CN105367862A - Car sealing strip material TPV and preparation method thereof - Google Patents
Car sealing strip material TPV and preparation method thereof Download PDFInfo
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
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Abstract
A car sealing strip material TPV is prepared by from a vulcanization mixture by the dynamic vulcanization process, the vulcanization mixture comprises at least 100 parts by weight of vulcanizable elastomer, 50 to 200 parts by weight of thermoplastic polyolefin, 5 to 75 parts by weight of cross-linked polystyrene, 0.5-15 parts by weight of benzimidazole-modified graphene oxide and 0.5-15 parts by weight of a crosslinking agent, the cross-linked polystyrene repeating unit is styrene containing one sulfonic acid group. The car sealing strip material TPV has excellent sealing property, weather resistance and stability in use.
Description
Technical field
The present invention relates to Thermoplastic Vulcanizate (TPV) field, particularly automobile sealed billot TPV and preparation method thereof.
Background technology
Weather strip for automobile is the class accessory that automobile uses rubber mass maximum except tire, be mainly used in the position that the door and window of automobile, Cang Gai etc. exist gap, play the effects such as sealing, damping, sound insulation, decoration, prevent outside dust storm, rainwater, dust etc. from invading in car, to improve working life and the riding comfort of trolley part, though it is little that it accounts for automobile total cost, vital effect is played to the quality of automobile.
At present, as a kind of novel weather strip for automobile material, dynamic vulcanization EPDM/PP thermoplastic elastomer (EPDM/PP-TPV) is progressively replacing heat cured expendable EPDM.The feature of dynamic vulcanization EPDM/PP thermoplastic elastomer had both had elastomeric desirable physical mechanical property, has again the excellent processing characteristics of plastics, be easy to forming process, again recyclable recycling, make it to economize on resources and clean environment firendly.
But more there is the problems such as poor sealing, weathering resistance are poor, poor solvent resistance in existing automobile sealed billot TPV elastomerics, bring a lot of inconvenience to actual use.Therefore, the formula by improving TPV and production technique is starved of, to obtain the automobile sealed billot with sealing property excellence, good weatherability and stability in use excellence.
Summary of the invention
In order to solve the problems of the technologies described above, a first aspect of the present invention provides a kind of automobile sealed billot TPV, and described TPV is prepared through Technology of Dynamic Vulcanized by cured blend, and with parts by weight, described cured blend at least comprises:
Vulcanizable elastomer 100 parts;
TPO 50 ~ 200 parts;
Crosslinked polystyrene 5 ~ 75 parts;
Benzoglyoxaline modified graphene oxide 0.5 ~ 15 part;
Linking agent 0.5 ~ 15 part;
The structural formula of described crosslinked polystyrene is as follows:
Wherein, m, n are the integer being more than or equal to 2, R
1be selected from hydrogen, alkyl that carbonatoms is 1-5, containing at least one hydroxyl and carbonatoms be the alkyl of 1-5, carbonatoms is any one in the alkoxyl group of 1-5, R
2be selected from hydrogen or sulfonic acid group.
As the preferred technical scheme of one of the present invention, the degree of crosslinking of described crosslinked polystyrene is 0.5-50%.
More preferably, the degree of crosslinking of described crosslinked polystyrene is 5-25%.
As the preferred technical scheme of one of the present invention, the weight ratio of described crosslinked polystyrene and benzoglyoxaline modified graphene oxide is 5-10:1.
As the preferred technical scheme of one of the present invention, described benzoglyoxaline modified graphene oxide is prepared by the raw material comprising epoxy type silane coupling agent, benzimidazoles compound and graphene oxide.
As the preferred technical scheme of one of the present invention, the weight ratio of described benzimidazoles compound and graphene oxide is 5-20:1.
Described benzimidazoles compound is selected from benzoglyoxaline, 2-tolimidazole, 5-tolimidazole, 2-ethyl benzo imidazole, 2-propylbenzimidazole, 2-butyl benzoglyoxaline, 1, 2-dimethylbenzimidazole, 5, 6-dimethylbenzimidazole, 2-methylol benzoglyoxaline, 5-methoxybenzimidazol, 2-isopropyl benzene imipramine, 4-azabenzimidazoles, 2-hydroxybenzimidazole, 5-hydroxyl-2 tolimidazole, 1-phenylbenzimidazol, 2-Phenylbenzimidazole, 2-aminobenzimidazole, 4-aminobenzimidazole, 5-aminobenzimidazole, 1-Hydroxymethylbenzimidazole, 1-methyl-2-Phenylbenzimidazole, 1, 5-dimethyl-1H-benzoglyoxaline, 1, 6-dimethyl-1H-benzoglyoxaline, 1-pseudoallyl-1H-benzoglyoxaline, one or more in 2-(3-hydroxypropyl)-benzoglyoxaline.
As the preferred technical scheme of one of the present invention, described vulcanizable elastomer is ethene/a-alkene/polyene copolymer.
As the preferred technical scheme of one of the present invention, described cured blend also comprises the extending oil of 10-150 weight part.
A kind of automobile sealed billot, is prepared from through extrusion process by the automobile sealed billot TPV described in any one of claim 1-9 claim.
Know-why of the present invention: thermoplastic elastomer with TPO and vulcanizable elastomer for main component, at the mixing initial stage, crosslinked polystyrene is dispersed in vulcanizable elastomer rubber phase, benzoglyoxaline modified graphene oxide is dispersed in TPO, rubber phase generates crosslinking structure after dynamic vulcanization, imidazole group wherein in the sulfonic acid group of crosslinked polystyrene and benzoglyoxaline modified graphene oxide produces ionomer, cross-linking set between the chain of crosslinked generation and chain suppresses the slip between macromolecular chain, avoid the Relative sliding of molecule, reduce permanentset, improve the compression tension set performance of automobile sealed material TPV, and polystyrene in system and the benzoglyoxaline modified graphene oxide phenyl ring respectively containing electron rich, carboxyl, sulfonic group, at the high temperature of polyphosphoric acid, under vacuum-treat, carboxyl, sulfonic group can with phenyl ring generation friedel-crafts acylation, thus the degree of crosslinking of further raising system, form the TPV sulfuration mixed system with dual network structure.This special construction improves ageing-resistant, compression tension set performance and the stability in use energy of thermoplastic elastomer greatly.
