CN102585416A - High-temperature-resistant oil-proof thermoplastic vulcanizate (TPV) - Google Patents
High-temperature-resistant oil-proof thermoplastic vulcanizate (TPV) Download PDFInfo
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- CN102585416A CN102585416A CN2012100655767A CN201210065576A CN102585416A CN 102585416 A CN102585416 A CN 102585416A CN 2012100655767 A CN2012100655767 A CN 2012100655767A CN 201210065576 A CN201210065576 A CN 201210065576A CN 102585416 A CN102585416 A CN 102585416A
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Abstract
High-temperature-resistant oil-proof thermoplastic vulcanizate (TPV) is characterized by comprising the following raw materials by weight part: 50 to 70 parts of acrylate rubber; 30 to 50 parts of polyester; 0.75 to 1.05 parts of vulcanizer; 1.13 to 1.58 parts of vulcanization accelerator; 1.0 to 1.4 parts of antiager; 0 to 10.5 parts of rubber plasticizing agent; 0.05 to 0.07 part of antioxygen; and 25 to 35 parts of reinforcing agent. The polyester is polyethylene terephthalate (PET). The high-temperature-resistant oil-proof TPV is prepared with the acrylate rubber (ACM) and the polyester (mainly the PET) by adopting a dynamic vulcanization technology, and can be used in a high-temperature oil solvent of 200 DEG C for a long time.
Description
Technical field
The present invention relates to a kind of high temperature resistant, oil-resisting type thermoplastic sulfurized rubber, present method is that acrylic elastomer and polyester adopt the dynamic vulcanization technology preparation.
Background technology
Thermoplastic elastomer is a kind of macromolecular material with vulcanized rubber and thermoplastics dual nature, at high temperature has the processing characteristics of thermoplastics, has the snappiness of traditional vulcanized rubber at normal temperatures.Compare with traditional vulcanized rubber, it need not pass through complicated technologies such as mixing, moulding, sulfuration, and its scrap stock and waster can repeat processing and utilization, thereby receives widely and paying attention to.TPV is as a kind of blending thermoplastic elastomer; It is one type of high-performance thermoplastic elastomer material with special construction; Its constitutional features is different from the thermoplastic elastomer with the preparation of Polymer Synthesizing method; A kind of baroque polymer composite that it is made up of rubber and plastics adopts dynamic vulcanization technology to prepare.Dynamic vulcanization technology is meant sneaks into rubber in the thermoplastic resin matrix; With linking agent mixing the time; Can make rubber " on the spot " produce chemically crosslinked fully, and under mixed at high speed and shearing action, crosslinked rubber is fractured into the great quantity of micron particle; Be dispersed in the successive a thermoplastic matrix, thereby form thermoplastic sulfurized rubber (TPV).
Since U.S. Monsanto Company in 1981 realizes dynamic full vulcanization EPDM/PP thermoplastic sulfurized rubber suitability for industrialized production, very active always to the research of said material.The kind of having reported at present mainly contains NBR/PP, NR/PP, IIR/PP, ACM/PP.The use temperature of these systems is lower, and the rare appearance of TPV kind that high temperature uses down, this mainly is when dynamic vulcanization, need under comparatively high temps, carry out dynamic vulcanization owing to TPV kind under the high temperature, and temperature rising dynamic vulcanization technology is difficult to control.
