CN105176101A - High-performance modified acrylate rubber material and preparation method thereof - Google Patents
High-performance modified acrylate rubber material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-performance modified acrylate rubber material. The high-performance modified acrylate rubber material comprises the following raw materials by weight: 90 to 130 parts of modified acrylate rubber, 15 to 30 parts of fluororubber, 10 to 15 parts of methacrylic acid polyester, 20 to 50 parts of carbon black, 5 to 10 parts of antimony trioxide, 3 to 5 parts of magnesium oxide, 2 to 6 parts of polyethylene wax, 1 to 3 parts of stearic acid, 1 to 3 parts of a titanate coupling agent, 1 to 3 parts of hexamethylene diamine carbamate, 0.02 to 0.05 part of sulphur, 2 to 6 parts of di-o-tolylguanidine, 1 to 3 parts of phthalate, 1 to 3 parts of dioctyl sebacate and 4 to 8 parts of an auxiliary agent. The modified acrylate rubber material has higher comprehensive mechanical properties, thermal aging resistance, high temperature oil resistance and low compression set.
Description
Technical field
The present invention relates to field of rubber technology, particularly relate to a kind of high-performance modified acrylic elastomer material and preparation method thereof.
Background technology
Along with the development of modern industry, to the demand of the performances such as material thermal resistance, oil-proofness, weather resistance, lightweight in continuous increase.Acrylic elastomer as one of specialty elastomer has excellent heat-resisting oil-proofness and relative superior cost performance, by people's extensive concern and research because of it.Because it is widely applied in the automotive industry, be called as especially " automobile-used rubber ".In the world, be that all kinds of automobile sealed goods of raw material have comparative advantage with acrylic elastomer, for the U.S., the acrylic elastomer consumption of more than 80% at this on the one hand, mainly makees high temperature oil sealing.Modern Engine, to the future development of high rotating speed, high compression ratio, cause the temperature of rotating engine components to rise, moreover the miniaturization of hydraulic power actuating system also promotes the increase of thermal reservoir, makes the temperature of hydraulic efficiency oil can up to 150 ~ 160 DEG C.Add various countries to go into overdrive in energy saving standard, these all propose new requirement to the resistance toheat of seal fitting and technical feature.Thus acrylic elastomer must have higher comprehensive mechanical property and heat aging property, high-temperature oil resistance performance and low compression set as sealing material.
For making the use of acrylic elastomer material meet above-mentioned requirements, the study on the modification of acrylic elastomer obtains tremendous development.Mainly utilize the method such as the modification of synthesis phase, diversification copolymerization, process segment and different blend rubber, rubber and plastic, interpolation auxiliary agent to improve the over-all properties of acrylic elastomer in existing methodical modification, achieved very large effect, a series of high-performance new variety occur in succession.But the effect of above-mentioned method of modifying is not fairly obvious, and modified feedstock large usage quantity, cost is relatively high.
Along with the development of oil and automotive industry, for making acrylic elastomer material have higher comprehensive mechanical property and heat aging property, high-temperature oil resistance performance and low compression set performance, find that more effective modification acrylate elastomeric material has great importance.
Summary of the invention
Based on the technical problem that background technology exists, the present invention proposes a kind of high-performance modified acrylic elastomer material and preparation method thereof, this modification acrylate elastomeric material not only has higher comprehensive mechanical property, also has heat aging property, high-temperature oil resistance performance and low compression set performance.
The high-performance modified acrylic elastomer material of one that the present invention proposes, comprises following raw material: modification acrylate rubber 90-130 part, viton 15-30 part, methacrylic acid polyester 10-15 part, carbon black 20-50 part, antimonous oxide 5-10 part, magnesium oxide 3-5 part, polyethylene wax 2-6 part, stearic acid 1-3 part, titanate coupling agent 1-3 part, hexamethylene diamine carbamate 1-3 part, sulphur 0.02-0.05 part, di-o-tolylguanidine 2-6 part, phthalic ester 1-3 part, dioctyl sebacate 1-3 part and auxiliary agent 4-8 part by weight;
Prepare described modification acrylate rubber to comprise: acrylate, vinyl cyanide, vinylformic acid, emulsifying agent, initiator and tensio-active agent are added in reactor and carries out free-radical emulsion polymerization reaction; When the transformation efficiency of described polyreaction reaches 80%-90%, in reactor, add resole continue reaction, obtain modified polymer emulsion; In described modified polymer emulsion, add industrial spirit obtain latex, after oven dry, obtain modification acrylate rubber.
