CN110229429A

CN110229429A - A kind of preparation method of new vulcanizing system TPV material

Info

Publication number: CN110229429A
Application number: CN201910540908.4A
Authority: CN
Inventors: 李保
Original assignee: Individual
Current assignee: Individual
Priority date: 2019-06-21
Filing date: 2019-06-21
Publication date: 2019-09-13

Abstract

The present invention relates to TPV preparation fields, relate more specifically to a kind of preparation method of new vulcanizing system TPV material, including at least following steps: (1) plasticating: the butadiene rubber of the ethylene propylene diene rubber of 10 parts by weight, (1~5) parts by weight is added in single screw extrusion machine, and the white oil of (5~14) parts by weight is added, it carries out rushing oil processing at 70~90 DEG C, obtains rubber components；(2) it is kneaded: rubber components obtained in step (1) is added in double screw extruder, and the polypropylene of (1~3) parts by weight is added, the graft polypropylene of (0.1~0.5) parts by weight, the hydrogenated styrene-butadiene block copolymer of (3~8) parts by weight, the vulcanizing agent of (0.1~0.4) parts by weight, the vulcanization accelerator of (0.1~0.4) parts by weight, the antioxidant of (0.01~0.15) parts by weight, the filler of (3~12) parts by weight, and it is kneaded at 165~200 DEG C, then it is granulated, vulcanize up to TPV material.

Description

A kind of preparation method of new vulcanizing system TPV material

Technical field

The present invention relates to TPV preparation fields, relate more specifically to a kind of preparation method of new vulcanizing system TPV material.

Background technique

TPV is thermoplasticity EPDM dynamic vulcanization elastomer, is that the ethylene propylene diene rubber particle of solid cure is dispersed in The macromolecular elastomer material formed in continuous polypropylene phase, the intensity of elasticity and engineering plastics with rubber, with rubber phase Than it has better processing performance and longer service life；Compared with engineering plastics, equally have the characteristics that intensity is high, Flexibility and dynamic mechanical are more preferable.And TPV material has high-ductility high resiliency, can repeat to process, use and recycle.Mesh The application of preceding TPV material is quite extensive, such as automobile parts hose, vehicle dust protector, weather strip for automobile, common and high-grade electric wire Cable insulation and sheath, all kinds of sealing materials and consumer appliance field.But it is the processing performance of TPV material, mechanical property, resistance to low It still needs further improvement for warm nature energy, wear-resisting property etc., and then expands the application of TPV material.

Summary of the invention

To solve the above-mentioned problems, the present invention provides a kind of preparation method of new vulcanizing system TPV material, the new sulphur The preparation method of change system TPV material includes at least:

(1) it plasticates: the butadiene rubber of the ethylene propylene diene rubber of 10 parts by weight, 1~5 parts by weight being added to single screw rod and is squeezed out In machine, and the white oil of 5~14 parts by weight is added, carries out rushing oil processing at 70~90 DEG C, obtain rubber components；

(2) it is kneaded: rubber components obtained in step (1) is added in double screw extruder, and 1~3 weight is added The hydrogenated styrene-butadiene block copolymerization of the polypropylene, the graft polypropylene, 3~8 parts by weight of 0.1~0.5 parts by weight of part Object, the vulcanizing agent of 0.1~0.4 parts by weight, the vulcanization accelerator of 0.1~0.4 parts by weight, 0.01~0.15 parts by weight antioxygen Agent, 3~12 parts by weight filler, and be kneaded at 165~200 DEG C, be then granulated；

(3) vulcanize: pellet obtained in step (2) being subjected to thermoplastic shaping, and carries out vulcanizing at 185~250 DEG C To the TPV material；

The graft polypropylene is maleic anhydride inoculated polypropylene, and grafting rate is 0.8~1.2wt%.

As a preferred technical solution of the present invention, white oil is 5~7 parts by weight, the step in the step (1) (2) it joined the white oil of 5~7 parts by weight in mixing process.

As a preferred technical solution of the present invention, mixing time is 5~30min, roll spacing 2 in the step (2) ~5mm.

As a preferred technical solution of the present invention, melt index of the polypropylene under 230 DEG C, 2.16kg load For 8~12g/10min.

As a preferred technical solution of the present invention, the butadiene rubber account for the ethylene propylene diene rubber 10~ 20wt%.

As a preferred technical solution of the present invention, the Third monomer of the ethylene propylene diene rubber is ethylidene norbornene Alkene, content are 5~10wt% of ethylene propylene diene rubber.

As a preferred technical solution of the present invention, in the ethylene propylene diene rubber, propylene accounts for the ethylene-propylene-diene monomer 36~45wt% of glue.

As a preferred technical solution of the present invention, the filler is barium salt and calcium salt, and weight ratio is 1:(1~3).

As a preferred technical solution of the present invention, the calcium salt is calcium carbonate, in the calcium carbonate containing 30~ 50wt% modified calcium carbonate.

As a preferred technical solution of the present invention, 0.1~0.3 parts by weight are added in step (2) mixing process Fungicide.

Compared with the prior art, the invention has the following beneficial effects: new vulcanizing system TPV material provided by the invention Preparation method simple process, processing performance are excellent；The TPV material prepared have high antiskid property, lower temperature resistance, antibiotic property and Wear resistence, and have many advantages, such as lightweight, environmental protection and outstanding comprehensive mechanical property；It can be applicable to medical space, chemical plant Deng.

Specific embodiment

The detailed description for preferred implementation method of the invention below of participating in the election of and including embodiment this hair can be more easily to understand Bright content.Unless otherwise defined, all technologies used herein and scientific term have common with fields of the present invention The normally understood identical meaning of technical staff.When there is a conflict, the definition in this specification shall prevail.

As used herein term " by ... preparation " it is synonymous with "comprising".Term "comprising" used herein, " comprising ", " having ", " containing " or its any other deformation, it is intended that cover non-exclusionism includes.For example, the combination comprising listed elements Object, step, method, product or device are not necessarily limited to those elements, but may include not expressly listed other elements or Such composition, step, method, product or the intrinsic element of device.

Conjunction " Consists of " excludes any element that do not point out, step or component.If in claim, this Phrase will make claim closed, so that it is not included the material in addition to the material of those descriptions, but relative normal Except rule impurity.When being rather than immediately following after theme in the clause that phrase " Consists of " appears in claim main body, It is only limited to element described in the clause；Other elements are not excluded except the claim as a whole.

Equivalent, concentration or other values or parameter are excellent with range, preferred scope or a series of upper limit preferred values and lower limit When the Range Representation that choosing value limits, this should be understood as specifically disclosing by any range limit or preferred value and any range Any pairing of lower limit or preferred value is formed by all ranges, regardless of whether the range separately discloses.For example, when open When range " 1 to 5 ", described range should be interpreted as including range " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to 5 ", " 1 to 3 and 5 " etc..When numberical range is described herein, unless otherwise stated, otherwise the range is intended to include its end Value and all integers and score in the range.

Singular includes that plural number discusses object, unless the context clearly dictates otherwise." optional " or it is " any It is a kind of " refer to that the item described thereafter or event may or may not occur, and the description include situation that event occurs and The situation that event does not occur.

Approximate term in specification and claims is used to modify quantity, and it is specific to indicate that the present invention is not limited to this Quantity further includes the acceptable modified part without will lead to the change of dependency basis this function close with the quantity.Phase It answers, modifies a numerical value with " about ", " about " etc., mean that the present invention is not limited to the exact numericals.In some examples, approximate Term likely corresponds to the precision of the instrument of measurement numerical value.In present specification and claims, range limits can be with Combination and/or exchange, these ranges if not stated otherwise include all subranges contained therebetween.

In addition, indefinite article "an" before element of the present invention or component and "one" quantitative requirement to element or component (i.e. frequency of occurrence) unrestriction.Therefore "one" or "an" should be read as including one or at least one, and odd number The element or component of form also include plural form, unless the obvious purport of the quantity refers to singular.

Illustrate the present invention below by way of specific embodiment, but is not limited to specific examples presented below.

The present invention provides a kind of preparation method of new vulcanizing system TPV material, the system of the new vulcanizing system TPV material Preparation Method includes at least:

In one embodiment, white oil is 5~7 parts by weight in step (1) of the present invention, and the step (2) is kneaded It joined the white oil of 5~7 parts by weight in the process.

