CN105482177A - Rear-earth butadiene rubber material and preparation method thereof - Google Patents
Rear-earth butadiene rubber material and preparation method thereof Download PDFInfo
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- CN105482177A CN105482177A CN201510941907.2A CN201510941907A CN105482177A CN 105482177 A CN105482177 A CN 105482177A CN 201510941907 A CN201510941907 A CN 201510941907A CN 105482177 A CN105482177 A CN 105482177A
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- C08L2205/00—Polymer mixtures characterised by other features
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Abstract
The invention discloses a rear-earth butadiene rubber material. The rear-earth butadiene rubber material is prepared from, by weight, 2-3.7 parts of polybenzimidazole, 0.06-0.1 part of cerium oxide, 0.07-0.1 part of lanthanum citrate, 50-60 part of hydroxy terminated polybutadiene, 200-300 parts of n-methyl-2-pyrrolidone, 5-7 parts of boric oxide, 160-200 parts of butadiene rubber, 3-5 parts of short-and long-chain acyl triglyceride molecules, 1-2 parts of aluminium stearate, 2-3 parts of diacetone alcohol, 0.5-1 part of tributyltin chloride, 10-12 parts of epoxidized soybean oil, 2-3 parts of anti-aging agent 4010, 1.3-2 parts of sulfur and 30-40 parts of carbon nanotubes. Cerium oxide and lanthanum citrate are added, and therefore the heat resistance of the finished product is effectively improved, and dispersibility of filler particles between rubber materials is improved.
Description
Technical field
The present invention relates to field of rubber technology, particularly relate to a kind of rare earth polybutadiene rubber material and preparation method thereof.
Background technology
Carbon nanotube is widely used in polymkeric substance to the heat conduction of raising polymkeric substance, conduction and physicals etc. because of the structure of its uniqueness and the physical and chemical performance of excellence.But carbon nanotube itself has very high surface free energy, easily reunites, and not easily disperses in polymeric matrix, limit its application.The surface modification treatment of carbon nanotube is one of important channel of improving its dispersive ability in the polymer and then the excellent carbon nano-tube/polymer composite material of processability;
Hydroxy-terminated polybutadienes is liquid because of it at normal temperatures, and transparency is good, the low good processability of viscosity; And it and chainextender, linking agent react the cured article that can generate tridimensional network at ambient temperature or elevated temperature, this cured article has excellent mechanical property, good oil resistant and water resistance, particularly acid and alkali-resistance, wear-resisting, low temperature resistant and electrical insulation capability is better, become output in distant pawl series of fluids rubber maximum, purposes is a kind the most widely, is mainly used in the aspects such as solid propellant tackiness agent, polyurethane elastomer, material of construction, speciality coating, tackiness agent, Embedding Material, rubber and plastic and epoxy resin modification.Hydroxy-terminated polybutadienes gives its more characteristic by modification later, improves its performance, has widened the Application Areas of hydroxy-terminated polybutadienes.
Summary of the invention
The object of the invention is exactly the defect in order to make up prior art, provides a kind of rare earth polybutadiene rubber material and preparation method thereof.
The present invention is achieved by the following technical solutions:
A kind of rare earth polybutadiene rubber material, it is made up of the raw material of following weight parts:
Polybenzimidazole 2-3.7, cerium oxide 0.06-0.1, citric acid lanthanum 0.07-0.1, hydroxy-terminated polybutadienes 50-60, n-methyl-2-pyrrolidone 200-300, boron oxide 5-7, cis-1,4-polybutadiene rubber 160-200, short and long-chain acyl triglyceride molecules 3-5, aluminum stearate 1-2, Pyranton 2-3, tributyl tin trichloride 0.5-1, epoxy soybean oil 10-12, antioxidant 4010 2-3, sulphur 1.3-2, carbon nanotube 30-40.
