Itaconate oil-resistant elastomer, composite material based on oil-resistant elastomer and preparation method of composite material
By combining itaconate with fluorinated acrylate monomers, an elastomer with both high-temperature oil resistance and mechanical properties was prepared, which solved the problem of insufficient oil resistance of elastomers in the existing technology and achieved environmentally friendly and efficient oil resistance.
Patent Information
- Application Number
- CN202510923863.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-04
- Publication Date
- 2025-10-10
AI Technical Summary
Existing elastomers are insufficient in combining mechanical properties with high-temperature oil resistance.
Itaconate is used as a bio-based material, combined with fluorinated acrylate monomers, and itaconate oil-resistant elastomer is prepared through a specific ratio and polymerization reaction to further improve its oil resistance.
Itaconate oil-resistant elastomers exhibit excellent oil resistance at high temperatures, while reducing dependence on petroleum fossil energy, reducing environmental pollution and achieving sustainable development.
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Figure CN120757704A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of elastomers, and in particular relates to an itaconate oil-resistant elastomer and a composite material based on the oil-resistant elastomer and a preparation method thereof. Background Art
[0002] Rubber oil resistance is often used to describe the ability of rubber to withstand the effects of oil, such as swelling, hardening, cracking, and mechanical property degradation. Oil-resistant rubber is used in a variety of fields, including crude oil extraction, automotive manufacturing, and aerospace, all of which are often exposed to oil. For example, oil-resistant rubber plays a key role in oilfield production. Even before the "bursting" of the Spindletop oil field during the Texas oil boom in 1901, rubber chemistry and technology played a key role in controlling the pressure and flow of hydrocarbons in reservoirs. The oil-resistant rubber's resistance to oil comes from two sources. First, the polar groups in the rubber's molecular chains repel non-polar oils, preventing them from penetrating the rubber. The greater the polarity of the groups, the greater the resistance to oil, and the better the oil resistance. Second, due to crosslinking between rubber molecular chains, the denser the crosslinking network, the more difficult it is for oil molecules to penetrate, resulting in better oil resistance. Summary of the Invention
[0003] In response to the above-mentioned prior art, the present invention provides an itaconate bio-based oil-resistant elastomer and its preparation method and application, which solves the problem in the prior art that the elastomer cannot have both mechanical properties and high-temperature oil resistance.
[0004] In order to achieve the above object, the technical solution adopted by the present invention is: providing an itaconate oil-resistant elastomer, wherein the molecular weight of the itaconate oil-resistant elastomer is 180,000 to 300,000 and the molecular weight distribution is 1.5 to 3.0; the raw materials for preparing the itaconate oil-resistant elastomer include the following components: an itaconate structural unit, a temperature resistance adjustment and cross-linking point providing structural unit and a polar monomer structural unit; the itaconate structural unit has the structure shown in Formula I, , Wherein, R1 is hydrogen or a C1~C8 alkyl group, and R2 is hydrogen or a C1~C8 alkyl group; The structural unit for adjusting temperature resistance and providing crosslinking points is at least one of butadiene and isoprene; the polar monomer structural unit is at least one of tetrafluoropropyl acrylate, pentafluorophenyl acrylate, pentafluorophenyl methacrylate, hexafluorobutyl acrylate, hexafluorobutyl methacrylate, heptafluorobutyl acrylate, heptafluorobutyl methacrylate, octafluoropentyl acrylate, dodecafluoroheptyl acrylate and tridecafluorooctyl acrylate.
[0005] On the basis of the above technical solution, the present invention can also be improved as follows.
[0006] Furthermore, the molecular weight of the itaconate oil-resistant elastomer is 200,000 to 240,000, and the molecular weight distribution is 2.0 to 2.25; the itaconate structural unit is monomethyl itaconate, monoethyl itaconate, dimethyl itaconate, diethyl itaconate, dipropyl itaconate or di-n-butyl itaconate; the mass ratio of the itaconate structural unit, the temperature resistance adjustment and cross-linking point providing structural unit and the polar monomer structural unit is 20 to 70:20 to 70:1 to 40.
[0007] Furthermore, the itaconate structural unit is dimethyl itaconate or diethyl itaconate; and the mass ratio of the itaconate structural unit, the temperature resistance adjustment and cross-linking point providing structural unit, and the polar monomer structural unit is 50:50:1~20.