Preferably, described high-performance modified acrylic elastomer material, comprises following raw material by weight: modification acrylate rubber 100-120 part, viton 20-25 part, methacrylic acid polyester 12-14 part, carbon black 30-40 part, antimonous oxide 6-8 part, magnesium oxide 3-4 part, polyethylene wax 3-5 part, stearic acid 1-2 part, titanate coupling agent 1-2 part, hexamethylene diamine carbamate 1-2 part, sulphur 0.03-0.04 part, di-o-tolylguanidine 3-4 part, phthalic ester 1-2 part, dioctyl sebacate 1-2 part and auxiliary agent 5-7 part.
Preferably, described auxiliary agent by quality proportioning be the hexamethylenetetramine of 5-7:1-3:0.2-0.5, magnesium oxide and lubricant form.
Preferably, prepare described modification acrylate rubber to comprise: acrylate 72-78%, vinyl cyanide 8-14%, vinylformic acid 4-10%, emulsifying agent 2-4%, initiator 0.2-0.3% and tensio-active agent 1-2% add in vacuum reaction still by percentage composition by weight, in water medium, carry out free-radical emulsion polymerization reaction, control polymeric reaction temperature is 50-70 DEG C; When the transformation efficiency of described polyreaction reaches 80%-90%, in described reactor, add resole 6-10% continue reaction, adjustment reacting liquid pH value is 2.3-2.5, reacts 1-1.5h, obtain modified polymer emulsion under 70-90 DEG C of condition; In described emulsion, add industrial spirit carry out breakdown of emulsion, obtain latex, the 60-80 DEG C of dry 30-50h of baking oven put into by described latex after water rinses repeatedly, obtains modification acrylate rubber.
Preferably, described acrylate is butyl acrylate; Described initiator is Potassium Persulphate; Described emulsifying agent is OP-10; Described tensio-active agent is sodium lauryl sulphate.
Preferably, prepare described resole to comprise: be that NaOH solution or the KOH solution of 30-40% is added drop-wise in the formaldehyde and phenol solution that quality proportioning is 2-3:1 by weight percentage, 1-3h is reacted under 50-70 DEG C of condition, carry out vacuum hydro-extraction after reaction solution being cooled to normal temperature, obtain described resole.
Preferably, the preparation method of described high-performance modified acrylic elastomer material, comprises the steps:
(1) modification acrylate rubber and auxiliary agent are put in mill discharge after the 20-25min that plasticates, cooling obtains material of plasticating;
(2) material of plasticating step (1) obtained drops in Banbury mixer, add viton to plasticate 20-25min, add methacrylic acid polyester, antimonous oxide, magnesium oxide, polyethylene wax, stearic acid and titanate coupling agent successively, mixing 3-5min, adds the mixing 3-4min of carbon black of 2/3, then adds remaining carbon black and to turn refining 3-4min, add phthalic ester and the mixing 3-4min of dioctyl sebacate, melting temperature all remains on less than 60 DEG C, discharge, and cooling obtains master batch;
(3) master batch step (2) obtained drops in Banbury mixer, 130-150 DEG C is warming up to after adding hexamethylene diamine carbamate, Sulfur and di-o-tolylguanidine, mixing 5-15min, continue to be warming up to 165-185 DEG C, mixing 3-5min, obtains described high-performance modified acrylic elastomer material.
Preferably, in step (1), adjustment mill temperature is to 80-90 DEG C, and rotating speed is after 30-35 rev/min, modification acrylate rubber and auxiliary agent is put in mill and plasticates.
