JPH0242853B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a chlorosulfonated polyethylene composition, and more particularly to a chlorosulfonated polyethylene composition in which the processability of an unvulcanized composition is significantly improved. [Prior art and problems] In general, chlorosulfonated polyethylene exhibits severe adhesion during processing, especially to rolls, and low molecular weight polyethylene, paraffin wax, stearic acid and its derivatives are used as processing aids. It's here. However, these processing aids have problems such as whitening of the surface due to bloom and the risk of scorch when compounding Resurge, and no processing aid has been found that has less adverse effects outside of processing. Furthermore, although there is a rubber composition with improved processability using polyhydric alcohol ester, wax, etc. in JP-A-59-27939, it is not sufficient. The rubber composition of the present invention further has an improved effect of preventing adhesion to rolls. The need for processing aids for chlorosulfonated polyethylene is well known, as it significantly reduces productivity due to severe adhesion to the surface of processing machines such as rolls, and also makes kneading impossible, resulting in poor dispersion of reinforcing agents, etc. It is considered indispensable from the viewpoint of processability, especially prevention of adhesion. As a result of intensive studies, the present inventors discovered that a specific polymeric acid ester, liquid polybutadiene derivative, low molecular weight polyethylene derivative, or rosin acid derivative has improved processability and less risk of blooming, leading to the present invention. . That is, the present invention uses chlorosulfonated polyethylene.
For 100 parts by weight, dimer acid ester, liquid polybutadiene derivative, polyethylene (molecular weight 1000
Chlorsulfonated polyethylene with improved processability, characterized in that it contains 0.5 part by weight or more of a compound selected from the group consisting of an acidic group-introduced product (~10,000), an ester thereof or an amide thereof, and a rosin acid soap. A composition is provided. The polymerized acid ester according to the present invention is preferably a dimer acid ester, and the alcohol component includes alcohols having 8 to 22 carbon atoms such as octanol, decyl alcohol, lauryl alcohol, myristyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol, etc. Examples of the alcohol include (poly)ethylene glycol, (poly)propylene glycol, glycerin, pentaerythritol, sorbitol, and trimethylolpropane. Moreover, the form of ester includes monoester, diester, and polyester. In addition, the liquid polybutadiene derivatives according to the present invention include those obtained by modifying liquid polybutadiene with a hydroxyl group, a carboxyl group, an epoxy group, or maleic anhydride, and a higher alcohol having 6 to 22 carbon atoms, a fatty acid having 8 to 22 carbon atoms, Examples include esterification or amidation with adipic acid, phthalic acid, maleic acid, etc., or fatty acid amines having 8 to 22 carbon atoms as bases. The low molecular weight polyethylene derivative is preferably a polyethylene wax having an acidic group obtained by introducing a carboxyl group or maleic anhydride into polyethylene having a molecular weight of 1,000 to 10,000, and a polyethylene wax having a carbon number of 6 to 6.
It is esterified or amidated with a higher alcohol having 22 carbon atoms or an aliphatic amine having 8 to 22 carbon atoms. Others include rosin acid soaps. These may be used alone or in combination. In the composition of the present invention, the amount of the processing aid shown above is
The amount is preferably 0.5 to 20 parts by weight, more preferably 2 to 10 parts by weight per 100 parts by weight. In addition to the processing aid of the present invention, the composition of the present invention may optionally contain compounding agents commonly used in the rubber industry, such as vulcanizing agents, vulcanization accelerators, fillers, softeners, anti-aging agents, etc. I can do things. [Examples] The composition of the present invention will be described with reference to Examples, but the present invention is not limited to these Examples. Furthermore, it goes without saying that there are other methods of synthesis and other conditions. A processing aid was synthesized as follows. Processing aid 1: 578 g (1.0 mol) of dimer acid, 274 g (1.0 mol) of stearyl alcohol, and 0.85 g (0.1% vs. total system) of tin dioctylate in a nitrogen stream.
