Transmission belt rubber composite material with low heat generation and high bio-based content as well as preparation method and application of transmission belt rubber composite material

Abstract

The invention provides a rubber composite material, which is prepared from the following raw materials in parts by weight: 100 parts of raw rubber, 30 to 40 parts of reinforcing filler, 15 to 25 parts of plant fiber, 5 to 8 parts of activating agent, 3 to 5 parts of active magnesium oxide, 3 to 10 parts of plasticizer, 1 to 4 parts of anti-aging agent, 1 to 3 parts of accelerant and 1 to 5 parts of vulcanizing agent, the raw rubber comprises itaconate rubber and chloroprene rubber. Chloroprene rubber in a traditional transmission belt formula is replaced with bio-based itaconate rubber, so that dependence on petrochemical raw materials is reduced, and energy conservation and carbon reduction are facilitated. Meanwhile, the plant fibers in the formula enhance the wear resistance and strength of the material, and the use of the environment-friendly plasticizer also reduces the carbon footprint of the formula. The obtained transmission belt composite material has low hysteresis loss and low compression heat generation, and conforms to the green and low-carbon development direction of transmission belt materials.

Description

Technical Field

[0001] The present invention belongs to the technical field of transmission belt rubber materials, and relates to a rubber composite material and a preparation method and application thereof, and in particular to a low-heat-generating, high-biobased content transmission belt rubber composite material and a preparation method and application thereof. Background Art

[0002] At present, under the general trend of global energy conservation and environmental protection, the use of automotive materials is developing towards lightweight, more environmentally friendly, low VOC, healthier and more comfortable. At present, the materials used for automobile bodies can be roughly divided into two categories. The first category is metal materials, including heavy metals such as steel plates and cast iron and alloy materials of certain light metals; the second category is non-metallic materials, including engineering plastics, fibers, resins, rubbers, etc. With the development of polymer material technology and the introduction of foreign technology, the transmission belt materials used in automobile engines have shifted from natural rubber and synthetic rubber to polyurethane, chlorosulfonated polyethylene rubber, hydrogenated nitrile rubber, EPDM rubber, etc., and the functional aspects have developed towards high temperature resistance, wear resistance, aging resistance, fatigue resistance, etc. Among them, chloroprene rubber (CR) is the main material for the working environment temperature of 60-120℃, but its disadvantages are poor storage stability and poor process performance, easy to burn and stick to the roller. On the other hand, although compared with traditional petroleum-based materials, bio-based materials have large reserves, are carbon neutral, and have advantages such as reducing raw material costs, existing research has also gradually adopted bio-based materials for various attempts, but the product performance is still not ideal. With the accelerated implementation of the green transformation and upgrading of the rubber additive industry and the increasing environmental pressure, various environmentally friendly additives have been gradually applied to various rubber products. The use of new environmentally friendly, non-toxic natural materials, green additives and other safe and environmentally friendly materials to replace various traditional additives and reinforcing fillers is of great significance to the sustainable development of the transmission belt industry and is also the main direction of technological development.

[0003] Therefore, how to obtain a suitable production process and rubber composite material to solve the above-mentioned problems existing in existing processes and rubber products, especially transmission belt rubber materials, and further improve the level of green environmental protection has become an important issue that many front-line production R&D personnel and industry manufacturers in the industry need to solve urgently. Summary of the invention

[0004] In view of this, the technical problem to be solved by the present invention is to provide a rubber composite material and its preparation method and application, in particular, a low heat generation, high bio-based content transmission belt rubber composite material. The rubber composite material prepared by the present invention has the characteristics of low rolling resistance (low dynamic heat generation, small hysteresis loss) and low compression heat generation. On the basis of meeting the basic performance requirements of the material, the service life of the transmission belt rubber product is extended; and the process is simple, the processing performance is excellent, and the equipment requirements are low, which is more suitable for the promotion and application of industrial production.

[0005] The present invention provides a rubber composite material, which comprises, by weight of raw materials:

[0006] 100 parts by weight of raw rubber;

[0007] The raw rubber includes itaconate rubber and chloroprene rubber;

[0008] 30 to 40 parts by weight of reinforcing filler;

[0009] 15-25 parts by weight of plant fiber;

[0010] Activator 5-8 parts by weight;

[0011] 3-5 parts by weight of active magnesium oxide;

[0012] 3 to 10 parts by weight of plasticizer;

[0013] 1 to 4 parts by weight of antioxidant;

[0014] 1 to 3 parts by weight of accelerator;

[0015] 1 to 5 parts by weight of vulcanizing agent.

[0016] Preferably, in the 100 parts by weight of the raw rubber, the mass fraction of itaconate rubber is 50 to 85 parts by weight;

[0017] The itaconate rubber is a binary, ternary or tetrapolymer containing itaconate and a bio-based diene or a petroleum-based conjugated diene;

[0018] The itaconate rubber is specifically a copolymer obtained by low-temperature emulsion polymerization of raw materials including dibutyl itaconate units and butadiene units;

[0019] The polymerization temperature of the low-temperature emulsion polymerization is 1-20°C.

[0020] Preferably, the itaconate is selected from one or more of dimethyl itaconate, diethyl itaconate, di-n-propyl itaconate, di-n-butyl itaconate, diisopropyl itaconate, diisobutyl itaconate, di-n-pentyl itaconate and diisopentyl itaconate;

[0021] The bio-based dienes are dienes produced by microbial fermentation or terpenes derived from plants;

[0022] The petroleum-based conjugated diene is isoprene and / or butadiene;

[0023] The rubber composite material is a rubber composite material for a transmission belt.