Preferably, in step (2), adjustment Banbury mixer temperature is to 40-50 DEG C, and rotating speed is after 30-35 rev/min, then the material of plasticating step (1) obtained drops in Banbury mixer.
Preferably, in step (3), master batch step (2) obtained drops in Banbury mixer, 140 DEG C are warming up to after adding hexamethylene diamine carbamate, Sulfur and di-o-tolylguanidine, mixing 10min, continue to be warming up to 175 DEG C, mixing 4min, obtain high-performance modified acrylic elastomer material.
The present invention proposes a kind of high-performance modified acrylic elastomer material and preparation method thereof, resole is added by the synthesis phase at acrylic elastomer, the methylol in resol and the carboxyl in acrylic elastomer and the phenolic hydroxyl group in resol and methylol is utilized on the one hand to react, by changing the chemical structure composition of acrylic elastomer, directly introduce rigid section in structure, make acrylic elastomer obtain good mechanical property and heat aging property, high-temperature oil resistance performance; Utilize the space structure of the cross-linked network of special resol on the other hand, in the sulfidation of acrylic elastomer, form particular network structure play reinforcing and stiffening and low compression set performance.In fact, common method of modifying is subject to the restriction of mixing condition, need to add a large amount of modified feedstocks, although also desirable toughness can be obtained, have lost the key propertys such as the intensity of material preciousness, rigidity, thermotolerance, and cost is high, and by resol and acrylic elastomer modification by copolymerization, acrylic elastomer and the resol of adding high-carboxyl-content have good consistency, can significantly improve the hardness of acrylic elastomer cross-linked rubber, intensity, wear resistance, and improve bond properties.There is the remarkable advantages such as modified feedstock consumption is few, cost is low, successful.
In addition, be the physicals improving acrylic elastomer further in the application, in this high-performance modified acrylic elastomer material, also add viton carry out blending and modifying.Wherein viton has most valuable heat-resisting, the characteristic such as ageing-resistant and corrosion-resistant, here acrylic elastomer and viton are also with technical formula, processing and the building-up properties of sizing material improve, and the intensity of cross-linked rubber is not suffered a loss, the cross-linked rubber of manufacture of the present invention simultaneously has very high high thermal resistance, and use temperature can reach 155-180 DEG C.
In this application, the vulcanization system of hexamethylene diamine carbamate, Sulfur and di-o-tolylguanidine can improve the vulcanization rate of rubber unvulcanizate and the physical and mechanical properties of cross-linked rubber, modification acrylate rubber is by under this vulcanization system condition, form specific cross-link bond and cross-linked network compactness extent, make the final blend composition obtained have high strength, low compression set, heat-resisting oil resistance.
In sum, the present invention is in conjunction with the advantage of acrylic elastomer, viton, and modification has been carried out to acrylic elastomer material property, and obtain under various auxiliary agent condition and a kind of there is higher comprehensive mechanical property, also there is the high-performance modified acrylic elastomer material of heat aging property, high-temperature oil resistance performance and low compression set performance, it can meet the service requirements of specific occasion, and to environment and human body without harm, has a extensive future.
Embodiment
Below, by specific embodiment, technical scheme of the present invention is described in detail.
Embodiment 1
A kind of high-performance modified acrylic elastomer material, comprises following raw material: modification acrylate rubber 90 parts, viton 30 parts, methacrylic acid polyester 10 parts, carbon black 50 parts, antimonous oxide 5 parts, 5 parts, magnesium oxide, polyethylene wax 2 parts, stearic acid 3 parts, titanate coupling agent 1 part, hexamethylene diamine carbamate 3 parts, 0.02 part, sulphur, di-o-tolylguanidine 6 parts, phthalic ester 1 part, dioctyl sebacate 3 parts and auxiliary agent 4 parts by weight; Wherein said auxiliary agent by quality proportioning be the hexamethylenetetramine of 7:1:0.5, magnesium oxide and lubricant form.