A dehydration reaction was carried out at 220°C for 2 hours to obtain dimer acid monostearate (DMS). Processing aid 2 578 g (1.0 mol) of dimer acid, 131 g (1.0 mol) of octyl alcohol, and 0.71 g (0.1% of the total system) of tin dioctylate were subjected to a dehydration reaction under the same conditions as processing aid 1, and dimer acid mono Octyl (DM) was obtained. Processing aid 3: 578 g (1.0 mol) of dimer acid, 548 g (2.0 mol) of stearyl alcohol, and 1.13 g (0.1% vs. total system) of tin dioctylate were added to processing aid 1.
A dehydration reaction was carried out under the same conditions as above to obtain dimer acid distearate (DDS). Processing aid 4 578 g (1.0 mol) of dimer acid, 31 g (0.5 mol) of ethylene glycol, and 0.61 g (0.1% of the total system) of tin dioctylate were dehydrated under the same conditions as processing aid 1 to produce ethylene dimer acid. Glycol ester (DEG) was obtained. Processing aid 5 Dimer acid 578g (1.0mol), propylene glycol 77g (1.0mol), oleyl alcohol 272g (1.0mol), tin dioctylate
0.93 g (0.1% vs. total system) was subjected to a dehydration reaction under the same conditions as Processing Aid 1 to obtain dimer acid propylene glycol oleyl alcohol ester (DP). Processing aid 6 hydroxyl terminal liquid polybutadiene 2500
g (1.0 mol), stearic acid 553 g (2.0 mol), tin dioctylate 3.1 g (0.1% vs. total system)
After dehydration reaction under the same conditions as Processing Aid 1, polybutadiene diol stearate (PB2S) was obtained. Processing aid 7 Maleic anhydride modified liquid polybutadiene 2500g (1.0mol) and octyl alcohol
262g (2.0mol), tin dioctylate 2.8g (0.1
% vs. total system) under the same conditions as Processing Aid 1 to obtain maleated polybutadiene octyl ester (MPB). Processing aid 8 hydroxyl terminal liquid polybutadiene 2500
g (1.0 mol) and phthalic anhydride 296 g (2.0 mol)
was added, esterified at 120℃ for 1 hour in a nitrogen stream, cooled, and further added with 534 g of stearylamine.
(2.0 mol) was added and amidation was performed at 155°C for 1 hour to obtain polybutadiene phthalate stearylamide (PBPSA). Processing aid 9 Carboxyl group-introduced low molecular weight polyethylene 2600g (1.0mol), stearyl alcohol 507g (1.85mol), tin dioctylate 3.1
(0.1% vs. total system) was esterified under the same conditions as processing aid 1 to obtain low molecular weight polyethylene stearate (PEST). Processing aid 10: 2600g (1.0mol) of carboxyl-introduced low molecular weight polyethylene and stearylamine
495 g (1.85 mol) was amidated under the same conditions as Processing Aid 1 to obtain low molecular weight polyethylene stearylamide (PESA). Processing aid 11 Rosin acid 320g (1.0mol), ZnO40.5
g (0.5 mol) was subjected to a dehydration reaction at 160° C. for 3 hours in a nitrogen stream to obtain rosin acid Zn salt (RZN). A composition of the present invention was obtained by adding 3.0 parts by weight of these processing aids to the following formulation. As a comparative example,
Low molecular weight polyethylene, paraffin wax, stearic acid, and stearic acid monoglyceride were added. The amount added was 3.0 parts by weight. Compound Hypalon #40 100 parts by weight MgO 4 Pentaerythritol 3 Accelerator TRA 2 Dixie clay 30 Shiroyahana CC 45 Empara #40 30 The processing characteristics, vulcanization characteristics, etc. of these compositions were examined. Kneading is done using oven rolls, and the unvulcanized properties are
Compliant with JIS K6300. In addition, the vulcanization physical properties are 160℃,
The composition was cured for 15 minutes in accordance with JIS K6301. Bloom was confirmed by leaving the vulcanized rubber in a room at 35°C for 7 days and observing its surface. Table 1 shows the results.
It was shown to.

【table】

【table】

[Table] As can be seen from Table 1, roll adhesion was improved in all Examples, and no bleeding was observed. It is also clear that the physical properties after vulcanization hardly deteriorate. Comparative examples include low molecular weight polyethylene and paraffin wax, which exhibits bleeding, and stearic acid, which is undesirable because it causes rapid scorch. Furthermore, stearic acid monoglyceride has insufficient anti-blocking properties.

Claims (1)

[Claims] 1. For 100 parts by weight of chlorosulfonated polyethylene, add a compound selected from the group consisting of dimer acid esters, liquid polybutadiene derivatives, acidic group introduction products to polyethylene (molecular weight 1000 to 10000), esters thereof or amides thereof, and rosin acid soaps. A chlorosulfonated polyethylene composition with improved processability, characterized in that it contains 0.5 parts by weight or more.