Along with developing of automobile industry; People have proposed more requirement to each item performance of automobile, particularly to the used sealing material of the fuel of automobile and oiling system and mover, material for oil delivering pipe to performances such as the oil resistant of rubber, heat-resisting, anti-various chemical corrosion.Product as automobile-used oil resistant pipe mainly is paracril, hydrogenated nitrile-butadiene rubber, viton at present.Propose to use tetrafluoroethylene propylene copolymer to prepare automobile in recent years and use oil resisting rubber.Paracril is one of the most frequently used rubber of present oil sealing and O type circle; It has good anti-water, anti-oil, anti-solvent and anti-highly compressed characteristic and good compression property; But because the defective of himself, can only be at life-time service below 120 ℃, the oil resistant mass change is approximately 20%; And anti-ozone is weather-proof relatively poor with radiation resistance, has satisfied not the seal requests of Motor vehicles such as motor car engine to mover.Hydrogenated nitrile-butadiene rubber is the hydrogenation products of paracril; It has good oil resistant, anti-ozone, wear-resisting and chemicals-resistant corrodibility; Have good heat-resisting and resistance to low temperature again, but its heatproof and oil resistance do not have big lifting than paracril and cost is higher.Viton is the best rubber of heat resistance in all rubber item, can't use on a large scale but its finished product is too high; Tetrafluoroethylene propylene copolymer is to fluororubber modified a kind of new type rubber, can anti-200 ℃ high temperature, can increase the service life, and enlarge the range of application of viton, but equally inevitably had the high problem of cost.Face the more and more phenomenon of shortage of elastomeric material at present, require material requested to have thermotolerance, oil-proofness and petrol-resistance ability simultaneously, but price is lower than viton, and can uses continuously down at 180-200 ℃.Viton can heatproof up to 300 ℃ but its bad mechanical property costs an arm and a leg; The temperature resistant grade of paracril is 100 ℃, relatively low and not anti-ozone; Acrylic elastomer has been filled up the blank of above-mentioned two kinds of rubber, use temperature can reach 180 ℃ also have anti-ozone, anti-ly subdue, photoaging in anti-day, advantage such as resistance to air loss is good, rubber is transparent and the fabric tackiness is good and price only is 1/10th of a viton.The side group of acrylic elastomer is the polarity ester group, has excellent oil resistance.Because special construction gives its many excellent characteristics, like heat-resisting, ageing-resistant, oil resistant, anti-ozone, Ginkgo Biloba Leaf Extract etc., mechanical property and processing characteristics are superior to viton and Zylox, and it is heat-resisting, stability to aging and oil-proofness are superior to paracril.Two performances of this of acrylic elastomer are widely used in the automotive industry it, are described as " high-performing car glue ".ACM is widely used in various high temperature, the oil resistant environment, becomes a kind of sealing material that automotive industry is in recent years focused on develop and spread, especially for the high temperature resistant oil sealing of automobile, bent axle, valve rod, head gasket, hydraulic pressure transition pipeline etc.
Acrylic elastomer and polyester are because of all having polar group; And the two surface energy is complementary; Comixing compatibility is preferably arranged; Both have excellent heatproof oil resistance, tensile strength and wear resistance preferably preferably through the thermoplastic elastomer of dynamic vulcanization prepared, also have the advantage that is prone to processing and repeats to process.
Summary of the invention
The object of the present invention is to provide a kind of its over-all properties of raising, enlarge high temperature resistant, the oil-resisting type thermoplastic sulfurized rubber of its range of application.
For realizing above purpose, technical scheme of the present invention provides the preparation method of a kind of high-temperature resistant, oil-proofness thermoplastic sulfurized rubber, it is characterized in that, it is processed by the raw material of following mass fraction:
Described polyester is a polyethylene terephthalate (PET) etc.; Described acrylic elastomer is the reactive chlorine type; Described vulcanizing agent is 1,3,5-tri-thiol-2,4,6-s-triazine (TCY); Described vulcanization accelerator is zinc dibutyl dithiocarbamate (BZ); Described anti-aging agent is an anti-aging agent 445; Described rubber plastizing agent is DOP (DOP), hexanodioic acid two (butoxy oxyethyl group second) ester (TP 95) and Octyl adipate (DOA) etc.; Described oxidation inhibitor is Hinered phenols antioxidant, is 1010; Described strengthening agent is carbon black, precipitated silica, precipitated silicate calcium, zeyssatite, talcum powder etc.
The selection of rubber and plastic system is a The key factor.Acrylic elastomer is chosen the reactive chlorine type and is convenient to sulfurized and carries out, and its mooney viscosity＞40 have higher molecular weight; That polyester is used is PET, and it has high melt point, is 255 ℃, can satisfy the requirement of using under the high temperature, and it has higher percent crystallinity and molecular weight simultaneously.
