CN103709527B - A kind of macromole expanding material and its production and use - Google Patents

A kind of macromole expanding material and its production and use Download PDF

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CN103709527B
CN103709527B CN201310727383.8A CN201310727383A CN103709527B CN 103709527 B CN103709527 B CN 103709527B CN 201310727383 A CN201310727383 A CN 201310727383A CN 103709527 B CN103709527 B CN 103709527B
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epdm
rubber
expanding material
broken
nbr
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CN103709527A (en
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夏迎松
章于川
严江威
李方山
朱宝林
吴兵
张海潮
陈晋阳
杨兆苇
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ANHUI ANDA ZHONGDING RUBBER TECHNOLOGY DEVELOPMENT Co Ltd
Anhui Zhongding Sealing Parts Co Ltd
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ANHUI ANDA ZHONGDING RUBBER TECHNOLOGY DEVELOPMENT Co Ltd
Anhui Zhongding Sealing Parts Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C08F255/06—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms on to ethene-propene-diene terpolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/02—Heterophasic composition

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

The invention discloses a kind of macromole expanding material and its production and use, wherein the general structure of macromole expanding material is:

Description

A kind of macromole expanding material and its production and use
One, technical field
The present invention relates to a kind of expanding material and its production and use, specifically a kind of for two kinds of blend rubbers and expanding material of used time and preparation method thereof, be mainly used in the blended increase-volume of terpolymer EP rubber and paracril.
Two, background technology
The main chain of terpolymer EP rubber (EPDM) is saturated chain, nonpolarity substituting group in molecular chain, and kindliness is good, is a kind of saturated amorphism rubber, has high chemical stability.The molecular structure of EPDM determines it and has following good performance:
1, ageing-resistant performance is excellent, has outstanding ozone resistance, weathering resistance, higher thermostability, generally can at 150 DEG C life-time service, at 200 DEG C, interval uses.Lower temperature resistance is also relatively good;
2, resistance to medium is good, has good stability to various polar chemical medicine;
3, there is excellent electrical insulating property, outstanding corona resistance, and water-absorbent is little.
But EPDM is Shortcomings equally also, there is not polar group in EPDM main chain, therefore the non-constant of its oil-proofness, autohension and mutual viscosity is low, not easily with unsaturated rubber covulcanization, time blended and the consistency of polar material not good.
Having many uses of EPDM is general, mainly for the manufacture of the insulation sheath of automobile rubber component, electric wire and sheath, building and water-proof material and various industry and civilian rubber item etc.
Paracril (NBR) is unsaturated carbon chains rubber, containing double bond on main chain, simultaneously containing the polarity side base cyano group-CN that electronegativity is very large, so NBR has:
The oils of 1, excellent resistance to nonpolar and low-pole and solvent, and increase with acrylonitrile content, oil-proofness is better, but low-temperature performance is poor, and reduces with butadiene content, and winter hardiness declines;
2, thermotolerance and ageing-resistant performance are better, because the strong electron attraction of-CN, make the hydrogen in allylic positions more stable, therefore increase thermotolerance with acrylonitrile content and ageing resistance improves, it can below 120 DEG C life-time service, heatproof can reach 150 DEG C in short-term.
3, chemical resistance is better, has good resistance to alkali and weak acid, but not powerful oxidation corrosion resistance acid.
Paracril mainly for the manufacture of oil-resistant article, solvent resistant rubber item, as oil sealing, oil pipe, oil lining, packing ring, oil resistant adhesive tape adhesive plaster, diaphragm of rubber and large-scale oil sac etc.
