JPS6272733A - Processing aid for diene rubber - Google Patents

Abstract

PURPOSE:To provide a processing aid for diene rubber capable of remarkably improving the processability of unvulcanized rubber, keeping the mechanical properties of vulcanized rubber and exhibiting extremely low blooming and bleeding tendency, by using a specific ester as a component. CONSTITUTION:The objective processing aid is composed of (A) an ester of a polymer acid or a 6-30C alkenylsuccinic acid (anhydride) and a 8-22C higher alcohol or a >=3 hydric polyhydric alcohol, (B) an ester of a liquid butadiene having OH group and phthalic acid (anhydride), trimellitic acid, pyromellitic acid (anhydride) or a 12-30C higher fatty acid and (C) an amide or ester of a liquid butadiene having COOH group or liquid polybutadiene modified with maleic anhydride and a 12-30C aliphatic amine or 8-22C higher alcohol. 1-20pts.wt. of the processing aid is added to 100pts.wt. of a diene rubber.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a processing aid for diene rubber.

More specifically, the present invention relates to a processing aid that significantly improves the processability of unvulcanized rubber, does not impair the mechanical properties of vulcanized rubber, and causes extremely little plume and bleed.

[Conventional technology and problems]

It is generally known that various process oils and plasticizers are added to diene rubbers in order to impart plasticity and improve processability. However, although these can improve the processability, particularly the plasticity, of unvulcanized rubber, they have the problem of deteriorating the mechanical properties of vulcanized rubber, particularly physical properties such as tensile properties and hardness.

In addition, various esters such as pentaerythritol tristearate, monoglyceride, rice bran wax, paraffin wax, fatty acid metal soap, etc. are usually used as processing aids. Although these can also be expected to improve processability, there are problems such as plume and bleed of the vulcanized rubber.

Taking the above points into consideration, the present inventors added plasticity to the diene rubber during processing to improve processability, and after vulcanization, the mechanical properties did not deteriorate and the occurrence of plume and bleed was minimized. As a result of intensive research into processing aids that can improve processability while reducing the amount of esters used, we found that when a specific ester is blended with diene rubber, processability is greatly improved, without deteriorating the mechanical properties of vulcanized rubber. In addition, it was discovered that plume bleed was extremely small, leading to the present invention.

That is, the present invention provides (1) a polymeric acid or a carbon atom having 6 to 3 carbon atoms;
Ester of 0 alkenylsuccinic acid (anhydride) and higher alcohol having 8 to 22 carbon atoms or polyhydric alcohol having 3 or more hydroxyl groups, (2) Liquid polybutadiene having a hydroxyl group in the molecule and phthalic acid (anhydride) or an ester of trimellitic acid or (anhydrous) pyromellitic acid or a higher fatty acid having 12 to 30 carbon atoms, and (3) liquid polybutadiene having a carboxyl group in the molecule or a liquid polybutadiene modified with maleic anhydride and 12 to 30 carbon atoms. 30 aliphatic amines or 8 to 2 carbon atoms
The present invention provides a processing aid for diene rubber comprising a compound selected from the group consisting of amides or esters with higher alcohols.

The alkenylsuccinic acid (anhydride) having 6 to 30 carbon atoms according to the present invention (1) is preferably a product obtained by reacting an α-olefin with 2 to 26 carbon atoms and maleic anhydride; It may be a specific α-olefin among 2 to 26, or a mixture thereof.

Polymer acids include unsaturated fatty acids having 14 to 22 carbon atoms;
For example, preferred are dimers or more of myristoleic acid, palmitoleic acid, oleic acid, erucic acid, linonylic acid, lylinic acid, and the like.

Examples of higher alcohols having 8 to 22 carbon atoms include saturated or unsaturated higher alcohols such as octatool, decanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, eicosanol, and docosanol.

Preferred polyhydric alcohols having 5 or more hydroxyl groups include glycerin, polyglycerin, trimethylolpropane, hentaerythritol, dipentaerythritol, mannitol, glucose, and sorbitol.