[0024] Preferably, the itaconate rubber further comprises a third component and / or a fourth component;

[0025] The third component and the fourth component are independently selected from one or more of glycidyl methacrylate, styrene, vinyl chloroacetate, acrylamide, cyclopentadiene, ethylidene norbornene, methyl acrylate, ethyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, hydroxyethyl methacrylate and 2-hydroxyethyl acrylate;

[0026] The reinforcing filler is one or more of carbon black, pyrolysis carbon black, calcium carbonate, calcium sulfate, dolomite powder, clay, clay, montmorillonite, clay, montmorillonite barium sulfate, talc, magnesium carbonate, magnesium silicate and graphene;

[0027] The vulcanizing agent is sulfur;

[0028] The mass content of the bio-based raw materials in the rubber composite material is 45% to 60%.

[0029] Preferably, the plant fiber is one or more of cotton, jute, sisal, flax, ramie, coconut shell and sisal;

[0030] The activator is zinc oxide and / or stearic acid;

[0031] The plasticizer is one or more of epoxidized soybean oil, palm oil, rapeseed oil, sunflower oil and low-erucic acid rapeseed oil;

[0032] The antioxidant is one or more of an amine antioxidant, a ketoamine antioxidant, a phenolic antioxidant and a heterocyclic antioxidant;

[0033] The accelerator is one or more of a sulfonamide accelerator, a thiazole accelerator and an imidazole accelerator.

[0034] The present invention also provides a method for preparing the rubber composite material as described in any one of the above technical solutions, comprising the following steps:

[0035] 1) The raw rubber is plasticized in an internal mixer to obtain plasticized rubber;

[0036] 2) adding a reinforcing filler, a plant fiber, an activator, an active magnesium oxide, a plasticizer and an antioxidant to the plasticized rubber obtained in the above step, mixing the mixture, and then removing the rubber to obtain a masterbatch;

[0037] 3) After cooling the first stage masterbatch obtained in the above step, the first stage masterbatch, the vulcanizing agent, the activator and the accelerator are further mixed, and the mixture is discharged to obtain the second stage final mixing;

[0038] 4) The second-stage final rubber mix obtained in the above step is thin-passed on an open mixing mill to obtain a mixed rubber, which is then vulcanized to obtain a rubber composite material.

[0039] Preferably, the mastication time is 1 to 2 minutes;

[0040] The temperature of the plasticizing is 115-120°C;

[0041] The speed of the internal mixer during plastication is 70-80 rpm;

[0042] The mixing temperature is 135-155°C;

[0043] The mixing time is 6 to 10 minutes.

[0044] Preferably, the temperature after cooling is less than or equal to 70°C;

[0045] The temperature of the continued banburying is 95-110°C;

[0046] The time for continuing the banburying is 2 to 3 minutes;

[0047] The number of thin passes is 4 to 6 times;

[0048] The roller distance of the thin pass is 1 to 2 mm;

[0049] Preferably, the thin pass further includes a parking step;

[0050] The parking time is 16 to 24 hours;

[0051] The vulcanization temperature is 150-180°C;

[0052] The vulcanization time is 5 to 8 minutes;

[0053] The vulcanization pressure is 38-40 tons.

[0054] The present invention also provides the use of the rubber composite material described in any one of the above technical solutions or the rubber composite material prepared by the preparation method described in any one of the above technical solutions in a transmission belt.

[0055] The present invention provides a rubber composite material, which comprises, by weight of raw materials, 100 parts by weight of raw rubber, 30-40 parts by weight of reinforcing filler, 15-25 parts by weight of plant fiber, 5-8 parts by weight of activator, 3-5 parts by weight of active magnesium oxide, 3-10 parts by weight of plasticizer, 1-4 parts by weight of antioxidant, 1-3 parts by weight of accelerator and 1-5 parts by weight of vulcanizing agent; the raw rubber comprises itaconate rubber and chloroprene rubber. Compared with the prior art, the present invention designs a low heat generation, high bio-based content transmission belt rubber matrix composite material by adding new bio-based rubber as a matrix material, and designing a vulcanization system, a reinforcing filling system, a plasticizing system and a processing technology. The invention reduces the dependence on petrochemical raw materials, is beneficial to energy conservation and carbon reduction, and the obtained rubber composite material has the characteristics of low rolling resistance (low dynamic heat generation and small hysteresis loss) and low compression heat generation. On the basis of meeting the basic performance requirements of the material, the service life of the transmission belt rubber product is extended; and the processing technology is simple, the processing performance is excellent, and the equipment requirements are low, which is more suitable for the promotion and application of industrial production.

[0056] The present invention replaces the chloroprene rubber in the traditional transmission belt formula with an equal amount of bio-based itaconate rubber prepared from biomass resources, thereby reducing dependence on petrochemical raw materials and meeting the strategic requirements of green, low-carbon and sustainable development. At the same time, the plant fiber in the formula enhances the wear resistance and strength of the material, and the use of environmentally friendly plasticizers also reduces the carbon footprint of the formula. The transmission belt composite material obtained by the present invention has lower hysteresis loss and lower compression heat generation, which is in line with the green and low-carbon development direction of transmission belt materials. In addition, the present invention has a simple processing technology, low equipment requirements, and excellent processing performance, and is suitable for wide use. BRIEF DESCRIPTION OF THE DRAWINGS

[0057] Figure 1 This is a hysteresis loss test chart of the rubber composite materials prepared in the embodiments and comparative examples provided by the present invention. DETAILED DESCRIPTION

[0058] In order to further understand the present invention, preferred embodiments of the present invention are described below in conjunction with examples, but it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, rather than limiting the claims of the invention.