According to the relative theory of superpolymer blending and modifying, if EPDM and NBR is carried out blended and uses, be the disperse phase order of magnitude of the general phase domain size (in submicron to micro-scaled range) if can be formed with NBR, EPDM is the morphological structure of the microphase-separated of external phase, so co-mixing system is by the premium properties of major embodiment external phase EPDM, disperse phase NBR then can play modifying function to external phase EPDM simultaneously, namely improve its oil-proofness, thus the range of application of EPDM can be expanded.But due to EPDM(δ=16 (J/cm 3) 1/2left and right) and NBR(δ=18-21 (J/cm 3) 1/2) the two solubility parameter difference is comparatively large, belong to thermodynamics Immiscible Polymer Blends, simple mechanical blend can present Phase Separating Morphology that is larger, even macroscopic view, and the physical and mechanical properties after blend compounds sulfuration is very poor.If develop the expanding material that compatibilization is excellent, make NBR in EPDM external phase, present the morphological structure of microphase-separated, then can give full play to the synergistic effect of the two advantage, obtain oil-proofness and be better than EPDM, high-low temperature resistant, resistance to ozone, the blending and modifying elastomeric material that weather-proof, ageing resistance is better than NBR, make EPDM/NBR blend compounds have wide application field more.
Three, summary of the invention
The present invention aims to provide a kind of macromole expanding material and its production and use, technical problem to be solved selects suitable structure by molecular designing to prepare macromole expanding material, the consistency between terpolymer EP rubber (EPDM) and paracril (NBR) mechanical blend can be improved, formation is disperse phase with NBR, EPDM is external phase, the morphological structure of the blended blend compounds of microphase-separated, thus both maintained the premium properties of EPDM, which in turn improve its oil resistance, widen the Application Areas of terpolymer EP rubber EPDM further.
Along with further developing of graft copolymerization technology, graft copolymerization has become the modification to macromolecular material, and carries out a kind of important means of surface-treated to some material.Graft copolymer itself is except can as except the new modified macromolecular material of one, and grafting density and the suitable A-g-B type graft copolymer of side chain length, can also as superpolymer P awith superpolymer P bblending and modifying, respond well non-reacted expanding material.Simultaneously they rely in its macromolecular structure to contain and blend components P aand P bidentical polymer chain, thus can at P aand P b" emulsification " or " coupling " effect is played at two-phase interface place, and the two consistency is improved.
The structure of the macromole expanding material that the present invention selects carries out to EPDM macromole the graft copolymer EPDM-g-PAN that graft polymerization reaction obtains with acrylonitrile monemer (AN), on the main chain of EPDM, namely connected the macromole of some amount, polyacrylonitrile different in size (PAN) side chain.
The general structure of macromole expanding material of the present invention is:
Wherein, m represents the number of structural unit ethene in molecular structure; N represents the number of structural unit propylene in molecular structure; X represents the number of structural unit vinyl cyanide in molecular structure; R is Third monomer ethylidene norbornene;
The percentage of grafting of described macromole expanding material vinyl cyanide is 15-25%; M:n:x=1:0.53-0.63:0.15-0.28.
The preparation method of macromole expanding material of the present invention, operates according to the following steps:
1) EPDM broken-(down)rubber and solvent S1 are added in reactor, dissolving is stirred in 50-70 DEG C, then 65-75 DEG C is warming up to, monomer A N(polymerization-grade is dripped in the protection downhill reaction still of rare gas element, stopper except), the mixing solutions of initiator and solvent S2, in 65-75 DEG C of stirring reaction 2-4h after dripping off, after reaction terminates, be cooled to room temperature; Described rare gas element is nitrogen, carbonic acid gas or argon gas; Stirring velocity in this step reaction process is 100-200rpm/min; The quality of described monomer A N is the 60-120% of described EPDM broken-(down)rubber quality;
2) reaction solution that step 1) obtains is transferred in separating still, precipitation agent is added under stirring, make product EPDM-g-PAN and the polyacrylonitrile (PAN) co-precipitation generated due to the homopolymerization of part AN and separated from solvent, underpressure distillation, except being washed by solid sediment after desolventizing, filtering and drying, obtains crude product;
3) described crude product is through extraction agent extraction purification, removes homopolymerization products PAN, then after washing, filtration and drying, obtains macromole expanding material EPDM-g-PAN successively.