[0008] Furthermore, the preparation method of the above-mentioned itaconate oil-resistant elastomer comprises the following steps: mixing an emulsifier, an activator, a molecular weight regulator, deionized water, an itaconate structural unit, a temperature resistance adjustment and crosslinking point providing structural unit and a polar monomer structural unit under an inert atmosphere, and pre-emulsifying at 0-15°C for 0.5-2 hours, then adding an initiator, and carrying out a polymerization reaction at 0-15°C for 2-18 hours to obtain the elastomer; The emulsifier is at least one of alkylphenol polyoxyethylene ether, sodium dodecylbenzene sulfonate and potassium disproportionated rosin acid; the initiator is at least one of tert-butyl hydroperoxide, potassium persulfate, ammonium persulfate, azobisisobutyronitrile and p-menthane hydroperoxide; the activator is at least one of sodium formaldehyde sulfoxylate, sodium ferric ethylenediaminetetraacetic acid, sodium bisulfite, sodium bicarbonate and ammonium bicarbonate; the molecular weight regulator is tert-dodecyl mercaptan; and the mass ratio of the emulsifier, initiator, activator and molecular weight regulator to the total amount of the three structural units is 1-2:0.01-1:0.8-2:0.01-1:100.
[0009] Furthermore, the polymerization reaction temperature is 2~10°C, the polymerization reaction time is 4~10h; the mass ratio of the emulsifier, initiator, activator, molecular weight regulator and the total amount of the three structural units is 1~1.25:0.06~0.085:1.1~1.5:0.06~0.085:100.
[0010] Furthermore, the emulsifier is sodium dodecylbenzenesulfonate, the initiator is p-menthane hydroperoxide, and the activator is sodium ferric ethylenediaminetetraacetic acid; the mass ratio of the emulsifier, initiator, activator, molecular weight regulator and the total amount of the three structural units is 1:0.067:1.17:0.067:100; the pre-emulsification temperature is 6°C and the time is 1 hour; the polymerization reaction temperature is 6°C and the time is 6 hours.
[0011] Furthermore, a composite material based on itaconate oil-resistant elastomer is provided, and its preparation raw materials include the above-mentioned itaconate oil-resistant elastomer.
[0012] Furthermore, a preparation method for a composite material based on itaconate oil-resistant elastomer includes the following steps: blending the itaconate oil-resistant elastomer with an additive and performing compression vulcanization at 140-160°C; the additives are carbon black, zinc oxide, stearic acid, paraffin, an accelerator, an antioxidant and a vulcanizing agent, the accelerator is diphenylguanidine and zinc dibutyldithiocarbamate, the antioxidant is 4,4'-di(phenylisopropyl)diphenylamine and N-(1,3-dimethyl)butyl-N'-phenyl-p-phenylenediamine, and the vulcanizing agent is sulfur.
[0013] Furthermore, a method for preparing a composite material of itaconate oil-resistant elastomer is provided, wherein the raw materials used are, in parts by mass: 90-110 parts of itaconate oil-resistant elastomer, 55-65 parts of carbon black, 1.5-2.5 parts of stearic acid, 2.5-3.5 parts of zinc oxide, 1.5-3 parts of antioxidant, 2.5-3.5 parts of accelerator, 0.5-1.5 parts of paraffin wax, and 2-3 parts of vulcanizing agent.
[0014] Furthermore, a method for preparing a composite material of itaconate oil-resistant elastomer is provided, wherein the raw materials used are calculated by mass as follows: 100 parts of itaconate oil-resistant elastomer, 60 parts of carbon black, 2 parts of stearic acid, 3 parts of zinc oxide, 2 parts of antioxidant, 3.1 parts of accelerator, 1 part of paraffin, and 1.5 parts of vulcanizing agent.
[0015] The beneficial effects of the present invention are as follows: the present invention utilizes the environmental friendliness of bio-based itaconate and the high polarity of fluorinated acrylate monomers to design an oil-resistant elastomer composite material; itaconate has two ester groups in its molecule, which has a more dense polar ester group than acrylate and has better oil resistance. At the same time, itaconate is a high-quality biomass-derived monomer. Using it as the main monomer for polymerization can reduce dependence on fossil energy such as petroleum, reduce environmental pollution, and achieve sustainable development, which is of great significance. The fluorinated groups in fluorinated acrylate monomers have high polarity. According to the rubber oil resistance mechanism, the polar groups on the molecular chain will repel non-polar oils and block non-polar oils from the rubber. The greater the group polarity, the better the oil resistance. The common group polarity is -F>-CN>-C=O>-Cl. Therefore, adding fluorinated acrylates can further improve the oil resistance of the target rubber. BRIEF DESCRIPTION OF THE DRAWINGS
[0016] Figure 1 This is the H NMR spectrum of the itaconate oil-resistant elastomer prepared in Examples 2 to 5; Figure 2 IR spectra of the itaconate oil-resistant elastomers prepared in Examples 2 to 5; Figure 3 2 is the DSC graph of the itaconate oil-resistant elastomer prepared in Examples 2 to 5. DETAILED DESCRIPTION
[0017] The specific embodiments of the present application will be described in detail below with reference to the examples.