In a preferred embodiment, mixing time is 5~30min, roll spacing 2 in step (2) of the present invention ~5mm.

In a preferred embodiment, plasticating temperature is 80 DEG C in step (1) of the present invention.

In a preferred embodiment, melting temperature is 180 DEG C in step (2) of the present invention.

In a preferred embodiment, curing temperature is 200 DEG C in step (3) of the present invention.

TPV, that is, thermoplasticity EPDM dynamic vulcanization elastomer or thermoplasticity EPDM dynamic perduren are height The ethylene propylene diene rubber EPDM particle of vulcanization is dispersed in the macromolecular elastomer material formed in continuous polypropylene PP phase.TPV is normal The lower physical property of temperature be functionally similar to thermoset rubber, show as the characteristic of thermoplastic at high temperature, can be quick Economic and easily machine-shaping.TPV thermoplasticity EPDM dynamic vulcanization elastomer/rubber passes through vulcanized rubber material dynamic State vulcanization is dispersed in ethylene propylene diene rubber EPDM in polypropylene PP plastic substrate with the particle lower than 2 micron-scales, rubber It is combined together well with the characteristic of plastics, obtains the high performance elastomer material of excellent combination property.Mainly have as follows Advantage: it is easy to weld, is reusable, environment-protecting and non-poisonous；Excellent anti-aging property and good weather-proof, heat resistance；It is excellent Resistance to permanent deformation performance；Excellent tensile strength, high tenacity and high resilience；Excellent environmental-protecting performance and reusable； Excellent electrical insulation capability；Hardness range is extensive；Use temperature range is extensive；It is easily worked molding.

The hardness for the TPV material that the preparation method of new vulcanizing system TPV material is prepared through the invention is 55- 70ShoreA, (25 DEG C) of density are 0.9-1.0g/cm³, (230 DEG C, 5kg) of melt index are 7-13g/10min, and have high Resistance to low temperature.

Hardness is that the material ability that locally the hard object of resistance is pressed into its surface is known as hardness.According to the difference of measurement method, firmly It is different to spend unit.Hardness of the present invention is Shore hardness, and Shore hardness refers to a kind of test and the representation method of material hardness. Test philosophy is by defined diamond hammer from the surface that fixed height falls in sample, and formed punch bounces certain altitude, will The ratio between bounce amount and height of drop are to calculate Shore hardness.

Density is the measurement to the quality in designated volume, can be measured with method well known to those skilled in the art, such as day Flat method and bottle method.

A kind of numerical value of mobility when melt index is expression plastic material processing.The survey of melt index of the present invention Method for testing is first to allow plastic pellet in certain time (10 minutes), under certain temperature (230 DEG C) and load (2.16kg), is melted into Plastic liquid, gram (g) number then flowed out by diameter by 2.095mm round tube.

Ethylene propylene diene rubber

Ethylene propylene diene rubber, abbreviation are EPDM, are the terpolymers of ethylene, propylene and non-conjugated diene hydrocarbon.It is non-conjugated Alkadienes has special structure, and only one of two keys could be copolymerized, unsaturated double bond primarily as interlinkage at.It is another It is a it is unsaturated will not become main polymer chain, only can become avris chain.The principal polymeric chain of EPDM is fully saturated 's.This characteristic allows EPDM to resist heat, light, oxygen, especially ozone.EPDM is substantially nonpolarity , resistant to polar solvent and chemicals, water absorption rate is low, has good insulation characterisitic.In ethylene propylene diene rubber Three monomers are that non-conjugated diene hydro carbons is to generate unsaturated bond, in the polymer by the copolymerization with ethylene and propylene so as to reality Now vulcanize, with the increase of alkadienes Third monomer, it will have faster vulcanization rate, lower compressed shape variability, high determines to stretch Intensity improves the scorch safety in production process.

Preferably, the Third monomer of ethylene propylene diene rubber of the present invention is ethylidene norbornene, the ethylidene drop Bornylene accounts for 5~10wt% of the ethylene propylene diene rubber.

It is highly preferred that ethylidene norbornene of the present invention accounts for the 7.5wt% of ethylene propylene diene rubber of the present invention.

Ethylidene norbornene can obtain ethylene propylene diene rubber, the rubber of preparation as Third monomer, with ethylene, propylene copolymerization Curingprocess rate it is faster than other Third monomers, the disadvantage that second the third EP rubbers curingprocess rate can be overcome slow.And ice drops in ethylidene Piece alkene has the performances such as resistance to ozone, chemical-resistant resistance (solvent, acid, alkali etc.), resistance to electric discharge, resistance to vapor.

It is further preferred that in ethylene propylene diene rubber of the present invention, propylene account for the ethylene propylene diene rubber 36~ 45wt%.

It is further preferred that propylene accounts for the ethylene propylene diene rubber in ethylene propylene diene rubber of the present invention 42.5wt%.

In a preferred embodiment, ethylene propylene diene rubber of the present invention is purchased from Dupont-Tao Shi, and the trade mark is (Third monomer is ethylidene norbornene to EPDM5565, accounts for the 7.5wt% of ethylene propylene diene rubber, and propylene accounts for ethylene propylene diene rubber 42.5wt%).

Third monomer and propylene content are by method well known to those skilled in the art in ethylene propylene diene rubber of the present invention It measures, such as ASTM D6047-2015 and ASTM D3900-2015.

In the polymer molecular chains such as presence and butadiene rubber, polypropylene due to ethylene propylene diene rubber Third monomer The unsaturated double-bond of reservation forms three-dimensional net structure under the action of crosslinking agent, through chemical crosslinking, has molding product The elastic restoration ratio having had.Simultaneously as high molecular for polyethylene etc. point of the polymer phases such as ethylene propylene diene rubber, polypropylene Subchain regularity is poor, it is not easy to which the interior rotation of ordered arrangement, chemical bond is not obstructed, and lower, glass transition temperature is built in inward turning indexing Spend it is low, so as to so that product can still keep good elasticity, material surface friction with higher at a lower temperature Coefficient.

Butadiene rubber

Butadiene rubber is cis--Isosorbide-5-Nitrae-polybutadiene rubber abbreviation, and abbreviation is BR, and butadiene rubber is by polymerizing butadiene Made of synthetic rubber.Butadiene rubber molecular structure regularity is good, and no side group, strand is very submissive, is a kind of crystalline rubber, But crystallizing power is not strong, and elasticity is good.Butadiene rubber is the second largest synthetic rubber for being only second to butadiene-styrene rubber.With natural rubber and fourth Benzene rubber phase ratio, its cold resistance, wearability and elasticity are especially excellent after vulcanization, generate heat under dynamic load few, resistance to ag(e)ing is fair.It is suitable Buna can also manufacture padded coaming and various rubber overshoes, adhesive plaster, adhesive tape especially suitable for manufacture automobile tire and cold-resistant product With sandwich rubber etc..When preparing TPV material using on-slip coefficient can be improved, skid resistance is improved.

Preferably, butadiene rubber of the present invention accounts for 10~20wt% of the ethylene propylene diene rubber.

It is found by the applicant that butadiene rubber content is excessive, although can improve the tearing strength of product to a certain extent, draw The performances such as intensity are stretched, but the wet-sliding resistant performance of product can be made to reduce, it may be possible to due in the case where other conditions are constant, when Butadiene rubber too high levels, unsaturated double bond therein are got higher, and the cross-linked network content that may cause in system becomes therewith It is more, and the degree of branching of butadiene rubber is low, coefficient of friction is not high, and anti-slip effect is caused to be affected.

White oil

White oil, alias paraffin oil, white oil, mineral oil are the mixtures of the refining liquid hydrocarbon obtained by petroleum, predominantly full The cycloalkane and alkane mixture of sum can be used for improving the processing performance and service performance of rubber, can increase the modeling of sizing material Property, temperature when reducing sizing material viscosity and being kneaded improves dispersibility and Combination, improves tensile strength, the elongation of vulcanizate And wearability.White oil of the present invention can be used for improving the processing performance and service performance of rubber as softening agent, increase sizing material Plasticity, reduce sizing material viscosity and be kneaded when temperature, improve dispersibility and Combination, improve the tensile strength of vulcanizate, stretch Long rate and wearability.

