in the presence of a catalyst or an alkaline catalyst. The dicarboxylic acid monoester thus obtained is reacted with epichlorohydrin or alkyl halohydrin by dropping epichlorohydrin or alkyl halohydrin onto the monoester at 80 to 120°C. After the reaction is completed, unreacted epichlorohydrin and the like are removed by distillation under reduced pressure. The synthetic polymer modifier of the present invention obtained as described above is a reaction product obtained in the same manner as described above using fatty acids made from natural fats and oils as a raw material. When kneaded into vinyl resin,
Although the synthetic polymer modifier of the present invention has several orders of magnitude better compatibility and less bleeding, it has antistatic properties and
It has excellent hygroscopicity and has unprecedented surface modification performance for vinyl chloride resin.

The modifier of the present invention is added to the vinyl chloride resin by a kneading method, but if an unsaturated dicarboxylic acid is used, a copolymerization method can also be applied, and the amount added is as follows:
It is 0.05 to 2% saliva volume, preferably 0.5 to 1% saliva volume.

The present invention will be explained below with reference to Examples.

Example 1 Obtained from olefin by oxo method.

(Rl, R2, R3 have 10 to 13 carbon atoms and 5 to 12 carbon atoms, respectively.
, 1 to 6 alkyl groups) in a weight ratio of (1):(2)=
An adduct obtained by reacting 2 parts of a mixed fatty acid having a total carbon number of 12 to 15 in a ratio of 45:55 with 2 parts of ethylene oxide at 160 to 180°C in the presence of 2.2 parts of caustic soda. 120 to 10% succinic anhydride and 10%
The reaction was carried out for 3 hours while stirring at 40°C.

The obtained ester had an acid value of 101.0 (theoretical acid value of 1
04.1) To the above ester, which had a hydroxyl value of 0.5 (theoretical hydroxyl value: 0), 1 part of epichlorohydrin was added to 9
The solution was added dropwise at 0°C, and the reaction was carried out for 3 hours after the completion of the addition.

After that, add 10 to 22 rT1 of unreacted epichlorohydrin.
Distillation was carried out at 120° C. under reduced pressure of mHg to obtain 6 portions of the reaction product. Its acid value was O. (This is reactant 1
) Comparative Example 1 204 parts of lauric acid (purity 95%) and 22 parts of ethylene oxide. 424 parts of the adduct obtained by reacting under the same conditions as in Example 1 and 1 part of succinic anhydride were reacted under the same conditions as in Example 1 to obtain 538 parts of an ester with an acid value of 105.2 and a hydroxyl value of 0.5. I got the department.

Example 1: Adding 102 parts of epichlorohydrin to the above ester
The reaction was carried out in the same manner as above, and unreacted epichlorohydrin was removed under reduced pressure to obtain 616 parts of a reaction product with an acid value of 0.2.
(This is referred to as Comparative Product 1) Measurement Example 1 Take 5 parts each of Reactant 1 and Comparative Product 1 obtained in Example 1 and Comparative Example 1 above, and add 100 parts of vinyl chloride resin, calcium stearate, and The mixture was uniformly kneaded with 2 parts of zinc to obtain a sheet having a thickness of 1.0 to 1.2.

At the same time, a sheet to which no reactant was added was kneaded as a target product 1. The processability, antistatic properties, and bleedability of this sheet were measured by the following methods. 1 Processability: When kneading into vinyl chloride resin with a roll, the time (seconds) required for uniform kneading was measured.

11 Antistatic property: The surface resistivity was measured using a super megohmmeter SM-10E model (manufactured by Toa Denpa Kogyo) under conditions of 20° C. and 50% RH.

111 Bleedability: Thickness 1, size 100 x 100W
A sheet of L was sandwiched between two glass plates, placed on a table, a load of 50k9 was applied to the flat surface, and the sheet was left for 15 days. Observe the adhesion of bleed material to the glass plates and evaluate using the following criteria. did.

◎: Almost no deposits.

0: Adhering in dots.

Δ: Partially adhered in a planar manner.

×: Adhered mostly in a planar manner.

Example 2 Obtained from olefin by oxo method.