Next, the liquid polybutadiene ester or amide (2) and (3) according to the present invention will be explained. The liquid polyphtadiene modified product constituting these esters and amides is preferably one in which one or more hydroxyl group, carboxyl group, or maleic anhydride is introduced into one molecule of polybutadiene having a molecular weight of 300 to 6,000. (2
) The higher fatty acids having 12 to 30 carbon atoms that are the constituent fatty acids of Examples include fatty acids. Further, the polybasic acids include phthalic acid, trimellitic acid, and pyromellitic acid, and of course, anhydrides of these acids may also be used. Examples of the aliphatic amine having 12 to 3 carbon atoms in (3) include laurylamine, tetradecylamine, cetylamine, octadecylamine, eicosylamine, tocodylamine, hexacosylamine, and the like. Examples of higher alcohols having 8 to 22 carbon atoms include saturated or unsaturated higher alcohols such as octatool, decanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, eicosanol, and docosanol.

The ester or amide compound according to the present invention may be further mixed with finely divided silica powder if necessary. A suitable mixing ratio is 30 to 200 parts by weight of silica powder to 100 parts by weight of the ester or amide compound, thereby improving milletability.

The amount of the processing aid added in the present invention is preferably 1 to 20 parts by weight per 100 parts by weight of the diene rubber. This tends to lower the physical properties of the rubber and is not very effective from a cost standpoint.Particularly preferred is 2 to 10 parts by weight.

When using the processing aid of the present invention, in addition to the processing aid of the present invention, compounding agents commonly used in the rubber industry, such as vulcanizing agents, vulcanization accelerators, fillers, softeners, and anti-aging agents, are required. etc. can be added as appropriate.

In addition, the processing aid of the present invention includes SBR, natural rubber, NBR%
It can be used for all diene rubbers such as F, PDM, OR%BR.

〔Example〕

Next, the processing aid 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 than these.

The processing aid of the present invention was synthesized as follows.

Processing aid 1 Flukenylsuccinic anhydride having 12 carbon atoms 2b6t (1,0 mol), lauryl alcohol 186
F (1.0 mol) was reacted at 130°C for 2 hours in a nitrogen stream to form alkenyl co-sulfur laurate (ASL).
) was obtained.

Processing aid 2 Alkenylcono-phosphoric acid with 6 carbon atoms! Water: 182 t (1.0 mol), oleyl alcohol: 26
8t (1,0 mol) was esterified under the same conditions as in Example 1 to form alkenylsuccinic acid oleate (AS
O) was obtained.

Processing aid 3 Dimer acid 578 F (1.0 mol)
, stearyl alcohol 274 t (1,a mol),
Tin dioctylate a, sst (o, 1% vs. the entire system) was subjected to dehydration reaction at 220°C for 2 hours in a nitrogen stream to obtain timer acid monostearate (DMS) Processing aid 4 Maleic anhydride modified liquid 1,300 f (1,0 mol) of polybutadiene, 360 f (1,3 mol) of stearyl alcohol, 1.
86f (0.1% vs. the entire system at 180°C in a nitrogen stream, 5
A time dehydration reaction was performed to obtain maleated polybutadiene stearate (MPBS).

Processing aid 5 Hydroxyl group-introduced liquid polybutadiene 2.00
0 F (1,0 mol) to 296 t of phthalic anhydride (2,0 mol)
0 mol) was added, esterification was carried out at 120°C for 1 hour in a nitrogen stream, then cooled, and 570 t of laurylamine was added.
(2.0 mol) was added and amidation was carried out at 155° C. for 2 hours to obtain polybutadiene phthalate laurylamide (PBPLA).

Processing aid 6 Carboxyl group-introduced liquid polybutadiene 3,300 t (1.0 mol), lauryl alcohol 372 t (2.0 mol), tin dioctylate 3.9
t (o, 1% vs. total system) was esterified under the same conditions as processing aid 4 to form polybutadiene laflate (PBL).
I got it.