Polypropylene

Polypropylene abbreviation is PP, is a kind of thermoplastic as prepared by propylene polymerization.It is divided by methyl arrangement position Isotactic polypropylene, random polypropylene and three kinds of syndiotactic polypropylene.In the acrylic resin generally used, predominantly isotactic structure, Compound with regular structure is a kind of hemicrystalline thermoplastic.It is heat-resisting, corrosion-resistant, toughness height, antiacid caustic corrosion, solvent resistant.Density It is small, it is most light general-purpose plastics.The disadvantage is that low-temperature impact resistance is poor, it is more easy to aging, but can be overcome respectively by modification.? To a certain extent, the anti-slippery of butadiene rubber can be improved by the synergistic effect of butadiene rubber.

Preferably, melt index of the polypropylene of the present invention under 230 DEG C, 2.16kg load is 8~12g/10min.

It is highly preferred that melt index of the polypropylene of the present invention under 230 DEG C, 2.16kg load is 10g/10min.

It is further preferred that polypropylene of the present invention is purchased from Taiwan Qiaofupaomian Co., Ltd., the trade mark is PP212LB。

Graft polypropylene

Graft polypropylene is to be modified by the method for grafting to polypropylene, such as connects elastic component, can improve poly- third The brittleness of alkene；Polar compound is connected, polyacrylic hydrophily, cohesiveness etc. can be improved.

Preferably, graft polypropylene of the present invention be maleic anhydride inoculated polypropylene, grafting rate be 0.8~ 1.2wt%.

Grafting rate, that is, grafting efficiency, grafting efficiency=[grafted monomers quality/(grafted monomers quality+grafted monomers are equal Polymers quality)] × 100%, it can be measured with titration, specific measuring method is to weigh the maleic anhydride grafting of 0.2g after purification to gather Propylene is added l00mL dimethylbenzene and is heated to 140 DEG C in the flask of 250mL.After temperature is cooled to 70 DEG C, 10mL is added The potassium hydroxide-ethanol solution of 0.05mol/L, 100 DEG C of reflux 2h, is cooled to 70 DEG C.Add 5 drop instructions phenolphthalein solutions, 0.05mol/L It is colourless that hydrochloric acid-aqueous isopropanol is titrated to solution while hot.Maleated polypropylene grafting rate calculation formula: G=M (maleic anhydride) [C (potassium hydroxide-ethanol) V-C (hydrochloric acid-isopropanol) (V₁-V₂)] × 10-3/2m, wherein M (maleic anhydride): maleic anhydride Molal weight, unit g/mol；C (potassium hydroxide-ethanol): the concentration of potassium hydroxide-ethanol solution, unit mol/L；V: The volume of potassium hydroxide-ethanol solution, unit mL；C (hydrochloric acid-isopropanol): hydrochloric acid-aqueous isopropanol concentration, unit are mol/L；V₁: the volumetric quantities of hydrochloric acid-aqueous isopropanol, unit mL before titrating；V₂: hydrochloric acid-aqueous isopropanol body after titration Product value, unit mL；M: the quality of maleic anhydride inoculated polypropylene, unit g.

It is highly preferred that graft polypropylene of the present invention is maleic anhydride inoculated polypropylene, grafting rate 1.0wt%.

Maleic anhydride inoculated polypropylene is also referred to as PP-g-MAH, introduces strong pole on nonpolar polypropylene molecule main chain Property maleic anhydride side group, make material have high polarity and reactivity, the compatibility and filler of composite material can be greatly improved Dispersibility, to improve the mechanical properties such as the tensile strength of material, bending strength and impact strength, and processing stream can be improved Denaturation improves surface smoothness.

It is further preferred that graft polypropylene of the present invention is plasticized Science and Technology Ltd. purchased from Dongguan City Sheng Mei, it is horse Maleic anhydride grafted polypropylene, grafting rate 1.0wt%.

It is found by the applicant that by the usage ratio of regulation EPDM, BR etc., the parameters such as polyacrylic melt index can improve The on-slip coefficient that product can also be effectively improved while the tensile strength of product, improves its antiskid effect, is more applicable for it In medical space, soldier's boots shoes etc..Applicant think itself the possible reason is, by the materials such as EPDM, BR, PP be blended preparation system When product, due to EPDM, the compatibility between the rubber phases flexible polymer strand such as butadiene rubber is preferable, is easily dispersed into continuous Phase.But since the polarity of the materials such as vulcanization accelerator, antioxidant, filler, antibacterial agent is relatively large, with above-mentioned rubber, Compatibility between the components such as elastomer is bad, influences the performance of TPV material.And by using with suitable melt index and stream The maleic anhydride graft PP of dynamic property, can promote effective dispersion of above-mentioned polar compound, disperse it in rubber, elastomer phase Obtain similar island structure.Wherein, due to there is no polar group in the polymer molecules chain structure such as EPDM, BR, PP, with filler, Poor compatibility between the components such as antioxidant, vulcanization accelerator can be effectively improved this problem by using graft PP, and wherein The grafting rate of maleic anhydride is unsuitable excessively high, otherwise will affect the performances such as elasticity, the elongation at break of product, becomes material very Crisp, processing performance is also deteriorated, and increases production cost on foot.

Hydrogenated styrene-butadiene block copolymer

Hydrogenated styrene-butadiene block copolymer abbreviation is SEBS, is using polystyrene as end segment, with polybutadiene The ethylene-butene copolymer for adding hydrogen to obtain is the linear tri-block copolymer of intermediate elastic block.SEBS is free of unsaturated double-bond, because This with good stability and resistance to ag(e)ing, and SEBS has good weatherability, heat resistance, compression resistant morphotropism and excellent Mechanical property, and have good dissolubility energy, blended characteristic and excellent oil-filled property, specific gravity it is lighter.SEBS both has can Plasticity, and there is high resiliency, it can be processed and uses without vulcanization, leftover pieces can be reused, and the high-grade elasticity of production is widely used in Body, modifying plastics, adhesive, lubricant tackifier, the filler material of wire and cable and protective cover material etc..

Preferably, SEBS of the present invention includes linear SEBS and star SEBS.

It is highly preferred that the weight ratio of star SEBS of the present invention and linear SEBS is 1:(0.8~2).

It is further preferred that the weight ratio of star SEBS of the present invention and linear SEBS is 1:1.2.

It is further preferred that viscosity of the linear SEBS of the present invention in 25 DEG C, 10wt% toluene solution is 1400 ~1600mPas.

In a preferred embodiment, linear SEBS of the present invention is glutinous in 25 DEG C, 10wt% toluene solution Degree is 1500mPas.

Viscosity is referred to as viscosity, refers to dynamic the showed resistance of fluid convection.Viscosity of the present invention is viscosmeter Test viscosity of the obtained elastomer in 25 DEG C, 10wt% toluene solution.

In a kind of preferred embodiment, in linear SEBS of the present invention butadiene molar content be 65~ 70%.

In a kind of further preferred embodiment, the molar content of butadiene is in linear SEBS of the present invention 67%.

In a kind of embodiment still more preferably, linear SEBS of the present invention is purchased from Yueyang Ba Ling Huaxing petrochemical industry Co., Ltd, trade mark YH-503.

In a preferred embodiment, butadiene molar content is 60~68% in star SEBS of the present invention.

In a kind of preferred embodiment, butadiene molar content is 65% in star SEBS of the present invention.

In a kind of further preferred embodiment, star SEBS of the present invention is at 25 DEG C, 10wt% toluene solution In viscosity be 750~900mPas.

In a kind of embodiment still more preferably, for star SEBS of the present invention at 25 DEG C, 10wt% toluene is molten Viscosity in liquid is 800mPas.

In a kind of embodiment still more preferably, star SEBS of the present invention is purchased from Yueyang Ba Ling Huaxing petrochemical industry Co., Ltd, trade mark YH-602.

It is found by the applicant that the mechanical performance of product can be improved to a certain extent by using the SEBS elastomer of compounding While, also contribute to its on-slip coefficient.Applicant speculates that it may be the SEBS polymer molecule due to star structure There is the branched structure of more entanglement in chain, causes its physical crosslinking degree relatively high, product is by force-extension, tearing etc. Network disentanglement speed is slower in its internal microstructure in the process, slows down under network strength, and intermolecular slippage is relatively less It is easy, to improve the mechanical performance of product.