Prepare described modification acrylate rubber to comprise: butyl acrylate 72%, vinyl cyanide 10%, vinylformic acid 4%, OP-104%, Potassium Persulphate 0.2% and sodium lauryl sulphate 2% adds in vacuum reaction still by percentage composition by weight, in water medium, carry out free-radical emulsion polymerization reaction, controlling polymeric reaction temperature is 50 DEG C; When the transformation efficiency of described polyreaction reaches 80%-90%, in described reactor, add resole 7.8% continue reaction, adjustment reacting liquid pH value is 2.3-2.5, reacts 1h, obtain modified polymer emulsion under 90 DEG C of conditions; Add in described emulsion after industrial spirit carries out breakdown of emulsion and obtain latex, 60 DEG C of dry 50h of baking oven put into by described latex after water rinses repeatedly, obtain modification acrylate rubber.
Wherein, preparing that described resole comprises weight percentage is that the NaOH solution of 30wt% is added drop-wise in the formaldehyde and phenol solution that quality proportioning is 3:1, under 50 DEG C of conditions, react 3h, carry out vacuum hydro-extraction after reaction solution being cooled to normal temperature, obtain described resole.
The preparation method of described high-performance modified acrylic elastomer material, comprises the steps:
(1) adjust mill temperature to 80 DEG C, rotating speed is after 35 revs/min, and modification acrylate rubber and auxiliary agent are put in mill discharge after the 20min that plasticates, cooling obtains material of plasticating;
(2) Banbury mixer temperature to 50 DEG C is adjusted, after rotating speed 30 is rev/min, the material of plasticating step (1) obtained drops in Banbury mixer, add viton to plasticate 25min, add the mixing 7min of methacrylic acid polyester, antimonous oxide, magnesium oxide, polyethylene wax, stearic acid and titanate coupling agent again, add the mixing 4min of carbon black of 2/3 subsequently, add remaining carbon black again, turn refining 3min, finally add phthalic ester and dioctyl sebacate, abundant mixing 4min, discharge, cooling obtains master batch;
(3) master batch step (2) obtained drops in Banbury mixer, 130 DEG C are warming up to after adding hexamethylene diamine carbamate, Sulfur and di-o-tolylguanidine, mixing 15min, continue to be warming up to 165 DEG C, mixing 5min, obtains described high-performance modified acrylic elastomer material.
Embodiment 2
A kind of high-performance modified acrylic elastomer material, comprises following raw material: modification acrylate rubber 100 parts, viton 25 parts, methacrylic acid polyester 12 parts, carbon black 40 parts, antimonous oxide 6 parts, 4 parts, magnesium oxide, polyethylene wax 3 parts, stearic acid 2 parts, titanate coupling agent 1 part, hexamethylene diamine carbamate 2 parts, 0.03 part, sulphur, di-o-tolylguanidine 4 parts, phthalic ester 1 part, dioctyl sebacate 2 parts and auxiliary agent 5 parts by weight; Wherein said auxiliary agent by quality proportioning be the hexamethylenetetramine of 6:2:0.4, magnesium oxide and lubricant form.
Prepare described modification acrylate rubber to comprise: butyl acrylate 73%, vinyl cyanide 10%, vinylformic acid 6%, OP-103%, Potassium Persulphate 0.2% and sodium lauryl sulphate 1% adds in vacuum reaction still by percentage composition by weight, in water medium, carry out free-radical emulsion polymerization reaction, controlling polymeric reaction temperature is 55 DEG C; When the transformation efficiency of described polyreaction reaches 80%-90%, in described reactor, add resole 6.8% continue reaction, adjustment reacting liquid pH value is 2.3-2.5, reacts 1.2h, obtain modified polymer emulsion under 85 DEG C of conditions; Add in described emulsion after industrial spirit carries out breakdown of emulsion and obtain latex, 75 DEG C of dry 35h of baking oven put into by described latex after water rinses repeatedly, obtain modification acrylate rubber.
Wherein, preparing that described resole comprises weight percentage is that the KOH solution of 37wt% is added drop-wise in the formaldehyde and phenol solution that quality proportioning is 2.2:1, under 65 DEG C of conditions, react 1.2h, carry out vacuum hydro-extraction after reaction solution being cooled to normal temperature, obtain described resole.