Vulcanizing agent at high temperature produces crosslinked action to rubber.Vulcanization accelerator can improve the speed of crosslinking reaction, improves the over-all properties of sizing material.Employed acrylic elastomer is a reactive chlorine type product in this patent; The vulcanization system that the most frequently used vulcanizing agent of reactive chlorine type ACM is formed has three kinds: (1) soap/sulphur and with vulcanization system (2) N, N '-two (cinnamylidene-1,6-hexanediamine) vulcanization system (3) TCY (1; 3; 5-tri-thiol-2,4, the 6-s-triazine) vulcanization system.Wherein the vulcanization rate of TCY vulcanization system is fast, and cross-linked rubber thermal ageing property is good, and compression set is little.Need the vulcanization rate of system and the parameter of forcing machine to mate each other for TPV, vulcanization rate can influence the dynamic vulcanization of system slowly, and therefore poor performance selects the fast vulcanization system of vulcanization rate for use.According to conventional cross-linked rubber prescription.
Oxidation inhibitor makes polyester in the course of processing, possess good processing stability, avoids color and luster, performance to change.Use according to conventional formulation.
Anti-aging agent can effectively protect the thermo-oxidative ageing of acrylic elastomer, prolongs its work-ing life.According to conventional cross-linked rubber prescription.
Softening agent is used for improving the processing characteristics of thermoplastic sulfurized rubber and the hardness that reduces system, disperses each phase component, improves the over-all properties of material.Use softening agent not only can improve the ACM resistance to low temperature, but also can improve the flowing property of oil-proofness and sizing material.Can not add softening agent among the present invention, when the softening agent that still adds was excessive, the viscosity degradation of sizing material was too big, is unfavorable for the transmission of shearing force, can not well accomplish dynamic vulcanization, each item degradation of system.
Strengthening agent is used for improving the intensity of acrylic elastomer, improves the over-all properties of sizing material.ACM is an amorphism rubber, and the physical strength of pure rubber only has about 2Mpa, must add the strengthening agent reinforcement and just can use, and ACM should not use acid reinforcing filler, like thermally oxidized black and thermal silica etc.Oil sealing generally is light with sizing material; So packing strengthening agent can be used white fillers such as the precipitated silica, precipitated silicate calcium, zeyssatite, talcum powder of neutrality or meta-alkalescence; Other products only play the effect of inert packing, and only WHITE CARBON BLACK has stronger strengthening action.If not with strengthening agent, the intensity of system is very low, is not suitable for using; Add its stress at definite elongation, tensile strength when very few, tear strength is all on the low side, but add when too much, higher stress at definite elongation and tear strength are arranged; And tensile yield obviously descends, and the hardness increase is too big, mechanical properties decrease.
The present invention adopts acrylic elastomer and polyester as matrix, makes a kind of high temperature resistant, oil-resisting type thermoplastic sulfurized rubber.
The performance test methods of acrylic elastomer of the present invention and polyester thermoplastic sulfurized rubber is following: carry out Mechanics Performance Testing by the ASTM standard.The test of Static Compression deformation performance is measured according to ISO815～1972.Use English home-made Instron-3211 type capillary rheometer test TPV rheological property.(GB/T1690-2010) carry out the oil resistance test of cross-linked rubber according to " the anti-liquid pilot method of vulcanized rubber or TPR ", test(ing) liquid is the 3# standard oil, test conditions: 200 ℃ * 72h.Heat-resistant air aging property experiment condition: 200 ℃ * 35d.
Embodiment
Acrylic elastomer in the embodiment is the reactive chlorine type.
Embodiment 1
Prepare 65/35 acrylic elastomer and polyester blend type thermoplastic sulfurized rubber.Wherein, acrylic elastomer is the reactive chlorine type, and polyester is PET.