[0018] Example 1 1. A itaconate ester oil-resistant elastomer, prepared by the following method: A 250 mL reactor was charged with emulsifier sodium dodecyl benzene sulfonate (SDBS) 0.75 g, activator iron sodium salt of ethylenediaminetetraacetic acid (EDTA-FeSO4-SFS) 0.875 g, molecular weight regulator tertiary dodecyl mercaptan (TDDM) 0.05 g, itaconate ester structural unit diethyl itaconate (DEI) 50 g, and water 50 g. The air in the reactor was replaced with nitrogen atmosphere by "vacuum-nitrogen filling". Then 50 g of butadiene (temperature resistance adjustment and crosslinking point providing structural unit) was injected by a metering pump. After the stirring device was turned on, pre-emulsification was carried out at 6 ℃ for 1 h, and then initiator p-menthane hydroperoxide (PMH) 0.05 g was injected into the reactor to initiate polymerization. After 6 h of reaction at 6 ℃, a uniform latex was obtained. The latex was flocculated by ethanol to obtain PDEBF wet glue, which was washed with water several times to remove impurities such as emulsifiers as much as possible, and then dried in an oven at 60 ℃ to constant weight to obtain the itaconate ester oil-resistant elastomer.
[0019] The number average molecular weight of the itaconate ester oil-resistant elastomer is Mn=20.5×10 4 , and Mw / Mn=2.25.
[0020] 2. A itaconate ester oil-resistant elastomer-based composite material, comprising the following raw materials by mass: 100 parts of the prepared itaconate ester oil-resistant elastomer, 60 parts of carbon black (N330), 2 parts of stearic acid, 3 parts of zinc oxide, 2 parts of antioxidant (4,4'-di(phenylisopropyl)diphenylamine and N-(1,3-dimethyl)butyl-N'-phenyl-p-phenylenediamine), 3.1 parts of accelerator (diphenyl guanidine and zinc dibutyldithiocarbamate), 1 part of paraffin wax, and 1.5 parts of vulcanizing agent (sulfur); and the preparation method is as follows: The prepared oil-resistant elastomer was placed in a Haake mixer and plasticized for 1 min, carbon black (N330) was added and mixed for 10 min, and then stearic acid, antioxidant, accelerator, and sulfur were added and mixed for 8 min, and then thin passed 5 times on an open mill. Hot press vulcanization was carried out on a flat vulcanization instrument at 150 ℃ to obtain the itaconate ester oil-resistant elastomer-based composite material.
[0021] Example 2 1. An itaconate oil-resistant elastomer comprises the following raw materials in parts by weight: 0.75 g of an emulsifier SDBS, 0.875 g of an activator EDTA-FeSO4-SFS, 0.0125 g of a molecular weight regulator TDDM, 50 g of an itaconate structural unit DEI, 5 g of a polar monomer structural unit hexafluorobutyl acrylate, 50 g of water, 50 g of a structural unit butadiene for adjusting temperature resistance and providing crosslinking points, and 0.05 g of an initiator para-menthane hydroperoxide (PMH). The preparation steps are the same as those in Example 1 to produce the itaconate oil-resistant elastomer.
[0022] The number average molecular weight of this itaconate oil-resistant elastomer is Mn=20.5×10 4 , Mw / Mn=2.25.
[0023] 2. A composite material based on itaconate oil-resistant elastomer, comprising the following raw materials in parts by mass: 100 parts of the prepared itaconate oil-resistant elastomer, 60 parts of carbon black (N330), 2 parts of stearic acid, 3 parts of zinc oxide, 2 parts of antioxidants (4,4'-di(phenylisopropyl)diphenylamine and N-(1,3-dimethyl)butyl-N'-phenyl-p-phenylenediamine), 3.1 parts of accelerators (diphenylguanidine and zinc dibutyldithiocarbamate), 1 part of paraffin and 1.5 parts of vulcanizing agent (sulfur); the preparation method is the same as that in Example 1, to obtain a composite material based on itaconate oil-resistant elastomer.