[0059] All raw materials of the present invention have no particular limitation on their sources, and can be purchased from the market or prepared according to conventional methods known to those skilled in the art.

[0060] There is no particular restriction on the purity of all raw materials in the present invention. The present invention preferably uses analytically pure materials or materials of conventional purity used in the field of rubber preparation for transmission belts.

[0061] The present invention provides a rubber composite material, which comprises, by weight of raw materials:

[0062] 100 parts by weight of raw rubber;

[0063] The raw rubber includes itaconate rubber and chloroprene rubber;

[0064] 30 to 40 parts by weight of reinforcing filler;

[0065] 15-25 parts by weight of plant fiber;

[0066] Activator 5-8 parts by weight;

[0067] 3-5 parts by weight of active magnesium oxide;

[0068] 3 to 10 parts by weight of plasticizer;

[0069] 1 to 4 parts by weight of antioxidant;

[0070] 1 to 3 parts by weight of accelerator;

[0071] 1 to 5 parts by weight of vulcanizing agent.

[0072] In the present invention, the content of the reinforcing filler is 30 to 40 parts by weight, can be 32 to 38 parts by weight, and can be 34 to 36 parts by weight.

[0073] In the present invention, the content of the plant fiber is 17 to 23 parts by weight, can be 19 to 21 parts by weight, and can be 34 to 36 parts by weight.

[0074] In the present invention, the content of the activator is 5 to 8 parts by weight, can be 5.5 to 7.5 parts by weight, and can be 6 to 7 parts by weight.

[0075] In the present invention, the content of the active magnesium oxide is 3 to 5 parts by weight, can be 3.4 to 4.6 parts by weight, can be 3.8 to 4.2 parts by weight.

[0076] In the present invention, the content of the plasticizer is 3 to 10 parts by weight, can be 4 to 9 parts by weight, can be 5 to 8 parts by weight.

[0077] In the present invention, the content of the antioxidant is 1 to 4 parts by weight, can be 1.5 to 3.5 parts by weight, and can be 2 to 3 parts by weight.

[0078] In the present invention, the content of the accelerator is 1 to 3 parts by weight, can be 1.4 to 2.6 parts by weight, and can be 1.8 to 2.2 parts by weight.

[0079] In the present invention, the content of the vulcanizing agent is 1 to 5 parts by weight, can be 1.5 to 4.5 parts by weight, can be 2 to 4 parts by weight, can be 2.5 to 3.5 parts by weight.

[0080] In the present invention, in the 100 parts by weight of the raw rubber, the mass fraction of itaconate rubber is preferably 50 to 85 parts by weight, more preferably 55 to 80 parts by weight, more preferably 60 to 75 parts by weight, more preferably 65 to 70 parts by weight.

[0081] In the present invention, the itaconate rubber is preferably a binary, ternary or tetrapolymer containing itaconate and a bio-based diene or a petroleum-based conjugated diene. Specifically, the itaconate rubber may be one or more of ItBR6600, ItBR6610, ItBR4710 and ItBR7410, and preferably ItBR6600.

[0082] In the present invention, the itaconate rubber is preferably a copolymer obtained by low-temperature emulsion polymerization of raw materials including dibutyl itaconate units and butadiene units, such as itaconate rubber with the brand ItBR6600. For details, please refer to the preparation method of itaconate / butadiene copolymer type bioengineering rubber disclosed in the Chinese patent application publication number CN104945817A, which specifically introduces the prepared bio-based itaconate rubber.

[0083] In the present invention, the polymerization temperature of the low-temperature emulsion polymerization is preferably 1 to 20°C, more preferably 5 to 16°C, and more preferably 10 to 11°C.

[0084] In the present invention, the itaconate is preferably selected from one or more of dimethyl itaconate, diethyl itaconate, di-n-propyl itaconate, di-n-butyl itaconate, diisopropyl itaconate, diisobutyl itaconate, di-n-pentyl itaconate and diisopentyl itaconate, more preferably dimethyl itaconate, diethyl itaconate, di-n-propyl itaconate, di-n-butyl itaconate, diisopropyl itaconate, diisobutyl itaconate, di-n-pentyl itaconate or diisopentyl itaconate.

[0085] In the present invention, the bio-based diene is preferably a diene produced by microbial fermentation or a terpene derived from a plant.

[0086] In the present invention, the petroleum-based conjugated diene is preferably isoprene and / or butadiene, more preferably isoprene or butadiene.

[0087] In the present invention, the rubber composite material is preferably a rubber composite material for a transmission belt.

[0088] In the present invention, the itaconate rubber preferably further comprises a third component and / or a fourth component, more preferably the third component or the fourth component.

[0089] In the present invention, the third component and the fourth component are each independently preferably selected from one or more of glycidyl methacrylate, styrene, vinyl chloroacetate, acrylamide, cyclopentadiene, ethylidene norbornene, methyl acrylate, ethyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, hydroxyethyl methacrylate and 2-hydroxyethyl acrylate, more preferably glycidyl methacrylate, styrene, vinyl chloroacetate, acrylamide, cyclopentadiene, ethylidene norbornene, methyl acrylate, ethyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, hydroxyethyl methacrylate or 2-hydroxyethyl acrylate.