The preparation method of described high-performance modified acrylic elastomer material, comprises the steps:
(1) adjust mill temperature to 88 DEG C, rotating speed is after 32 revs/min, and modification acrylate rubber and auxiliary agent are put in mill discharge after the 24min that plasticates, cooling obtains material of plasticating;
(2) Banbury mixer temperature to 43 DEG C is adjusted, after rotating speed 33 is rev/min, the material of plasticating step (1) obtained drops in Banbury mixer, add viton to plasticate 22min, add the mixing 9min of methacrylic acid polyester, antimonous oxide, magnesium oxide, polyethylene wax, stearic acid and titanate coupling agent again, add the mixing 3.3min of carbon black of 2/3 subsequently, add remaining carbon black again, turn refining 3.8min, finally add phthalic ester and dioctyl sebacate, abundant mixing 3.2min, discharge, cooling obtains master batch;
(3) master batch step (2) obtained drops in Banbury mixer, 145 DEG C are warming up to after adding hexamethylene diamine carbamate, Sulfur and di-o-tolylguanidine, mixing 9min, continue to be warming up to 175 DEG C, mixing 4min, obtains described high-performance modified acrylic elastomer material.
Embodiment 3
A kind of high-performance modified acrylic elastomer material, comprises following raw material: modification acrylate rubber 110 parts, viton 22 parts, methacrylic acid polyester 13 parts, carbon black 35 parts, antimonous oxide 8 parts, 4 parts, magnesium oxide, polyethylene wax 4 parts, stearic acid 2 parts, titanate coupling agent 2 parts, hexamethylene diamine carbamate 2 parts, 0.04 part, sulphur, di-o-tolylguanidine 4 parts, phthalic ester 2 parts, dioctyl sebacate 2 parts and auxiliary agent 6 parts by weight; Wherein said auxiliary agent by quality proportioning be the hexamethylenetetramine of 6:2:0.3, magnesium oxide and lubricant form.
Prepare described modification acrylate rubber to comprise: butyl acrylate 75%, vinyl cyanide 8%, vinylformic acid 6%, OP-103%, Potassium Persulphate 0.3% and sodium lauryl sulphate 1.5% adds in vacuum reaction still by percentage composition by weight, in water medium, carry out free-radical emulsion polymerization reaction, controlling polymeric reaction temperature is 60 DEG C; When the transformation efficiency of described polyreaction reaches 80%-90%, in described reactor, add resole 6.2% continue reaction, adjustment reacting liquid pH value is 2.3-2.5, reacts 1.3h, obtain modified polymer emulsion under 80 DEG C of conditions; Add in described emulsion after industrial spirit carries out breakdown of emulsion and obtain latex, 70 DEG C of dry 40h of baking oven put into by described latex after water rinses repeatedly, obtain modification acrylate rubber.
Wherein, preparing that described resole comprises weight percentage is that the NaOH solution of 35wt% is added drop-wise in the formaldehyde and phenol solution that quality proportioning is 2.5:1, under 60 DEG C of conditions, react 1.5h, carry out vacuum hydro-extraction after reaction solution being cooled to normal temperature, obtain described resole.
The preparation method of described high-performance modified acrylic elastomer material, comprises the steps:
(1) adjust mill temperature to 85 DEG C, rotating speed is after 33 revs/min, and modification acrylate rubber and auxiliary agent are put in mill discharge after the 22min that plasticates, cooling obtains material of plasticating;
(2) Banbury mixer temperature to 45 DEG C is adjusted, rotating speed is after 32 revs/min, the material of plasticating step (1) obtained drops in Banbury mixer, add viton to plasticate 23min, add the mixing 8min of methacrylic acid polyester, antimonous oxide, magnesium oxide, polyethylene wax, stearic acid and titanate coupling agent again, add the mixing 3.5min of carbon black of 2/3 subsequently, add remaining carbon black again, turn refining 3.5min, finally add phthalic ester and dioctyl sebacate, abundant mixing 3.5min, discharge, cooling obtains master batch;
(3) master batch step (2) obtained drops in Banbury mixer, 140 DEG C are warming up to after adding hexamethylene diamine carbamate, Sulfur and di-o-tolylguanidine, mixing 10min, continue to be warming up to 175 DEG C, mixing 4min, obtains described high-performance modified acrylic elastomer material.