[0024] Example 3 1. An itaconate oil-resistant elastomer comprises the following raw materials in parts by weight: 0.75 g of an emulsifier SDBS, 0.875 g of an activator EDTA-FeSO4-SFS, 0.0125 g of a molecular weight regulator TDDM, 50 g of an itaconate structural unit DEI, 10 g of a polar monomer structural unit hexafluorobutyl acrylate, 50 g of water, 50 g of a structural unit butadiene for adjusting temperature resistance and providing crosslinking points, and 0.05 g of an initiator para-menthane hydroperoxide (PMH). The preparation steps are the same as those in Example 1 to obtain the itaconate oil-resistant elastomer.
[0025] The number average molecular weight of this itaconate oil-resistant elastomer is Mn=19.7×10 4 , Mw / Mn=2.20.
[0026] 2. A composite material based on itaconate oil-resistant elastomer, comprising the following raw materials in parts by mass: 100 parts of the prepared itaconate oil-resistant elastomer, 60 parts of carbon black (N330), 2 parts of stearic acid, 3 parts of zinc oxide, 2 parts of antioxidants (4,4'-di(phenylisopropyl)diphenylamine and N-(1,3-dimethyl)butyl-N'-phenyl-p-phenylenediamine), 3.1 parts of accelerators (diphenylguanidine and zinc dibutyldithiocarbamate), 1 part of paraffin and 1.5 parts of vulcanizing agent (sulfur); the preparation method is the same as that in Example 1, to obtain a composite material based on itaconate oil-resistant elastomer.
[0027] Example 4 1. An itaconate oil-resistant elastomer comprises the following raw materials in parts by weight: 0.75 g of an emulsifier SDBS, 0.875 g of an activator EDTA-FeSO4-SFS, 0.0125 g of a molecular weight regulator TDDM, 50 g of an itaconate structural unit DEI, 15 g of a polar monomer structural unit hexafluorobutyl acrylate, 50 g of water, 50 g of a structural unit butadiene for adjusting temperature resistance and providing crosslinking points, and 0.05 g of an initiator para-menthane hydroperoxide (PMH). The preparation steps are the same as those in Example 1 to obtain the itaconate oil-resistant elastomer.
[0028] The number average molecular weight of this itaconate oil-resistant elastomer is Mn=24.4×10 4 , Mw / Mn=2.00.
[0029] 2. A composite material based on itaconate oil-resistant elastomer, comprising the following raw materials in parts by mass: 100 parts of the prepared itaconate oil-resistant elastomer, 60 parts of carbon black (N330), 2 parts of stearic acid, 3 parts of zinc oxide, 2 parts of antioxidants (4,4'-di(phenylisopropyl)diphenylamine and N-(1,3-dimethyl)butyl-N'-phenyl-p-phenylenediamine), 3.1 parts of accelerators (diphenylguanidine and zinc dibutyldithiocarbamate), 1 part of paraffin and 1.5 parts of vulcanizing agent (sulfur); the preparation method is the same as that in Example 1, to obtain a composite material based on itaconate oil-resistant elastomer.
[0030] Example 5 1. An itaconate oil-resistant elastomer comprises the following raw materials in parts by weight: 0.75 g of an emulsifier SDBS, 0.875 g of an activator EDTA-FeSO4-SFS, 0.0125 g of a molecular weight regulator TDDM, 50 g of an itaconate structural unit DEI, 20 g of a polar monomer structural unit hexafluorobutyl acrylate, 50 g of water, 50 g of a structural unit butadiene for adjusting temperature resistance and providing crosslinking points, and 0.05 g of an initiator para-menthane hydroperoxide (PMH). The preparation steps are the same as those in Example 1 to obtain the itaconate oil-resistant elastomer.
[0031] The number average molecular weight of this itaconate oil-resistant elastomer is Mn=24.5×104 , Mw / Mn=2.04.