[0090] In the present invention, the reinforcing filler is preferably one or more of carbon black, pyrolysis carbon black, calcium carbonate, calcium sulfate, dolomite powder, clay, clay, montmorillonite, clay, montmorillonite barium sulfate, talc, magnesium carbonate, magnesium silicate and graphene, more preferably carbon black, pyrolysis carbon black, calcium carbonate, calcium sulfate, dolomite powder, clay, clay, montmorillonite, clay, montmorillonite barium sulfate, talc, magnesium carbonate, magnesium silicate or graphene.

[0091] In the present invention, the vulcanizing agent is preferably sulfur.

[0092] In the present invention, the mass content of the bio-based raw materials (bio-based content, mass content) of the rubber composite material is preferably 45% to 60%, more preferably 48% to 57%, and more preferably 51% to 53%.

[0093] In the present invention, the plant fiber is preferably one or more of cotton, jute, sisal, flax, ramie, coconut shell and sisal, more preferably cotton, jute, sisal, flax, ramie, coconut shell or sisal.

[0094] In the present invention, the activator is preferably zinc oxide and / or stearic acid, more preferably zinc oxide or stearic acid.

[0095] In the present invention, the plasticizer is preferably one or more of epoxidized soybean oil, palm oil, rapeseed oil, sunflower oil and low-erucic acid rapeseed oil, more preferably epoxidized soybean oil, palm oil, rapeseed oil, sunflower oil or low-erucic acid rapeseed oil.

[0096] In the present invention, the antioxidant is preferably one or more of an amine antioxidant, a ketoamine antioxidant, a phenolic antioxidant and a heterocyclic antioxidant, more preferably an amine antioxidant, a ketoamine antioxidant, a phenolic antioxidant or a heterocyclic antioxidant.

[0097] In the present invention, the accelerator is preferably one or more of a sulfonamide accelerator, a thiazole accelerator and an imidazole accelerator, and more preferably a sulfonamide accelerator, a thiazole accelerator or an imidazole accelerator.

[0098] The present invention provides a method for preparing a rubber composite material as described in any one of the above technical solutions, comprising the following steps:

[0099] 1) The raw rubber is plasticized in an internal mixer to obtain plasticized rubber;

[0100] 2) adding a reinforcing filler, a plant fiber, an activator, an active magnesium oxide, a plasticizer and an antioxidant to the plasticized rubber obtained in the above step, mixing the mixture, and then removing the rubber to obtain a masterbatch;

[0101] 3) After cooling the first stage masterbatch obtained in the above step, the first stage masterbatch, the vulcanizing agent, the activator and the accelerator are further mixed, and the mixture is discharged to obtain the second stage final mixing;

[0102] 4) The second-stage final rubber mix obtained in the above step is thin-passed on an open mixing mill to obtain a mixed rubber, which is then vulcanized to obtain a rubber composite material.

[0103] The invention firstly plasticates the raw rubber in an internal mixer to obtain plasticated rubber.

[0104] In the present invention, the mastication time is preferably 1 to 2 min, more preferably 1.2 to 1.8 min, more preferably 1.4 to 1.6 min, and specifically 1.5 min.

[0105] In the present invention, the temperature of the mastication is preferably 115 to 120°C, more preferably 116 to 119°C, and even more preferably 117 to 118°C.

[0106] In the present invention, the rotation speed of the internal mixer during the plasticating is preferably 70 to 80 rpm, more preferably 70 to 76 rpm, more preferably 70 to 72 rpm, and specifically can be 70 rpm.

[0107] In the present invention, reinforcing filler, plant fiber, activator, active magnesium oxide, plasticizer and antioxidant are added to the plasticized rubber obtained in the above steps for mixing, and then the rubber is discharged to obtain a masterbatch.

[0108] In the present invention, the kneading temperature is preferably 135 to 155°C, more preferably 139 to 151°C, and even more preferably 144 to 147°C.

[0109] In the present invention, the kneading time is preferably 6 to 10 minutes, more preferably 6.5 to 9.5 minutes, more preferably 7 to 9 minutes, and more preferably 7.5 to 8.5 minutes.

[0110] The present invention then cools the first stage masterbatch obtained in the above steps, and then continues to mix the first stage masterbatch, the vulcanizing agent, the activator and the accelerator, and discharges the masterbatch to obtain the second stage final mix.

[0111] In the present invention, the temperature after cooling is preferably less than or equal to 70°C, more preferably less than or equal to 65°C, and more preferably less than or equal to 60°C.

[0112] In the present invention, the temperature of the continued banburying is preferably 95-110°C, more preferably 98-107°C, and more preferably 101-104°C.

[0113] In the present invention, the time for continuing the banburying is preferably 2 to 3 minutes, more preferably 2.2 to 2.8 minutes, and more preferably 2.4 to 2.6 minutes.

[0114] In the present invention, the second-stage final rubber mix obtained in the above steps is finally thin-passed on an open mixing mill to obtain a mixed rubber, which is then vulcanized to obtain a rubber composite material.

[0115] In the present invention, the number of thin passes is preferably 4 to 6 times, specifically 6 times.