Although in addition, it is found by the applicant that the addition of star SEBS can be improved to a certain extent product tensile strength, The performances such as tearing strength, if but the parameters such as wherein butadiene content, relative viscosity are not defined, it can be seriously affected The performances such as processing performance, elasticity, elongation.Applicant passes through the viscosity by star SEBS in 25 DEG C, 10wt% toluene solution Control is in 750~900mpa.s, and in 60~68%, the above problem is resolved butadiene content, and it is high, elastic to obtain intensity It is good, and the material being easily worked.

However applicant has found during formula adjusting, need in SEBS linear and star component dosage and Butadiene (B) content is controlled in SEBS, and the too high levels of star SEBS can significantly affect the elasticity of product, or even also can shadow On-slip coefficient is rung, especially above-mentioned influence is more significant when the few polymer flexibility deficiency of butadiene content in SEBS.It can It can be that the energy that the movement of polymer segment is required is got higher, by outside since physical cross-linked network therein is excessively intensive Stimulation, polymer molecular chain cannot cracking its conformation of change, absorb energy by modes such as deformation, and sound is made to the stimulation It answers, to reduce the performances such as the elasticity of material.Meanwhile excessively high crosslink density can also significantly affect SEBS and EPDM, BR, PP etc. Mutual dispersibility between material.It crosses under high crosslink density, material polymer molecular chain in mixing or mixing process is not easy Be driven into inside above-mentioned physical cross-linked network, cannot form the Phase stracture of uniformly continuous well, in addition above-mentioned material it Between there are certain interface and stress concentration points, to significantly affect the performances such as its elongation at break, impact strength.

In addition, also contributing to the compatibility of the ingredients such as filler in system, white oil to the regulation of star and linear SEBS ingredient And dispersibility effectively avoids the ingredients such as white oil toward product surface under the premise of improving plasticity, not influencing materiel machining performance Migration avoids the coefficient of friction for therefore reducing material.It may be since the physical crosslinking structure in system is formed by cavity energy It is enough to improve stability of the above-mentioned polar compound in rubber and elastomer phase to a certain extent.

Vulcanizing agent

Vulcanizing agent is the substance that rubber can be made under certain condition to vulcanize, and so-called vulcanization is to make rubber linear molecule knot Structure becomes solid netted mechanism by " bridge formation " of vulcanizing agent, so that the mechanical and physical performance of rubber be made significantly to be changed It is kind.

In one embodiment, vulcanizing agent of the present invention is selected from quinoxaline vulcanizing agent, mercapto triazines vulcanize Agent, bisphenols vulcanizing agent, sulfur vulcanizing agent, peroxide-based curing dose one or more.

As the example of quinoxaline vulcanizing agent, including but not limited to, bis- mercaptan of quinoxaline -2,3-, 1,3- dithiolane And [4,5-b] quinoxaline -2- ketone, 6- methyl-1,3- dithiolane simultaneously [4,5-b] quinoxaline -2- ketone, 5,8- dimethyl -1,3- Dithiolane simultaneously [4,5-b] quinoxaline -2- ketone.

As the example of mercapto triazines vulcanizing agent, including but not limited to, 2,4,6- tri- mercaptos -1,3,5-triazines, Two mercaptan of 6- hexylamino -1,3,5- triazine -2,4-, two mercaptan of 6- diethylamino -1,3,5- triazine -2,4-, 6- cyclohexyl Two mercaptan of amino -1,3,5- triazine -2,4-, two mercaptan of 6- dibutylamino -1,3,5- triazine -2,4-, 2- anilino- -4,6- two Mercapto triazine, two mercaptan of 6- phenyl amino -1,3,5- triazine -2,4-.

As the example of bisphenols vulcanizing agent, including but not limited to, bisphenol AF, bisphenol S.

As the example of sulfur vulcanizing agent, including but not limited to, powder-sulphur, insoluble sulfur, sedimentation Sulfur, colloid Sulphur.

As peroxide-based curing dose of example, including but not limited to, tert-butyl hydroperoxide, to lid alkane peroxidating Hydrogen, dicumyl peroxide, tert-butyl peroxide, two-(t-butylperoxyisopropyl) benzene, 2,5- dimethyl -2,5- two (t-butyl peroxy) hexane, benzoyl peroxide, peroxidized t-butyl perbenzoate, tasteless DCP.

Preferably, vulcanizing agent of the present invention is tasteless DCP.

Vulcanization accelerator

Vulcanization accelerator is the substance for promoting sulfurization.Vulcanization time can be shortened, reduce curing temperature, reduce vulcanizing agent Dosage and the physical mechanical property etc. for improving rubber.

In one embodiment, vulcanization accelerator of the present invention be selected from sulfenamide, thiazoles, thiurams, Thiourea, guanidine, dithiocarbamates, aldehyde amines, aldehyde ammonia class, imidazolines, in xanthic acid salt vulcanization accelerator It is one or more.

As the example of sulfenamide vulcanization accelerator, including but not limited to, selected from N- cyclohexyl -2-[4-morpholinodithio Sulfonamide, N tert butyl benzothiazole 2 sulfenamide, N, the sub- second of N- dicyclohexyl -2-[4-morpholinodithio sulfenamide, N- oxygen two Base -2-[4-morpholinodithio sulfenamide, N, N- diisopropyl -2-[4-morpholinodithio sulfenamide.

As the example of thiazoles vulcanization accelerator, including but not limited to, 2-mercaptobenzothiazole, two thio dibenzo thiophenes Azoles, the sodium salt of 2-mercaptobenzothiazole, the zinc salt of 2-mercaptobenzothiazole, the mantoquita of 2-mercaptobenzothiazole, 2- sulfydryl benzo Cyclohexyl amine salt, 2- (dinitrophenyl group) mercaptobenzothiazoler, 2- (2,6- diethyl 4- morpholinothio) benzene of thiazole And thiazole.

As the example of thiurams vulcanization accelerator, including but not limited to, tetramethyl thiuram disulfide, tetraethyl Thiuram disulfides, tetra methylthiuram monosulfide, double pentamethylene thiuram disulfides, double pentamethylene thiurams Monosulfide, double pentamethylene thiuram tetrasulfides, double pentamethylene thiuram hexasulfides, tetrabutyl thiuram curing Object, pentamethylene thiuram tetrasulfide.

As the example of Thiourea vulcanization accelerator, including but not limited to, thiocarbamide, diethyl thiourea, dibutyl thiourea, three Methylthiourea, di-o-tolyl-thiourea.

As the example of guanidine vulcanization accelerator, including but not limited to, diphenylguanidine, di-o-tolylguanidine, triphenyl guanidine, adjacent toluene Biguanides, diphenylguanidine phthalic acid ester.

As the example of dithiocarbamates vulcanization accelerator, including but not limited to, the thio ammonia of ethylphenyl two Base zinc formate, butyl phenyl zinc dithiocarbamate, sodium dimethyl dithiocarbamate, dimethyl dithiocarbamic acid Zinc, zinc diethyl dithiocarbamate, zinc dibutyl dithiocarbamate, zinc diamyldithiocarbamate, dipropyl Base zinc dithiocarbamate, the double salt of zinc pentamethylene dithiocarbamate and piperidines, cetyl isopropyl two are thio Carbaminate, zinc octadecylisopropyldithiocarbamate, zinc dibenzyl dithiocarbamate, diethyl-dithio Carbamic acid sodium, pentamethylene aminodithioformic acid piperidines, Selenium dimethyl dithiocarbamate, diethyl-dithio amino Formic acid tellurium, diamyl dithiocarbamate cadmium.

As the example of aldehyde amines or aldehyde ammonia class vulcanization accelerator, including but not limited to, acetaldehyde-aniline reaction object, butyraldehyde- Aniline condensation object, hexa, acetaldehyde-ammonia reactant.

As the example of imidazolines vulcanization accelerator, including but not limited to, 2- mercaptoimidazoline.

As the example of xanthic acid salt vulcanization accelerator, including but not limited to, dibutyl xanthic acid zinc.

Preferably, vulcanization accelerator of the present invention is tetramethylthiuram disulfide.

Antioxidant

Antioxidant is a kind of chemical substance, in the presence of it is only a small amount of in polymeric system, so that it may delay or inhibit poly- The progress for closing object oxidation process, to prevent the aging of polymer and prolong its service life.

In one embodiment, antioxidant of the present invention is selected from phenolic antioxidant, phosphorous acid kind antioxidant, compound One of type antioxidant and green antioxidant are a variety of.