Be easier to understand the above-mentioned of the application and other features, aspect and advantage with reference to following detailed description.
Embodiment
Unless otherwise defined, all technology used herein and scientific terminology have the identical implication usually understood with one skilled in the art of the present invention.When there is contradiction, be as the criterion with the definition in this specification sheets.
Term as used herein " by ... preparation " and " comprising " synonym.Term used herein " comprises ", " comprising ", " having ", " containing " or its other distortion any, be intended to cover the comprising of non-exclusionism.Such as, comprise the composition of listed elements, step, method, goods or device and need not be only limitted to those key elements, but other key element of clearly not listing or the intrinsic key element of this kind of composition, step, method, goods or device can be comprised.
Conjunction " by ... composition " get rid of any key element, step or the component do not pointed out.If in claim, this phrase will make claim be closed, make it not comprise material except those materials described, but except relative customary impurities.When phrase " by ... composition " to appear in the clause of claim main body instead of immediately preceding after theme time, it is only limited to the key element described in this clause; Other key element is not excluded outside described claim as a whole.
During the Range Representation that equivalent, concentration or other value or parameter limit with scope, preferable range or a series of upper limit preferred value and lower preferable values, this is appreciated that all scopes specifically disclosing and formed by arbitrary pairing of any range limit or preferred value and any range lower limit or preferred value, no matter and whether this scope separately discloses.Such as, when disclosing scope " 1 to 5 ", described scope should be interpreted as comprising scope " 1 to 4 ", " 1 to 3 ", " 1-2 ", " 1-2 and 4-5 ", " 1-3 and 5 " etc.When numerical range is described in this article, unless otherwise indicated, otherwise this scope intention comprises its end value and all integers within the scope of this and mark.
In addition, the indefinite article " one " before key element of the present invention or component and " one " are to quantitative requirement (i.e. occurrence number) unrestriction of key element or component.Therefore " one " or " one " should be read as and comprise one or at least one, and the key element of singulative or component also comprise plural form, unless the obvious purport of described quantity refers to singulative.
" polymkeric substance " means the polymerizable compound prepared by the monomer by being polymerized identical or different type.Generic term " polymkeric substance " comprises term " homopolymer ", " multipolymer ", " terpolymer " and " interpolymer ".
" multipolymer " means the polymkeric substance prepared by polymerization at least two kinds of different monomers.Generic term " interpolymer " comprises term " multipolymer " (it is generally in order to refer to the polymkeric substance prepared by two kinds of different monomers) and term " terpolymer " (it is generally in order to refer to the polymkeric substance prepared by three kinds of different monomers).It also comprises plants monomer and the polymkeric substance that manufactures by being polymerized four or more.
A kind of automobile sealed billot TPV, described TPV is prepared through Technology of Dynamic Vulcanized by cured blend, and with parts by weight, described cured blend at least comprises:
Vulcanizable elastomer 100 parts;
TPO 50 ~ 200 parts;
Crosslinked polystyrene 5 ~ 75 parts;
Benzoglyoxaline modified graphene oxide 0.5 ~ 15 part;
Linking agent 0.5 ~ 15 part;
vulcanizable elastomer
Elastomerics is the material experiencing significantly reversible deformation under relative low-stress.The general feature of elastomerics for have structure irregularity, non-polar conformations in polymer chain, or flexible unit.Vulcanizable elastomer is by ethene and at least one C
3-20the arbitrary combination of 'alpha '-olefin monomers and at least one polyenoid is made.Technician can easily for the combination of monomers that any required selection is suitable.In one preferably embodiment, described vulcanizable elastomer is ethene/a-alkene/polyene copolymer.
Alpha-olefin can be aliphatic series or aromatic substance, also such as, containing ethene unsaturated or ring compound, cyclobutene, cyclopentenes or norbornylene, can be included in 5 or 6 by C
1-20the norbornylene that alkyl replaces.Alpha-olefin is preferably C
1-20aliphatic cpd, are more preferably C
3-10aliphatic cpd, then be preferably C
3-8aliphatic cpd.
Alpha-olefin includes, but not limited to propylene, iso-butylene, 1-butylene, 1-amylene, 1-hexene, 3-Methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene and 1-laurylene and their mixture.Other ethylenically unsaturated monomers comprises 4 vinyl cyclohexene, vinyl cyclohexane, norbornadiene and their mixture.Most preferred alpha-olefin is propylene, 1-butylene, 1-hexene and 1-octene.The ethylene content of vulcanizable elastomer is preferably 40 to the 90wt% of mutual aggressiveness gross weight, more preferably 55wt% to 75wt%, most preferably 60wt% to 75wt%.
Polyenoid, is referred to as diolefine or diene monomers sometimes, is desirably non-conjugated diene hydrocarbon, but also can be conjugated diene.Non-conjugated diene hydrocarbon can be straight chain, side chain or cyclic hydrocarbon diene.
