Rubber operating oil and preparation method thereof

Abstract

The invention relates to the technical field of rubber processing aids, in particular to rubber processing oil and a preparation method thereof. The rubber operation oil is prepared from the following raw materials in parts by weight: 10-20 parts of petroleum-based resin, 10-20 parts of biological asphalt, 40-60 parts of biological base oil, 10-20 parts of petroleum-based oil and 0-2 parts of a catalyst. The rubber operating oil provided by the invention is healthy, harmless and sustainable, and can improve the wear resistance and tear resistance of a rubber compound.

Description

Technical Field

[0001] The invention relates to the technical field of rubber processing aids, and in particular to a rubber processing oil and a preparation method thereof. Background Art

[0002] Rubber operating oil plays an important role in the rubber processing process. It can improve the dispersibility of the formula materials by swelling the rubber, and enhance the compatibility of other raw materials with rubber during the processing process, thereby improving the processability and fluidity of the unvulcanized rubber compound, and further improving the dispersibility and performance of the raw materials in the rubber compound. At present, rubber operating oil is mainly petroleum-based mineral oil, but petroleum-based mineral oil is non-renewable and unsustainable, and mineral oil contains carcinogenic aromatic hydrocarbons.

[0003] A Chinese patent with patent publication number CN112063186A discloses a method for preparing an environmentally friendly rubber oil and the prepared environmentally friendly rubber oil. The environmentally friendly rubber oil is prepared by blending a modified resin liquid and a raw material oil. The problem that the rubber oil has poor compatibility with rubber is that it is difficult to meet environmental protection and performance requirements. However, there is no public technical solution for improving the wear resistance and tear resistance of the mixed rubber.

[0004] Therefore, providing a rubber operating oil that is healthy, harmless and sustainable and can improve the wear resistance and tear resistance of the mixed rubber is the main technical problem that needs to be solved at present. Summary of the invention

[0005] In the context of sustainable development and carbon emission reduction, this application aims at the requirements of production and material environmental protection sustainable development faced in the rubber processing process, and improves the wear resistance and tear resistance of rubber compounds. The first aspect of the present invention provides a rubber operating oil, which is prepared by raw materials including 10-20 parts of petroleum-based resin, 10-20 parts of bio-asphalt, 40-60 parts of bio-based oil, 10-20 parts of petroleum-based oil, and 0-2 parts of catalyst, by weight.

[0006] In one embodiment, the mass ratio of the petroleum-based resin to the bio-based oil is 1:(2.5-4).

[0007] In one embodiment, the petroleum-based resin includes one or more combinations of aliphatic petroleum resin, aromatic petroleum resin, copolymerized petroleum resin, alicyclic petroleum resin, and hydrogenated petroleum resin.

[0008] In one embodiment, the petroleum-based resin is a copolymerized petroleum resin, and the copolymerized petroleum resin is a C5 / C9 copolymerized petroleum resin.

[0009] In one embodiment, the C5 / C9 copolymer petroleum resin can be purchased from Henghe Materials Technology Co., Ltd., and the model is C5 / C9 copolymer petroleum resin.

[0010] In one embodiment, the bioasphalt comprises vegetable asphalt.

[0011] In one embodiment, the vegetable asphalt includes waste cooking oil and waste residue from soybean oil processing.

[0012] In this application, waste cooking oil and waste residue from soybean oil processing are used as plant asphalt, which can make the preparation of raw materials environmentally sustainable, and the use of waste cooking oil achieves the environmental sustainability of using recyclable raw materials as preparation raw materials.

[0013] In one embodiment, the bioasphalt is vegetable asphalt.

[0014] In one embodiment, the plant asphalt can be purchased from Weifang Daming Biotechnology Co., Ltd. and the model is plant asphalt.

[0015] In one embodiment, the bio-based oil includes rice bran oil and soybean oil.

[0016] In one embodiment, the bio-based oil is rice bran oil.

[0017] In one embodiment, the rice bran oil can be purchased from Jiangsu Delekang Biotechnology Co., Ltd., and the model is grade 3 rice bran oil.

[0018] In this application, bio-based oil and plant asphalt are used as raw materials for preparation and combined to achieve biorecyclability, and bio-based oil is used to replace petroleum-based rubber operating oil, which can achieve the effects of non-toxicity, environmental protection, low carbon, low cost, and sustainable development. It can also improve the compatibility of petroleum-based resins and bio-based oils in rubber operating oils, and further improve the wear resistance and tear resistance of the rubber compound during the application process of the rubber operating oil.

[0019] In one embodiment, the petroleum-based oil includes a combination of one or more of paraffin-based oil, naphthenic oil, and aromatic-based oil.