Operation steps is following:
260g acrylic elastomer, 140gPET, 1.4g antioxidant 1010 are put into 240 ℃ of two rollers to be moulded in the experienced machine and mixes.Adding 5.2g anti-aging agent 445,15.6g zinc oxide, 5.2g Triple Pressed Stearic Acid, 39g plasticizer DOP, 130g strengthening agent precipitated silica, 3.9g vulcanizing agent TCY, 5.85g vulcanization aid BZ mix in the normal temperature mill then.Carry out dynamic vulcanization at twin screw extruder at last, 400 rev/mins of screw speeds, the dynamic vulcanization temperature is 260 ℃, extrudes the back granulation.Compressing tablet, moulding on vulcanizing press obtain acrylic elastomer and PET blending type thermoplastic cross-linked rubber.Physicals is seen table 1.
Embodiment 2
Prepare 65/35 acrylic elastomer and polyester blend type thermoplastic sulfurized rubber.Become 104g with the embodiment 1 different consumptions that add the strengthening agent precipitated silica that are, operation steps is identical with embodiment 1.The physical and mechanical properties of TPV is seen table 1.
Embodiment 3
Prepare 65/35 acrylic elastomer and polyester blend type thermoplastic sulfurized rubber.Different screw speeds when being that twin screw extruder carries out dynamic vulcanization with embodiment 1 are different, and screw speed is 300 rev/mins.Operation steps is identical with embodiment 1.The physical and mechanical properties of TPV is seen table 1.
Embodiment 4
Prepare 65/35 acrylic elastomer and PET blending type thermoplastic cross-linked rubber, different with embodiment 1 is not add plasticizer DOP.Operation steps is identical with embodiment 1.Physical and mechanical properties is seen table 1.
Embodiment 5
Prepare 60/40 acrylic elastomer and polyester blend type thermoplastic sulfurized rubber.Wherein, acrylic elastomer is the reactive chlorine type, and polyester is PET.The TPV physical and mechanical properties is seen table 1.Operation steps is following:
240g acrylic elastomer, 160gPET, 1.6g antioxidant 1010 are put into 240 ℃ of two rollers to be moulded in the experienced machine and mixes.Adding 4.8g anti-aging agent 445,14.4g zinc oxide, 4.8g Triple Pressed Stearic Acid, 34g plasticizer DOP, 120g strengthening agent precipitated silica, 3.4g vulcanizing agent TCY, 5.4gBZ vulcanization aid mix in the normal temperature mill then.Carry out dynamic vulcanization at Banbury mixer at last, 80 rev/mins of rotating speeds, the dynamic vulcanization temperature is 260 ℃, the time is 7 minutes, extrudes the back granulation.The TPV physical and mechanical properties is seen table 1.
Embodiment 6
Prepare 70/30 acrylic elastomer and polyester blend type thermoplastic sulfurized rubber.Wherein, acrylic elastomer is the reactive chlorine type, and polyester is PET.
Operation steps is following:
280g acrylic elastomer, 120gPET, 1.2g antioxidant 1010 are put into 240 ℃ of two rollers to be moulded in the experienced machine and mixes.Adding 5.6g anti-aging agent 445,16.8g zinc oxide, 5.6g Triple Pressed Stearic Acid, 42g plasticizer DOP, 140g strengthening agent precipitated silica, 4.2g vulcanizing agent TCY, 6.3gBZ vulcanization aid mix in the normal temperature mill then.Carry out dynamic vulcanization at twin screw extruder at last, 400 rev/mins of screw speeds, the dynamic vulcanization temperature is 260 ℃, extrudes the back granulation.The TPV physical and mechanical properties is seen table 1.
Embodiment 7
Prepare 50/50 acrylic elastomer and polyester blend type thermoplastic sulfurized rubber.Wherein, acrylic elastomer is the reactive chlorine type, and polyester is PET.
Operation steps is following:
200g acrylic elastomer, 200gPET, 2.0g antioxidant 1010 are put into 240 ℃ of two rollers to be moulded in the experienced machine and mixes.Adding 4.0g anti-aging agent 445,12.0g zinc oxide, 4.0g Triple Pressed Stearic Acid, 30g plasticizer DOP, 100g strengthening agent precipitated silica, 3.0g vulcanizing agent TCY, 4.5g vulcanization aid BZ mix in the normal temperature mill then.Carry out dynamic vulcanization in mill at last, the dynamic vulcanization temperature is 260 ℃, and the time is 7 minutes, extrudes the back granulation.Compressing tablet, moulding on vulcanizing press obtain acrylic elastomer and PET blending type thermoplastic cross-linked rubber.Physicals is seen table 1.