Non-conjugated diene, such as Isosorbide-5-Nitrae-hexadiene, 1,5-hexadiene, 1,6-octadiene and 1,9-decadiene;
Side chain acyclic diene, such as 2-methyl isophthalic acid, 5-hexadiene, 6-methyl isophthalic acid, 5-heptadiene, 7-methyl isophthalic acid, 6-octadiene, 3,7-dimethyl-1,6-octadienes, 3,7-dimethyl-1, the mixed isomers of 7-octadiene, 5,7-dimethyl-1,7-octadienes and dihydromyrcene;
Single ring alicyclic dienes, such as 1，4-cyclohexadiene, 1,5-cyclooctadiene and 1,5-ring 12 diene;
Many rings are alicyclic to be condensed and bridged ring diene, such as tetrahydroindene, methyl tetrahydroindene, Dicyclopentadiene (DCPD) (DCPD), dicyclo-(2,2,1) diene in-heptan-2,5-(norbornadiene or NBD), methyl norbornadiene;
Alkenyl, alkylidene group, cycloalkenyl group and ring alkylidene group norbornylene, such as 5-methylene-2-norbornene (MNB), 5-ethylidene-2-norbornene (ENB), 5-vinyl-2-norbornylene (VNB), 5-propenyl-2-norbornylene, 5-isopropylidene-2-norbornylene, 5-(4-cyclopentenyl)-2-norbornylene and 5-cyclohexylene-2-norbornylene.
When diene is conjugated diolefine, it can be 1,3-pentadiene, 1,3-butadiene, 2-methyl isophthalic acid, 3-divinyl, 4-methyl isophthalic acid, 3-pentadiene or 1，3-cyclopentadiene.
Diene is selected from ENB, VNB or NBD, is more preferably selected from ENB or VNB, is most preferably selected from the non-conjugated diene of ENB.What vulcanizable elastomer polyenic monomer content was preferably ethene and alpha-olefin mole number is greater than 0 to about 10% (% by mole).By weight, vulcanizable elastomer polyenic monomer content is converted to molar percentage limit, and can change according to the weight of polyenoid.Generally speaking, with the weighing scale of mutual aggressiveness, polyene content for being greater than 0 to 15wt%, more preferably 0.3 to 12wt%, most preferably 0.5 to 10wt%.
The preparation method of vulcanizable elastomer of the present invention can adopt those methods known in the field to prepare.
tPO
Any suitable thermoplastic material can be used as the thermoplasticity phase of TPV of the present invention.Thermoplastic material normally can at least at the softening temperature of material or the material of melting temperature molding or shaping and reprocessing.Polyolefine is preferred thermoplastic material.Polyolefine is the fundamental building block of polymer science and engineering, because the thermoplastic material low cost of producing based on petroleum chemistry and high-throughput.
TPO includes but not limited to homopolymer and the multipolymer of following monomer: a-alkene is as 1-butylene, 1-amylene, 1-hexene, 2-methyl-1-propylene, 3-Methyl-1-pentene, 4-methyl-1-pentene and 5-methyl isophthalic acid-hexene, and ethene, butylene and propylene, but the homopolymer of preferred propylene and multipolymer.
crosslinked polystyrene
Crosslinked polystyrene in the application refers to and carries out UV-light (UV) radiation treatment under vacuo to the polystyrene of sulfonation, thus the crosslinked polystyrene obtained.
The structural formula of described crosslinked polystyrene is as follows:
Wherein, m, n represent the number of repeating styrene units in molecule, be the integer being more than or equal to 2, and m, n are separate.R
1be selected from hydrogen, C
1-C
5alkyl or alkoxyl group, C containing at least one hydroxyl
1-C
5alkyl, R
2be selected from hydrogen or sulfonic acid group.In one embodiment, C
1-C
5alkyl or alkoxyl group include but not limited to, methyl, butyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, methoxyl group, oxyethyl group, isopropoxy, tert.-butoxy etc.In one preferably embodiment, R
1be selected from hydrogen, now the repeating unit of this crosslinked polystyrene is the vinylbenzene containing at least one sulfonic acid group.
UV-light (UV) irradiation can be used under vacuo to prepare crosslinked polystyrene: the polystyrene of sulfonation is placed on (~ 1 ╳ 10 in little vacuum cavity
-3holder), this vacuum cavity is provided with a quartz window.Adopt UV-light (λ=255nm, power=50W), be about at distance quartz window the polystyrene that sulfonation is irradiated at 10cm place, the polystyrene be cross-linked after irradiating 2-6h, can be obtained.
In one preferably embodiment, the reaction process of crosslinked polystyrene is as follows:
The Photogenerated Radicals obtained after treatment with ultraviolet light can be levied by FT-IR test chart and be confirmed ,-SO
3h group, c h bond ,-CH
2the disappearance of-key all can cause the powerful width in peak to reduce in corresponding beam location, and the crosslinked polystyrene generated both water insoluble, be also insoluble to organic solvent, therefore crosslinked polystyrene can be obtained by solvability testing authentication.
When preparing crosslinked polystyrene, usually adopting the polystyrene phenyl ring of styrene monomer repeating unit having a sulfonate substituent group, after treatment with ultraviolet light, obtaining partly sulfonated crosslinked polystyrene.The term " partly sulfonated crosslinked polystyrene " used in the application refer to sulfonation degree lower than 100% sulfonation crosslinked polystyrene, namely the benzene substitution in ring of some styrene monomer repeating units of styrenic cross-linked polymer has sulfonic group, and the phenyl ring of other styrene monomer repeating units of styrenic cross-linked polymer does not have sulfonic group.Sulfonation degree is defined as: the phenyl ring (being namely connected to a sulfonic phenyl ring) that sulfonation occurs in crosslinked polystyrene structure accounts for the per-cent of total phenyl ring number.
Sulfonation degree can calculate as follows:
Wherein
represent the mole number of sulfonic mole number and phenyl ring respectively.
If each phenyl ring replaces and has sulfonic group, then sulfonation degree=100%.The measurement of sulfonation degree can according to methods known in the art, such as volumetry and
1h-NMR etc. carry out.
Sulfonated polystyrene for the application can carry out sulfonation by sulfonated reagent to styrenic polymer and obtain.In one embodiment, the example that may be used for the sulfonated reagent of the application includes but not limited to, the vitriol oil, oleum, SO
3, acyl group sulphonate etc.
In above-mentioned sulfonation process, usually solvent can be used.Described solvent can comprise all kinds of SOLVENTS well known by persons skilled in the art, and such as, halogenated alkane is as chloroparaffin, and naphthenic hydrocarbon is as hexanaphthene etc.The vitriol oil also can use as solvent, now this vitriol oil itself or sulfonated reagent.