As the example of Hinered phenols antioxidant, including but not limited to, 2,2'- methylene-bis- (4- methyl-6-tert butyl Phenol) (antioxidant 2246), N, N- [3- (3,5- di-tert-butyl-hydroxy phenyl) propionyl] hexamethylene diamine, 4,4'- thiobis Bis- [1,1- dimethyl -2- [(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyl) the propionyl oxygen of (6- tert-butyl -3- methylphenol), 3,9- Base] ethyl] four oxaspiro of -2,4,8,10-, di-tert-butyl hydroquinone.

As the example of phosphorous acid kind antioxidant, including but not limited to, phosphorous acid three (2,4- di-tert-butyl-phenyl) ester, (2,4- di-tert-butylphenol) -4,4- xenyl diphosphites.

As the example of complex type antioxidant, including but not limited to, bis- [3- (3', the 5'- di-t-butyl -4'- hydroxyls of N, N'- Phenyl) propionyl hexamethylene diamine (antioxidant 1098).

As the example of green antioxidant, including but not limited to, alpha-tocopherol, p-cresol and dicyclopentadiene butyl The product of combination reaction.

Filler

Filler refers to the material being filled in other objects.In chemical products, filler is also known as filler, refers to change Kind processing performance, Mechanical Properties of Products simultaneously (or) reduce the solid material of cost.

Preferably, filler of the present invention is barium salt and calcium salt, and weight ratio is 1:(1~3).

It is highly preferred that barium salt of the present invention is barium sulfate.

It is further preferred that calcium salt of the present invention is calcium carbonate, contain 30~50wt% carbon modified in the calcium carbonate Sour calcium.

Barium sulfate

Barium sulfate has chemical inertness strong, and stability is good, and acid and alkali-resistance, hardness is moderate, high specific gravity, Gao Baidu, and can absorb has The advantages that evil ray, be a kind of material with environment-friendly function, therefore be widely used in various coating, and medium-to-high grade ink, medicine closes At chemical industry, the fields such as rubber, papermaking, ceramics, cosmetics.When be used for rubber and plastic products when, improve Article Stiffness Determination, intensity, The performances such as rigidity, wearability, high temperature resistant, resistance to acid and alkali, uvioresistant and water resistance, prevent surface aging, reduce product at This.

Preferably, the partial size of barium sulfate of the present invention is 0.1~0.3 μm.

It is highly preferred that barium sulfate of the present invention is 0.1 μm purchased from prosperous chemical industry, partial size is praised.

Calcium carbonate

Calcium carbonate is in rubber industry using earliest and one of maximum filler of amount, calcium carbonate be largely filled in rubber it In, the volume of product can be increased, achieve the purpose that reduce cost to save expensive natural rubber, calcium carbonate inserts rubber Tensile strength wearability more higher than pure rubber sulfide, tearing strength can be obtained, and is had in natural rubber and synthetic rubber Significant reinforcing effect, while adjustable consistency.

Preferably, the partial size of calcium carbonate of the present invention is 1250~1500 mesh.

It is highly preferred that calcium carbonate of the present invention is purchased from Qingzhou Yu Xingai industry limited liability company.

It is found by the applicant that regulated and controled by carrying out the parameters such as component, usage ratio and partial size to the filler in step (2), It can be effectively improved the rub resistance ability of product, improve on-slip coefficient.Especially under the premise of regulating and controlling SEBS respective components, into one Using the filler of specific compounding, mechanical property, anti-slip effect of resulting product etc. significantly improve step.May be due to Under the action of the ingredients such as graft PP, filler can be effectively distributed to inside the ingredients such as the elastomers such as the rubber phases such as EPDM and SEBS, Again due to the network cavity structure that physical chemistry therein is cross-linked to form, facilitate the inorganic grains such as effectively fixed and constraint calcium carbonate Son, and be dispersed in rubber, these inorganic particulates in elastomer can power suffered by absorbing material, avoid the further of stress Diffusion, to further improve the mechanical performance of product.

Furthermore, it is possible to be since the inorganic particulates such as barium sulfate, the calcium carbonate of different size partial size are in groups such as rubber, elastomers / dispersibility and migration etc. it is different, the small inorganic particulate of partial size may more readily migrate into product surface, increase Add its roughness, improves on-slip coefficient.It is found by the applicant that if using the inorganic particulate of same particle size as filler, resulting product On-slip coefficient promoted it is unobvious, it may be possible to since dispersion of the inorganic particulate in different-grain diameter in system and migration can It mutually promotes, improves its surface roughness while improving dispersibility, to improve on-slip coefficient.

Modified calcium carbonate of the present invention disperses the preparation method comprises the following steps: deionized water will be added in a certain amount of calcium carbonate 30min (can use ultrasonic wave added, improve dispersion effect), and system temperature is then heated to 60~70 DEG C, organosilicon is added Surfactant is stirred to react 2~3 hours, after being cooled to room temperature, filtering, and filter cake washing, drying is ground to obtain the final product.

Surfactant, which refers to, is added the substance that significant change occurs for the interface state that can make its solution system on a small quantity.With solid Fixed hydrophilic lipophilic group can align on the surface of solution, and the molecular structure of surfactant has amphipathic: one end is Hydrophilic radical, the other end are hydrophobic grouping.

It is further preferred that organic silicon surfactant of the present invention is C3~C8 alkylsiloxane.

In a preferred embodiment, organic silicon surfactant of the present invention be propyl trimethoxy silicane and Octyl trimethoxy silane, weight ratio 1:1.

It is found by the applicant that although the addition of filler can improve the performances such as tensile strength, the tearing strength of product, its time Elasticity, processing performance etc. decrease.Although the graft PP in system can improve to a certain extent filler and EPDM, Compatibility between organic non-polar component such as BR, SEBS, but its improvement degree need to be improved.In the present invention in filler It is added after a certain amount of modified calcium carbonate, it is found by the applicant that the performances such as tensile strength of product are not significantly affected, Even also it is improved, and its elastic, elongation at break, processing performance etc. significantly improve.It may be due to calcium carbonate It is modified to carry out surface, is formed on its surface nonpolar segment, improves the compatibility in the components such as itself and rubber, elastomer.

In addition, the discovery that applicant is unexpected, is changed by carrying out particular silicone surfactant surface to calcium carbonate Property, moreover it is possible to improve the skid resistance and abrasive resistance of product, improves on-slip coefficient.Simultaneously it is found by the applicant that C3 alkylsiloxane and When C8 alkylsiloxane is used in compounding, the improvement of above-mentioned performance is the most significant.It may be modified due to carrying out surface to calcium carbonate Later, while improving its compatibility, moreover it is possible to further change its migration and diffusivity in system, enable calcium carbonate The surface for enough moving to material, forms the surface of relative coarseness, to improve the on-slip coefficient and crocking resistance of material surface. And it is found by the applicant that when the carbochain of alkyl chain siloxanes is too small or excessive, to the on-slip coefficient of product and the improvement of wearability It is not significant, or even on-slip coefficient can be also further decreased when carbochain is too long.It may be the influence that is changed significantly of carbon chain lengths The transfer ability of calcium carbonate, so that the roughness variation of material surface is less, the improvement of wearability and antiskid effect is not significant.

In one embodiment, the raw material of TPV material of the present invention further includes fungicide.

Fungicide

Fungicide is the chemicals that can efficiently control or kill microorganism.

Preferably, the fungicide of 0.1~0.3 parts by weight is added in step (2) mixing process of the present invention.

It is highly preferred that fungicide of the present invention is organic bactericide and/or inorganic fungicide.

As the example of organic bactericide, including but not limited to, isothiazolinone biocide agent, has organochlorine fungicide Machine thiophanate fungicide.

As the example of isothiazolinone biocide agent, including but not limited to, 5- chloro-2-methyl -4- isothiazoline -3- Ketone, 2-methyl-4-isothiazolin-3-one, 1,2- benzisothiazole-3-ketone, Kathon, 2- first Base -4,5- propylidene -4- isothiazoline -3- ketone, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one.

As the example of organochlorine fungicide, including but not limited to, antiphen, dodecylbenzyl ammonium chloride, bromine chlorine sea Cause, cypermethrin, sodium dichloro cyanurate, sym-closene

As the example of organosulfureous fungicide, including but not limited to, 1,2- ethylenebis ammonium dithiocarbamate, diformazan Base zinc dithiocarbamate.