Embodiment 8
Prepare 65/35 acrylic elastomer and polyester blend type thermoplastic sulfurized rubber.Differently with embodiment 1 be to add 39g softening agent DOA.Operation steps is identical with embodiment 1.The physical and mechanical properties of TPV is seen table 1.
Embodiment 9
Prepare 65/35 acrylic elastomer and polyester blend type thermoplastic sulfurized rubber.Differently with embodiment 1 be to add 130g strengthening agent carbon black.Operation steps is identical with embodiment 1.The physical and mechanical properties of TPV is seen table 1.
Embodiment 10
Prepare 65/35 acrylic elastomer and polyester blend type thermoplastic sulfurized rubber.Differently with embodiment 1 be to add 130g strengthening agent precipitated silicate calcium.Operation steps is identical with embodiment 1.The physical and mechanical properties of TPV is seen table 1.
Comparative Examples 1
Prepare 65/35 acrylic elastomer and polyester blend type thermoplastic sulfurized rubber.Wherein, acrylic elastomer is the reactive chlorine type, and polyester is PET.
Operation steps is following:
260g acrylic elastomer, 140gPET, 1.4g antioxidant 1010 are put into 240 ℃ of two rollers to be moulded in the experienced machine and mixes.In the normal temperature mill, add 5.2g anti-aging agent 445,15.6g zinc oxide, 5.2g Triple Pressed Stearic Acid, 39g plasticizer DOP, 130g strengthening agent WHITE CARBON BLACK, 6.5g N then, N '-two (cinnamylidene-1,6-hexanediamine) mixes.Carry out dynamic vulcanization at twin screw extruder at last, 400 rev/mins of screw speeds, the dynamic vulcanization temperature is 260 ℃, extrudes the back granulation.Compressing tablet, moulding on vulcanizing press obtain acrylic elastomer and PET blending type thermoplastic cross-linked rubber.Physicals is seen table 1.
Comparative Examples 2
Prepare 65/35 acrylic elastomer and PET blending type thermoplastic cross-linked rubber, different with embodiment 1 is not add the strengthening agent WHITE CARBON BLACK.Operation steps is identical with embodiment 1.Physical and mechanical properties is seen table 1.
Comparative Examples 3
Prepare 65/35 acrylic elastomer and PET blending type thermoplastic cross-linked rubber, different with embodiment 1 is to add 156g strengthening agent WHITE CARBON BLACK.
Comparative Examples 4
Prepare 65/35 acrylic elastomer and PET blending type thermoplastic cross-linked rubber, different with embodiment 1 is to add the 52g plasticizer DOP.
Table 1
Claims (5)
1. high temperature resistant, an oil-resisting type thermoplastic sulfurized rubber is characterized in that, is processed by the raw material of following mass fraction:
Described polyester is a polyethylene terephtalate.
2. a kind of high temperature resistant, oil-resisting type thermoplastic sulfurized rubber according to claim 1 is characterized in that described acrylic elastomer is the reactive chlorine type.
3. a kind of high temperature resistant, oil-resisting type thermoplastic sulfurized rubber according to claim 1 is characterized in that described vulcanizing agent is 1,3,5-tri-thiol-2,4, and 6-s-triazine TCY, vulcanization accelerator are zinc dibutyl dithiocaarbamate BZ.
4. a kind of high temperature resistant, oil-resisting type thermoplastic sulfurized rubber according to claim 1 is characterized in that described rubber plastizing agent is DOP DOP, di butoxyethoxyethyl adipate TP 95 or Octyl adipate DOA.
5. a kind of high temperature resistant, oil-resisting type thermoplastic sulfurized rubber according to claim 1 is characterized in that described strengthening agent is carbon black, precipitated silica, precipitated silicate calcium, zeyssatite or talcum powder.