Sulfonated polystyrene for the application also can be commercially available.
In one preferably embodiment, the sulfonation degree of described crosslinked polystyrene is 0.5-50%.More preferably, the sulfonation degree of described crosslinked polystyrene is 5-25%.If the sulfonation degree of crosslinked polystyrene is too low, then joined in cured blend, make the elastomeric cross-linking density of final TPV smaller, thus to improving the DeGrain of compression tension set performance of automobile sealed material; If the sulfonation degree of crosslinked polystyrene is too high, cross-linking set between the chain produced when then this partly sulfonated crosslinked polystyrene and cured blend are cross-linked and chain is too much, cause the final elastomeric cross-linking density of TPV obtained too large, be unfavorable for the recovery of elasticity of TPV, be subject to compression set after External Force Acting comparatively large, cause the phenomenons such as poorly sealed, cold draining.
In one embodiment, the weight-average molecular weight that may be used for the crosslinked polystyrene of the application is about 500 ~ 3000 atomic mass units.If the molecular weight of crosslinked polystyrene is too low, Granular composite is mutually less, and particle diameter is less, and molecule segment is relatively short, and sub-chain motion is easy, cause the TPV elastomerics of final synthesis be difficult to obtain needed for intensity; On the other hand, if molecular weight is too high, then the melt temperature of crosslinked polystyrene is higher than curing temperature, cause its processing fluidity in sulfidation poor, and the reactive force between cured blend is more weak, make the final elastomeric cross-linking density of TPV obtained smaller, thus obviously cannot improve the compression tension set performance of automobile sealed material.
It should be noted that, in this manual, weight-average molecular weight uses gel permeation chromatography (GPC) retention time (retention volume) that measures, the retention time (retention volume) of polystyrene standard known for the molecular weight measured under identical conditions is converted into the molecular weight of polystyrene and the value of trying to achieve.Specifically, as gel permeation chromatography device, use 4 " TSKgelG-SWXL ", " TSKgelG-2000SWXL ", " TSKgelG-3000SWXL " and " TSKgelG-4000SWXL " (trade(brand)name, be Japanese Dong Caoda company to produce), differential refractometer is used, moving phase: tetrahydrofuran (THF), measure temperature: 40 DEG C, measure under the condition of flow velocity: 1mL/min as detector.
Adding of crosslinked polystyrene both can introduce sulfonic acid group, provided and for crosslinked group, can be improved again solvent resistance and the thermostability of cured blend, thus provide beneficial effect of the present invention by the crosslinking structure of polystyrene.
benzoglyoxaline modified graphene oxide
Benzoglyoxaline modified graphene oxide in the application refers to and carries out graft modification process with benzoglyoxaline to graphene oxide, comprises and uses the benzimidazoles compound modified graphene oxide of single component or use other components to coordinate modified graphene oxide with benzimidazoles compound.
The benzimidazoles compound that may be used for the application comprises various compound well known by persons skilled in the art, the example includes but not limited to, benzoglyoxaline, 2-tolimidazole, 5-tolimidazole, 2-ethyl benzo imidazole, 2-propylbenzimidazole, 2-butyl benzoglyoxaline, 1, 2-dimethylbenzimidazole, 5, 6-dimethylbenzimidazole, 2-methylol benzoglyoxaline, 5-methoxybenzimidazol, 2-isopropyl benzene imipramine, 4-azabenzimidazoles, 2-hydroxybenzimidazole, 5-hydroxyl-2 tolimidazole, 1-phenylbenzimidazol, 2-Phenylbenzimidazole, 2-aminobenzimidazole, 4-aminobenzimidazole, 5-aminobenzimidazole, 1-Hydroxymethylbenzimidazole, 1-methyl-2-Phenylbenzimidazole, 1, 5-dimethyl-1H-benzoglyoxaline, 1, 6-dimethyl-1H-benzoglyoxaline, 1-pseudoallyl-1H-benzoglyoxaline, one or more in 2-(3-hydroxypropyl)-benzoglyoxaline.In one preferably embodiment, described benzimidazoles compound is benzoglyoxaline.
In one embodiment, described benzoglyoxaline modified graphene oxide is prepared by the raw material comprising epoxy type silane coupling agent, benzimidazoles compound and graphene oxide.
Described benzoglyoxaline modified graphene oxide can adopt following synthetic method:
(1) preparation of epoxy silane modification benzimidazole compound
In the there-necked flask of complete drying, add benzoglyoxaline 10 parts, epoxy type silane coupling agent 1 ~ 30 part and appropriate good solvent, under protection of inert gas after stir about 30min, be heated to about 75 ~ 85 DEG C react about 2h after, be down to room temperature, solution poured in methyl alcohol, has Precipitation; After filtering after removing solvent with methyl alcohol repetitive scrubbing, in vacuum drying oven, dry about 22 ~ 24h at about 50 DEG C, obtain the benzimidazole compound of epoxy silane modification;
(2) preparation of benzoglyoxaline modified graphene oxide
By the benzimidazole compound 50 parts of epoxy silane modification obtained for step (1), and graphene oxide 5 ~ 10 parts adds in deionized water, add appropriate bases and regulate PH to 8 ~ 10, after ultrasonic about 30min, at about 65 ~ 75 DEG C after stirring reaction about 80 ~ 100min, add appropriate hydrochloric acid again, regulate PH to 1 ~ 2, after proton exchange is about 24h, then neutralize this solution, suction filtration also, after removing solvent, obtains benzoglyoxaline modified graphene oxide.
Above material number used is weight part.
In cured blend, adding of benzoglyoxaline modified graphene oxide both can by the introducing of imidazoles, made the sulfonic acid group of itself and crosslinked polystyrene produce particle and was cross-linked, effectively improve the cross-linking density of TPV system; The introducing of imidazoles, graphene oxide can be passed through again, improve intensity and the ageing-resistant performance of sealing billot, therefore beneficial effect of the present invention is provided.