[0032] 2. A composite material based on itaconate oil-resistant elastomer, comprising the following raw materials in parts by mass: 100 parts of the prepared itaconate oil-resistant elastomer, 60 parts of carbon black (N330), 2 parts of stearic acid, 3 parts of zinc oxide, 2 parts of antioxidants (4,4'-di(phenylisopropyl)diphenylamine and N-(1,3-dimethyl)butyl-N'-phenyl-p-phenylenediamine), 3.1 parts of accelerators (diphenylguanidine and zinc dibutyldithiocarbamate), 1 part of paraffin and 1.5 parts of vulcanizing agent (sulfur); the preparation method is the same as that in Example 1, to obtain a composite material based on itaconate oil-resistant elastomer.
[0033] Example 6 1. An itaconate oil-resistant elastomer comprises the following raw materials in parts by weight: 0.75 g of an emulsifier SDBS, 0.875 g of an activator EDTA-FeSO4-SFS, 0.0125 g of a molecular weight regulator TDDM, 50 g of a dimethyl itaconate structural unit DMI, 20 g of a polar monomer structural unit tetrafluoropropyl acrylate, 50 g of water, 50 g of a temperature resistance regulating and crosslinking point providing structural unit butadiene, and 0.05 g of an initiator para-menthane hydroperoxide (PMH). The remaining steps are the same as those in Example 1 to prepare the itaconate oil-resistant elastomer.
[0034] The number average molecular weight of this itaconate oil-resistant elastomer is Mn=24.5×10 4 , Mw / Mn=2.03.
[0035] 2. A composite material based on itaconate oil-resistant elastomer, comprising the following raw materials in parts by mass: 100 parts of the prepared itaconate oil-resistant elastomer, 60 parts of carbon black (N330), 2 parts of stearic acid, 3 parts of zinc oxide, 2 parts of antioxidants (4,4'-di(phenylisopropyl)diphenylamine and N-(1,3-dimethyl)butyl-N'-phenyl-p-phenylenediamine), 3.1 parts of accelerators (diphenylguanidine and zinc dibutyldithiocarbamate), 1 part of paraffin and 1.5 parts of vulcanizing agent (sulfur); the preparation method is the same as that in Example 1, to obtain a composite material based on itaconate oil-resistant elastomer.
[0036] Example 7 1. An itaconate oil-resistant elastomer comprises the following raw materials in parts by weight: 0.75 g of an emulsifier SDBS, 0.875 g of an activator EDTA-FeSO4-SFS, 0.0125 g of a molecular weight regulator TDDM, 50 g of a diethyl itaconate structural unit DEI, 20 g of a polar monomer structural unit tridecafluorooctyl acrylate, 50 g of water, 50 g of a temperature-resistance-adjusting and crosslinking point-providing structural unit butadiene, and 0.05 g of a para-menthane hydroperoxide (PMH) initiator. The preparation steps are the same as those in Example 1 to obtain the itaconate oil-resistant elastomer.
[0037] The number average molecular weight of this itaconate oil-resistant elastomer is Mn=23.1×10 4 , Mw / Mn=2.12.
[0038] 2. A composite material based on itaconate oil-resistant elastomer, comprising the following raw materials in parts by mass: 100 parts of the prepared itaconate oil-resistant elastomer, 60 parts of carbon black (N330), 2 parts of stearic acid, 3 parts of zinc oxide, 2 parts of antioxidants (4,4'-di(phenylisopropyl)diphenylamine and N-(1,3-dimethyl)butyl-N'-phenyl-p-phenylenediamine), 3.1 parts of accelerators (diphenylguanidine and zinc dibutyldithiocarbamate), 1 part of paraffin and 1.5 parts of vulcanizing agent (sulfur); the preparation method is the same as that in Example 1, to obtain a composite material based on itaconate oil-resistant elastomer.
[0039] Example 8 1. An itaconate oil-resistant elastomer comprises the following raw materials in parts by weight: 0.75 g of an emulsifier SDBS, 0.875 g of an activator EDTA-FeSO4-SFS, 0.0125 g of a molecular weight regulator TDDM, 50 g of a diethyl itaconate structural unit DEI, 20 g of a polar monomer structural unit tetrafluoropropyl acrylate, 50 g of water, 50 g of a temperature-resistance-adjusting and crosslinking point-providing structural unit butadiene, and 0.05 g of a para-menthane hydroperoxide (PMH) initiator. The preparation steps are the same as those in Example 1 to produce the itaconate oil-resistant elastomer.
[0040] The number average molecular weight of this itaconate oil-resistant elastomer is Mn=22.1×10 4 , Mw / Mn=2.16.