A preparation method for described rare earth polybutadiene rubber material, comprises the following steps:
(1) above-mentioned aluminum stearate is joined in 3-5 times of deionized water, stir;
(2) above-mentioned carbon nanotube is placed in its weight 40-50 doubly, massfraction is the aqueous hydrogen peroxide solution ultrasonic disperse 30-40 minute of 0.3-0.5%, is incubated 100-120 minute, filters, vacuum-drying at 75-80 DEG C, obtains pre-treatment carbon nanotube;
(3) get sulfuric acid that volume ratio is 3-4:1, salpeter solution mixing, stir, described sulfuric acid concentration is 70-75%, concentration of nitric acid is 80-85%;
(4) get above-mentioned cerium oxide, join in the aluminum stearate aqueous solution in step (1), stir, add mixed acid solution, 200-300 rev/min is stirred 7-10 minute, obtains rare earth mixed acid solution;
(5) above-mentioned pre-treatment carbon nanotube is joined in rare earth mixed acid solution, ultrasonic 100-110 minute at 50-60 DEG C, carbon nanotube deionized water repetitive scrubbing to the filtrate obtained is neutral by filtration under diminished pressure, the vacuum drying oven putting into 76-80 DEG C is dried, and obtains acidifying carbon nanotube;
(6) by above-mentioned polybenzimidazole, the mixing of citric acid lanthanum, joining in n-methyl-2-pyrrolidone, stir, is premixed liquid;
(7) above-mentioned acidifying carbon nanotube is mixed with hydroxy-terminated polybutadienes, magnetic agitation 2-3 minute, join in above-mentioned premixed liquid, ultrasonic 10-16 minute, suction filtration, by filter cake dry 20-30 minute at 100-105 DEG C, obtain hydroxyl modification acidifying carbon nanotube;
(8) mixed with boron oxide by above-mentioned hydroxyl modification acidifying carbon nanotube, ball milling is even; Being sent to concentration is in the phosphoric acid solution of 10-15%, constant temperature dipping 120-130 minute at 150-160 DEG C, discharging, and dry, send in reactor, under nitrogen protection, thermal treatment 100-120 minute at 400-450 DEG C, obtains phosphate impregnation compounded mix;
(9) by phosphate impregnation compounded mix, cis-1,4-polybutadiene rubber mixing, plasticate 2-3 minute at 46-50 DEG C, add each raw material of residue, mixing 4-6 minute, is placed in two roller mills by the rubber unvulcanizate obtained, mixing 6-10 minute is supplemented at 30-40 DEG C, discharging, at room temperature parks 20-25 hour by sizing material, sends in vulcanizing press, at 150-155 DEG C, carry out sulfuration, to obtain final product;
The preparation method of described a kind of rare earth polybutadiene rubber material, the weight of described mixed acid solution is 18-20 times of pre-treatment carbon nanotubes.
Advantage of the present invention is:
First the present invention carries out Carboxylation process to carbon nanotube, then react with hydroxy-terminated polybutadienes, the intensity of sizing material can be strengthened, this is due to the hydroxyl reaction in the carboxyl of carbon nano tube surface and hydroxy-terminated polybutadienes, carbon nano tube surface is connected by covalent linkage with hydroxy-terminated polybutadienes molecular chain, thus improve its dispersiveness in the base, and enhance the bounding force of itself and rubber matrix, make it in rubber matrix, show better reinforcing effect;
Then the carboxylic acid carbon nanotube after hydroxy-terminated polybutadienes process is mixed with boron oxide, use phosphate impregnation compounded mix, the pyrogenous origin product P 4O10 of phosphoric acid is phosphorus oxygen glass structure, introduce B2O3 in the melt, [BPO4] structural unit can be formed, glass structure is made to change rack-like into by chain, these rack-like structures are cross-linked with each other, strengthen network structure, strengthen the bonding strength with matrix, one deck coating can be covered at matrix surface, covering surfaces hole more effectively, confining surface active site, effective prevention oxidizing gas enters intrinsic silicon by micropore or crackle, effectively raise physical strength and the antioxidant property of finished product,
Present invention adds cerium oxide, citric acid lanthanum, effectively raise the resistance toheat of finished product, improve the dispersiveness of filler grain between rubber mass.
Embodiment
A kind of rare earth polybutadiene rubber material, it is made up of the raw material of following weight parts:
Polybenzimidazole 2, cerium oxide 0.06, citric acid lanthanum 0.07, hydroxy-terminated polybutadienes 50, n methyl-2-pyrrolidone 200, boron oxide 5, cis-1,4-polybutadiene rubber 160, short and long-chain acyl triglyceride molecules 3, aluminum stearate 1, Pyranton 2, tributyl tin trichloride 0.5, epoxy soybean oil 10, antioxidant 4010 2, sulphur 1.3, carbon nanotube 30.