[0020] In one embodiment, the content of benzo(a)pyrene in the petroleum-based oil is less than or equal to 1 mg / kg, the content of polycyclic aromatic hydrocarbons containing benzene compounds in the petroleum-based oil is less than or equal to 10 mg / kg, and the petroleum-based oil can be purchased from Hansheng Petrochemical (Ningbo) Co., Ltd., model V500.

[0021] The benzene-containing compounds include benzo(a)pyrene, benzo(a)anthracene, benzo(e)pyrene, benzo(b)fluoranthene, dibenzo(a,h)anthracene, benzo(j)fluoranthene and benzo(k)fluoranthene.

[0022] In one embodiment, the catalyst includes aluminum chloride and ferric chloride.

[0023] In one embodiment, the catalyst is aluminum trichloride.

[0024] In one embodiment, the aluminum trichloride can be purchased from Shanghai MacLean Biochemical Technology Co., Ltd., and the model is aluminum trichloride.

[0025] In order to improve the compatibility of petroleum-based resin and bio-based oil in rubber operating oil, which is healthy, harmless and sustainable, and to improve the wear resistance and tear resistance of the rubber compound during the application of the rubber operating oil, the inventors found in the experimental process that by using 10-20 parts of petroleum-based resin, 10-20 parts of bio-asphalt, 40-60 parts of bio-based oil, 10-20 parts of petroleum-based oil, and 0-2 parts of catalyst for coordination, especially using a mass ratio of petroleum-based resin to bio-based oil of 1:

[0026] (2.5-4), the petroleum-based resin used is C5 / C9 copolymer petroleum resin, the bio-based oil used is rice bran oil, the vegetable asphalt used includes waste cooking oil and waste residue from soybean oil processing, and the petroleum-based oil model V500 is used for compounding. The compatibility of petroleum-based resin and bio-based oil can be improved, and the wear resistance and tear resistance of rubber operating oil can be further improved during the application process, so as to achieve the effect of health, harmlessness and sustainable development; the possible reason is that the double bonds in petroleum-based resin and bio-based oil undergo chemical reaction, thereby changing the lipophilicity of bio-based oil, and further increasing the compatibility of bio-based oil with petroleum-based resin.

[0027] A second aspect of the present invention provides a method for preparing a rubber processing oil, comprising the following steps:

[0028] The bio-based oil, petroleum-based resin and bio-asphalt are stirred, heated and mixed to obtain a mixture a;

[0029] A catalyst is added to the mixture a and mixed to obtain a mixture b, and petroleum-based oil is added to the mixture b and mixed to obtain a rubber processing oil.

[0030] In one embodiment, the method for preparing the rubber processing oil comprises the following steps:

[0031] The bio-based oil, petroleum-based resin and bio-asphalt are stirred and heated to 115-140° C. to obtain a mixture a;

[0032] Add a catalyst to mixture a, mix and keep warm for 1.5-2h to obtain mixture b. Stop heating and cool to 80-90°C, then add petroleum-based oil to mixture b to obtain rubber processing oil. Cool the rubber processing oil to room temperature before use.

[0033] Beneficial Effects

[0034] 1. In this application, bio-based oil and plant asphalt are used as raw materials for preparation, which can achieve bio-recyclability, and bio-based oil is used to replace petroleum-based rubber operating oil, which can achieve the effects of non-toxicity, environmental protection, low carbon, low cost, and sustainable development. It can also improve the compatibility of petroleum-based resins and bio-based oils in rubber operating oils, and further improve the wear resistance and tear resistance of the rubber compound during the application of rubber operating oils.

[0035] 2. In this application, waste cooking oil and waste residue from soybean oil processing are used as plant asphalt, which can make the preparation of raw materials environmentally sustainable, and the use of waste cooking oil achieves the environmental sustainability of using recyclable raw materials as preparation raw materials.

[0036] 3. This application improves the compatibility of petroleum-based resins and bio-based oils in rubber operating oils, which is healthy, harmless and sustainable, and improves the wear resistance and tear resistance of the rubber compound during the application process of the rubber operating oil.

[0037] 4. The rubber operating oil provided in this application can improve the tear strength and abrasion resistance of the mixed rubber and has excellent tear resistance and wear resistance.

[0038] 5. The rubber operating oil provided in this application is healthy, harmless and sustainable, and can improve the wear resistance and tear resistance of the mixed rubber. DETAILED DESCRIPTION

[0039] Example 1

[0040] The first aspect of the present embodiment provides a rubber processing oil, the raw materials for its preparation are, by weight, 17.62 parts of petroleum-based resin, 17.62 parts of bio-asphalt, 45.81 parts of bio-based oil, 17.62 parts of petroleum-based oil, and 1.32 parts of catalyst.