[0041] 2. A composite material based on itaconate oil-resistant elastomer, comprising the following raw materials in parts by mass: 100 parts of the prepared itaconate oil-resistant elastomer, 60 parts of carbon black (N330), 2 parts of stearic acid, 3 parts of zinc oxide, 2 parts of antioxidants (4,4'-di(phenylisopropyl)diphenylamine and N-(1,3-dimethyl)butyl-N'-phenyl-p-phenylenediamine), 3.1 parts of accelerators (diphenylguanidine and zinc dibutyldithiocarbamate), 1 part of paraffin and 1.5 parts of vulcanizing agent (sulfur); the preparation method is the same as that in Example 1, to obtain a composite material based on itaconate oil-resistant elastomer.
[0042] Example 9 1. An itaconate oil-resistant elastomer, prepared by the following method: A 250 mL reactor was charged with 1.5 g of alkylphenol polyoxyethylene ether (emulsifier), 0.015 g of ammonium bicarbonate (activator), 0.015 g of tert-dodecyl mercaptan (TDDM) (molecular weight modifier), 50 g of monomethyl itaconate (itaconate building block), 20 g of heptafluorobutyl methacrylate, and 100 g of water. The air in the reactor was replaced with a nitrogen atmosphere by vacuum-filling and nitrogen-purging. 50 g of isoprene (to adjust temperature resistance and provide crosslinking sites) was then added via a metering pump. Pre-emulsification was performed at 6°C with stirring for 0.5 h. Then, 0.015 g of tert-butyl hydroperoxide (t-butyl hydroperoxide) was added to the reactor to initiate polymerization. After reacting at 6°C for 10 h, a homogeneous latex was obtained. The latex was flocculated with ethanol to obtain a wet latex. The latex was washed several times with water to remove impurities such as the emulsifier and then dried in an oven at 60°C to a constant weight, yielding an itaconate oil-resistant elastomer.
[0043] The number average molecular weight of this itaconate oil-resistant elastomer is Mn=27.5×10 4 , Mw / Mn=1.67.
[0044] 2. A composite material based on itaconate oil-resistant elastomer, comprising the following raw materials in parts by mass: 100 parts of the prepared itaconate oil-resistant elastomer, 60 parts of carbon black (N330), 2 parts of stearic acid, 3 parts of zinc oxide, 2 parts of antioxidants (4,4'-di(phenylisopropyl)diphenylamine and N-(1,3-dimethyl)butyl-N'-phenyl-p-phenylenediamine), 3.1 parts of accelerators (diphenylguanidine and zinc dibutyldithiocarbamate), 1 part of paraffin and 1.5 parts of vulcanizing agent (sulfur); the preparation method is the same as that in Example 1, to obtain a composite material based on itaconate oil-resistant elastomer.
[0045] Sample test: The 1H-NMR spectra of the itaconate oil-resistant elastomer prepared in Examples 2 to 5 are as follows: Figure 1 The peak at 1.17 ppm corresponds to the displacement of methyl hydrogen in the DEI side group (d). The peaks at 1.28-2.40 ppm correspond to the displacement of hydrogen on the non-double bond in the Bd unit. The peaks at 1.96 ppm and 1.93 ppm correspond to the methylene hydrogen in the trans-1,4-structure of Bd, the peaks at 1.84 ppm and 1.57 ppm correspond to the methylene hydrogen in the cis-1,4-structure, the peaks at 2.00 ppm correspond to the methylene hydrogen in the 1,2-structure main chain, and the peaks at 1.36 ppm correspond to the methine hydrogen in the 1,2-structure main chain.
[0046] from Figure 2 The infrared spectra shown can further confirm the chemical bonds or functional groups corresponding to the polymer macromolecules of Examples 2 to 5. -1The peaks at 2950 and 2920 cm are the antisymmetric stretching vibrations of -CH3. -1 The stretching vibration of -CH2- is at 1730 cm -1 The strong peak at 1500~1650cm represents the stretching vibration of -C=O brought by the introduction of DEI. -1 The area represents the stretching vibration of -C=C-. 1300~1500cm -1 The peaks between 1180 cm and 1180 cm contain the CH in-plane bending vibration peak and the CC single bond skeleton vibration peak. -1 The stronger peak represents the asymmetric stretching vibration of -CO in the ester group. -1 The peak is the out-of-plane deformation vibration absorption peak of the trans-1,4 structure of Bd in PDEIB, 913 cm -1 The peaks are the absorption peaks of 1,2-structure, at 1362, 1232, 840 cm -1 The wave numbers generated by each functional group or chemical bond in the infrared spectrum can correspond to the structural units in the itaconate oil-resistant elastomer prepared in Examples 2 to 5.