As the example of inorganic fungicide, including but not limited to, titanium oxide, magnesia, boric acid.

It is found by the applicant that bactericidal property can be effectively improved by adding fungicide in TPV material of the present invention.

Since ethylene propylene diene rubber (EPDM) is a kind of unformed noncrystalline rubber, the ethylene and third on molecular backbone The random arrangement of alkene monomer unit, loses the regularity of polyethylene or Polypropylene structural, becomes flexible rubber bodies.But It is that cannot be easy to plasticate as natural rubber etc. since the effect of plasticating of EPDM rubber is poor, and between EPDM and other components In the case that melting effect is bad, its curingprocess rate and vulcanization effect will affect.Especially, EPDM Third monomer in the present invention Content and ethylene contents are relatively high, and a certain proportion of star structure is also contained in used SEBS, these conditions can be straight Connecing influences its curingprocess rate and vulcanization effect, to influence the processing performance of product and prepare the mechanical property of products obtained therefrom.? By carrying out EPDM and BR component to rush oil processing in white oil in the present invention, then carried out again with ingredients such as other SEBS, PP Mixing, and part white oil is added again in second step mixed process, the polymer molecular chain to tangle in system is sufficiently unlocked, With the mobility and dispersibility of material in this improvement system, raising prepares the comprehensive performance of products obtained therefrom.

Embodiment

The present invention is specifically described below by embodiment.It is necessarily pointed out that following embodiment is only used In the invention will be further described, it should not be understood as limiting the scope of the invention, professional and technical personnel in the field The some nonessential modifications and adaptations made according to the content of aforementioned present invention, still fall within protection scope of the present invention.

In addition, if without other explanations, it is raw materials used to be all commercially available, it is purchased from traditional Chinese medicines chemical reagent.

Embodiment 1

The embodiment of the present invention 1 provides a kind of preparation method of new vulcanizing system TPV material, new vulcanizing system TPV material The preparation method comprises the following steps:

(1) it plasticates: the butadiene rubber of the ethylene propylene diene rubber of 10 parts by weight, 2 parts by weight is added to single screw extrusion machine In, and the white oil of 12 parts by weight is added, it carries out rushing oil processing at 80 DEG C, obtains rubber components；

(2) it is kneaded: rubber components obtained in step (1) is added in double screw extruder, and 3 parts by weight are added Polypropylene, the graft polypropylene of 0.5 parts by weight, the hydrogenated styrene-butadiene block copolymer of 8 parts by weight, 0.4 parts by weight Vulcanizing agent, the vulcanization accelerator of 0.4 parts by weight, the antioxidant of 0.15 parts by weight, 12 parts by weight filler, and at 165~200 DEG C Under be kneaded, be then granulated；

(3) vulcanize: pellet obtained in step (2) is subjected to thermoplastic shaping, and vulcanized at 250 DEG C to obtain described TPV material.

Mixing time is 30min, roll spacing 5mm in the step (2).

The ethylene propylene diene rubber is purchased from american exxon, trade mark EPDM8800, wherein Third monomer is ethylidene drop Bornylene, accounts for the 10wt% of ethylene propylene diene rubber, and propylene accounts for the 36.5wt% of ethylene propylene diene rubber.

The butadiene rubber is purchased from Changzhou Heshan limited rubber company.

The white oil is purchased from Hangzhou Fuda goods and materials petrochemical industry Co., Ltd, and the trade mark is 36# white oil.

The polypropylene thinks chemical products Co., Ltd, trade mark R200467, melt index 12g/ purchased from Chengdu auspicious one 10min。

The graft polypropylene is purchased from Dongguan City ring plastic material Co., Ltd, and trade mark TY105H is maleic acid Acid anhydride graft polypropylene, grafting rate are 1.0~1.2wt%.

The hydrogenated styrene-butadiene block copolymer is made of linear SEBS and star SEBS, weight ratio 1: 0.8。

The star SEBS is purchased from petrochemical industry Co., Ltd, Yueyang Ba Ling Huaxing, trade mark YH-602, viscosity 800mPa S, butadiene divine by astrology shape SEBS molar ratio be 65%.

The linear SEBS is purchased from petrochemical industry Co., Ltd, Yueyang Ba Ling Huaxing, trade mark YH-503, viscosity 1500mPa S, butadiene divine by astrology shape SEBS molar ratio be 67%.

The vulcanizing agent is tasteless DCP, reaches Chemical Company purchased from Shanghai Fang Rui, the trade mark is FARIDA BIPB 96。

The vulcanization accelerator is tetramethylthiuram disulfide, and No. CAS is 137-26-8.

The antioxidant is di-tert-butyl hydroquinone, is purchased from Hubei Ju Sheng Science and Technology Ltd..

The filler is barium sulfate and calcium carbonate, mass ratio 1:1.

The partial size of the barium sulfate is 0.1 μm, purchased from praising prosperous chemical industry.

The partial size of the calcium carbonate is 1250 mesh, is purchased from Qingzhou Yu Xingai industry limited liability company.

Embodiment 2

The embodiment of the present invention 2 provides a kind of preparation method of new vulcanizing system TPV material, the new vulcanizing system TPV Material the preparation method comprises the following steps:

(1) it plasticates: the butadiene rubber of the ethylene propylene diene rubber of 10 parts by weight, 1 parts by weight is added to single screw extrusion machine In, and the white oil of 12 parts by weight is added, it carries out rushing oil processing at 80 DEG C, obtains rubber components；

(2) it is kneaded: rubber components obtained in step (1) is added in double screw extruder, and 1 parts by weight are added Polypropylene, the graft polypropylene of 0.1 parts by weight, the hydrogenated styrene-butadiene block copolymer of 3 parts by weight, 0.1 parts by weight Vulcanizing agent, the vulcanization accelerator of 0.1 parts by weight, the antioxidant of 0.01 parts by weight, 3 parts by weight filler, and carried out at 165 DEG C It is kneaded, is then granulated；

(3) vulcanize: pellet obtained in step (2) is subjected to thermoplastic shaping, and vulcanized at 185 DEG C to obtain described TPV material.

Mixing time is 5min, roll spacing 2mm in the step (2).

The fungicide of 0.1 parts by weight is added in step (2) mixing process.

The ethylene propylene diene rubber is purchased from Dupont-Tao Shi, trade mark EPDM4640, wherein Third monomer is sub- second Base norbornene, accounts for the 5wt% of ethylene propylene diene rubber, and propylene accounts for the 40wt% of ethylene propylene diene rubber.

The butadiene rubber is purchased from Changzhou Heshan limited rubber company.

The graft polypropylene is purchased from Jiangsu great Teng new material Co., Ltd, and trade mark DT-0918 is grafted for maleic anhydride Polypropylene, grafting rate are 0.8~1.0wt%.

The hydrogenated styrene-butadiene block copolymer is made of linear SEBS and star SEBS, weight ratio 1:2.

The filler is barium sulfate and calcium carbonate, mass ratio 1:3.

The fungicide is 5-Chloro-2-methyl-4-isothiazolin-3-one, and No. CAS is 26172-55.

Embodiment 3

The embodiment of the present invention 3 provides a kind of preparation method of new vulcanizing system TPV material, the new vulcanizing system TPV Material the preparation method comprises the following steps:

(1) it plasticates: the butadiene rubber of the ethylene propylene diene rubber of 10 parts by weight, 1.5 parts by weight being added to single screw rod and is squeezed out In machine, and the white oil of 12 parts by weight is added, carries out rushing oil processing at 80 DEG C, obtain rubber components；

(2) it is kneaded: rubber components obtained in step (1) is added in double screw extruder, and 2 parts by weight are added Polypropylene, the graft polypropylene of 0.2 parts by weight, the hydrogenated styrene-butadiene block copolymer of 5 parts by weight, 0.15 parts by weight Vulcanizing agent, the vulcanization accelerator of 0.2 parts by weight, the antioxidant of 0.05 parts by weight, 8 parts by weight filler, and at 180 DEG C into Row is kneaded, and is then granulated；

(3) vulcanize: pellet obtained in step (2) is subjected to thermoplastic shaping, and vulcanized at 200 DEG C to obtain described TPV material.

Mixing time is 15min, roll spacing 3mm in the step (2).

The fungicide of 0.3 parts by weight is added in step (2) mixing process.