The weight ratio of benzimidazoles compound and graphene oxide, has material impact to the effect that benzoglyoxaline modified graphene oxide plays in cured blend.In one preferably embodiment, the weight ratio of described benzimidazoles compound and graphene oxide is 5-20:1.If the weight ratio of benzimidazoles compound and graphene oxide is too low, large percentage then shared by graphene oxide, though the intensity of TPV system can be improved, but can interformational sliding be there is under external force, between macromolecular chain, recovery of elasticity is poor, Compression Set is comparatively large, easily causes poorly sealed; If the weight ratio of benzimidazoles compound and graphene oxide is too high, there is after joining vulcanization system more fragrant heterocycle structure, imidazoles and sulfonic acid group form stronger molecular chain intermolecular forces, though the intensity of the final TPV obtained significantly can be promoted, but affect the elastomeric processing characteristics of TPV in sulfidation.
Cross-linking density meeting influence elastane recoverability, the compression permanentset performance of further influence elastane body, and the cross-linking density that can be controlled vulcanization system by the add-on ratio regulating and controlling crosslinked polystyrene and benzoglyoxaline graphene oxide.
As the preferred technical scheme of one of the present invention, the weight ratio of described crosslinked polystyrene and benzoglyoxaline modified graphene oxide is 5-10:1.If the weight ratio of crosslinked polystyrene and benzoglyoxaline modified graphene oxide is too high, then the cross-linking density of vulcanization system is lower, when sealing material TPV is subject to stronger External Force Acting, cross-linking system easily ruptures, and compression tension set performance is poor, stability in use is poor; If the weight ratio of polystyrene and benzoglyoxaline modified graphene oxide is too low, then the cross-linking density of vulcanization system is too high, and cause melt viscosity large, processing fluidity is poor, particle size uniformity and particle distribution uniformity reduce greatly, make material performance uniformity variation everywhere.
linking agent
Any substantially do not degrade and/or to solidify under the thermoplastic polymer that is used in TPV can the linking agent of curing elastomer, all can be used in the specific embodiment of the present invention.Preferred linking agent is resol.Other solidifying agent comprises, but be not restricted to superoxide, nitrine, aldehyde-amine reaction product, the xanthate of the urea of vinyl silanes graft, replacement, the guanidine of replacement, replacement, the dithiocarbamate of replacement, thiazole, imidazoles, sulfinyl amine, thiuram disulfide, paraquinonedioxime, dibenzo paraquinonedioxime, sulphur.Certainly, more than one combination can also to be selected in above-mentioned solidifying agent.
Suitable superoxide as linking agent comprises, but be not limited to aromatics diacyl peroxide, aliphatics diacyl peroxide, dibasic acid peroxides, ketone peroxide, alkyl peroxyesters, alkyl hydroperoxide (such as diacetyl peroxide, dibenzoyl peroxide, two-2, 4-dichlorobenzoyl peroxide, two-tert-butyl peroxide, dicumyl peroxide, TBPB tertiary butyl perbenzoate, tert-butyl cumyl peroxide, 2, 5-bis(t-butylperoxy)-2, 5-dimethylhexane, 2, 5-bis(t-butylperoxy)-2, 5-dimethylhexyne-3, 4, 4, 4 ', 4 '-four-(t-butylperoxy)-2, 2-dicyclohexyl propane, 1, 4-pair-(tert butylperoxyisopropyl)-benzene, 1, 1-pair-(t-butylperoxy)-3, 3, 5-trimethyl-cyclohexane, lauroyl peroxide, succinic acid peroxide, Cyclohexanone peroxides, t-butyl peracetate ester, butyl hydroperoxide etc.
extending oil
As the preferred technical scheme of one of the present invention, described cured blend also comprises the extending oil of 10 ~ 150 weight parts.
Described extending oil can select aromatics mineral oil, naphthenic mineral oils, paraffin class mineral oil, preferred paraffin class mineral oil.In addition, preferred molecular-weight average is 300 ~ 1500.Add extending oil amount depend on required character, its upper limit depends on the consistency of concrete oil and blend composition, when the extending oil of excessive outflow occurs, namely beyond this restriction.
other
Various additive can be contained within the scope without prejudice to the object of the present invention.As the object lesson of additive, the various oxidation inhibitor such as phenol oxidation inhibitor, Phosphorus oxidation inhibitor, sulfur type antioxidant can be enumerated; The various thermo-stabilizers such as hindered amines thermo-stabilizer; The various UV light absorber such as Benzophenones UV light absorber, Benzotriazole Ultraviolet Stabilizer, benzoate UV light absorber; The various static inhibitor such as non-ionic antistatic agent, cationic antistatic agent, anionic antistatic agent; The various dispersion agents such as bisamide class dispersion agent, paraffin class dispersion agent, organo-metallic salt dispersion agent; The various chlorine scavenger such as the metal carboxylate chlorine scavenger of alkaline earth salt; The various lubricants such as amides lubricant, paraffin class lubricant, organic metal salt series lubricant agent, ester lubricant; The various decomposition agents such as oxide-based decomposition agent, hydrotalcite decomposition agent; The various metal passivators such as hydrazine metalloid passivator, amine metal passivator; The various fire retardants such as brominated organic fire retardant, phosphoric acid based flame retardant, ANTIMONY TRIOXIDE SB 203 99.8 PCT, magnesium hydroxide, red phosphorus; The various inorganic fillers such as talcum powder, mica, clay, calcium carbonate, aluminium hydroxide, magnesium hydroxide, barium sulfate, glass fibre, carbon fiber, silicon-dioxide, Calucium Silicate powder, potassium titanate, wollastonite; Organic filler; Pigment dyestuff; Mineral dye; Inorganic antiseptic; Organic antibacterial agent etc.
technology of Dynamic Vulcanized
Dynamic vulcanization, relative to " static state " sulfuration, term " dynamically " means during vulcanisation step, and mixture is subject to shear action.
