Bio-based low-rolling-resistance improving auxiliary agent as well as preparation method and application thereof

Abstract

The invention discloses a bio-based low-rolling-resistance improving auxiliary agent as well as a preparation method and application thereof. The auxiliary agent is prepared by heating and mixing a bio-based raw material, PEG (polyethylene glycol) and a high-flash-point amine raw material, the bio-based raw material is one or more of oleamide, erucyl amide, octadecanamide and bis (ethylene) octadecanamide; the molecular weight of PEG is more than 1000g / mol; the amine raw material with the high flash point is N, N-dimethylethanolamine and / or N, N-dimethyl-3-methoxypropylamine, and the amine raw material with the high flash point is N, N-dimethylethanolamine and / or N, N-dimethyl-3-methoxypropylamine. The preparation method comprises the following steps: heating and stirring the bio-based raw materials until the bio-based raw materials are molten, then adding PEG, continuously stirring, sufficiently and uniformly mixing, then adding the high-flash-point amine raw materials, and continuously heating and stirring until all the raw materials are molten into a liquid state. A rubber tire prepared by adding the improvement auxiliary agent into a tread rubber material can effectively reduce the rolling resistance and improve the production safety, and is environment-friendly.

Description

Technical Field

[0001] The invention relates to the technical field of rubber production, and in particular to a bio-based low rolling resistance improving additive and a preparation method and application thereof. Background Art

[0002] Tire rolling resistance refers to the deformation of the tire during the rolling process on the road, which causes part of the energy of the car to be consumed in the form of heat energy, increasing the fuel consumption of the car and reducing the fuel efficiency of the car. Rolling resistance not only affects the fuel consumption of the vehicle, but also affects the service life of the tire.

[0003] As people's environmental awareness and safety awareness are increasing, higher requirements are placed on the performance of tires. After the formal implementation of the EU tire labeling law, tires with low rolling resistance and high wet skid resistance have become a research hotspot in recent years. As the part of the tire that directly contacts the ground, the tread has a great impact on the tire's rolling resistance and wet skid resistance. Therefore, the formula design of the tread rubber compound is particularly important. Various tire manufacturers and scientific research institutions have been researching and developing low rolling resistance and high wet skid resistance tread rubber compositions.

[0004] In order to reduce rolling resistance, the improvement method of tread rubber materials is generally to add unsaturated fatty acid zinc salt as a dispersant to the tread rubber material composition. Since the dispersant contains unsaturated double bonds, part of the vulcanizing agent will be consumed during the vulcanization process, resulting in a low crosslinking density of the vulcanized rubber, affecting the physical properties. Some countries recommend limiting the use of zinc or zinc oxide in tires and prohibiting the sale of tire products containing a certain amount of zinc, because the release of zinc can be toxic to microorganisms and aquatic organisms. Adding silane coupling agents can improve the dispersibility of white carbon black, but its principle is mainly that the silane coupling agent and white carbon black undergo a condensation reaction to release volatile organic alcohol gases, which greatly increases VOC emissions, and low flash point alcohols can also cause safety hazards in the workshop. Summary of the invention

[0005] The purpose of the present invention is to provide a bio-based low rolling resistance improving additive, which can effectively improve the dispersibility of white carbon black, has no zinc additive in the formula, is environmentally friendly, has no VOC emissions, has a mild preparation process, and improves production safety.

[0006] The technical solution of the present invention is described in detail as follows: In a first aspect, the present invention provides a bio-based low rolling resistance improving agent, which is prepared by heating and mixing a bio-based raw material, PEG and a high flash point amine raw material; The bio-based raw material is one or more of oleamide, erucamide, stearamide and diethylene stearamide; The PEG molecular weight is above 1000 g / mol; The high flash point amine raw material is N,N-dimethylethanolamine and / or N,N-dimethyl-3-methoxypropylamine.

[0007] Optionally or preferably, in the above-mentioned bio-based low rolling resistance improving agent, the PEG molecular weight is 4000 g / mol.

[0008] Optionally or preferably, in the above-mentioned bio-based low rolling resistance improving agent, the ratio of the bio-based raw material, PEG and high flash point amine raw material is 60~70: 30~20:1~5 by mass.

[0009] In a second aspect, the present invention provides a method for preparing any of the above-mentioned bio-based low rolling resistance improving additives, which comprises heating and stirring the bio-based raw materials until they are melted, then adding PEG and stirring and mixing them thoroughly, then adding a high flash point amine raw material, and continuously heating and stirring and mixing until all the raw materials are melted into a liquid state. During the preparation process, the heating temperature should be maintained at a temperature that can melt all the raw materials.

[0010] Optionally or preferably, in the preparation method, the heating temperature is 72°C-146°C.

[0011] Optionally or preferably, in the preparation method, the stirring rate is 60 r / min ~100 r / min.

[0012] Optionally or preferably, in the preparation method, the stirring time during the preparation process is 30 min to 60 min.

[0013] In a third aspect, the present invention provides the use of any of the above-mentioned bio-based low rolling resistance improving additives in the preparation of rubber products.

[0014] In a fourth aspect, the present invention provides a rubber tire product, comprising any of the above-mentioned bio-based low rolling group improvement additives, wherein the amount of the bio-based low rolling group improvement additive added to the rubber tire raw material formula is 0.5-1phr.

