CN1045095C - Plasticized EPDM ternary rubber sulfonate zinc salt products - Google Patents

Abstract

A new plasticized ethylene propylene ternary rubber (EPDM) sulfonate zinc salt product is characterized in that the plasticizer is linseed oil modified or soybean oil modified alkyd resin. Use oil-modified alkyd resin to plasticize EPDM sulfonate zinc salt, the dosage is less than 10%, which is less than the conventionally used zinc stearate, and can greatly reduce the glass transition temperature and melt surface of EPDM sulfonate zinc salt. The apparent viscosity, the processing temperature is about 120°C, which can improve the processing performance of zinc EPDM sulfonate, and can also improve the mechanical properties of zinc EPDM sulfonate.

Description

Plasticized EPDM ternary rubber sulfonate zinc salt products

The invention belongs to the field of plastic molding processing.

The ionomer formed after introducing ionic groups into the polymer molecular chain can significantly improve the polymer's modulus, elongation at break, tear resistance, wear resistance, Glass transition temperature and melt viscosity, etc. H. S. Makowiski et al., Polym. Preprints, 19(2), 292-295 (1978). These unique properties open up broad prospects for their industrial applications. By blending with ethylene-propylene terpolymer (EPDM) sulfonate zinc salt, the impact strength of polypropylene can be increased by 20 times, and that of polyethylene can be increased by 5 times, and it can maintain high tensile strength. Therefore, adding an appropriate amount of EPDM sulfonate zinc salt to polyolefin is an effective way to solve the problem of polyolefin toughening without significantly reducing its strength. Xi Xu, Shaoyun Guo and Huilin Li, Polymer-Plastics Techn. & Eng., 30(7), 251(1991). Xi Xu, Xiangsheng Zeng and Huilin Li, J. Appl. Polym. Sci., 44 (1992). However, the increase in melt viscosity will significantly lead to processing difficulties; the difference in viscosity from polyolefin melt is too large and it is difficult to blend the two evenly. An effective way to solve this problem is to use plasticizers. However, the amount of plasticizer used to plasticize ionomers is generally large (greater than 10%). If the amount of plasticizer is large, the strength of the ionomer will decrease. EPDM sulfonate is a newly developed ionomer in the past ten years with excellent performance. According to related reports, plasticizing EPDM sulfonate with alcohols, phthalates, stearic acid and its salts can make The apparent viscosity of the melt decreases, but the strength also decreases. H·S·Makowiski and R·D·Lundberg, Adv.Chem.Ser., 37, 187(1980); H·S·Makowiski et al., Am.Chem.Soc., Polym.Preprint, 20(2), 281( 1979). In recent years, zinc stearate has been used as a plasticizer. Although it can improve the mechanical properties and processing properties of ionomers, the temperature must be as high as 160°C to start melting and flowing, and the dosage is as high as 10%. H·S·Makowiski et al., Polymer Preprints, 19(2), 304(1978); R.D.Lundberg et al., Polymer Preprints, 19(2), 310(1978); Preferential Plasticization of Iono-meric Compounds, N· H. Canter, Edison and D. J. Buckley, Sr., U. S. Patent 3,847,854, Nov. 12, 1974, to Esso Research and Engineering Co.,.

The purpose of the invention is to provide a kind of plasticized EPDM sulfonic acid zinc salt new product for the deficiencies in the prior art. The plasticizer may be a linseed oil modified alkyd resin or a soybean oil modified alkyd resin. When using oil-modified alkyd resin to plasticize EPDM sulfonate zinc salt, the dosage is small (less than 10%), which can greatly reduce the glass transition temperature and melt apparent viscosity of EPDM sulfonate zinc salt, and improve the EPDM sulfonate zinc salt. Excellent processing performance, the processing temperature is about 120 ° C, and at the same time can improve the mechanical properties of EPDM sulfonate zinc salt.

The formula component (by weight) of the ethylene-propylene ternary rubber sulfonic acid zinc salt new product provided by the invention is:

EPDM sulfonic acid zinc salt (sulfonation degree 1.1075mol/kg) 80-98 parts

Oil-modified alkyd resin (soybean oil or linseed oil can be used to modify alkyd resin) 2-20 parts

Solvent (cycloethane) The optimum formula composition in appropriate amount (by weight):

Zinc salt of EPDM sulfonate 97.5 parts

Oil-modified alkyd resin 2.5 parts

Solvent (cycloethane) Appropriate amount

Weigh EPDM sulfonate zinc salt and oil-modified alkyd resin according to the above formula components, add oil-modified alkyd resin to the solution of EPDM sulfonate zinc salt and mix evenly, after flashing liquid and drying, in double The above-mentioned new product can be obtained by kneading at about 120°C for about 5 minutes on a roller rubber mill.

Provided below is a comparative example of prior art zinc EPDM sulfonate and its plasticized zinc EPDM sulfonate product and the new product of zinc EPDM sulfonate plasticized by the oil-modified alkyd resin of the present invention.

Comparative example 1

Add appropriate amount of acetylsulfuric acid to 5% EPDM cyclohexane solution at room temperature, stop the reaction with ethanol after 30 minutes, and neutralize with zinc acetate to obtain EPDM sulfonate zinc salt solution, then flash the solvent and dry in vacuo. The measured sulfonation degree of zinc EPDM sulfonate is 1.1075 mol/kg, and the glass transition temperature is 136°C.