Embodiment 4
A kind of high-performance modified acrylic elastomer material, comprises following raw material: modification acrylate rubber 130 parts, viton 15 parts, methacrylic acid polyester 15 parts, carbon black 20 parts, antimonous oxide 10 parts, 3 parts, magnesium oxide, polyethylene wax 6 parts, stearic acid 1 part, titanate coupling agent 3 parts, hexamethylene diamine carbamate 1 part, 0.05 part, sulphur, di-o-tolylguanidine 2 parts, phthalic ester 3 parts, dioctyl sebacate 1 part and auxiliary agent 8 parts by weight; Wherein said auxiliary agent by quality proportioning be the hexamethylenetetramine of 5:3:0.2, magnesium oxide and lubricant form.
Prepare described modification acrylate rubber to comprise: butyl acrylate 74.7%, vinyl cyanide 8%, vinylformic acid 4%, OP-102%, Potassium Persulphate 0.3% and sodium lauryl sulphate 1% adds in vacuum reaction still by percentage composition by weight, in water medium, carry out free-radical emulsion polymerization reaction, controlling polymeric reaction temperature is 70 DEG C; When the transformation efficiency of described polyreaction reaches 80%-90%, in described reactor, add resole 10% continue reaction, adjustment reacting liquid pH value is 2.3-2.5, reacts 1.5h, obtain modified polymer emulsion under 70 DEG C of conditions; Add in described emulsion after industrial spirit carries out breakdown of emulsion and obtain latex, 80 DEG C of dry 30h of baking oven put into by described latex after water rinses repeatedly, obtain modification acrylate rubber.
Wherein, preparing that described resole comprises weight percentage is that the KOH solution of 40wt% is added drop-wise in the formaldehyde and phenol solution that quality proportioning is 2:1, under 70 DEG C of conditions, react 1h, carry out vacuum hydro-extraction after reaction solution being cooled to normal temperature, obtain described resole.
The preparation method of described high-performance modified acrylic elastomer material, comprises the steps:
(1) adjust mill temperature to 90 DEG C, rotating speed is after 30 revs/min, and modification acrylate rubber and auxiliary agent are put in mill discharge after the 25min that plasticates, cooling obtains material of plasticating;
(2) Banbury mixer temperature to 40 DEG C is adjusted, after rotating speed 35 is rev/min, the material of plasticating step (1) obtained drops in Banbury mixer, add viton to plasticate 20min, add the mixing 10min of methacrylic acid polyester, antimonous oxide, magnesium oxide, polyethylene wax, stearic acid and titanate coupling agent again, add the mixing 3min of carbon black of 2/3 subsequently, add remaining carbon black again, turn refining 4min, finally add phthalic ester and dioctyl sebacate, abundant mixing 3min, discharge, cooling obtains master batch;
(3) master batch step (2) obtained drops in Banbury mixer, 150 DEG C are warming up to after adding hexamethylene diamine carbamate, Sulfur and di-o-tolylguanidine, mixing 5min, continue to be warming up to 185 DEG C, mixing 3min, obtains described high-performance modified acrylic elastomer material.
