CN105367978A - TPE composition and liquor bottle stopper prepared from TPE composition - Google Patents
TPE composition and liquor bottle stopper prepared from TPE composition Download PDFInfo
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- CN105367978A CN105367978A CN201510795322.4A CN201510795322A CN105367978A CN 105367978 A CN105367978 A CN 105367978A CN 201510795322 A CN201510795322 A CN 201510795322A CN 105367978 A CN105367978 A CN 105367978A
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Abstract
The present invention discloses a TPE composition which comprises 100 parts by weight of MAH-g-SEBS, 40-80 parts by weight of MAH-g-PP, 10-20 parts by weight of sulfonated SEBS, 1-15 parts by weight of hyperbranched polyamide intercalated montmorillonite and 30-50 parts by weight of white oil. The present invention also discloses a good air impermeability liquor bottle stopper prepared from the TPE composition.
Description
Technical field
The invention belongs to technical field of polymer materials, more specifically, the present invention relates to a kind of TPE composition and the good white wine bottle stopper of resistance to air loss therefrom.
Background technology
Thermoplastic elastomer TPE(ThermoplasticElastomer) be a kind of snappiness, high strength, high resilience with rubber, having again can the material of injection molding feature.TPE has environment-protecting asepsis safety, durometer level is wide, has excellent tint permanence, soft-touch, weathering resistance, fatigue resistance and temperature tolerance, processing characteristics is superior, need not the plurality of advantages such as sulfuration, therefore, as a kind of novel multifunctional environment friendly material, TPE has boundless application market, as household electrical appliance, sports goods, automotive material, medicine equipment, construction industry and shoe industry etc.At present, TPE material generally with thermoplastic elastomer hydrogenated styrene-butadiene-styrene block copolymers (SEBS), thermoplastics polypropylene and some suitable fillers be raw material preparation obtain.The hydrogenation completely of SEBS elastomer block, makes it have excellent weather resistance, has good tolerance, also make it have resistance to low temperature to ozone, ultraviolet, electric arc, still keeps the features such as good snappiness under-60 DEG C of conditions.Although SEBS has excellent caoutchouc elasticity, excellent weathering resistance, lower temperature resistance, environmental-protecting performance etc., but be separately with there are some problems using SEBS as elastomer material, if SEBS is compared with traditional vulcanized rubber, there is the shortcomings such as rigidity is excessive, compression set is large, density is high; Its use temperature upper limit and the aspect such as solvent resistance, oil-proofness are usually all not as good as conventional vulcanized rubbers etc.Employing is added other components in the elastomer and is carried out modification to elastomerics, is that exploitation has one of optimal path of the novel high polymer elastomer material of over-all properties.Use PP modified SEBS, the melt viscosity of SEBS can be reduced on the one hand, make SEBS be easy to processing; Effectively can improve the mechanical property of SEBS elastomer system on the other hand.In addition, PP is cheap, can reduce the cost of SEBS elastomer material.Therefore, filler being applied in the polymer can be improved the mechanical property of material and thermomechanical property to a certain extent, meanwhile, filler add the cost also greatly reducing material, become more economical and practical.
When TPE uses as white wine bottle stopper, requirement has good elasticity, intensity, resistance to air loss and environmental-protecting performance, also needs to reduce production cost, therefore simultaneously, be starved of by formula and the improvement of production technique, develop a kind of resistance to air loss better and the TPE white wine bottle stopper of environmental protection.
Summary of the invention
In order to solve the problem, first aspect of the present invention provides a kind of TPE composition, and it comprises:
The MAH-g-SEBS of 100 weight parts;
The MAH-g-PP of 40 ~ 80 weight parts;
The sulfonated SEBS of 10 ~ 20 weight parts;
The ultrabranching polyamide intercalated montmorillonite of 1 ~ 15 weight part; With
The white oil of 30 ~ 50 weight parts;
Wherein, described ultrabranching polyamide is the spherical ultrabranching polyamide of carboxy blocking; Described polynite is amination polynite.