The broken-(down)rubber of EPDM described in step 1) be in two roller mill by EPDM rubber and peptizer blended, at 50-70 DEG C, thin-pass is to mooney viscosity ML 1+4(125 DEG C) are 21-23, obtain EPDM broken-(down)rubber.Obtained EPDM broken-(down)rubber is cut into small pieces so that follow-up dissolving in solvent S1.
Described peptizer is selected from 2, one or more in 2'-dibenzamidodiphenyl disulfide (BASS), dibenzoyl thiophenol zinc salt (BASZ), pentachlorothiophenol (PCTP), xylenethiol (TX), rubber peptizer HTA, the addition of described peptizer is the 0.5-2.0% of described EPDM rubber quality.
The mooney viscosity ML1+4(125 DEG C of described EPDM rubber) be 28-33, ethylene content is 48-52%.
Initiator described in step 1) is selected from benzoyl peroxide (BPO), dilauroyl peroxide (LPO) or peroxidation (4-toluyl) (MBPO), and addition is the 1.0-5.0% of described EPDM broken-(down)rubber quality.
The S of solvent described in step 1) 1for one or more in normal heptane, chloroform, toluene, dimethylbenzene, hexanaphthene, consumption is 10-15 times of described EPDM broken-(down)rubber quality;
The S of solvent described in step 1) 2be selected from one or more in toluene, dimethylbenzene, tetracol phenixin, chloroform, consumption is the 50-70% of described EPDM broken-(down)rubber quality.
Step 2) described in precipitation agent be selected from acetone, butanone, methyl alcohol, ethanol one or both, the addition of described precipitation agent be the 5-6 of described EPDM broken-(down)rubber quality doubly.
Step 2) described in extraction agent be selected from N, N '-dimethyl formamide (DMF), N, N '-N,N-DIMETHYLACETAMIDE (DMA) or dimethyl sulfoxide (DMSO) (DMSO).
The purposes of macromole expanding material of the present invention, is characterized in that: described macromole expanding material terpolymer EP rubber and paracril blended time as the application of expanding material.
Because ethylene-propylene rubber(EPR) is formed by ethene and propylene polymerization, its molecular backbone chain is completely saturated, can not sulfur cross-linking be realized, therefore introduce the dienes such as ethylidene norbornene (ENB) or dicyclopentadiene (DCPD) in building-up process as vulcanization crosslinking point more, be called Third monomer.The Third monomer of the present invention's EPDM rubber used is ethylidene norbornene (ENB), and content is 7.2-8.0%.
The syntheti c route of macromole expanding material of the present invention is as follows:
The object that solution moulded by EPDM rubber by the present invention is the molecular weight in order to reduce EPDM, and one is to increase EPDM dissolution degree in a solvent, improves degree and the percentage of grafting of EPDM and AN graft reaction; Two be EPDM molecular weight reduce be conducive to synthesize macromole expanding material EPDM-g-PAN disperse in what rubber unvulcanizate when EPDM and NBR mechanical blending, and non-reacted increase-volume is formed on the interface of disperse phase and external phase, impel the morphological structure forming less, the kinetically relatively stable microphase-separated in phase domain, the mechanism of its increase-volume can represent with Fig. 1.
The solution graft polymerization of EPDM broken-(down)rubber and monomer A N is the core preparing EPDM-g-PAN expanding material.Add the fracture that peptizer can accelerate EPDM rubber macromolecular main chain, reduce the molecular weight of EPDM, make it dissolve in solvent S1 better; Monomer A N and initiator are dissolved in solvent S2, are mixed with solution and progressively drip, and make it be distributed to more equably in broken-(down)rubber solution and cause free yl graft polymerization, are conducive to improving being uniformly distributed of percentage of grafting and polyacrylonitrile (PAN) side chain graft site and size; Inert atmosphere can the inhibition of anti-block, ensures that free yl graft polymerization reaction is normally carried out; Due under the initiation of initiator primary group of free radicals, also can there is autohemagglutination and generate homopolymer polypropylene nitrile PAN in partial monosomy AN.Use extraction agent extraction purification, the PAN homopolymer be wrapped in solid sediment can be removed, obtain comparatively pure macromole expanding material.By changing consumption and the reaction conditions of various component in EPDM broken-(down)rubber and solution thereof, the macromole expanding material that percentage of grafting is different with a chain size can be obtained.