The ethylene propylene diene rubber is purchased from Dupont-Tao Shi, trade mark EPDM5565, wherein Third monomer is sub- second Base norbornene, accounts for the 7.5wt% of ethylene propylene diene rubber, and propylene accounts for the 42.5wt% of ethylene propylene diene rubber.

The butadiene rubber is purchased from Changzhou Heshan limited rubber company.

The polypropylene is purchased from Taiwan Qiaofupaomian Co., Ltd., trade mark PP212LB, melt index 10g/ 10min。

The graft polypropylene is plasticized Science and Technology Ltd. purchased from Dongguan City Sheng Mei, is maleic anhydride inoculated polypropylene, connects Branch rate is 1.0wt%.

The hydrogenated styrene-butadiene block copolymer is made of linear SEBS and star SEBS, weight ratio 1: 1.2。

The filler is barium sulfate and calcium carbonate, mass ratio 1:2.

Embodiment 4

The embodiment of the present invention 4 provides a kind of preparation method of new vulcanizing system TPV material, the new vulcanizing system TPV Material the preparation method comprises the following steps:

(1) it plasticates: the butadiene rubber of the ethylene propylene diene rubber of 10 parts by weight, 1.5 parts by weight being added to single screw rod and is squeezed out In machine, and the white oil of 6 parts by weight is added, carries out rushing oil processing at 80 DEG C, obtain rubber components；

(2) it is kneaded: rubber components obtained in step (1) is added in double screw extruder, and 2 parts by weight are added Polypropylene, the graft polypropylene of 0.2 parts by weight, the hydrogenated styrene-butadiene block copolymer of 5 parts by weight, 0.15 parts by weight Vulcanizing agent, the vulcanization accelerator of 0.2 parts by weight, the antioxidant of 0.05 parts by weight, the filler of 8 parts by weight and 6 parts by weight it is white Oil, and be kneaded at 180 DEG C, then it is granulated；

Mixing time is 15min, roll spacing 3mm in the step (2).

The fungicide of 0.2 parts by weight is added in step (2) mixing process.

The butadiene rubber is purchased from Changzhou Heshan limited rubber company.

The filler is barium sulfate and calcium carbonate, mass ratio 1:2.

Embodiment 5

The embodiment of the present invention 5 provides a kind of preparation method of new vulcanizing system TPV material, the new vulcanizing system TPV Material the preparation method comprises the following steps:

Mixing time is 15min, roll spacing 3mm in the step (2).

The fungicide of 0.2 parts by weight is added in step (2) mixing process.

The butadiene rubber is purchased from Changzhou Heshan limited rubber company.

The filler is barium sulfate and calcium carbonate, mass ratio 1:2.

Contain 40wt% modified calcium carbonate in the calcium carbonate.

The preparation method of the modified calcium carbonate includes at least following steps:

Deionized water dispersion 30min will be added in a certain amount of calcium carbonate (can use ultrasonic wave added, improve dispersion effect Fruit), system temperature is then heated to 65 DEG C, organic silicon surfactant is added, is stirred to react 2.5 hours, is cooled to room temperature Afterwards, it filters, filter cake washing, drying is ground to obtain the final product.

The surfactant is propyl trimethoxy silicane and octyl trimethoxy silane, weight ratio 1:1.

No. CAS of the propyl trimethoxy silicane is 1067-25-0.

No. CAS of the octyl trimethoxy silane is 3069-40-7.

Embodiment 6

The embodiment of the present invention 6 provides a kind of preparation method of new vulcanizing system TPV material, the new vulcanizing system TPV Material the preparation method comprises the following steps:

Mixing time is 15min, roll spacing 3mm in the step (2).

The fungicide of 0.2 parts by weight is added in step (2) mixing process.

The butadiene rubber is purchased from Changzhou Heshan limited rubber company.

The filler is barium sulfate and calcium carbonate, mass ratio 1:2.

Contain 40wt% modified calcium carbonate in the calcium carbonate.

The surfactant is propyl trimethoxy silicane, and No. CAS is 1067-25-0.

Comparative example 1

Comparative example 1 of the invention provides a kind of preparation method of new vulcanizing system TPV material, and specific embodiment is the same as real Example 5 is applied, the difference is that, the filler is calcium carbonate, is purchased from Qingzhou Yu Xingai industry limited liability company, and partial size is 1250 mesh.

Comparative example 2

Comparative example 2 of the invention provides a kind of preparation method of new vulcanizing system TPV material, and specific embodiment is the same as real Example 5 is applied, the difference is that, the calcium carbonate is purchased from Qingzhou Yu Xingai industry limited liability company, and partial size is 0.1 μm.

Comparative example 3

Comparative example 3 of the invention provides a kind of preparation method of new vulcanizing system TPV material, and specific embodiment is the same as real Example 5 is applied, the difference is that, the organic silicon surfactant is hexadecyl trimethoxy silane, and No. CAS is 16415- 12-6。

Comparative example 4

Comparative example 4 of the invention provides a kind of preparation method of new vulcanizing system TPV material, and specific embodiment is the same as real Example 5 is applied, the difference is that, the butadiene rubber is that the weight ratio of 10 parts by weight and ethylene propylene diene rubber is 1:1.

Comparative example 5

Comparative example 5 of the invention provides a kind of preparation method of new vulcanizing system TPV material, and specific embodiment is the same as real Example 5 is applied, the difference is that, the polypropylene is purchased from auspicious think of reagent, trade mark R766967, melt index 2.2g/10min.

Comparative example 6

Comparative example 6 of the invention provides a kind of preparation method of new vulcanizing system TPV material, and specific embodiment is the same as real Example 5 is applied, the difference is that, the graft polypropylene is maleic anhydride inoculated polypropylene, grafting rate 2.

Maleic anhydride inoculated polypropylene described in this comparative example the preparation method comprises the following steps: by weight, by a certain amount of horse Come acid anhydrides, 5 parts of cumyl peroxides, 3 parts of styrene to be added separately in 100 parts of polypropylene powders, in a high speed mixer 5min is mixed, extruding pelletization is then carried out and masterbatch is made, 250mL xylene soluble is added in 70 DEG C of dryings, quiet with 250mL acetone It sets, filter, purify.The extruding pelletization temperature is 180 DEG C, and feed screw revolving speed is 90r/min, and main-machine screw revolving speed is 90r/ min。

The maleic anhydride is purchased from the rich Chemical Co., Ltd. in the Wuhan northern part of the country；

The cumyl peroxide is purchased from Tianjin Bo Di Chemical Co., Ltd.；

The styrene is purchased from Jinan century sensible Chemical Co., Ltd.；

The dimethylbenzene is purchased from Jinan Li Yang Chemical Co., Ltd..

Comparative example 7

Comparative example 7 of the invention provides a kind of preparation method of new vulcanizing system TPV material, and specific embodiment is the same as real Example 5 is applied, the difference is that, the hydrogenated styrene-butadiene block copolymer is made of linear SEBS and star SEBS, weight Amount is than being 1:10.

Comparative example 8

Comparative example 8 of the invention provides a kind of preparation method of new vulcanizing system TPV material, and specific embodiment is the same as real Example 5 is applied, the difference is that, the star SEBS is purchased from petrochemical industry Co., Ltd, Yueyang Ba Ling Huaxing, trade mark YH-604, viscosity For 1500mPas, the divine by astrology molar ratio of shape SEBS of butadiene is 66%.

Comparative example 9

Comparative example 9 of the invention provides a kind of preparation method of new vulcanizing system TPV material, and specific embodiment is the same as real Example 5 is applied, the difference is that, the ethylene propylene diene rubber is purchased from Dupont-Tao Shi, trade mark EPDM3640, Third monomer For ethylidene norbornene, the 1.8wt% of ethylene propylene diene rubber is accounted for, propylene accounts for the 43.2wt% of ethylene propylene diene rubber.

Comparative example 10

Comparative example 10 of the invention is the preparation method of general TPV material, is included the following steps:

(1) by the ethylene propylene diene rubber of 10 parts by weight, the butadiene rubber of 1.5 parts by weight, the white oil of 12 parts by weight, 2 weight Polypropylene, the graft polypropylene of 0.2 parts by weight, the hydrogenated styrene-butadiene block copolymer of 5 parts by weight, 0.05 weight of part Measure the antioxidant of part, the filler of 8 parts by weight, 0.3 parts by weight fungicide be added in mixer, mix and plasticates at 170 DEG C, it is crowded It is granulated out, obtains one step material of TPV material.