[0041] The petroleum-based resin is C5 / C9 copolymerized petroleum resin.

[0042] The C5 / C9 copolymer petroleum resin is purchased from Henghe Materials Technology Co., Ltd. and its model is C5 / C9 copolymer petroleum resin.

[0043] The bio-asphalt is plant asphalt.

[0044] The manufacturer of the vegetable asphalt is Weifang Daming Biotechnology Co., Ltd. and the model is vegetable asphalt.

[0045] The bio-based oil is rice bran oil.

[0046] The rice bran oil was purchased from Jiangsu Delekang Biotechnology Co., Ltd. and the model is grade 3 rice bran oil.

[0047] The content of benzo(a)pyrene in the petroleum-based oil is less than or equal to 1 mg / kg, and the content of polycyclic aromatic hydrocarbons containing benzene compounds in the petroleum-based oil is less than or equal to 10 mg / kg. The petroleum-based oil is purchased from Hansheng Petrochemical (Ningbo) Co., Ltd., model V500.

[0048] The catalyst is aluminum chloride.

[0049] The aluminum chloride was purchased from Shanghai MacLean Biochemical Technology Co., Ltd., and the model is aluminum chloride.

[0050] A second aspect of the present embodiment provides a method for preparing rubber processing oil, comprising the following steps:

[0051] The bio-based oil, petroleum-based resin and bio-asphalt are stirred and heated to 140° C. to obtain a mixture a;

[0052] A catalyst was added to mixture a, mixed and kept warm for 1.5 hours to obtain mixture b. After stopping heating and cooling to 80°C, petroleum-based oil was added to mixture b and mixed to obtain rubber processing oil. The rubber processing oil was cooled to room temperature before use.

[0053] Example 2

[0054] In a first aspect, the present embodiment provides a rubber processing oil, wherein the raw materials for preparing the rubber processing oil are, by weight, 16.67 parts of petroleum-based resin, 16.67 parts of bio-asphalt, 50 parts of bio-based oil, and 16.67 parts of petroleum-based oil.

[0055] The petroleum-based resin is C5 / C9 copolymerized petroleum resin.

[0056] The C5 / C9 copolymer petroleum resin is purchased from Henghe Materials Technology Co., Ltd. and its model is C5 / C9 copolymer petroleum resin.

[0057] The bio-asphalt is plant asphalt.

[0058] The manufacturer of the vegetable asphalt is Weifang Daming Biotechnology Co., Ltd. and the model is vegetable asphalt.

[0059] The bio-based oil is rice bran oil.

[0060] The rice bran oil was purchased from Jiangsu Delekang Biotechnology Co., Ltd. and the model is grade 3 rice bran oil.

[0061] The content of benzo(a)pyrene in the petroleum-based oil is less than or equal to 1 mg / kg, and the content of polycyclic aromatic hydrocarbons containing benzene compounds in the petroleum-based oil is less than or equal to 10 mg / kg. The petroleum-based oil is purchased from Hansheng Petrochemical (Ningbo) Co., Ltd., model V500.

[0062] A second aspect of the present embodiment provides a method for preparing rubber processing oil, comprising the following steps:

[0063] The bio-based oil, petroleum-based resin and bio-asphalt are stirred and heated to 140° C. to obtain a mixture a;

[0064] After the mixture is heated and cooled to 80°C, petroleum-based oil is added to the mixture a and mixed to obtain rubber processing oil. The rubber processing oil is cooled to room temperature before use.

[0065] Example 3

[0066] The first aspect of the present embodiment provides a rubber processing oil, the raw materials for its preparation are, by weight, 14.55 parts of petroleum-based resin, 14.55 parts of bio-asphalt, 55.27 parts of bio-based oil, 14.55 parts of petroleum-based oil, and 1.09 parts of catalyst.

[0067] The petroleum-based resin is C5 / C9 copolymerized petroleum resin.

[0068] The C5 / C9 copolymer petroleum resin is purchased from Henghe Materials Technology Co., Ltd. and its model is C5 / C9 copolymer petroleum resin.

[0069] The bio-asphalt is plant asphalt.

[0070] The manufacturer of the vegetable asphalt is Weifang Daming Biotechnology Co., Ltd. and the model is vegetable asphalt.

[0071] The bio-based oil is rice bran oil.

[0072] The rice bran oil was purchased from Jiangsu Delekang Biotechnology Co., Ltd. and the model is grade 3 rice bran oil.