The high-performance modified acrylic elastomer material obtained by above-described embodiment 1-4 carries out Performance Detection, and test result is as follows:
In embodiment 1-4, resole is added by the synthesis phase at acrylic elastomer, the methylol in resol and the carboxyl in acrylic elastomer and the phenolic hydroxyl group in resol and methylol is utilized on the one hand to react, by changing the chemical structure composition of acrylic elastomer, directly introduce rigid section in structure, make acrylic elastomer obtain good mechanical property and heat aging property, high-temperature oil resistance performance; Utilize the space structure of the cross-linked network of special resol on the other hand, in the sulfidation of acrylic elastomer, form particular network structure play reinforcing and stiffening and low compression set performance.In fact, common method of modifying is subject to the restriction of mixing condition, need to add a large amount of modified feedstocks, although also desirable toughness can be obtained, have lost the key propertys such as the intensity of material preciousness, rigidity, thermotolerance, and cost is high, and by resol and acrylic elastomer modification by copolymerization, acrylic elastomer and the resol of adding high-carboxyl-content have good consistency, can significantly improve the hardness of acrylic elastomer cross-linked rubber, intensity, wear resistance, and improve bond properties.There is the remarkable advantages such as modified feedstock consumption is few, cost is low, successful.
In addition, be the physicals improving acrylic elastomer further in the application, in this high-performance modified acrylic elastomer material, also add viton carry out blending and modifying.Wherein viton has most valuable heat-resisting, the characteristic such as ageing-resistant and corrosion-resistant, here acrylic elastomer and viton are also with technical formula, processing and the building-up properties of sizing material improve, and the intensity of cross-linked rubber is not suffered a loss, the cross-linked rubber of manufacture of the present invention simultaneously has very high high thermal resistance, and use temperature can reach 155-180 DEG C.
The vulcanization system of hexamethylene diamine carbamate, Sulfur and di-o-tolylguanidine can improve the vulcanization rate of rubber unvulcanizate and the physical and mechanical properties of cross-linked rubber, modification acrylate rubber is by under this vulcanization system condition, form specific cross-link bond and cross-linked network compactness extent, make the final blend composition obtained have high strength, low compression set, heat-resisting oil resistance.
In sum, the present invention is in conjunction with the advantage of acrylic elastomer, viton, and modification has been carried out to acrylic elastomer material property, and obtain under various auxiliary agent condition and a kind of there is higher comprehensive mechanical property, also there is the high-performance modified acrylic elastomer material of heat aging property, high-temperature oil resistance performance and low compression set performance, it can meet the service requirements of specific occasion, and to environment and human body without harm, has a extensive future.
The above; be only the present invention's preferably embodiment; but protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; be equal to according to the technical scheme of inventing and inventive concept thereof and replace or change, all should be encompassed within protection scope of the present invention.
Claims (10)
1. a high-performance modified acrylic elastomer material, it is characterized in that, comprise following raw material by weight: modification acrylate rubber 90-130 part, viton 15-30 part, methacrylic acid polyester 10-15 part, carbon black 20-50 part, antimonous oxide 5-10 part, magnesium oxide 3-5 part, polyethylene wax 2-6 part, stearic acid 1-3 part, titanate coupling agent 1-3 part, hexamethylene diamine carbamate 1-3 part, sulphur 0.02-0.05 part, di-o-tolylguanidine 2-6 part, phthalic ester 1-3 part, dioctyl sebacate 1-3 part and auxiliary agent 4-8 part;
Prepare described modification acrylate rubber to comprise: acrylate, vinyl cyanide, vinylformic acid, emulsifying agent, initiator and tensio-active agent are added in reactor and carries out free-radical emulsion polymerization reaction; When the transformation efficiency of described polyreaction reaches 80%-90%, in reactor, add resole continue reaction, obtain modified polymer emulsion; In described modified polymer emulsion, add industrial spirit obtain latex, after oven dry, obtain modification acrylate rubber.
2. high-performance modified acrylic elastomer material according to claim 1, it is characterized in that, comprise following raw material by weight: modification acrylate rubber 100-120 part, viton 20-25 part, methacrylic acid polyester 12-14 part, carbon black 30-40 part, antimonous oxide 6-8 part, magnesium oxide 3-4 part, polyethylene wax 3-5 part, stearic acid 1-2 part, titanate coupling agent 1-2 part, hexamethylene diamine carbamate 1-2 part, sulphur 0.03-0.04 part, di-o-tolylguanidine 3-4 part, phthalic ester 1-2 part, dioctyl sebacate 1-2 part and auxiliary agent 5-7 part.