TPV general dynamic vulcanization, is prepared by fusion plasticity and curing rubber.Cured blend is prepared, as mixed in the mixing equipment such as Banbury mixer, forcing machine by any method for mixed rubber polymkeric substance suitably.In the step coordinated, fusion tradition ancillary component.This type of ancillary component can comprise carbon black and other filler of one or more types, such as clay, silicon-dioxide etc., tackifier, wax etc., zinc oxide, antioxidant, antiozonant, processing aid and solidification activator.By heating solidification in about 5 minutes to about 60 minutes at about 150 DEG C to about 200 DEG C, to form TPV.
vacuum forming technique
As those forming methods that moulding process of the present invention can adopt this area common; as blow molding, injection moulding and vacuum forming; the TPV obtained due to the present invention contains sulfonic group, carboxyl; by vacuum and polyphosphoric acid process; again can be cross-linked with the phenyl ring generation friedel-crafts acylation in benzoglyoxaline; make the TPV of acquisition have dual network structure, thus greatly improve ageing-resistant, compression tension set performance and the stability in use of thermoplastic elastomer.
As the preferred technical scheme of one, the present invention adopts vacuum forming technique, and vacuum forming is often called plastic uptake, is a kind of plastic processing, and cardinal principle is by after open and flat sheet material heating deliquescing, adopts vacuum suck in die surface, cooling aftershaping.In vacuum forming process, the moisture on TPV surface leaves TPV quickly in vacuum environment, friedel-crafts acylation is occurred more effective.
The term " vacuum forming " used in the application, refer to rely on vacuum pump by vacuum state between mould and thermoforming sheet (plate) material of heating, cause sheet (plate) material to produce pressure reduction up and down, thus make sheet material tightly note overlay on the shaping method of die surface.Vacuum forming can be divided into single formpiston (punch) single former (die), without several forms such as moulds.Vacuum forming of the present invention can adopt following several concrete moulding process.
Vacuum forming over amale mold also known as punch vacuum forming, the shaping or vacuum forming of covering vacuum.Its technological process is plastics sheet folder frame clamping post-heating, and the aperture vacuumized is opened on punch surface, after sheet material is softening, folder frame moves down or punch moves, and sheet material is stretched, and all round to contact and after sealing to folder frame with punch, punch vacuumizes, and it is shaping that pressure reduction makes sheet material note overlay on convex mould surface.Through cooling and shaping, air blowing mould release, obtains product after finishing.
Female mould vacuum forming also known as die vacuum forming, directly or simple forming.Its technological process be sheet clamping on die, die lower curtate die cavity has the aperture vacuumized, and die is vacuum chamber, is again forming cavity.Sheet material is by after thermal softening, and die vacuumizes, and the pressure official post sheet material of normal atmosphere and vacuum is stretched and is close on concave die cavity shaping, and after cooling and shaping, air blowing mould release, through repairing and obtaining product.
Vacuum forming without mould claims mould-free forming, also known as free forming.This forming method is used in the various hood-shaped body of blowing.
More electedly, the present invention adopts female mould vacuum forming technique or vacuum forming over amale mold technique.
The invention still further relates to and provide a kind of automobile sealed billot, described automobile sealed billot TPV is prepared from through extrusion process.
Hereinafter, by embodiment, the present invention is explained in more detail, but should be understood that these embodiments are only illustrative and nonrestrictive.If do not have other to illustrate, raw materials used is all commercially available.
Embodiment:
Embodiment 1, a kind of automobile sealed billot TPV, described TPV is prepared through Technology of Dynamic Vulcanized by cured blend, and with parts by weight, described cured blend at least comprises:
Vulcanizable elastomer 100 parts;
TPO 50 ~ 200 parts;
Crosslinked polystyrene 5 ~ 75 parts;
Benzoglyoxaline modified graphene oxide 0.5 ~ 15 part;
Linking agent 0.5 ~ 15 part;
The structural formula of described crosslinked polystyrene is as follows:
Wherein, m, n are the integer being more than or equal to 2, R
1be selected from hydrogen, C
1-C
5alkyl or alkoxyl group, C containing at least one hydroxyl
1-C
5alkyl, R
2be selected from hydrogen or sulfonic acid group.In one embodiment, C
1-C
5alkyl or alkoxyl group include but not limited to, methyl, butyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, methoxyl group, oxyethyl group, isopropoxy, tert.-butoxy etc.
R in described crosslinked polystyrene
1, R
2be hydrogen, the repeating unit of polystyrene is the vinylbenzene containing a sulfonic acid group.
The sulfonation degree of described crosslinked polystyrene is 0.5-50%.
The weight-average molecular weight of described crosslinked polystyrene is about 500 ~ 3000 atomic mass units.
Described benzoglyoxaline modified graphene oxide is prepared by the raw material comprising epoxy type silane coupling agent, benzimidazoles compound and graphene oxide.Wherein, the weight ratio of described benzimidazoles compound and graphene oxide is 5-20:1.
Described benzimidazoles compound is selected from benzoglyoxaline, 2-tolimidazole, 5-tolimidazole, 2-ethyl benzo imidazole, 2-propylbenzimidazole, 2-butyl benzoglyoxaline, 1, 2-dimethylbenzimidazole, 5, 6-dimethylbenzimidazole, 2-methylol benzoglyoxaline, 5-methoxybenzimidazol, 2-isopropyl benzene imipramine, 4-azabenzimidazoles, 2-hydroxybenzimidazole, 5-hydroxyl-2 tolimidazole, 1-phenylbenzimidazol, 2-Phenylbenzimidazole, 2-aminobenzimidazole, 4-aminobenzimidazole, 5-aminobenzimidazole, 1-Hydroxymethylbenzimidazole, 1-methyl-2-Phenylbenzimidazole, 1, 5-dimethyl-1H-benzoglyoxaline, 1, 6-dimethyl-1H-benzoglyoxaline, 1-pseudoallyl-1H-benzoglyoxaline, one or more in 2-(3-hydroxypropyl)-benzoglyoxaline.