Compared with the prior art, beneficial effect of the present invention is embodied in:
1, the main chain of macromole expanding material EPDM-g-PAN of the present invention is ethylene-propylene diene copolymer, and side chain is polyacrylonitrile (PAN).Because EPDM is the rare mechanism of reacting with random copolymers and the AN free yl graft polymerization of propylene of second, the position of PAN side chain grafting and number are depended on, and sequence main chain being easily initiated the propylene structural unit generating tertiary carbon free radical distributes and the consumption of initiator, and side chain is different in size, and limited percentage of grafting also illustrate that PAN side chain can not be oversize.The macromolecular molecular structure feature of this graftomer, determine it except having the characteristics such as the stability of the saturated main chain of ethylene-propylene random copolymer, kindliness and low-pole, it also has the PAN side chain of strong polarity, and this is just with to its and serves characteristic.Such as: intermolecular Interaction enhanced, glass transition temperature Tg, melt temperature Tm raise, the performance of the oil plant of resistance to petroleum base and benzene series non-polar solvent improves, with compatible (molten) property increase etc. of polar polymer, polar solvent, more valuable is impart to have " amphiphilic ", namely its main chain and nonpolar or low-pole polymkeric substance such as EPDM can affinity, compatible, and side chain then can with polar polymer as NBR affinity, compatible.The present invention make use of its this " amphiphilic " just, and designs its expanding material as EPDM and NBR.
2, macromole expanding material of the present invention to the blended of EPDM and NBR and the used time there is good compatibilization.When ratio of quality and the number of copies is EPDM:NBR:EPDM-g-PAN=(60-70): (40-30): time (5-6), the microphase-separated heterogeneous structure form of the dynamic stabilization that it is external phase that blended rubber is formed with EPDM, NBR is disperse phase, thus after making blended rubber sulfuration, both the high-low temperature resistant of EPDM, resistance to ozone, weather-proof, ageing-resistant premium properties had been maintained, simultaneously because disperse phase NBR is to the synergistic effect of external phase EPDM modification, turn improve its oil-proofness.
Four, accompanying drawing explanation
Fig. 1 is the mechanism schematic diagram of macromole expanding material EPDM-g-PAN increase-volume EPDM/NBR blending and modifying of the present invention.
Fig. 2 is attenuated total reflectance attenuated total refraction (ATR) the Fourier transform infrared spectroscopy figure of macromole expanding material of the present invention.As can be seen from Fig. 2, infrared absorption wavelength 1375cm -1place is-CH on EPDM molecular chain 3scissoring vibration absorption peak, 2921cm -1and 2852cm -1for the methyl (-CH of EPDM 3) and methylene radical (-CH 2-) hydrocarbon stretching vibration absorption peak, 2239cm -1for the stretching vibration absorption peak of the feature of-CN.A series of macromole expanding material should be the graft copolymer (EPDM-g-PAN) of terpolymer EP rubber and acrylonitrile monemer as seen from Figure 2.
Fig. 3 is the blended and DSC curve of used time of EPDM and NBR, and wherein curve a does not add the DSC curve that expanding material records, and curve b is the DSC curve recorded after adding macromole expanding material of the present invention, and curve a is identical with the compounding conditions of curve b sample.The temperature that the curve left side marks is the Tg of EPDM, and the right is the Tg of NBR.As can be seen from Figure 3, along with adding of expanding material, the difference Δ Tg of the second-order transition temperature of two rubber phase EPDM and NBR diminishes, and when not adding expanding material, Δ Tg is 23.9 DEG C, and when adding expanding material, Δ Tg is reduced into 19.2 DEG C.This illustrates that expanding material enhances two alternate interface interactions, and make the consistency increase that two is alternate, microfacies dispersiveness improves, and make two-phase second-order transition temperature bringing together, macromole expanding material of the present invention serves compatibilization effect.