[0116] In the present invention, the roller distance of the thin pass is preferably 1 to 2 mm, more preferably 1.4 to 2 mm, more preferably 1.8 to 2 mm, and specifically may be 2 mm.

[0117] In the present invention, the thin-pass process preferably further includes a parking step.

[0118] In the present invention, the parking time is preferably 16 to 24 hours, more preferably 17 to 23 hours, more preferably 18 to 22 hours, and more preferably 19 to 21 hours.

[0119] In the present invention, the vulcanization temperature is preferably 150 to 180°C, more preferably 155 to 175°C, and even more preferably 160 to 170°C.

[0120] In the present invention, the vulcanization time is preferably 5 to 8 minutes, more preferably 5.5 to 7.5 minutes, and more preferably 6 to 7 minutes.

[0121] In the present invention, the vulcanization pressure is preferably 38 to 40 tons, more preferably 38.5 to 40 tons, more preferably 39 to 40 tons, and specifically 40 tons (t).

[0122] The present invention provides the use of the rubber composite material described in any one of the above technical solutions or the rubber composite material prepared by the preparation method described in any one of the above technical solutions in a transmission belt.

[0123] The present invention is to complete and refine the overall technical solution, better ensure the composition and ratio of the rubber composite material, and further improve the comprehensive performance of the rubber composite material. The above-mentioned low heat generation, high bio-based content transmission belt rubber composite material and its preparation method and application may specifically include the following contents:

[0124] A low heat generation, high bio-based content transmission belt rubber composite material, comprising the following components in parts by weight of raw materials:

[0125] Raw rubber: 100 parts;

[0126] Reinforcing filler: 30-40 parts;

[0127] Plant fiber: 15-25 parts;

[0128] Activator: 5-8 parts;

[0129] Active magnesium oxide: 3-5 parts;

[0130] Plasticizer: 3-10 parts;

[0131] Anti-aging agent: 1-4 parts;

[0132] Accelerator: 1-3 parts;

[0133] Sulfur: 1-5 parts;

[0134] The raw rubber consists of itaconate rubber and chloroprene rubber.

[0135] Specifically, based on 100 parts of raw rubber, itaconate rubber is preferably 50 parts or more, more preferably 60 parts or more. If the content of this component is less than 30 parts, the advantage is not obvious; if the content of this component is more than 85 parts, the mechanical strength is reduced and the wear resistance is also reduced to a certain extent.

[0136] Specifically, the itaconate rubber is a binary, ternary or tetrapolymer containing itaconate and a bio-based diene or a petroleum-based conjugated diene.

[0137] Specifically, the itaconate ester may be selected from one or two of dimethyl itaconate, diethyl itaconate, di-n-propyl itaconate, di-n-butyl itaconate, diisopropyl itaconate, diisobutyl itaconate, di-n-pentyl itaconate and diisopentyl itaconate.

[0138] Specifically, bio-based dienes refer to one or more terpenes produced by microbial fermentation or derived from plants, such as isoprene, butadiene, myrcene, limonene, etc.

[0139] Specifically, the petroleum-based conjugated diene is isoprene or butadiene. It may also contain other third or fourth components, including one or two of glycidyl methacrylate, styrene, vinyl chloroacetate, acrylamide, cyclopentadiene, ethylidene norbornene, methyl acrylate, ethyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, hydroxyethyl methacrylate, and 2-hydroxyethyl acrylate.

[0140] Specifically, the itaconate rubber is a copolymer obtained by low-temperature emulsion polymerization of dibutyl itaconate units and butadiene units.

[0141] Specifically, the reinforcing filler can be one or more of carbon black, pyrolysis carbon black, calcium carbonate, calcium sulfate, dolomite powder, clay, clay, montmorillonite, clay, montmorillonite barium sulfate, talc, magnesium carbonate, magnesium silicate, and graphene, and the amount used is 30 to 40 parts, preferably 30 parts of carbon black N774.

[0142] Specifically, the plant fiber can be one or more of cotton, jute, sisal, flax, ramie, coconut shell, and sisal, and the usage amount is 15 to 25 parts.

[0143] Specifically, the activator is composed of zinc oxide and stearic acid, wherein the zinc oxide is 3 to 7 parts and the stearic acid is 0.5 to 2 parts.

[0144] Specifically, the plasticizer can be epoxidized soybean oil, palm oil, rapeseed oil, sunflower oil, and low-erucic acid rapeseed oil, all of which are taken from natural materials and can replace chemical plasticizer oils to increase the bio-based content in the formula.

[0145] Specifically, the antioxidant can be one or more of amine antioxidants, ketone amine antioxidants, phenolic antioxidants and heterocyclic antioxidants, and each antioxidant is used in an amount of 1 to 4 parts. Among them, amine antioxidants are suitable for protecting rubber from aging factors such as light, heat, and oxygen, such as antioxidant 3100 (N,N'-dimethylphenylene diamine) and antioxidant 445 (4,4'-bis-dimethylbenzyl diphenylamine), which can be used as preferred, specifically 1 part of antioxidant 3100 and 2 parts of antioxidant 445.

[0146] Specifically, the accelerator can be one or more of sulfonamide accelerators, thiazole accelerators and imidazole accelerators, and the dosage of each accelerator is 0.1 to 1 part. Among them, thiazole accelerators (such as accelerator DM) and imidazole accelerators (such as accelerator NA-22, which can make chloroprene rubber vulcanize quickly and burn safely) can be used as preferred, and specifically, the dosage of accelerator DM can be 0.75 parts, and the dosage of accelerator NA-22 can be 0.3 parts.

