CN105482178A - Macromolecular butadiene rubber material and preparation method thereof - Google Patents
Macromolecular butadiene rubber material and preparation method thereof Download PDFInfo
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- CN105482178A CN105482178A CN201510941949.6A CN201510941949A CN105482178A CN 105482178 A CN105482178 A CN 105482178A CN 201510941949 A CN201510941949 A CN 201510941949A CN 105482178 A CN105482178 A CN 105482178A
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Abstract
The invention discloses a macromolecular butadiene rubber material which comprises, by weight parts, 4-8 parts of diatomaceous earth, 30-40 parts of carbon nanotube, 50-60 parts of hydroxyl-terminated polybutadiene, 200-300 parts of n-methyl pyrrolidone, 5-7 parts of boron trioxide, 160-200 parts of butadiene rubber, 2-3 parts of anti-aging agent rd, 1.3-2 parts of sulfur, 4-7 parts of polyacrylamide, 1-2 parts of polyimide, 1-2 parts of potassium fluosilicate, 10-14 parts of microcrystalline wax, 0.6-1 part of coco fatty acid diethanol amide, 0.7-1 part of zinc dibutyl dithiocaarbamate, 4-6 parts of dioctyl azelate and 0.1-0.2 part of trimethylolpropane. High polymer materials such as polyacrylamide and polyimide are added into the macromolecular butadiene rubber material, the compatibility of the raw materials is effectively improved, and the comprehensive quality of the finished product is improved.
Description
Technical field
The present invention relates to field of rubber technology, particularly relate to a kind of polymer cis-1,4-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 polymer cis-1,4-polybutadiene rubber material and preparation method thereof.
The present invention is achieved by the following technical solutions:
A kind of polymer cis-1,4-polybutadiene rubber material, it is made up of the raw material of following weight parts:
Diatomite 4-8, carbon nanotube 30-40, hydroxy-terminated polybutadienes 50-60, n-methyl-2-pyrrolidone 200-300, boron oxide 5-7, cis-1,4-polybutadiene rubber 160-200, anti-aging agent rd2-3, sulphur 1.3-2, polyacrylamide 4-7, polyimide 1-2, potassium silicofluoride 1-2, microcrystalline wax 10-14, lauric acid amide of ethanol 0.6-1, zinc dibutyl dithiocarbamate 0.7-1, dioctyl azelate 4-6, TriMethylolPropane(TMP) 0.1-0.2.
A preparation method for described polymer cis-1,4-polybutadiene rubber material, comprises the following steps:
(1) above-mentioned lauric acid amide of ethanol is got, join in its weight 46-50 times dehydrated alcohol, stir, add diatomite, raised temperature is 70-80 DEG C, adds microcrystalline wax, carbon nanotube, insulated and stirred 10-15 minute, suction filtration, at 70-80 DEG C, vacuum-drying 1-2 hour, obtains composite carbon nanometer tube;
(2) above-mentioned composite carbon nanometer tube be 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) pre-treatment carbon nanotube obtained above is joined in above-mentioned mixed acid solution, ultrasonic 100-110 minute at 50-60 DEG C, filtration under diminished pressure, be neutral by carbon nanotube deionized water repetitive scrubbing to the filtrate obtained, the vacuum drying oven putting into 76-80 DEG C is dried, and obtains acidifying carbon nanotube;
(5) above-mentioned acidifying carbon nanotube is mixed with hydroxy-terminated polybutadienes, magnetic agitation 2-3 minute, join in said n-methyl-2-pyrrolidone, ultrasonic 10-16 minute, suction filtration, by filter cake dry 20-30 minute at 100-105 DEG C, obtains hydroxyl modification acidifying carbon nanotube;
(6) joined in 17-20 times of deionized water by above-mentioned polyacrylamide, stir, add zinc dibutyl dithiocarbamate, insulated and stirred 3-4 minute at 60-67 DEG C, secure satisfactory grades sub-solution;
(7) 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, join in above-mentioned macromolecular solution, 100-200 rev/min is stirred 20-30 minute, filtration, drying, in feeding reactor, under nitrogen protection, thermal treatment 100-120 minute at 400-450 DEG C, obtains phosphate impregnation compounded mix;
(8) 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 cis-1,4-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 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 the macromolecular material such as polyacrylamide, polyimide, effectively improve the consistency between each raw material, improve the overall quality of finished product.
Embodiment
A kind of polymer cis-1,4-polybutadiene rubber material, it is made up of the raw material of following weight parts:
Diatomite 4, carbon nanotube 30, hydroxy-terminated polybutadienes 50, n methyl-2-pyrrolidone 200, boron oxide 5, cis-1,4-polybutadiene rubber 160, anti-aging agent rd2, sulphur 1.3, polyacrylamide 4, polyimide 1, potassium silicofluoride 1, microcrystalline wax 10, lauric acid amide of ethanol 0.6, zinc dibutyl dithiocarbamate 0.7, dioctyl azelate 4, TriMethylolPropane(TMP) 0.1.