R1-CH2-COOH and (Rl, R2, R3 each have 14 to 17 carbon atoms and 7 to 16 carbon atoms
, 1 to 8 alkyl groups) in a weight ratio of (1):(2
) = 65:35 ratio of total carbon number 16 to 1
853 parts of an adduct obtained by reacting 2B parts of the mixed fatty acid of No. 9 with 58 parts of propylene oxide at 165 to 185°C in the presence of 4 m parts of caustic potassium, 195 parts of itaconic acid, and balatoluenesulfonic acid (hereinafter referred to as P) as a catalyst. '1SA) and 1 part of hydroquinone as a polymerization inhibitor at 140 to 150°C while blowing nitrogen gas.
A dehydration esterification reaction was carried out for a period of time to obtain a reaction product of 10 nodules.

Add 102 parts of epichlorohydrin to the total amount of the reaction product obtained.
After dropping at 0° C., reaction was carried out for 3 hours, and unreacted epichlorohydrin was distilled off in the same manner as in Example 1. After washing this reaction product with water to remove PTSAI hydroquinone and excess itaconic acid, the analytical values were: acid value 0.2 (theoretical acid value 0), ester value 104.7 (theoretical ester value 105.6). Ta.

(This is referred to as Reactant 2) Comparative Example 2 5 (a) parts of propylene oxide was added to 270 parts of decomposed fatty acids of hardened beef tallow (IVll.5) in the presence of 4 parts of caustic soda at 165 to 185°C. Obtained adduct 8
Add 195 parts of itaconic acid, 1 part of PTSAll, and 1 part of hydroquinone to the marked area, and heat at 140 to 150°C under a nitrogen gas stream.
The esterification reaction was carried out for 5 hours to obtain 1025 parts of a reaction product.

One part of epichlorohydrin was added dropwise to the entire amount of the obtained reaction product at 80 to 90°C, and the reaction was completed by stirring at the same temperature for 3 hours, and unreacted epichlorohydrin was distilled off in the same manner as in Example 1. The residue was removed, washed with water, and then dehydrated to obtain 1040 parts of a reaction product. Analysis of this resulted in an acid value of 0.4. (This is referred to as comparative product 2) Measurement example 2 3 parts each of the above reactant 2 and comparative product 2 were added to 1 part of vinyl chloride resin.
(1) part, calcium stearate - knead uniformly with 3 parts of zinc to a thickness of 1.0 to 1.17V! I got a sheet of

At the same time, as a target product, a sheet of the above formulation to which no reactant was added was kneaded. The processability, antistatic property, and bleedability of the obtained sheet were measured in the same manner as in Measurement Example 1. The results are shown in Table 2. Example 3 Vinyl chloride
1 part polyvinyl alcohol 0.
8 parts azobisisobutyronitrile 1.6 parts distilled water 4 (1) parts To the above formulation,
Two parts of Reactant 2 was added, charged into a pressure vessel, and emulsion polymerized for one cry while stirring at 40±5°C. The obtained latex was washed several times with methanol, dried under reduced pressure, and then copolymer A was prepared. I got it.

Copolymer B was obtained by adding 2 parts of Comparative Product 2 in place of Reactant 2 and carrying out emulsion polymerization in the same manner. Further, copolymer C was obtained by carrying out emulsion polymerization in the same manner using only the above formulation. 10(2) each of the obtained copolymers A, B, and Cl and 2 parts of calcium-zinc stearate were uniformly kneaded to a thickness of 1.1 to 1.2 mm.
I got a sheet of The electrical resistance of the sheets of copolymers A, B, and C was measured. The results are shown in Table 3. The calcium-zinc stearate used in the above kneading is a composite stabilizer of calcium stearate and zinc stearate.

Claims (1)

[Claims] 1 General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) (However, R_
1 is an alkyl group having 8 to 20 carbon atoms) and ▲ mathematical formula, chemical formula,
There are tables, etc.▼(2) (However, R_2 has 4 to 1 carbon atoms.
9 alkyl group, R_3 is an alkyl group having 1 to 10 carbon atoms), (1) and (2) are 30:70 to 70:3
One part of ethylene oxide or propylene oxide is added to a fatty acid having a total carbon number of 10 to 22 mixed at a weight ratio of 0.
The reaction product obtained by reacting epichlorohydrin or alkyl halohydrin with the carboxyl group of a monoester of an aliphatic dicarboxylic acid obtained by reacting the adduct with ~50 moles added with an aliphatic dicarboxylic acid is used. Characteristic synthetic polymer modifier.