[0147] The present invention also proposes a method for preparing a low-heat-generating, high-biobased content transmission belt rubber composite material, the steps of which are as follows:

[0148] (1) Plasticizing the raw rubber in an internal mixer according to a certain mass ratio;

[0149] (2) adding a reinforcing filler, plant fiber, stearic acid, active magnesium oxide, an antioxidant and a plasticizer in expected weight portions to the plasticized rubber and mixing the mixture for 6 to 10 minutes;

[0150] (3) When the temperature in the internal mixer reaches 135-155°C, the rubber is discharged to obtain a masterbatch;

[0151] (4) After the first stage masterbatch in step (3) is cooled to below 70° C., the masterbatch, sulfur, zinc oxide, and accelerator are added to an internal mixer and further mixed. When the temperature in the internal mixer reaches 95 to 110° C., the masterbatch is discharged to obtain a second stage final mix;

[0152] (5) The second-stage final rubber is thinned on an open mixing mill for 6 times, rolled off with a 2 mm roller spacing, and left to stand for 16 to 24 hours to obtain a mixed rubber.

[0153] (6) The mixed rubber obtained in step (5) is tested for vulcanization properties using a rotorless vulcanizer, and a vulcanized rubber sample is obtained using a flat plate vulcanizer.

[0154] Specifically, in step (1), the raw rubber plasticizing time is 1.5 min, and the rotation speed of the internal mixer is 70 rpm.

[0155] Specifically, the storage temperature in step (5) is 20-30°C.

[0156] Specifically, the vulcanization temperature in step (6) is 150-180° C., the vulcanization time is 5-8 min, and the pressure is 40t.

[0157] The above content of the present invention provides a low heat generation, high bio-based content transmission belt rubber composite material and its preparation method and application. The present invention designs a low heat generation, high bio-based content transmission belt rubber matrix composite material by adding new bio-based rubber as the matrix material and designing the vulcanization system, reinforcement filling system, plasticizing system and processing technology. The present invention reduces the dependence on petrochemical raw materials, is conducive to energy conservation and carbon reduction, and the obtained rubber composite material has the characteristics of low rolling resistance (low dynamic heat generation, small hysteresis loss) and low compression heat generation. On the basis of meeting the basic performance requirements of the material, the service life of the transmission belt rubber product is extended; and the processing technology is simple, the processing performance is excellent, and the equipment requirements are low, which is more suitable for the promotion and application of industrial production.

[0158] The present invention replaces the chloroprene rubber in the traditional transmission belt formula with an equal amount of bio-based itaconate rubber prepared from biomass resources, thereby reducing dependence on petrochemical raw materials and meeting the strategic requirements of green, low-carbon and sustainable development. At the same time, the plant fiber in the formula enhances the wear resistance and strength of the material, and the use of environmentally friendly plasticizers also reduces the carbon footprint of the formula. The transmission belt composite material obtained by the present invention has lower hysteresis loss and lower compression heat generation, which is in line with the green and low-carbon development direction of transmission belt materials. In addition, the present invention has a simple processing technology, low equipment requirements, and excellent processing performance, and is suitable for wide use.

[0159] In order to further illustrate the present invention, a rubber composite material provided by the present invention and its preparation method and application are described in detail below in combination with embodiments. However, it should be understood that these embodiments are implemented on the premise of the technical solution of the present invention, and detailed implementation methods and specific operation processes are given only to further illustrate the features and advantages of the present invention, rather than to limit the claims of the present invention, and the protection scope of the present invention is not limited to the following embodiments.

[0160] Example 1

[0161] A low heat generation and high bio-based content transmission belt rubber composite material contains the following components in parts by mass: 50 parts of itaconate rubber ItBR6600 and 50 parts of chloroprene rubber; 30 parts of carbon black N774 and 20 parts of lignin short fibers; 5 parts of zinc oxide, 1.5 parts of stearic acid and 5 parts of magnesium oxide; 3 parts of palm oil; 1 part of antioxidant 3100 and 2 parts of antioxidant 445; 0.75 parts of accelerator DM and 0.3 parts of accelerator NA-22; and 1.5 parts of sulfur.

[0162] A method for preparing a low heat generation, high bio-based content transmission belt rubber composite material, the steps of the preparation method are as follows:

[0163] (1) Plasticize itaconate rubber and chloroprene rubber in an internal mixer for 1.5 min at a speed of 70 rpm.

[0164] (2) adding carbon black, plant fiber, stearic acid, active magnesium oxide, palm oil, and antioxidant to the plasticized rubber in sequence and mixing for 6 to 10 minutes at a temperature of 135 to 155° C. to obtain a masterbatch;

[0165] (3) After the masterbatch obtained in step (2) is cooled to below 70° C., accelerator DM, accelerator NA-22, zinc oxide and sulfur are added to an internal mixer and further mixed. When the temperature in the internal mixer reaches 95 to 110° C., the masterbatch is discharged to obtain a second-stage final mixing;

[0166] (4) The final rubber mix obtained in step (3) was thinned on an open mill for 6 times, rolled off with a roller distance of 2 mm, and left to stand for 18 hours at a temperature of 20 to 30° C. to obtain a transmission belt rubber mix.