A preparation method for described rare earth polybutadiene rubber material, comprises the following steps:
(1) above-mentioned aluminum stearate is joined in 3 times of deionized waters, stir;
(2) above-mentioned carbon nanotube is placed in its weight 40 times, massfraction be 0.3% aqueous hydrogen peroxide solution ultrasonic disperse 30 minutes, at 75 DEG C, be incubated 100 minutes, filter, vacuum-drying, obtain pre-treatment carbon nanotube;
(3) get sulfuric acid that volume ratio is 3:1, salpeter solution mixing, stir, described sulfuric acid concentration is 70%, concentration of nitric acid is 80%;
(4) get above-mentioned cerium oxide, join in the aluminum stearate aqueous solution in step (1), stir, add mixed acid solution, 200 revs/min are stirred 7 minutes, obtain rare earth mixed acid solution;
(5) above-mentioned pre-treatment carbon nanotube is joined in rare earth mixed acid solution, at 50 DEG C ultrasonic 100 minutes, carbon nanotube deionized water repetitive scrubbing to the filtrate obtained was neutral by filtration under diminished pressure, the vacuum drying oven putting into 76 DEG C is dried, and obtains acidifying carbon nanotube;
(6) by above-mentioned polybenzimidazole, the mixing of citric acid lanthanum, joining in n methyl-2-pyrrolidone, stir, is premixed liquid;
(7) above-mentioned acidifying carbon nanotube is mixed with hydroxy-terminated polybutadienes, magnetic agitation 2 minutes, join in above-mentioned premixed liquid, ultrasonic 10 minutes, suction filtration, by filter cake at 100 DEG C dry 20 minutes, obtain hydroxyl modification acidifying carbon nanotube;
(8) mixed with boron oxide by above-mentioned hydroxyl modification acidifying carbon nanotube, ball milling is even; Being sent to concentration is in the phosphoric acid solution of 10%, and at 150 DEG C, constant temperature floods 120 minutes, discharging, dry, and send in reactor, under nitrogen protection, at 400 DEG C, thermal treatment 100 minutes, obtains phosphate impregnation compounded mix;
(9) by phosphate impregnation compounded mix, cis-1,4-polybutadiene rubber mixing, plasticate at 46 DEG C 2 minutes, add each raw material of residue, mixing 4 minutes, the rubber unvulcanizate obtained is placed in two roller mills, supplement mixing 6 minutes at 30 DEG C, discharging, at room temperature parks 20 hours by sizing material, sends in vulcanizing press, at 150 DEG C, carry out sulfuration, to obtain final product;
The preparation method of described a kind of rare earth polybutadiene rubber material, the weight of described mixed acid solution is 18 times of pre-treatment carbon nanotubes.
Stretch breaking strength (MPa): 18.8;
Surely modulus 100%(MPa is stretched): 2.3;
Mooney viscosity: 64;
70 DEG C × 70h air oven aging test:
Tensile strength at yield reduced rate: 4.3%, elongation at break reduced rate: 8.4%.
Claims (3)
1. a rare earth polybutadiene rubber material, is characterized in that, it is made up of the raw material of following weight parts:
Polybenzimidazole 2-3.7, cerium oxide 0.06-0.1, citric acid lanthanum 0.07-0.1, hydroxy-terminated polybutadienes 50-60, n-methyl-2-pyrrolidone 200-300, boron oxide 5-7, cis-1,4-polybutadiene rubber 160-200, short and long-chain acyl triglyceride molecules 3-5, aluminum stearate 1-2, Pyranton 2-3, tributyl tin trichloride 0.5-1, epoxy soybean oil 10-12, antioxidant 4010 2-3, sulphur 1.3-2, carbon nanotube 30-40.