[0047] The DSC graphs of Examples 2 to 5 show that the glass transition temperatures of the itaconate oil-resistant elastomers are -20.8, -18.9, -17.6, and -15.6° C., respectively, indicating that they have good applicability as rubbers.
[0048] Comparative Example 1 Commercially available NBR240S was selected for mixing processing, and 100 parts of the itaconate oil-resistant elastomer in the composite material based on itaconate oil-resistant elastomer prepared in Example 1 was replaced with 100 parts of NBR240S. The remaining steps were the same as in Example 1, and a composite material based on commercially available NBR240S was obtained.
[0049] The mixing formula was the same as that in Example 1, and the product was vulcanized at 150°C.
[0050] The composite materials based on itaconate oil-resistant elastomer prepared in Examples 1 to 9 and the composite material based on commercially available NBR240S in Comparative Example 1 were tested respectively. The test results are shown in Tables 1 and 2.
[0051] Table 1 Mechanical properties test results of each sample
[0052] Table 2 Volume mass change test results of each sample
[0053] The above properties were tested according to the following standards: tensile strength (GB / T 528-2009), elongation at break (GB / T 528-2009), and oil resistance of vulcanized rubber according to GB / T 1690-2006. Tensile bars and rectangular specimens (mass m1, volume V) of the mixture were placed in a sealed cylinder of ASTM 3# oil. These specimens were then placed in an aging oven at 100°C for 72 hours. After aging, the specimens were removed, cooled to room temperature, and blotted dry with filter paper. Mechanical properties and hardness of the aged specimens were measured at 25°C as described above. The mass and volume change tests were as follows: Mass change rate test: After absorbing the oil, the mass m2 after oil resistance test is calculated by formula (1); Δm=(m2-m1) / m1×100%(1) Volume change rate test: After absorbing the oil, the length, width and height of the oil-resistant material are tested. The volume is recorded as Vˊ and calculated using formula (2).
[0054] ΔV=(Vˊ-V) / V×100% (2) As can be seen from Examples 1-5 and Comparative Example 1, the addition of fluorinated acrylate monomers improves the rubber's oil resistance compared to Examples 2-4 and Example 1, and the greater the amount of fluorinated acrylate monomer added, the better the oil resistance. Compared to commercially available NBR240S nitrile rubber, the fluorinated acrylate-modified itaconate bio-based oil-resistant elastomer, using fluorinated acrylate as the modifying monomer, exhibits superior mechanical properties and similar mass-volume changes when used in oily environments.
[0055] Although the specific embodiments of the present invention have been described in detail in conjunction with the embodiments, this should not be construed as limiting the scope of protection of this patent. Within the scope described by the claims, various modifications and variations that can be made by those skilled in the art without creative work still fall within the scope of protection of this patent.
Claims
1. An itaconate oil-resistant elastomer, characterized in that: The molecular weight of the itaconate oil-resistant elastomer is 180,000 to 300,000, and the molecular weight distribution is 1.5 to 3. The raw materials for preparing the itaconate oil-resistant elastomer include the following components: an itaconate structural unit, a temperature resistance adjustment and cross-linking point providing structural unit, and a polar monomer structural unit; the itaconate structural unit has the structure shown in Formula I, ， Wherein, R1 is hydrogen or a C1~C8 alkyl group, and R2 is hydrogen or a C1~C8 alkyl group; The temperature resistance regulating and cross-linking point providing structural unit is at least one of butadiene and isoprene; the polar monomer structural unit is at least one of tetrafluoropropyl acrylate, pentafluorophenyl acrylate, pentafluorophenyl methacrylate, hexafluorobutyl acrylate, hexafluorobutyl methacrylate, heptafluorobutyl acrylate, heptafluorobutyl methacrylate, octafluoropentyl acrylate, dodecafluoroheptyl acrylate and tridecafluorooctyl acrylate.
2. The itaconate oil-resistant elastomer according to claim 1, characterized in that: The molecular weight of the itaconate oil-resistant elastomer is 200,000 to 240,000, and the molecular weight distribution is 2.0 to 2.25; the itaconate structural unit is monomethyl itaconate, monoethyl itaconate, dimethyl itaconate, diethyl itaconate, dipropyl itaconate or di-n-butyl itaconate; the mass ratio of the itaconate structural unit, the temperature resistance adjustment and cross-linking point providing structural unit and the polar monomer structural unit is 20 to 70:20 to 70:1 to 40.