[0167] (5) The mixed rubber obtained in step (4) is tested for vulcanization properties using a rotorless vulcanizer, and a vulcanized rubber sample is obtained using a flat plate vulcanizer.

[0168] The vulcanization temperature in step (5) is 150° C., the vulcanization time is 8 to 15 minutes, and the pressure is 40t.

[0169] Example 2

[0170] A low heat generation and high bio-based content transmission belt rubber composite material contains the following components in parts by mass: 60 parts of itaconate rubber ItBR6600, 40 parts of chloroprene rubber, 35 parts of carbon black N774, 15 parts of lignin short fibers, 5 parts of zinc oxide, 1.5 parts of stearic acid, 5 parts of magnesium oxide, 3 parts of palm oil, 1 part of antioxidant 3100, 2 parts of antioxidant 445, 0.75 parts of accelerator DM, 0.3 parts of accelerator NA-22, and 1.5 parts of sulfur.

[0171] A transmission belt material was prepared in the same manner as in Example 1.

[0172] Example 3

[0173] A low heat generation and high bio-based content transmission belt rubber composite material contains the following components in parts by mass: 75 parts of itaconate rubber ItBR6600 and 25 parts of chloroprene rubber; 30 parts of carbon black N774 and 15 parts of lignin short fibers; 5 parts of zinc oxide, 1.5 parts of stearic acid and 5 parts of magnesium oxide; 3 parts of palm oil; 1 part of antioxidant 3100 and 2 parts of antioxidant 445; 0.75 parts of accelerator DM and 0.3 parts of accelerator NA-22; and 2 parts of sulfur.

[0174] A transmission belt material was prepared in the same manner as in Example 1.

[0175] Comparative Example 1

[0176] A low heat generation and high bio-based content transmission belt rubber composite material contains the following components in parts by mass: 20 parts of itaconate rubber ItBR6600 and 80 parts of chloroprene rubber; 30 parts of carbon black N774 and 20 parts of lignin short fibers; 5 parts of zinc oxide, 1.5 parts of stearic acid and 5 parts of magnesium oxide; 3 parts of palm oil; 1 part of antioxidant 3100 and 2 parts of antioxidant 445; 0.75 parts of accelerator DM and 0.3 parts of accelerator NA-22; and 1.5 parts of sulfur.

[0177] Comparative Example 2

[0178] A low heat generation and high bio-based content transmission belt rubber composite material contains the following components in parts by mass: 100 parts of chloroprene rubber; 30 parts of carbon black N774, 20 parts of lignin short fibers; 5 parts of zinc oxide, 1.5 parts of stearic acid, 5 parts of magnesium oxide; 3 parts of palm oil; 1 part of antioxidant 3100, 2 parts of antioxidant 445; 0.75 parts of accelerator DM, and 0.3 parts of accelerator NA-22.

[0179] A transmission belt material was prepared in the same manner as in Example 1.

[0180] See Table 1, which shows the performance test results of the transmission belt materials prepared in the examples of the present invention and the comparative examples.

[0181] Table 1

[0182] Test items Detection basis Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Hardness(Shore A) GB / T 531.2-2009 64.1 63.9 63.5 65.2 66.0 Tensile strength(MPa) GB / T 528-2009 19.6 19.2 19.0 20.1 20.3 50% Elongation at break / % GB / T 528-2009 3.1 2.9 2.9 3.2 3.5 Elongation at break (%) GB / T 528-2009 515 510 508 520 531 <![CDATA[DIN wear / mm 3 > GB / T 9687-2008 110 110 111 109 105 Compression heat / ℃ GB / T 1687-93 38.1 37.1 36.2 46.8 48.7 Loss factor tanδ@80℃ GB / T 40396-2021 0.106 0.103 0.097 0.117 0.118 Normal temperature stretch fatigue / times GB / T 1688-2008 880,000 920,000 990,000 820,000 800,000

[0183] Because polymer materials such as rubber produce strain under stress, and the strain has hysteresis. The mechanical energy generated by the hysteresis loss will be converted into heat energy, thereby increasing the temperature of the rubber material. Rubber itself is temperature sensitive and is a poor thermal conductor, so a large amount of heat will accumulate inside it. When the temperature is higher than a certain critical value, the material ages and the product life is reduced.

[0184] It can be seen from the examples that the transmission belt material prepared in each example of the present formula has excellent mechanical properties, good tensile strength and wear resistance, meets the basic properties of transmission belt rubber materials, and has excellent low heat generation and low hysteresis loss performance, and the service life of the material is improved.

[0185] See also Figure 1 , Figure 1 This is a hysteresis loss test chart of the rubber composite materials prepared in the embodiments and comparative examples provided by the present invention.

[0186] Depend on Figure 1 It can be seen that when bio-based itaconate rubber is used in chloroprene rubber, the hysteresis loss at high temperature decreases by up to 23%.

[0187] Among them, the size of Tanδ can represent the amount of energy loss. The smaller the value, the smaller the energy loss and the lower the dynamic heat generation of the rubber. Since the main chain of itaconate rubber molecules has no side groups and small steric hindrance, the friction between the molecular chains in the dynamic process is small and the heat generation is low. Figure 1 It can be seen that at low temperature (20℃), working temperature (80℃), and high temperature (120℃), the loss factor shows a trend of decreasing as a whole, which is consistent with the law reflected by the compression heat generation data. At the same time, the higher the temperature, the lower the loss factor, because the chain segments move more easily at high temperatures, and the hysteresis loss is correspondingly lower.