[0015] Compared with the prior art, the present invention has the following beneficial effects: The bio-based low rolling resistance improvement agent provided by the present invention has simple raw materials and a mild preparation process, can effectively improve the dispersibility of white carbon black, and has no zinc additive in the formula, is environmentally friendly, and has no VOC emissions. When added to the tread rubber material composition, it can significantly improve the environmental performance of rubber products and reduce the rolling resistance of rubber tires. The amount of white carbon black added to a general semi-steel radial tire is relatively high, and the dispersibility requirements of white carbon black are relatively high. The bio-based low rolling resistance improvement agent of the present invention can well disperse white carbon black, so in addition to being applied to general rubber tires, it is more suitable for application to semi-steel radial tires. DETAILED DESCRIPTION

[0016] In order to make the technical personnel in this field better understand the present application scheme, the present application will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are only embodiments of a part of the present application, rather than all embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without making creative work should belong to the scope of protection of this application. The instruments and reagents used in the embodiments are all derived from commercial channels unless otherwise specified.

[0017] Example 1 60g of oleic acid amide was placed in a reaction flask, heated to 80°C to melt it, and stirred at 60r / min; then 30g of PEG with a molecular weight of 4000g / mol was added, and after the PEG became molten, 4g of N,N-dimethylethanolamine was added, and stirred at a constant speed for 45min to fully mix the ingredients until all the raw materials were melted into a liquid state; after the end, the material was filtered to obtain a bio-based low rolling resistance improvement additive.

[0018] Example 2 65g of erucic acid amide was placed in a reaction flask, heated to 80°C to melt it, and stirred at 60r / min; then 30g of PEG with a molecular weight of 4000g / mol was added, and after the PEG became molten, 3g of N,N-dimethylethanolamine was added, and stirred at a constant speed for 45min to fully mix the ingredients until all the raw materials were melted into a liquid state; after the end, the material was filtered to obtain a bio-based low rolling resistance improvement additive.

[0019] Example 3 70g of stearic acid amide was placed in a reaction flask, heated to 80°C to melt it, and stirred at 60r / min; then 20g of PEG with a molecular weight of 4000g / mol was added, and after the PEG became molten, 1g of N,N-dimethyl-3-methoxypropylamine was added, and stirred at a constant speed for 45min to fully mix the ingredients; after the end, the material was filtered to obtain a bio-based low rolling resistance improvement additive.

[0020] Comparative Example 1 55 g of molecular weight PEG4000 was placed in a reaction flask, heated to 80°C, and kept stirring at 60 r / min; after PEG became molten, it was stirred at a constant speed for 45 min at room temperature; the temperature was lowered to room temperature, 1 g of AMP-95 was added, and the material was filtered out.

[0021] The above-mentioned Examples 1-3 and Comparative Example 1 are added as functional additives to the tread rubber material composition, with the same addition amount and the same rubber preparation process. The rubber raw material formula is shown in the following table: Table 1 Rubber raw material formula and addition amount Note: Phr (Parts per Hundred) refers to the number of parts added per 100 parts (by mass) of rubber. SSBR2257S is an oil-extended solution-polymerized styrene-butadiene rubber, with 75.7phr added, of which 55phr is styrene-butadiene rubber and the remaining 20.7phr is oil, which plays a plasticizing role in the formula.

[0022] The obtained rubber was subjected to a temperature scanning experiment using a DMA (dynamic mechanical analyzer), with a temperature scanning range of -50 to 80°C, a frequency of 20 Hz, a static strain of 10%, and a dynamic strain of 2%.

[0023] The test results show that the rolling resistance values ​​of the rubber products prepared by adding the functional additives of Examples 1-3 are all lower than 0.15, which is significantly better than the rubber product prepared in Comparative Example 1. In addition, the formula contains no zinc and does not emit VOC, and the production safety and environmental friendliness are significantly improved.

[0024] The invention concept is described in detail using specific examples herein, and the description of the above embodiments is only used to help understand the core idea of ​​the invention. It should be pointed out that any obvious modification, equivalent substitution or other improvement made by a person of ordinary skill in the art without departing from the invention concept should be included in the protection scope of the present invention.

Claims

1. A bio-based low rolling resistance improving agent, characterized in that: Made by heating and mixing bio-based raw materials, PEG and high flash point amine raw materials; The bio-based raw material is one or more of oleamide, erucamide, stearamide and diethylene stearamide; The PEG molecular weight is above 1000 g / mol; The high flash point amine raw material is N,N-dimethylethanolamine and / or N,N-dimethyl-3-methoxypropylamine.

2. The bio-based low rolling resistance improving agent according to claim 1, characterized in that: The PEG molecular weight is 4000 g / mol.

3. The bio-based low rolling resistance improving agent according to claim 1, characterized in that: By mass, the ratio of the bio-based raw materials, PEG and high flash point amine raw materials is 60~70: 30~20:1~5.

4. The method for preparing the bio-based low rolling resistance improving agent according to any one of claims 1 to 3, characterized in that: Heat and stir the bio-based raw materials until they are melted, then add PEG and continue stirring to mix thoroughly, then add the high flash point amine raw materials, continue heating and stirring until all the raw materials are melted into a liquid state.

5. The preparation method according to claim 4, characterized in that: The heating temperature is 72℃~146℃.

6. The preparation method according to claim 4, characterized in that: The stirring rate is 60 r / min to 100 r / min.

7. The preparation method according to claim 4, characterized in that: The stirring time during the preparation process is 30min~60min.

8. Use of the bio-based low rolling resistance improving agent according to any one of claims 1 to 3 in the preparation of rubber products.

9. A rubber tire product, characterized in that: The invention contains the bio-based low rolling group improving agent as claimed in any one of claims 1 to 3, wherein the addition amount of the bio-based low rolling group improving agent in the rubber tire raw material formula is 0.5-1phr.

Images