Processing aid 7 Ester of processing aid 1 (ASL) 100
Add Tokusil U (powdered silica) 30F to f,
A mixture (5tAsL) was obtained.

Processing aid 8 Ester of processing aid 4 (MPBS) 1
00t, 200t of Tokusil U (powdered silica) was added to obtain a mixture (SiMPBS).

Processing aid 9 Ester of processing aid 6 (PBL) 100
Toxil U (powdered silica) Sat was added to f to obtain a mixture (51 pBL).

In order to clarify the effects of these processing aids of the present invention, the following test N was conducted. 12 Test Example 1 Styrene-butadiene copolymer rubber 1oo M esters and ester mixtures of processing aids 1 to 9 as examples, pentaerythritol tristearate, paraffin wax, and zinc stearate for comparison. 5 parts by weight were added to the following formulation and kneaded with an oven roll to prepare a rubber composition.

(Formulation) EJBR 1300 100 parts HAF Black 30I ZnO No. 5 3 # Stearic acid 11 Sulfur 1 part Accelerator CZ 1 # Unvulcanized properties conform to JIS K2SO3, vulcanized physical properties are compositions cured at 145°C for 55 minutes The work was carried out in accordance with J Engineering 5K6301.

The plume was confirmed by leaving the vulcanized rubber in a room at 35° C. for 7 days and observing its surface. The results are shown in Table-1.

As shown in Table 1, pentaerythritol tristearate and rough-in wax have lower Mooney viscosity and improved processability, but some plumes are observed in the vulcanizate. In addition, zinc stearate has a low viscosity reduction and has poor processability.

In all Examples, the viscosity decreased, the vulcanized physical properties were not impaired, and no plume was observed.

Test Example 2 For ethylene propylene copolymer rubber 100 tiiK, esters and ester mixtures of the above processing aids 1 to 9 were used as examples, and for comparison, bare; Three parts by weight of zinc stearate were added to each of the following formulations and kneaded using an open roll to prepare a rubber composition.

(Composition) EPDM (Nisglen 522) 100 parts FMF blank 1201 Paraffin oil 701 Stearic acid 11 Zinc white No. 5 5 parts Accelerator BZ 1.5 ##
TT
1##M
1.5# Iok 1
．． 51 Unvulcanized properties are based on I K-6300, and vulcanized physical properties are obtained by vulcanizing the composition at 160°C for 10 minutes.
-6301.

The plume was confirmed by leaving the vulcanized rubber in a room at 35° C. for 7 days and observing its surface. The results are shown in Table-2.

As shown in Table 2, the processing viscosity of pentaerythritol tristaneate decreased, but some plumes were observed. Paraffin wax and zinc stearate showed little decrease in processing viscosity, and zinc stearate showed a slight decrease in vulcanized physical properties. In all Examples, the processing viscosity was reduced, the vulcanized physical properties were not impaired, and no bloom was observed.

Claims (1)

[Scope of Claims] 1 (1) An ester of a polymeric acid or alkenylsuccinic acid (anhydride) having 6 to 30 carbon atoms and a higher alcohol having 8 to 22 carbon atoms or a polyhydric alcohol having 5 or more hydroxyl groups, ( 2) An ester of liquid polybutadiene having a hydroxyl group in the molecule and (anhydrous) phthalic acid, trimellitic acid, (anhydrous) pyromellitic acid, or a higher fatty acid having 12 to 30 carbon atoms, and (3) a carboxyl group in the molecule. Processing for diene rubber comprising a compound selected from the group consisting of an amide or an ester of liquid polybutadiene or a maleic anhydride-modified liquid polybutadiene having the formula and an aliphatic amine having 12 to 30 carbon atoms or a higher alcohol having 8 to 22 carbon atoms. Auxiliary agent.