2. a preparation method for rare earth polybutadiene rubber material as claimed in claim 1, is characterized in that, comprise the following steps:
(1) above-mentioned aluminum stearate is joined in 3-5 times of deionized water, stir;
(2) above-mentioned carbon nanotube is placed in its weight 40-50 doubly, massfraction is the aqueous hydrogen peroxide solution ultrasonic disperse 30-40 minute of 0.3-0.5%, is incubated 100-120 minute, filters, vacuum-drying at 75-80 DEG C, obtains pre-treatment carbon nanotube;
(3) get sulfuric acid that volume ratio is 3-4:1, salpeter solution mixing, stir, described sulfuric acid concentration is 70-75%, concentration of nitric acid is 80-85%;
(4) get above-mentioned cerium oxide, join in the aluminum stearate aqueous solution in step (1), stir, add mixed acid solution, 200-300 rev/min is stirred 7-10 minute, obtains rare earth mixed acid solution;
(5) above-mentioned pre-treatment carbon nanotube is joined in rare earth mixed acid solution, ultrasonic 100-110 minute at 50-60 DEG C, carbon nanotube deionized water repetitive scrubbing to the filtrate obtained is neutral by filtration under diminished pressure, the vacuum drying oven putting into 76-80 DEG C is dried, and obtains acidifying carbon nanotube;
(6) by above-mentioned polybenzimidazole, the mixing of citric acid lanthanum, joining in n-methyl-2-pyrrolidone, stir, is premixed liquid;
(7) above-mentioned acidifying carbon nanotube is mixed with hydroxy-terminated polybutadienes, magnetic agitation 2-3 minute, join in above-mentioned premixed liquid, ultrasonic 10-16 minute, suction filtration, by filter cake dry 20-30 minute at 100-105 DEG C, obtain hydroxyl modification acidifying carbon nanotube;
(8) mixed with boron oxide by above-mentioned hydroxyl modification acidifying carbon nanotube, ball milling is even; Being sent to concentration is in the phosphoric acid solution of 10-15%, constant temperature dipping 120-130 minute at 150-160 DEG C, discharging, and dry, send in reactor, under nitrogen protection, thermal treatment 100-120 minute at 400-450 DEG C, obtains phosphate impregnation compounded mix;
(9) by phosphate impregnation compounded mix, cis-1,4-polybutadiene rubber mixing, plasticate 2-3 minute at 46-50 DEG C, add each raw material of residue, mixing 4-6 minute, is placed in two roller mills by the rubber unvulcanizate obtained, mixing 6-10 minute is supplemented at 30-40 DEG C, discharging, at room temperature parks 20-25 hour by sizing material, sends in vulcanizing press, at 150-155 DEG C, carry out sulfuration, to obtain final product.
3. the preparation method of a kind of rare earth polybutadiene rubber material according to claim 2, is characterized in that, the weight of described mixed acid solution is 18-20 times of pre-treatment carbon nanotubes.
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| CN201510941907.2A CN105482177A (en) | 2015-12-16 | 2015-12-16 | Rear-earth butadiene rubber material and preparation method thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103694505A (en) * | 2013-12-24 | 2014-04-02 | 苏州华东橡胶工业有限公司 | Compound carbon nanotube and rubber material and preparation method thereof |
| CN104961983A (en) * | 2015-05-21 | 2015-10-07 | 青岛科凯达橡塑有限公司 | High-electrical conductivity high-thermal conductivity oil-resistant aging-resistant rubber material, and preparation method and applications thereof |
-
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- 2015-12-16 CN CN201510941907.2A patent/CN105482177A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103694505A (en) * | 2013-12-24 | 2014-04-02 | 苏州华东橡胶工业有限公司 | Compound carbon nanotube and rubber material and preparation method thereof |
| CN104961983A (en) * | 2015-05-21 | 2015-10-07 | 青岛科凯达橡塑有限公司 | High-electrical conductivity high-thermal conductivity oil-resistant aging-resistant rubber material, and preparation method and applications thereof |
Non-Patent Citations (2)
| Title |
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| 王中光: "碳纳米管表面包覆聚合物方法的探索及其聚合物材料的性能研究", 《青岛科技大学硕士学位论文》 * |
| 雷卓研等: "氧化硼-磷酸浸渍对中间相炭微球复合材料抗氧化及力学性能的影响", 《无机材料学报》 * |
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