Fig. 4 is EPDM/NBR Blend rubber (figure a, mass ratio: EPDM/NBR=70/30) and EPDM/NBR/EPDM-g-NBR Blend rubber (figure b, mass ratio: EPDM/NBR/EPDM-g-AN=70/30/6) ultrathin section(ing) through osmium tetroxide solution dyeing after transmission electron microscope photo, wherein dark parts is the imaging of NBR phase, and light-colored part is the imaging of EPDM phase region.As can be seen from Figure 4, macromole expanding material of the present invention NBR disperse phase is disperseed in EPDM external phase evenly, raise also less mutually.Do not add NBR phase in the sample of expanding material to assemble significantly, and add NBR after macromole expanding material and form microphase-separated, phase size mostly≤2 μm, illustrate that macromole expanding material EPDM-g-PAN of the present invention serves compatibilization really.
Five, embodiment
Embodiment 1:
1) in two roller mill by EPDM rubber and peptizer BASS blended, at 65 DEG C, thin-pass is to mooney viscosity ML 1+4(125 DEG C) are 21.3, obtain EPDM broken-(down)rubber.Obtained EPDM broken-(down)rubber is cut into small pieces so that follow-up dissolving in a solvent.The addition of peptizer BASS is 0.3% of EPDM rubber quality.
The mooney viscosity ML of described EPDM rubber 1+4(125 DEG C) are 28, and ethylene content is 48%, and Third monomer is norbornylene ENB content is 7.8%.
2) EPDM broken-(down)rubber 5g and normal heptane 25g and toluene 30g is added in reactor, dissolving is stirred in 50 DEG C, then 70 DEG C are warming up to, the mixing solutions of monomer A N6g, initiator B PO0.15g and solvent toluene 2.5g is dripped in nitrogen atmosphere protection downhill reaction still, 10min drips off, in 70 DEG C of stirring reaction 2.5h after dripping off, after reaction terminates, be cooled to room temperature; Stirring velocity in this step reaction process is 100rpm/min;
3) by step 2) reaction solution that obtains is transferred in separating still, precipitation agent acetone is added under stirring, make product EPDM-g-PAN and the polyacrylonitrile (PAN) co-precipitation generated due to the homopolymerization of part AN and separated from solvent, underpressure distillation, except being washed by solid sediment after desolventizing, filtering and vacuum-drying, obtains crude product;
4) described crude product is through extraction agent DMF extraction purification, removes homopolymerization products PAN, then after washing, filtration and drying, obtains macromole expanding material EPDM-g-PAN successively, and percentage of grafting is 24%.
Embodiment 2:
1) in two roller mill by EPDM rubber and peptizer PCTP blended, at 60 DEG C, thin-pass is to mooney viscosity ML 1+4(125 DEG C) are 22.6, obtain EPDM broken-(down)rubber.Obtained EPDM broken-(down)rubber is cut into small pieces so that follow-up dissolving in a solvent.The addition of peptizer PCTP is 0.2% of EPDM rubber quality.
The mooney viscosity ML of described EPDM rubber 1+4(125 DEG C) are 28, and ethylene content is 48%, and Third monomer is norbornylene ENB content is 7.8%.