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Cited By (10)
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| CN103275443A (en) * | 2013-05-09 | 2013-09-04 | 蔡德扬 | Fluororubber and acrylate combined vulcanized rubber and preparation method thereof |
| CN105860396A (en) * | 2016-05-08 | 2016-08-17 | 丰泽工程橡胶科技开发股份有限公司 | High-damping rubber and preparation method thereof |
| CN106589851A (en) * | 2016-12-14 | 2017-04-26 | 四川晨光科新塑胶有限责任公司 | Modified TPEE (thermoplastic polyester elastomer) composition with extinction property |
| CN106700482A (en) * | 2017-01-19 | 2017-05-24 | 青岛思锐科技有限公司 | Low-temperature-resistant high-temperature-resistant and oil-resistant air spring rubber material for automobile and preparation method thereof |
| CN106944125A (en) * | 2016-01-07 | 2017-07-14 | 中国石油化工股份有限公司 | A kind of preparation method of hydrocracking catalyst |
| CN110698755A (en) * | 2019-11-03 | 2020-01-17 | 南通林格橡塑制品有限公司 | Thermoplastic acrylate TPV material |
| CN111040539A (en) * | 2019-12-18 | 2020-04-21 | 浙江传化涂料有限公司 | Coating and self-spraying paint |
| US10738180B2 (en) | 2018-12-07 | 2020-08-11 | Industrial Technology Research Institute | Thermoplastic vulcanizate and manufacturing method thereof |
| CN111825970A (en) * | 2020-08-04 | 2020-10-27 | 浙江科普特新材料有限公司 | ACM thermoplastic vulcanized rubber and preparation method and application thereof |
| WO2022262559A1 (en) * | 2021-06-18 | 2022-12-22 | 歌尔股份有限公司 | Diaphragm applicable to sound production device, preparation method thereof, and sound production device |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103275443A (en) * | 2013-05-09 | 2013-09-04 | 蔡德扬 | Fluororubber and acrylate combined vulcanized rubber and preparation method thereof |
| CN106944125A (en) * | 2016-01-07 | 2017-07-14 | 中国石油化工股份有限公司 | A kind of preparation method of hydrocracking catalyst |
| CN105860396A (en) * | 2016-05-08 | 2016-08-17 | 丰泽工程橡胶科技开发股份有限公司 | High-damping rubber and preparation method thereof |
| CN106589851B (en) * | 2016-12-14 | 2020-11-13 | 四川晨光科新塑胶有限责任公司 | Extinction modified thermoplastic polyester elastomer composition |
| CN106589851A (en) * | 2016-12-14 | 2017-04-26 | 四川晨光科新塑胶有限责任公司 | Modified TPEE (thermoplastic polyester elastomer) composition with extinction property |
| CN106700482A (en) * | 2017-01-19 | 2017-05-24 | 青岛思锐科技有限公司 | Low-temperature-resistant high-temperature-resistant and oil-resistant air spring rubber material for automobile and preparation method thereof |
| US10738180B2 (en) | 2018-12-07 | 2020-08-11 | Industrial Technology Research Institute | Thermoplastic vulcanizate and manufacturing method thereof |
| CN110698755A (en) * | 2019-11-03 | 2020-01-17 | 南通林格橡塑制品有限公司 | Thermoplastic acrylate TPV material |
| CN111040539A (en) * | 2019-12-18 | 2020-04-21 | 浙江传化涂料有限公司 | Coating and self-spraying paint |
| CN111040539B (en) * | 2019-12-18 | 2021-08-03 | 浙江传化涂料有限公司 | Coating and self-spraying paint |
| CN111825970A (en) * | 2020-08-04 | 2020-10-27 | 浙江科普特新材料有限公司 | ACM thermoplastic vulcanized rubber and preparation method and application thereof |
| CN111825970B (en) * | 2020-08-04 | 2022-09-09 | 浙江科普特新材料有限公司 | ACM thermoplastic vulcanized rubber and preparation method and application thereof |
| WO2022262559A1 (en) * | 2021-06-18 | 2022-12-22 | 歌尔股份有限公司 | Diaphragm applicable to sound production device, preparation method thereof, and sound production device |
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Application publication date: 20120718 |