Described benzimidazoles compound is benzoglyoxaline.
The weight ratio of described crosslinked polystyrene and benzoglyoxaline modified graphene oxide is 5-10:1.
Described cured blend also comprises the extending oil of 10 ~ 150 weight parts.
A kind of automobile sealed billot, described automobile sealed billot TPV is prepared from through vacuum forming technique.
Hereinafter, by embodiment, the present invention is explained in more detail, but should be understood that these embodiments are only illustrative and nonrestrictive.If do not have other to illustrate, raw materials used is all commercially available.
The present invention is described in detail referring to several example.
A: ethylene/alpha-olefin/polyene copolymer
B: TPO
C: crosslinked polystyrene, it has following formula structure:
C1: crosslinked polystyrene (R
1for methyl, R
2for hydrogen, sulfonation degree is 5%, and relative molecular mass is 1000)
C2: crosslinked polystyrene (R
1for oxyethyl group, R
2for hydrogen, sulfonation degree is 5%, and relative molecular mass is 1000)
C3: crosslinked polystyrene (R
1for methylol, R
2for hydrogen, sulfonation degree is 5%, and relative molecular mass is 1000)
C4: crosslinked polystyrene (R
1for hydrogen, R
2for sulfonic group, sulfonation degree is 5%, and relative molecular mass is 1000)
C5: crosslinked polystyrene (R
1for hydrogen, R
2for hydrogen, sulfonation degree is 5%, and relative molecular mass is 1000)
C6: crosslinked polystyrene (R
1for hydrogen, R
2for hydrogen, sulfonation degree is 0.5%, and relative molecular mass is 500)
C7: crosslinked polystyrene (R
1for hydrogen, R
2for hydrogen, sulfonation degree is 5%, and relative molecular mass is 500)
C8: crosslinked polystyrene (R
1for hydrogen, R
2for hydrogen, sulfonation degree is 25%, and relative molecular mass is 500)
C9: crosslinked polystyrene (R
1for hydrogen, R
2for hydrogen, sulfonation degree is 50%, and relative molecular mass is 500)
C10: crosslinked polystyrene (R
1for hydrogen, R
2for hydrogen, sulfonation degree is 50%, and relative molecular mass is 3000)
D1: benzoglyoxaline modified graphene oxide (benzimidazoles compound is benzoglyoxaline, and the weight ratio of benzoglyoxaline and graphene oxide is 5:1)
D2: benzoglyoxaline modified graphene oxide (benzimidazoles compound is 2-tolimidazole, and the weight ratio of benzoglyoxaline and graphene oxide is 10:1)
D3: benzoglyoxaline modified graphene oxide (benzimidazoles compound is 1-Hydroxymethylbenzimidazole, and the weight ratio of benzoglyoxaline and graphene oxide is 20:1)
D4: benzoglyoxaline modified graphene oxide (benzimidazoles compound is benzoglyoxaline, and the weight ratio of benzoglyoxaline and graphene oxide is 3:1)
D5: benzoglyoxaline modified graphene oxide (benzimidazoles compound is benzoglyoxaline, and the weight ratio of benzoglyoxaline and graphene oxide is 25:1)
E: linking agent
F: extending oil
Other: tin protochloride; Thermo-stabilizer is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and three (2,4-di-t-butyl) phenyl-phosphite composite (mass ratio 1:1); Zinc oxide selects rubber grade zinc oxide, purity 99.7%, comes from Hengshan Mountain, Anqiu chemical company; Zinic stearas selected by lubricant, middle vast and boundless chemical industry YT-500.
The preparation of crosslinked polystyrene
The polystyrene of sulfonation is placed on (~ 1 ╳ 10 in little vacuum cavity
-3holder), this vacuum cavity is provided with a quartz window.Adopt UV-light (λ=255nm, power=50W), be about at distance quartz window the polystyrene that sulfonation is irradiated at 10cm place, the polystyrene be cross-linked after irradiating 2-6h, can be obtained.
The preparation of benzoglyoxaline modified graphene oxide
(1) preparation of epoxy silane modification benzimidazole compound
In the there-necked flask of complete drying, add benzoglyoxaline 10 parts, epoxy type silane coupling agent 5 parts and appropriate good solvent, under protection of inert gas after stir about 30min, be heated to about 80 DEG C react about 2h after, be down to room temperature, solution poured in methyl alcohol, has Precipitation; After filtering after removing solvent with methyl alcohol repetitive scrubbing, in vacuum drying oven, dry about 24h at about 50 DEG C, obtain the benzimidazole compound of epoxy silane modification;
(2) preparation of benzoglyoxaline modified graphene oxide
By the benzimidazole compound 50 parts of epoxy silane modification obtained for step (1), and graphene oxide 5 parts adds in deionized water, add appropriate bases and regulate PH to 8 ~ 10, after ultrasonic about 30min, after stirring reaction is about 80min at about 70 DEG C, add appropriate hydrochloric acid again, regulate PH to 2, after proton exchange is about 24h, then neutralize this solution, suction filtration also, after removing solvent, obtains benzoglyoxaline modified graphene oxide.
Above material number used is weight part.
Preparation method:
By the benzoglyoxaline modified graphene oxide mixing and stirring of the TPO of 50-200 weight part, 0.5-15 weight part, by the crosslinked polystyrene of 100 weight part vulcanizable elastomers, 5-75 weight part and the linking agent mixing and stirring of 0.5 ~ 10 weight part, or add other components further, as, the zinc oxide of 1.5 weight part tin protochlorides, 1 weight part, the stablizer of 0.5 weight part, the Zinic stearas of 2 weight parts weighs up, and pours agitator into and stirs.Join in the hopper of twin screw extruder by the material mixed separately, the extending oil of 10-150 weight part joins forcing machine by microprocessor pump drive from the fluxing zone of forcing machine, and through melt blending, extruding pelletization becomes matrix material.Wherein, screw rod each heating region temperature arranges and is respectively: district's temperature: 160 DEG C; 2nd district: 170 DEG C; 3rd district: 180 DEG C; 4th district: 170 DEG C; Head: 180 DEG C; The residence time 2 ~ 3min.Pressure is 14MPa.