2) EPDM broken-(down)rubber 5g and solvent xylene 50g is added in reactor, dissolving is stirred in 60 DEG C, then 70 DEG C are warming up to, the mixing solutions of monomer A N6g, initiator B PO0.15g and solvent toluene 2.5g is dripped in nitrogen atmosphere protection downhill reaction still, 15min drips off, in 70 DEG C of stirring reaction 3h after dripping off, after reaction terminates, be cooled to room temperature; Stirring velocity in this step reaction process is 100rpm/min;
3) by step 2) reaction solution that obtains is transferred in separating still, precipitation agent methanol is added under stirring, make product EPDM-g-PAN and the polyacrylonitrile (PAN) co-precipitation generated due to the homopolymerization of part AN and separated from solvent, underpressure distillation, except being washed by solid sediment after desolventizing, filtering and vacuum-drying, obtains crude product;
4) described crude product is through extraction agent DMA extraction purification, removes homopolymerization products PAN, then after washing, filtration and drying, obtains macromole expanding material EPDM-g-PAN successively, and percentage of grafting is 21%.
Embodiment 3:
1) in two roller mill by EPDM rubber and peptizer BASS blended, at 50 DEG C, thin-pass is to mooney viscosity ML 1+4(125 DEG C) are 23, obtain EPDM broken-(down)rubber.Obtained EPDM broken-(down)rubber is cut into small pieces so that follow-up dissolving in a solvent.The addition of peptizer BASS is 0.2% of EPDM rubber quality.
The mooney viscosity ML of described EPDM rubber 1+4(125 DEG C) are 28, and ethylene content is 48%, and Third monomer is norbornylene ENB content is 7.8%.
2) EPDM broken-(down)rubber 5g and tetracol phenixin 35g and toluene 25g is added in reactor, dissolving is stirred in 56 DEG C, then 75 DEG C are warming up to, the mixing solutions of monomer A N5g, initiator LPO0.2g and solvent toluene 3g is dripped in argon gas atmosphere protection downhill reaction still, 10min drips off, in 75 DEG C of stirring reaction 3h after dripping off, after reaction terminates, be cooled to room temperature; Stirring velocity in this step reaction process is 100rpm/min.
3) by step 2) reaction solution that obtains is transferred in separating still, methyl alcohol and ethanol (volume ratio 1:1) mixed precipitant is added under stirring, make product EPDM-g-PAN and the polyacrylonitrile (PAN) co-precipitation generated due to the homopolymerization of part AN and separated from solvent, underpressure distillation, except being washed by solid sediment after desolventizing, filtering and vacuum-drying, obtains crude product;
4) described crude product is through extraction agent DMA extraction purification, removes homopolymerization products PAN, then after washing, filtration and drying, obtains macromole expanding material EPDM-g-PAN successively, and percentage of grafting is 18%.
Embodiment 4:
1) in two roller mill by EPDM rubber and peptizer PCTP blended, at 55 DEG C, thin-pass is to mooney viscosity ML 1+4(125 DEG C) are 21.8, obtain EPDM broken-(down)rubber.Obtained EPDM broken-(down)rubber is cut into small pieces so that follow-up dissolving in a solvent.The addition of peptizer PCTP is 0.4% of EPDM rubber quality.
The mooney viscosity ML of described EPDM rubber 1+4(125 DEG C) are 28, and ethylene content is 48%, and Third monomer is norbornylene ENB content is 7.8%.
2) EPDM broken-(down)rubber 5g and dimethylbenzene 35g and chloroform 30g is added in reactor, dissolving is stirred in 55 DEG C, maintain the temperature at 70 DEG C, monomer A N4g, initiator MBPO0.2 gram is dripped in nitrogen atmosphere protection downhill reaction still, 15min drips off, in 70 DEG C of stirring reaction 2.5h after dripping off, after reaction terminates, be cooled to room temperature; Stirring velocity in this step reaction process is 100rpm/min;
3) by step 2) reaction solution that obtains is transferred in separating still, precipitation agent butanone is added under stirring, make product EPDM-g-PAN and the polyacrylonitrile (PAN) co-precipitation generated due to the homopolymerization of part AN and separated from solvent, underpressure distillation, except being washed by solid sediment after desolventizing, filtering and vacuum-drying, obtains crude product;
4) described crude product is through extraction agent DMSO extraction purification, removes homopolymerization products PAN, then after washing, filtration and drying, obtains macromole expanding material EPDM-g-PAN successively, and percentage of grafting is 20%.