[0073] The content of benzo(a)pyrene in the petroleum-based oil is less than or equal to 1 mg / kg, and the content of polycyclic aromatic hydrocarbons containing benzene compounds in the petroleum-based oil is less than or equal to 10 mg / kg. The petroleum-based oil is purchased from Hansheng Petrochemical (Ningbo) Co., Ltd., model V500.

[0074] The catalyst is aluminum chloride.

[0075] The aluminum chloride was purchased from Shanghai MacLean Biochemical Technology Co., Ltd., and the model is aluminum chloride.

[0076] A second aspect of the present embodiment provides a method for preparing rubber processing oil, comprising the following steps:

[0077] The bio-based oil, petroleum-based resin and bio-asphalt are stirred and heated to 140° C. to obtain a mixture a;

[0078] A catalyst was added to mixture a, mixed and kept warm for 1.5 hours to obtain mixture b. After stopping heating and cooling to 80°C, petroleum-based oil was added to mixture b and mixed to obtain rubber processing oil. The rubber processing oil was cooled to room temperature before use.

[0079] Comparative Example 1

[0080] This comparative example provides a rubber processing oil, which is a petroleum-based oil. The petroleum-based oil is purchased from Hansheng Petrochemical (Ningbo) Co., Ltd., and the model is V500.

[0081] The rubber processing oils provided in Examples 1-3 and Comparative Example 1 were respectively applied to rubber processing to obtain compound rubber.

[0082] Application Example 1

[0083] Application Example 1 provides a rubber compound, the raw materials for its preparation are, by weight, 100 parts of natural rubber, 55 parts of carbon black N330, 10 parts of rubber processing oil provided in Example 1, 5 parts of zinc oxide, 2 parts of stearic acid, 2 parts of antioxidant RD, 1.5 parts of antioxidant 4020, 2 parts of sulfur, and 1 part of accelerator NS.

[0084] The natural rubber used in Application Example 1 is purchased from Vietnamese natural rubber SVR3L.

[0085] The carbon black N330, zinc oxide, stearic acid, antioxidant RD, antioxidant 4020, sulfur, and accelerator NS used in Application Example 1 are all commercially available products.

[0086] Application Example 1 provides a method for preparing a rubber compound, comprising the following steps:

[0087] S1. Set the speed of the internal mixer to 45 rpm and the temperature to 120°C, add the natural rubber to the internal mixer for plasticization for 60 seconds, then add rubber operating oil and 50 wt% carbon black N330 for mixing for 60 seconds, then add zinc oxide, stearic acid, antioxidant RD, antioxidant 4020 and mix for 60 seconds, then add 50 wt% carbon black N330 and mix for 60 seconds to obtain a rubber mixture, discharge the rubber within 120 seconds, and leave the rubber mixture at room temperature for 8 hours for standby use;

[0088] S2. The rubber mixture is thinned on an open mixing mill, sulfur and accelerator are added to the rubber mixture, and then the mixture is thinned through a triangle bag 6 times to obtain a rubber mixture, which is then sheeted for standby use.

[0089] Application Example 2

[0090] Application Example 2 provides a rubber compound, the raw materials for its preparation are, by weight, 100 parts of natural rubber, 55 parts of carbon black N330, 10 parts of rubber processing oil provided in Example 2, 5 parts of zinc oxide, 2 parts of stearic acid, 2 parts of antioxidant RD, 1.5 parts of antioxidant 4020, 2 parts of sulfur, and 1 part of accelerator NS.

[0091] The natural rubber used in Application Example 2 is purchased from Vietnamese natural rubber SVR3L.

[0092] The carbon black N330, zinc oxide, stearic acid, antioxidant RD, antioxidant 4020, sulfur, and accelerator NS used in Application Example 2 are all commercially available products.

[0093] Application Example 2 provides a method for preparing a rubber compound, and the specific implementation method is the same as that of Application Example 1.

[0094] Application Example 3

[0095] Application Example 3 provides a rubber compound, the raw materials for its preparation are, by weight, 100 parts of natural rubber, 55 parts of carbon black N330, 10 parts of rubber processing oil provided in Example 3, 5 parts of zinc oxide, 2 parts of stearic acid, 2 parts of antioxidant RD, 1.5 parts of antioxidant 4020, 2 parts of sulfur, and 1 part of accelerator NS.

[0096] The natural rubber used in Application Example 3 is purchased from Vietnamese natural rubber SVR3L.

[0097] The carbon black N330, zinc oxide, stearic acid, antioxidant RD, antioxidant 4020, sulfur, and accelerator NS used in Application Example 3 are all commercially available products.

[0098] Application Example 3 provides a method for preparing a rubber compound, and the specific implementation method is the same as that of Application Example 1.