3. high-performance modified acrylic elastomer material according to claim 1 or 2, is characterized in that, described auxiliary agent by quality proportioning be the hexamethylenetetramine of 5-7:1-3:0.2-0.5, magnesium oxide and lubricant form.
4. high-performance modified acrylic elastomer material according to any one of claim 1-3, it is characterized in that, prepare described modification acrylate rubber to comprise: acrylate 72-78%, vinyl cyanide 8-14%, vinylformic acid 4-10%, emulsifying agent 2-4%, initiator 0.2-0.3% and tensio-active agent 1-2% add in vacuum reaction still by percentage composition by weight, in water medium, carry out free-radical emulsion polymerization reaction, control polymeric reaction temperature is 50-70 DEG C; When the transformation efficiency of described polyreaction reaches 80%-90%, in described reactor, add resole 6-10% continue reaction, adjustment reacting liquid pH value is 2.3-2.5, reacts 1-1.5h, obtain modified polymer emulsion under 70-90 DEG C of condition; In described emulsion, add industrial spirit carry out breakdown of emulsion, obtain latex, the 60-80 DEG C of dry 30-50h of baking oven put into by described latex after water rinses repeatedly, obtains modification acrylate rubber.
5. high-performance modified acrylic elastomer material according to claim 4, it is characterized in that, described acrylate is butyl acrylate; Described initiator is Potassium Persulphate; Described emulsifying agent is OP-10; Described tensio-active agent is sodium lauryl sulphate.
6. high-performance modified acrylic elastomer material according to any one of claim 1-5, it is characterized in that, prepare described resole to comprise: be that NaOH solution or the KOH solution of 30-40% is added drop-wise in the formaldehyde and phenol solution that quality proportioning is 2-3:1 by weight percentage, 1-3h is reacted under 50-70 DEG C of condition, carry out vacuum hydro-extraction after reaction solution being cooled to normal temperature, obtain described resole.
7. the preparation method of high-performance modified acrylic elastomer material according to any one of claim 1-6, is characterized in that, comprise the steps:
(1) modification acrylate rubber and auxiliary agent are put in mill discharge after the 20-25min that plasticates, cooling obtains material of plasticating;
(2) material of plasticating step (1) obtained drops in Banbury mixer, add viton to plasticate 20-25min, add the mixing 7-10min of methacrylic acid polyester, antimonous oxide, magnesium oxide, polyethylene wax, stearic acid and titanate coupling agent, add the mixing 3-4min of carbon black of 2/3, add remaining carbon black again to turn refining 3-4min, add phthalic ester and the mixing 3-4min of dioctyl sebacate, discharge, cooling obtains master batch;
(3) master batch step (2) obtained drops in Banbury mixer, 130-150 DEG C is warming up to after adding hexamethylene diamine carbamate, Sulfur and di-o-tolylguanidine, mixing 5-15min, continue to be warming up to 165-185 DEG C, mixing 3-5min, obtains described high-performance modified acrylic elastomer material.
8. the preparation method of high-performance modified acrylic elastomer material according to claim 7, it is characterized in that, in step (1), adjustment mill temperature is to 80-90 DEG C, rotating speed is after 30-35 rev/min, modification acrylate rubber and auxiliary agent is put in mill and plasticates.
9. the preparation method of high-performance modified acrylic elastomer material according to claim 7 or 8, it is characterized in that, in step (2), adjustment Banbury mixer temperature is to 40-50 DEG C, rotating speed is after 30-35 rev/min, then the material of plasticating step (1) obtained drops in Banbury mixer.
10. the preparation method of high-performance modified acrylic elastomer material according to any one of claim 7-9, it is characterized in that, in step (3), master batch step (2) obtained drops in Banbury mixer, be warming up to 140 DEG C after adding hexamethylene diamine carbamate, Sulfur and di-o-tolylguanidine, mixing 10min, continue to be warming up to 175 DEG C, mixing 4min, obtains high-performance modified acrylic elastomer material.
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