[performance test]
1, testing location: Anhui Anda Zhongding Rubber Technology Development Co., Ltd.
2, method for making sample: first by the time of Banbury mixer, temperature and rotary speed parameter are set to 10min respectively, 140 DEG C and 70rpm/min, by EPDM rubber after temperature and stabilization of speed, NBR rubber (acrylonitrile content is 33 ~ 40%) and macromole expanding material EPDM-g-PAN join in Banbury mixer according to the ratio of mass ratio 70:30:6, epoxy glue (needing refinement) is taken out after 10min, afterwards by obtained epoxy glue in the mill being connected with water coolant, conventionally add softening agent DOS in turn, anti-aging agent RD, reinforcement system N330, vulcanization system ZnO, SA, DM, S-60, DCP, to be mixed evenly after roll spacing is adjusted to minimum, thin-pass plays triangle bag 8 times, adjusts bottom sheet after roll spacing to about 3mm clot 6 times, obtains EPDM/NBR/EPDM-g-PAN Blend rubber.
By Blend rubber press vulcanization on vulcanizing press, cure conditions is 170 DEG C × 10min, cuts test sample according to the regulation of GB2941-2006.
3, testing method: stretching and tear resistance test the regulation according to GB528-1982, draw speed 500mm/min; Shore a hardness test, according to the regulation of GB/T531, tests thickness 6mm; Resistance to ASTM3 #oil performance test is according to the regulation of GB/T1690-92, and immersion oil condition is 100 DEG C × 70h.
4, test-results
Macromole expanding material of the present invention is application in EPDM and NBR also uses, and the results are shown in Table 1.
Table 1EPDM-g-PAN at EPDM and NBR and with in application result and comparing
* fill a prescription (mass parts): EPDM/NBR100, RD2, N33040, ZnO5, SA1, DCP3, S-601, DM1.5, DOS2.1.
* EPDM rubber and NBR(acrylonitrile content are 33% ~ 40%) rubber and ratio be EPDM/NBR=70/30.
* NE-2, NE-3, NE-4 be this serial macromole expanding material make the trade mark by oneself, the macromole expanding material of respectively corresponding embodiment 1, embodiment 2 and embodiment 3 preparation, its addition is all account for rubber total amount 6%.
As can be seen from Table 1, large all than EPDM/NBR Blend rubber of the tensile strength of EPDM cross-linked rubber and elongation at break, this is because the poor compatibility of EPDM and NBR, the adding of NBR makes two-phase disperse uneven, the covulcanization degree of blend compounds is little, causes intensity and elongation at break to reduce; But after add this serial macromole expanding material in EPDM/NBR Blend rubber, expanding material enhances two alternate interface interactions, make two alternate attractions stronger, so the performances such as tensile strength all obtain corresponding raising.
The oil resistance of EPDM cross-linked rubber is poor, this is because its main chain saturated chain and there is not polar group, but after EPDM and NBR also uses, NBR to add the EPDM cross-linked rubber making the oil-proofness of Blend rubber more independent good, this is because NBR is unsaturated carbon chains rubber, containing double bond on main chain, simultaneously containing the polarity side base cyano group-CN that electronegativity is very large, so oil-proofness is good, simultaneously this serial macromole expanding material add the covulcanization degree adding two-phase, the cross-linking density of Blend rubber is further increased, two combine more tight, thus oil resistance is more excellent.