(2) vulcanization accelerator of the vulcanizing agent of 0.15 parts by weight, 0.2 parts by weight is uniformly mixed to stand-by, obtained component A.

(3) after mixing by the one step material of TPV material of step (1) preparation and component A, together from double screw extruder Main spout is added, and 200 DEG C of melting mixing is passed through in double screw extruder, and water cooled tie rod air-dries pelletizing and TPV material is made Material.

The butadiene rubber is purchased from Changzhou Heshan limited rubber company.

The filler is barium sulfate and calcium carbonate, mass ratio 1:2.

Performance evaluation

1, dynamic on-slip coefficient: by the preparation side of embodiment 1-6 and comparative example the 1-10 new vulcanizing system TPV material provided The TPV material that method is prepared is tested according to SATRA TM144, using ceramic tile as medium, applies defined loading, setting is specified Rubbing number and speed, to predict sole coefficient of friction, to determine the antiskid property of shoes.Sliding speed: (1.3 ± 0.03) m/ S tests the dynamic on-slip coefficient on dry and wet medium, the results are shown in Table 1.

2, processing performance: the preparation for the new vulcanizing system TPV material that the formula of embodiment 1-6 and comparative example 1-10 is provided Method, and phenomena such as observe the absorption of filler and additive in preparation process, the incipient scorch of glue, configuration of surface, bubble, and in spiral shell Bar squeeze out when extrudate expansion and contraction, to evaluate processing performance, and grade to processing performance, from it is excellent to difference be 1 ~5 grades, wherein 1 grade absorbs well for filler and additive, and without phenomena such as burning, the configuration of surface of glue is smooth, and 5 grades are filler Seriously uneven with the dispersions such as additive, incipient scorch phenomenon is serious, and the surface of glue is very coarse.

3, it wearability: prepared by the preparation method of embodiment 1-6 and comparative example the 1-10 new vulcanizing system TPV material provided Obtained TPV material according to GB/T-9867-2008 vulcanized rubber or thermoplastic elastomer wear-resisting property measurement (rotating roller cartridge type Abrasion machine method) it is tested, the speed of roller is (40 ± 1) r/min, and abrasion stroke is (40.0 ± 0.2) m, and test sample exists The volume worn amount for being rubbed and being generated on the gauze of certain rank measures wearability, and is divided into from high to low according to wearability It is excellent, good, qualified and unqualified, it the results are shown in Table 1.

4, tensile property is tested: by the preparation side of embodiment 1-6 and comparative example the 1-10 new vulcanizing system TPV material provided The TPV material that method is prepared is according to National Standard of the People's Republic of China GB/T528-2009 vulcanized rubber or thermoplastic elastomer Sample is made dumbbell shape I type sample and carries out tensile property test, test condition: environment by the measurement of tensile stress-strain performance Temperature (23 ± 2) DEG C, relative humidity (50 ± 2) %, test rate, 200mm/min, each sample test 5 times, and it is average to calculate it Value obtains tensile strength, elongation at break and 300% stretching strength, the results are shown in Table 2.

5, tearing strength: by the preparation method system of embodiment 1-6 and comparative example the 1-10 new vulcanizing system TPV material provided Standby obtained TPV material is torn according to the People's Republic of China's standard GB/T/T529-2008 vulcanized rubber or thermoplastic elastomer Sample is made square sample progress tearing strength test and uses pulling force in environment temperature (23 ± 2) DEG C by the measurement of intensity Testing machine, with the external force of notch in-plane is parallel on defined trousers shape sample, test speed is (500 ± 50) Power needed for sample tearing is obtained tearing strength, each sample test 5 divided by sample thickness until sample is torn by mm/min It is secondary, and its average value is calculated, it the results are shown in Table 2.

6, elastic restoration ratio: by the preparation method of embodiment 1-6 and comparative example the 1-10 new vulcanizing system TPV material provided The TPV material being prepared is restored according to the People's Republic of China's standard GB/T/the 17th partial elastic of T13477.10-2017 Rate measurement, tests the original width W that sample is made₀, sample is then packed into cupping machine with the speed of (5~6) mm/min Tensile sample, the width W after record test specimen stretching₁Width W after restoring with elasticity₂, and elastic restoration ratio R is calculated,Each sample test 5 times, calculates its average value, the results are shown in Table 2.

The test of 1 performance characterization of table

The test of 2 performance characterization of table

By Tables 1 and 2 test result it is found that the preparation method of new vulcanizing system TPV material provided by the invention is with excellent Different processing performance, the new vulcanizing system TPV material that the preparation method of the TPV material provided through the invention is prepared have height Dry and wet non-skid property, wear-resisting property and preferable mechanical property improve and be prepared and by the addition auxiliary agents such as fungicide TPV material anti-microbial property, in addition, passing through the survey of density, temperature tolerance to TPV material made from preparation method of the present invention etc. Examination finds that the TPV material obtained has lightweight and good resistance to low temperature.

Example above-mentioned is merely illustrative, and is used to explain the present invention some features of the method.Appended right is wanted The range as wide as possible for being intended to require to be contemplated that is sought, and embodiments as presented herein is only according to all possible implementation The explanation of the embodiment of the combined selection of example.Therefore, the purpose of applicant is that the attached claims are not illustrated this hair The exemplary selectional restriction of bright feature.Some numberical ranges used also include sub- model in the claims It encloses, the variation in these ranges should also be construed to be covered by the attached claims in the conceived case.

Claims

1. a kind of preparation method of new vulcanizing system TPV material, which is characterized in that the preparation of the new vulcanizing system TPV material Method includes at least:

(1) it plasticates: the butadiene rubber of the ethylene propylene diene rubber of 10 parts by weight, 1~5 parts by weight is added to single screw extrusion machine In, and the white oil of 5~14 parts by weight is added, it carries out rushing oil processing at 70~90 DEG C, obtains rubber components；

(2) it is kneaded: rubber components obtained in step (1) is added in double screw extruder, and 1~3 parts by weight are added Polypropylene, the graft polypropylene of 0.1~0.5 parts by weight, the hydrogenated styrene-butadiene block copolymer of 3~8 parts by weight, 0.1 The vulcanizing agent of~0.4 parts by weight, the vulcanization accelerator of 0.1~0.4 parts by weight, the antioxidant of 0.01~0.15 parts by weight, 3~12 The filler of parts by weight, and be kneaded at 165~200 DEG C, then it is granulated；

(3) vulcanize: pellet obtained in step (2) being subjected to thermoplastic shaping, and is vulcanized to obtain institute at 185~250 DEG C State TPV material；

2. the preparation method of new vulcanizing system TPV material according to claim 1, which is characterized in that in the step (1) White oil is 5~7 parts by weight, joined the white oil of 5~7 parts by weight in step (2) mixing process.

3. the preparation method of new vulcanizing system TPV material according to claim 1, which is characterized in that in the step (2) Mixing time is 5~30min, and roll spacing is 2~5mm.

4. the preparation method of new vulcanizing system TPV material according to claim 1, which is characterized in that the polypropylene exists 230 DEG C, the melt index under 2.16kg load is 8~12g/10min.

5. the preparation method of new vulcanizing system TPV material according to claim 1, which is characterized in that the butadiene rubber Account for 10~20wt% of the ethylene propylene diene rubber.

6. the preparation method of new vulcanizing system TPV material according to claim 1, which is characterized in that the EPDM The Third monomer of rubber is ethylidene norbornene, and content is 5~10wt% of ethylene propylene diene rubber.

7. the preparation method of new vulcanizing system TPV material according to claim 1, which is characterized in that the EPDM In rubber, propylene accounts for 36~45wt% of the ethylene propylene diene rubber.

8. the preparation method of new vulcanizing system TPV material according to claim 1, which is characterized in that the filler is barium Salt and calcium salt, weight ratio are 1:(1~3).

9. the preparation method of new vulcanizing system TPV material according to claim 1, which is characterized in that the calcium salt is carbon Sour calcium contains 30~50wt% modified calcium carbonate in the calcium carbonate.

10. the preparation method of new vulcanizing system TPV material described in any one according to claim 1~9, which is characterized in that The fungicide of 0.1~0.3 parts by weight is added in step (2) mixing process.