Comparative example 2

180 grams of EPDM zinc sulfonate and 20 grams of zinc stearate prepared in the comparative example 1 were mixed for 5 minutes at a temperature of 180° C. on a two-roll rubber mill, and the melt of the plasticized zinc salt of EPDM sulfonate obtained was The apparent viscosity, glass transition temperature and mechanical properties are shown in Fig. 1, Table 1 and Table 2, respectively.

Example 1

5 grams of soybean oil modified alkyd resin (containing soybean oil 43%) and 195 grams of EPDM zinc sulfonate salts prepared in comparative example 1 are mixed uniformly in the solution, and the solvent is flashed after drying. Mix at 120°C for 5 minutes to obtain zinc EPDM sulfonate product plasticized with soybean oil-modified alkyd resin. Get 10 grams of soybean oil modified alkyd resin (containing soybean oil 43%) and 190 grams of EPDM zinc sulfonate equally, or get 20 grams of soybean oil modified alkyd resin (containing soybean oil 43%) and 180 grams of EPDM zinc sulfonate, The EPDM sulfonate zinc salt product of soybean oil modified alkyd resin plasticization was obtained under the above-mentioned conditions, as shown in Figure 1, Table 1 and Table 2, which are the melt apparent viscosity of these plasticized EPDM sulfonate zinc salt , glass transition temperature and mechanical properties.

Example 2

20 grams of linseed oil modified alkyd resins (containing linseed oil 55%) and 180 grams of EPDM sulfonic acid zinc salt that comparative example 1 makes are mixed in the solution, dry after the flash solvent, on the two-roll rubber mill Mix at 120°C for 5 minutes to obtain EPDM zinc sulfonate product plasticized with linseed oil modified alkyd resin. Get 20 grams of linseed oil modified alkyd resins (containing linseed oil 60%) and the EPDM zinc sulfonate salt that 180 grams of comparative example 1 makes equally in the solution and mix, dry after the flash solvent, on the two-roll rubber mill Knead at a temperature of 120°C for 5 minutes to obtain a zinc EPDM sulfonate product plasticized with linseed oil-modified alkyd resin. Figure 2 and Table 1 show the measured apparent melt viscosity and glass transition temperature of these plasticized zinc EPDM sulfonate salts, respectively.

Fig. 1 The relationship between apparent melt viscosity and shear rate of EPDM sulfonate zinc salt plasticized with soybean oil modified alkyd resin*

*Test temperature 190°C; 1-Zinc stearate 10%; 2-Soybean oil modified alkyd resin 2.5%; 3-Soybean oil modified alkyd resin 5%; 4-Soybean oil modified alkyd resin 10%.

Figure 2 The relationship between apparent melt viscosity and shear rate of EPDM sulfonate zinc salt plasticized with linseed oil modified alkyd resin*

*Test temperature 190°C; a-zinc stearate 10%; b-linseed oil (containing linseed oil 60%) modified alkyd resin 10%; c-linseed oil (containing linseed oil 55%) modified alkyd resin 10%.

Table 1 Glass transition temperature (Tg) of EPDM sulfonate zinc salt plasticized with oil-modified alkyd resin ^* sample 1 2 3 4 5 6 7 Tg(°C) 136 -59 -55 -57 -58 -50 -48

*1-EPDM zinc sulfonate; 2-Zinc stearate 10%; 3-Linseed oil (60% containing linseed oil) modified alkyd resin 10%; 4-Linseed oil (55% containing linseed oil) modified Alkyd resin 10%; 5- soybean oil (containing 43% soybean oil) modified alkyd resin 10%; 6- soybean oil (containing soybean oil 43%) modified alkyd resin 5%; 7- soybean oil (containing soybean oil 43%) modified Resistant alkyd resin 2.5%.

Table 2 Mechanical properties of zinc EPDM sulfonate plasticized with soybean oil-modified alkyd resin ^* sample 1 2 3 4 Tensile Strength (MPa) Elongation at Break (%) 9.11584 17.2800 14.1700 9.73553

*1 - Zinc Stearate 10%; 2 - Soybean Oil Modified Alkyd Resin 2.5%; 3 - Soybean Oil Modified Alkyd Resin 5%; 4 - Soybean Oil Modified Alkyd Resin 10%.

The plasticized EPDM zinc sulfonate product of the present invention has the following advantages compared with the EPDM zinc sulfonate plasticized with zinc stearate:

1. The processing temperature of EPDM sulfonate zinc salt is greatly reduced from 180°C to about 120°C;

2. The amount of oil-modified alkyd resin is less than 10%;

3. The glass transition temperature and apparent melt viscosity of EPDM zinc sulfonate plasticized with oil-modified alkyd resin were greatly reduced.

4. Significantly improved the mechanical properties of EPDM sulfonate zinc salt.

Claims (3)

1. A plasticized ethylene propylene ternary rubber sulfonate zinc salt product is characterized in that the formulation components (by weight) of the product are: Ethylene-propylene ternary rubber sulfonate zinc salt 80-98 parts Oil-modified alkyd resin 2-20 parts Cyclohexane Appropriate amount 2. According to the plasticized ethylene-propylene ternary rubber sulfonate zinc salt product according to claim 1, it is characterized in that the formula component (by weight) of the product is: Zinc salt of ethylene propylene ternary rubber sulfonate 97.5 parts Oil-modified alkyd resin 2.5 parts Cyclohexane Appropriate amount 3. The plasticized ethylene-propylene ternary rubber sulfonate zinc salt product according to claim 1 or 2, wherein the oil-modified alkyd resin is soybean oil-modified alkyd resin or linseed oil-modified alkyd resin.

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