Claims (5)

1. a preparation method for macromole expanding material, is characterized in that operating according to the following steps:
1) EPDM broken-(down)rubber and solvent S1 are added in reactor, dissolving is stirred in 50-70 DEG C, then 65-75 DEG C is warming up to, the mixing solutions of monomer A N, initiator and solvent S2 is dripped in the protection downhill reaction still of rare gas element, in 65-75 DEG C of stirring reaction 2-4h after dripping off, after reaction terminates, be cooled to room temperature; Described rare gas element is nitrogen, carbonic acid gas or argon gas; The quality of described monomer A N is the 60-120% of described EPDM broken-(down)rubber quality; Described solvent S1 is normal heptane, and consumption is 10-15 times of described EPDM broken-(down)rubber quality; Described solvent S2 is selected from one or more in toluene, dimethylbenzene, tetracol phenixin, chloroform, and consumption is the 50-70% of described EPDM broken-(down)rubber quality; Described EPDM broken-(down)rubber be in two roller mill by EPDM rubber and peptizer blended, at 50-70 DEG C, thin-pass is to mooney viscosity ML 1+4be 21-23 when 125 DEG C, obtain EPDM broken-(down)rubber; The mooney viscosity ML of described EPDM rubber 1+4be 28-33 when 125 DEG C, ethylene content is 48-52%;
2) by step 1) reaction solution that obtains is transferred in separating still, adds precipitation agent under stirring, and underpressure distillation, except being washed by solid sediment after desolventizing, filtering and dry, obtains crude product;
3) described crude product is through extraction agent extraction purification, then after washing, filtration and drying, obtains macromole expanding material EPDM-g-PAN successively;
The general structure of described macromole expanding material is:
Wherein, m represents the number of structural unit ethene in molecular structure; N represents the number of structural unit propylene in molecular structure; X represents the number of structural unit vinyl cyanide in molecular structure; R is Third monomer ethylidene norbornene;
The percentage of grafting of described macromole expanding material vinyl cyanide is 15-25%; M:n:x=1:0.53-0.63:0.15-0.28.
2. preparation method according to claim 1, is characterized in that:
Described peptizer is selected from one or more in 2,2'-dibenzamidodiphenyl disulfide, pentachlorothiophenol, xylenethiol, rubber peptizer HTA, and the addition of described peptizer is the 0.5-2.0% of described EPDM rubber quality.
3. preparation method according to claim 1, is characterized in that:
Step 1) described in initiator be selected from benzoyl peroxide, dilauroyl peroxide or peroxidation (4-toluyl), addition is the 1.0-5.0% of described EPDM broken-(down)rubber quality.
4. preparation method according to claim 1, is characterized in that:
Step 2) described in precipitation agent be selected from acetone, butanone, methyl alcohol, ethanol one or both, the addition of described precipitation agent be the 5-6 of described EPDM broken-(down)rubber quality doubly.
5. preparation method according to claim 1, is characterized in that:
Step 3) described in extraction agent be selected from N, N '-dimethyl formamide, N, N '-N,N-DIMETHYLACETAMIDE or dimethyl sulfoxide (DMSO).
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101649030A (en) * 2009-07-17 2010-02-17 金发科技股份有限公司 Method of preparing ethylene propylene diene monomer graft polymer through solution grafting copolymerization and application thereof
CN102304074A (en) * 2011-06-21 2012-01-04 聊城大学 Method for preparing rubber peptizing agent, namely 2,2'-dibenzamido diphenyl disulfide compound

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Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101649030A (en) * 2009-07-17 2010-02-17 金发科技股份有限公司 Method of preparing ethylene propylene diene monomer graft polymer through solution grafting copolymerization and application thereof
CN102304074A (en) * 2011-06-21 2012-01-04 聊城大学 Method for preparing rubber peptizing agent, namely 2,2'-dibenzamido diphenyl disulfide compound

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
三元乙丙橡胶溶液接枝丙烯腈;张卫英 等;《弹性体》;20000930;第10卷(第3期);第18页第1栏第10-15行、1.1主要原料、第2栏1.2接枝共聚及后处理,第19页第1栏倒数第1-2段，第20页第1栏第4-8行，表1，表3 *

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