[0099] Comparative application example 1

[0100] Comparative Application Example 1 provides a rubber compound, the raw materials for its preparation are, by weight, 100 parts of natural rubber, 55 parts of carbon black N330, 10 parts of rubber operating oil provided in Comparative Example 1, 5 parts of zinc oxide, 2 parts of stearic acid, 2 parts of antioxidant RD, 1.5 parts of antioxidant 4020, 2 parts of sulfur, and 1 part of accelerator NS.

[0101] The natural rubber used in Comparative Application Example 1 is purchased from Vietnamese natural rubber SVR3L.

[0102] The carbon black N330, zinc oxide, stearic acid, antioxidant RD, antioxidant 4020, sulfur, and accelerator NS used in comparative application example 1 are all commercially available products.

[0103] Comparative Application Example 1 provides a method for preparing a rubber compound, and the specific implementation method is the same as that of Application Example 1.

[0104] Performance Testing

[0105] 1. Processing performance test:

[0106] The rubber processing oils provided in Examples 1-3 and Comparative Example 1 were respectively applied to rubber processing to obtain rubber compounds, and the processing properties of the rubber compounds provided in Application Examples 1-3 and Comparative Application Example 1 were tested. The testing method for the vulcanization characteristics was as follows:

[0107] The vulcanization characteristics were determined according to GBT16584-1996 Determination of vulcanization characteristics of rubber using rotorless vulcanizer, and the test results are shown in Table 1; the Mooney viscosity was tested according to GB / T-1232.1-2016 Determination of unvulcanized rubber using disc shear viscometer Part 1 Mooney viscosity, and the test results are shown in Table 1.

[0108] 2. Strength performance test:

[0109] The rubber processing oils provided in Examples 1-3 and Comparative Example 1 were respectively applied to rubber processing to obtain rubber compounds. The strength properties of the rubber compounds provided in Application Examples 1-3 and Comparative Application Example 1 were tested. The test results are shown in Table 2.

[0110] Table 1

[0111]

[0112]

[0113] Table 2

[0114]

[0115] It can be seen from the test results in Table 1 that the rubber operating oils provided in Examples 1-3 and Comparative Example 1 are respectively applied to rubber processing to obtain small differences in the processing properties of the mixed rubbers; it can be seen from the test results in Table 2 that the rubber operating oils provided in Examples 1-3 and Comparative Example 1 have a great influence on the right-angle tear strength and abrasion properties of the mixed rubber, and the rubber operating oils provided in Examples 1-3 can improve the tear strength and abrasion properties of the mixed rubber, and have excellent tear resistance and wear resistance.

Claims

1. A rubber processing oil, characterized in that: The raw materials for its preparation include 10-20 parts of petroleum-based resin, 10-20 parts of bio-asphalt, 40-60 parts of bio-based oil, 10-20 parts of petroleum-based oil and 0-2 parts of catalyst by weight.

2. The rubber processing oil according to claim 1, characterized in that The mass ratio of the petroleum-based resin to the bio-based oil is 1:(2.5-4).

3. The rubber processing oil according to claim 1, characterized in that The petroleum-based resin includes one or more combinations of aliphatic petroleum resin, aromatic petroleum resin, copolymerized petroleum resin, alicyclic petroleum resin, and hydrogenated petroleum resin.

4. The rubber processing oil according to claim 1, characterized in that The bio-asphalt includes plant asphalt.

5. The rubber processing oil according to claim 4, characterized in that The vegetable asphalt includes waste cooking oil and waste residue from soybean oil processing.

6. The rubber processing oil according to claim 1, characterized in that The bio-based oil includes rice bran oil and soybean oil.

7. The rubber processing oil according to claim 1, characterized in that The petroleum-based oil includes a combination of one or more of paraffin-based oil, naphthenic oil, and aromatic-based oil.

8. The rubber processing oil according to claim 7, characterized in that The content of benzo(a)pyrene in the petroleum-based oil is less than or equal to 1 mg / kg, and the content of polycyclic aromatic hydrocarbons containing benzene compounds in the petroleum-based oil is less than or equal to 10 mg / kg.

9. The rubber processing oil according to claim 1, characterized in that The catalyst includes aluminum trichloride and ferric chloride.

10. A method for preparing the rubber process oil according to any one of claims 1 to 9, characterized in that: The following steps are involved: The bio-based oil, petroleum-based resin and bio-asphalt are stirred, heated and mixed to obtain a mixture a; A catalyst is added to the mixture a and mixed to obtain a mixture b, and petroleum-based oil is added to the mixture b and mixed to obtain a rubber processing oil.

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