A preparation method for described polymer cis-1,4-polybutadiene rubber material, comprises the following steps:
(1) get above-mentioned lauric acid amide of ethanol, join in its weight 46 times of dehydrated alcohols, stir, add diatomite, raised temperature is 70 DEG C, adds microcrystalline wax, carbon nanotube, insulated and stirred 10 minutes, suction filtration, at 70 DEG C, vacuum-drying 1 hour, obtains composite carbon nanometer tube;
(2) above-mentioned composite carbon nanometer tube be 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) pre-treatment carbon nanotube obtained above is joined in above-mentioned 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;
(5) above-mentioned acidifying carbon nanotube is mixed with hydroxy-terminated polybutadienes, magnetic agitation 2 minutes, join in said n methyl-2-pyrrolidone, ultrasonic 10 minutes, suction filtration, by filter cake at 100 DEG C dry 20 minutes, obtain hydroxyl modification acidifying carbon nanotube;
(6) joined in 17 times of deionized waters by above-mentioned polyacrylamide, stir, add zinc dibutyl dithiocarbamate, insulated and stirred 3 minutes at 60 DEG C, secure satisfactory grades sub-solution;
(7) 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, joins in above-mentioned macromolecular solution, 100 revs/min are stirred 20 minutes, filtration, drying, send in reactor, under nitrogen protection, at 400 DEG C, thermal treatment 100 minutes, obtains phosphate impregnation compounded mix;
(8) 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 cis-1,4-polybutadiene rubber material, the weight of described mixed acid solution is 18 times of pre-treatment carbon nanotubes.
Stretch breaking strength (MPa): 18.3;
Surely modulus 100%(MPa is stretched): 2.2;
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 polymer cis-1,4-polybutadiene rubber material, is characterized in that, it is made up of the raw material of following weight parts:
Diatomite 4-8, carbon nanotube 30-40, hydroxy-terminated polybutadienes 50-60, n-methyl-2-pyrrolidone 200-300, boron oxide 5-7, cis-1,4-polybutadiene rubber 160-200, anti-aging agent rd2-3, sulphur 1.3-2, polyacrylamide 4-7, polyimide 1-2, potassium silicofluoride 1-2, microcrystalline wax 10-14, lauric acid amide of ethanol 0.6-1, zinc dibutyl dithiocarbamate 0.7-1, dioctyl azelate 4-6, TriMethylolPropane(TMP) 0.1-0.2.
2. a preparation method for polymer cis-1,4-polybutadiene rubber material as claimed in claim 1, is characterized in that, comprise the following steps:
(1) above-mentioned lauric acid amide of ethanol is got, join in its weight 46-50 times dehydrated alcohol, stir, add diatomite, raised temperature is 70-80 DEG C, adds microcrystalline wax, carbon nanotube, insulated and stirred 10-15 minute, suction filtration, at 70-80 DEG C, vacuum-drying 1-2 hour, obtains composite carbon nanometer tube;
(2) above-mentioned composite carbon nanometer tube be 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) pre-treatment carbon nanotube obtained above is joined in above-mentioned mixed acid solution, ultrasonic 100-110 minute at 50-60 DEG C, filtration under diminished pressure, be neutral by carbon nanotube deionized water repetitive scrubbing to the filtrate obtained, the vacuum drying oven putting into 76-80 DEG C is dried, and obtains acidifying carbon nanotube;
(5) above-mentioned acidifying carbon nanotube is mixed with hydroxy-terminated polybutadienes, magnetic agitation 2-3 minute, join in said n-methyl-2-pyrrolidone, ultrasonic 10-16 minute, suction filtration, by filter cake dry 20-30 minute at 100-105 DEG C, obtains hydroxyl modification acidifying carbon nanotube;
(6) joined in 17-20 times of deionized water by above-mentioned polyacrylamide, stir, add zinc dibutyl dithiocarbamate, insulated and stirred 3-4 minute at 60-67 DEG C, secure satisfactory grades sub-solution;
(7) 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, join in above-mentioned macromolecular solution, 100-200 rev/min is stirred 20-30 minute, filtration, drying, in feeding reactor, under nitrogen protection, thermal treatment 100-120 minute at 400-450 DEG C, obtains phosphate impregnation compounded mix;
(8) 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 cis-1,4-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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CN106589737A (en) * | 2016-11-28 | 2017-04-26 | 天津盼易科技有限公司 | Novel macromolecular composite material and preparation method thereof |
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CN103937243A (en) * | 2014-04-18 | 2014-07-23 | 芜湖凯奥尔环保科技有限公司 | Carbon nanotube modified polyphenylene oxide material for automotive plastic parts |
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CN106589737A (en) * | 2016-11-28 | 2017-04-26 | 天津盼易科技有限公司 | Novel macromolecular composite material and preparation method thereof |
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