[0188] The above is a detailed introduction to a low heat generation, high bio-based content transmission belt rubber composite material provided by the present invention, and its preparation method and application. Specific examples are used in this article to illustrate the principles and implementation methods of the present invention. The description of the above embodiments is only used to help understand the method and its core ideas of the present invention, including the best mode, and also enables any technician in the field to practice the present invention, including the manufacture and use of any device or system, and the implementation of any combined method. It should be pointed out that for ordinary technicians in this technical field, without departing from the principles of the present invention, the present invention can also be improved and modified in a number of ways, and these improvements and modifications also fall within the scope of protection of the claims of the present invention. The scope of patent protection of the present invention is defined by the claims and may include other embodiments that can be thought of by those skilled in the art. If these other embodiments have structural elements that are not different from the literal expression of the claims, or if they include equivalent structural elements that are not substantially different from the literal expression of the claims, then these other embodiments should also be included in the scope of the claims.

Claims

1. A rubber composite material, characterized in that: Calculated by weight of raw materials, including: 100 parts by weight of raw rubber; The raw rubber includes itaconate rubber and chloroprene rubber; 2. The rubber composite material according to claim 1, characterized in that: In the 100 parts by weight of the raw rubber, the mass fraction of itaconate rubber is 50 to 85 parts by weight; The itaconate rubber is a binary, ternary or tetrapolymer containing itaconate and a bio-based diene or a petroleum-based conjugated diene; The itaconate rubber is specifically a copolymer obtained by low-temperature emulsion polymerization of raw materials including dibutyl itaconate units and butadiene units; The polymerization temperature of the low-temperature emulsion polymerization is 1-20°C.

3. The rubber composite material according to claim 2, characterized in that: The itaconate ester is selected from one or more of dimethyl itaconate, diethyl itaconate, di-n-propyl itaconate, di-n-butyl itaconate, diisopropyl itaconate, diisobutyl itaconate, di-n-pentyl itaconate and diisopentyl itaconate; The bio-based dienes are dienes produced by microbial fermentation or terpenes derived from plants; The petroleum-based conjugated diene is isoprene and / or butadiene; The rubber composite material is a rubber composite material for a transmission belt.

4. The rubber composite material according to claim 2, characterized in that: The itaconate rubber further comprises a third component and / or a fourth component; The third component and the fourth component are independently selected from one or more of glycidyl methacrylate, styrene, vinyl chloroacetate, acrylamide, cyclopentadiene, ethylidene norbornene, methyl acrylate, ethyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, hydroxyethyl methacrylate and 2-hydroxyethyl acrylate; The reinforcing filler is one or more of carbon black, pyrolysis carbon black, calcium carbonate, calcium sulfate, dolomite powder, clay, clay, montmorillonite, clay, montmorillonite barium sulfate, talc, magnesium carbonate, magnesium silicate and graphene; The vulcanizing agent is sulfur; The mass content of the bio-based raw materials in the rubber composite material is 45% to 60%.

5. The rubber composite material according to claim 1, characterized in that: The plant fiber is one or more of cotton, jute, sisal, flax, ramie, coconut shell and sisal; The activator is zinc oxide and / or stearic acid; The plasticizer is one or more of epoxidized soybean oil, palm oil, rapeseed oil, sunflower oil and low-erucic acid rapeseed oil; The antioxidant is one or more of an amine antioxidant, a ketoamine antioxidant, a phenolic antioxidant and a heterocyclic antioxidant; The accelerator is one or more of a sulfonamide accelerator, a thiazole accelerator and an imidazole accelerator.

6. A method for preparing the rubber composite material according to any one of claims 1 to 5, characterized in that: The following steps are involved: 1) The raw rubber is plasticized in an internal mixer to obtain plasticized rubber; 2) adding a reinforcing filler, a plant fiber, an activator, an active magnesium oxide, a plasticizer and an antioxidant to the plasticized rubber obtained in the above step, mixing the mixture, and then removing the rubber to obtain a masterbatch; 3) After cooling the first stage masterbatch obtained in the above step, the first stage masterbatch, the vulcanizing agent, the activator and the accelerator are further mixed, and the mixture is discharged to obtain the second stage final mixing; 4) The second-stage final rubber mix obtained in the above step is thin-passed on an open mixing mill to obtain a mixed rubber, which is then vulcanized to obtain a rubber composite material.

7. The preparation method according to claim 6, characterized in that: The plasticizing time is 1 to 2 minutes; The temperature of the plasticizing is 115-120°C; The speed of the internal mixer during plastication is 70-80 rpm; The mixing temperature is 135-155°C; The mixing time is 6 to 10 minutes.

8. The preparation method according to claim 6, characterized in that: The temperature after cooling is less than or equal to 70°C; The temperature of the continued banburying is 95-110°C; The time for continuing the banburying is 2 to 3 minutes; The number of thin passes is 4 to 6 times; The roller distance of the thin pass is 1 to 2 mm.

9. The preparation method according to claim 6, characterized in that: The thin pass also includes a parking step; The parking time is 16 to 24 hours; The vulcanization temperature is 150-180°C; The vulcanization time is 5 to 8 minutes; The vulcanization pressure is 38-40 tons.

10. Use of the rubber composite material according to any one of claims 1 to 5 or the rubber composite material prepared by the preparation method according to any one of claims 6 to 9 in a transmission belt.

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