3. The itaconate oil-resistant elastomer according to claim 1, characterized in that: The itaconate structural unit is dimethyl itaconate or diethyl itaconate; the mass ratio of the itaconate structural unit, the temperature resistance adjustment and cross-linking point providing structural unit and the polar monomer structural unit is 50:50:1~20.
4. The method for preparing the itaconate oil-resistant elastomer according to any one of claims 1 to 3, characterized in that: The following steps are involved: Under an inert atmosphere, an emulsifier, an activator, a molecular weight regulator, deionized water, an itaconate structural unit, a temperature resistance regulating and cross-linking point providing structural unit, and a polar monomer structural unit are mixed, and pre-emulsified at 0-15°C for 0.5-2h, and then an initiator is added, and a polymerization reaction is carried out at 0-15°C for 2-18h to obtain the product; The emulsifier is at least one of alkylphenol polyoxyethylene ether, sodium dodecylbenzene sulfonate and potassium disproportionated rosin acid; the initiator is at least one of tert-butyl hydroperoxide, potassium persulfate, ammonium persulfate, azobisisobutyronitrile and p-menthane hydroperoxide; the activator is at least one of sodium formaldehyde sulfoxylate, sodium ferric ethylenediaminetetraacetic acid, sodium bisulfite, sodium bicarbonate and ammonium bicarbonate; the molecular weight regulator is tert-dodecyl mercaptan; and the mass ratio of the emulsifier, initiator, activator and molecular weight regulator to the total amount of the three structural units is 1-2:0.01-1:0.8-2:0.01-0.1:
100.
5. The method for preparing an itaconate oil-resistant elastomer according to claim 4, wherein: The polymerization reaction temperature is 2-10° C., and the polymerization reaction time is 4-10 hours. The mass ratio of the emulsifier, initiator, activator, molecular weight regulator and the total amount of the three structural units is 1-1.25:0.06-0.085:1.1-1.5:0.06-0.085:
100.
6. The method for preparing an itaconate oil-resistant elastomer according to claim 5, wherein: The emulsifier is sodium dodecylbenzenesulfonate, the initiator is p-menthane hydroperoxide, and the activator is sodium ferric ethylenediaminetetraacetic acid; the mass ratio of the emulsifier, initiator, activator, molecular weight regulator and the total amount of the three structural units is 1:0.067:1.17:0.067:100; the pre-emulsification temperature is 6°C and the time is 1 hour; the polymerization reaction temperature is 6°C and the time is 6 hours.
7. A composite material based on itaconate oil-resistant elastomer, characterized in that: The raw materials for its preparation include the itaconate oil-resistant elastomer according to any one of claims 1 to 3.
8. The method for preparing the composite material based on itaconate oil-resistant elastomer according to claim 7, characterized in that: The following steps are involved: The itaconate oil-resistant elastomer is blended with additives and subjected to compression vulcanization at 140-160° C.; the additives are carbon black, zinc oxide, stearic acid, paraffin, an accelerator, an antioxidant and a vulcanizing agent; the accelerator is diphenylguanidine and zinc dibutyldithiocarbamate; the antioxidant is 4,4'-di(phenylisopropyl)diphenylamine and N-(1,3-dimethyl)butyl-N'-phenyl-p-phenylenediamine; and the vulcanizing agent is sulfur.
9. The method for preparing the composite material of itaconate oil-resistant elastomer according to claim 8, characterized in that: The raw materials used are calculated by mass as follows: 90-110 parts of itaconate oil-resistant elastomer, 55-65 parts of carbon black, 1.5-2.5 parts of stearic acid, 2.5-3.5 parts of zinc oxide, 1.5-3 parts of antioxidant, 2.5-3.5 parts of accelerator, 0.5-1.5 parts of paraffin, and 2-3 parts of vulcanizing agent.
10. The method for preparing the composite material of itaconate oil-resistant elastomer according to claim 9, characterized in that: The raw materials used are calculated by mass as follows: 100 parts of itaconate oil-resistant elastomer, 60 parts of carbon black, 2 parts of stearic acid, 3 parts of zinc oxide, 2 parts of antioxidant, 3.1 parts of accelerator, 1 part of paraffin, and 1.5 parts of vulcanizing agent.