Performing leak test:
The main performance index of sealing material is tensile strength, compression rebound rate and creep relaxation rate, and wherein compression rebound rate and creep relaxation rate have reacted the sealing property of material.The electronic universal tester Instron3367 that compression recovery performance manufactures in Instron Corporation of Britain according to ASTMF36-99 standard tests; Creep relaxation rate is tested on special gasket material creep relaxation testing table according to GB/T12621-1990 standard B kind test method.
Weathering resistance is tested:
Weather resistance: according to the program of the SA method of JISK6266, carries out degeneration experiment to sealing billot.By sealed strip charge level to structural carbon arc lamp light source, experimental temperature 63 DEG C, this light of continuous irradiation, and water is sprayed on the sealing billot of pad, circulation in every 102 minutes 18 minutes, annealing time is 96 hours.Constant strain fatigue experiment is carried out to each the sealing billot sample after experiment of degenerating, at 20 DEG C, with the circulation of 6.7Hz, 40% is applied to sample repeat elongation strain, and evaluate its endurance quality.The terminal evaluated is considered to when splitting in the surface sealing billot.Repeat fatigue and cyclic with 1,000 ten thousand times to stop evaluating.
Embodiment:
As can be seen from the above data, with do not use crosslinked polystyrene, benzoglyoxaline modified graphene oxide and do not adopt preparation method provided by the present invention to prepare product compared with, sealing billot prepared by the present invention is while having excellent seal performance, also have excellent weather resistance concurrently, because herein is provided Advantageous Effects of the present invention.
Aforesaid example is only illustrative, for explaining some features of feature of the present disclosure.Appended claim is intended to the scope wide as far as possible that requirement it is contemplated that, and the embodiment presented herein is only the explanation of the embodiment of the selection of combination according to all possible embodiment.Therefore, the purpose of applicant is the selectional restriction that appended claim is not illustrated the example of feature of the present invention.And progress in science and technology is not replaced to be formed due to the inaccurate reason of language performance by the possible equivalent considered at present or son, and these changes also should be interpreted as being covered by appended claim in the conceived case.
Claims (10)
1. an automobile sealed billot TPV, is characterized in that, described TPV is prepared through Technology of Dynamic Vulcanized by cured blend, and with parts by weight, described cured blend at least comprises:
Vulcanizable elastomer 100 parts;
TPO 50 ~ 200 parts;
Crosslinked polystyrene 5 ~ 75 parts;
Benzoglyoxaline modified graphene oxide 0.5 ~ 15 part;
Linking agent 0.5 ~ 15 part;
The structural formula of described crosslinked polystyrene is as follows:
，
Wherein, m, n are the integer being more than or equal to 2, R
1be selected from hydrogen, alkyl that carbonatoms is 1-5, containing at least one hydroxyl and carbonatoms be the alkyl of 1-5, carbonatoms is any one in the alkoxyl group of 1-5, R
2be selected from hydrogen or sulfonic acid group.
2. automobile sealed billot TPV according to claim 1, is characterized in that, the sulfonation degree of described crosslinked polystyrene is 0.5-50%.
3. automobile sealed billot TPV according to claim 1, is characterized in that, the sulfonation degree of described crosslinked polystyrene is 5-25%.
4. automobile sealed billot TPV according to claim 1, is characterized in that, the weight ratio of described crosslinked polystyrene and benzoglyoxaline modified graphene oxide is 5-10:1.
5. automobile sealed billot TPV according to claim 1, is characterized in that, described benzoglyoxaline modified graphene oxide is prepared by the raw material comprising epoxy type silane coupling agent, benzimidazoles compound and graphene oxide.
6. automobile sealed billot TPV according to claim 5, is characterized in that, the weight ratio of described benzimidazoles compound and graphene oxide is 5-20:1.
7. automobile sealed billot TPV according to claim 5, it is characterized in that, described benzimidazoles compound is selected from benzoglyoxaline, 2-tolimidazole, 5-tolimidazole, 2-ethyl benzo imidazole, 2-propylbenzimidazole, 2-butyl benzoglyoxaline, 1, 2-dimethylbenzimidazole, 5, 6-dimethylbenzimidazole, 2-methylol benzoglyoxaline, 5-methoxybenzimidazol, 2-isopropyl benzene imipramine, 4-azabenzimidazoles, 2-hydroxybenzimidazole, 5-hydroxyl-2 tolimidazole, 1-phenylbenzimidazol, 2-Phenylbenzimidazole, 2-aminobenzimidazole, 4-aminobenzimidazole, 5-aminobenzimidazole, 1-Hydroxymethylbenzimidazole, 1-methyl-2-Phenylbenzimidazole, 1, 5-dimethyl-1H-benzoglyoxaline, 1, 6-dimethyl-1H-benzoglyoxaline, 1-pseudoallyl-1H-benzoglyoxaline, one or more in 2-(3-hydroxypropyl)-benzoglyoxaline.
8. automobile sealed billot TPV according to claim 1, is characterized in that, described vulcanizable elastomer is ethene/a-alkene/polyene copolymer.
9. automobile sealed billot TPV according to claim 1, it is characterized in that, described cured blend also comprises the extending oil of 10-150 weight part.
10. an automobile sealed billot, is prepared from through extrusion process by the automobile sealed billot TPV described in any one of claim 1-9 claim.
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| CN108981121A (en) * | 2018-05-25 | 2018-12-11 | 广州市设计院工程建设总承包公司 | Air-conditioning system installation method |
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Application publication date: 20160302 |