In one embodiment, the loading capacity of described sulfonated SEBS is 0.3 ~ 1.0.
In one embodiment, in described ultrabranching polyamide intercalated montmorillonite, the weight ratio of ultrabranching polyamide and polynite is 1 ~ 5:10.
In one embodiment, the weight-average molecular weight of described ultrabranching polyamide is: 5000 ~ 30000.
In one embodiment, the weight-average molecular weight of described ultrabranching polyamide is: 10000 ~ 20000.
In one embodiment, the weight-average molecular weight of described ultrabranching polyamide is: 12000.
In one embodiment, in described ultrabranching polyamide intercalated montmorillonite, it also comprises containing amino POSS; The weight ratio of described ultrabranching polyamide, polynite and POSS is 1 ~ 5:10:0.5 ~ 3.
In one embodiment, it also comprises the silica nanosphere of 1 ~ 3 weight part; The nanometer sphere diameter of described silica nanosphere is 0.5 ~ 1.2nm.
Another aspect of the present invention provides a kind of white wine bottle stopper, it uses described TPE composition.
The preparation method providing again described white wine bottle stopper on the other hand of the present invention, comprising:
(1) after described raw material being mixed by weight, through double-screw extruding pelletizing;
(2) product that step (1) obtains is placed on 30 ~ 60 DEG C of hot air type hopper inner dryings 1 ~ 4 hour;
(3) by the product of step (2) gained, in 160 ~ 210 DEG C of vacuum injections in mould, and under vacuum, keep this injection temperature after 3 ~ 15 hours, then cooling curing, obtain the white wine bottle stopper that resistance to air loss is good.
Be easier to understand the above-mentioned of the application and other features, aspect and advantage with reference to following detailed description.
Embodiment
The detailed description of the following preferred implementation method of the present invention of participation in the election and the embodiment comprised can more easily understand content of the present invention.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 to 2 ", " 1 to 2 and 4 to 5 ", " 1 to 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.
Singulative comprises plural number and object is discussed, unless clearly indicated in addition in context." optional " or " any one " refer to that the item that describes thereafter or event can occur or not occur, and this description comprises situation that event occurs and the situation that event does not occur.
Approximate term in specification sheets and claims is used for modifying quantity, represents that the present invention is not limited to this concrete quantity, also comprises close to this quantity acceptable and can not cause the part of the correction of the change of relevant basic function.Accordingly, modify a numerical value with " approximately ", " about " etc., mean and the invention is not restricted to this exact numerical.In some example, approximate term may correspond to the precision of the instrument measuring numerical value.In present specification and claims, scope limits and can combine and/or exchange, if do not illustrate that these scopes comprise contained all subranges therebetween in addition.
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 ".
" interpolymer " 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." blend " mean two or more polymkeric substance by physics or the method for chemistry jointly mix and the polymkeric substance formed.
First aspect of the present invention provides a kind of TPE composition, is prepared from by the raw material comprising following weight part:
The MAH-g-SEBS of 100 weight parts;
The MAH-g-PP of 40 ~ 80 weight parts;
The sulfonated SEBS of 10 ~ 20 weight parts;
The ultrabranching polyamide intercalated montmorillonite of 1 ~ 15 weight part; With
The white oil of 30 ~ 50 weight parts;
Wherein, described ultrabranching polyamide is the spherical ultrabranching polyamide of carboxy blocking; Described polynite is amination polynite.
MAH-g-PP：
In this specification sheets, term " MAH-g-PP " refers to maleic anhydride (MAH) graft modification polypropylene (PP), and the MAH-g-PP as raw material of the present invention is not particularly limited, and can be commercially available acquisition, also can pass through solution method, supercritical CO
2the method synthesis well-known to those skilled in the art such as solution method, scorification, radiation method and solid phase method obtains.Wherein, when solution method carries out PP grafting MAH, the graft reaction time is long, and grafting efficiency is low, needs to consume poisonous, flammable solvent in a large number, and production cost is high, large to human injury, contaminate environment, takes up an area large, is difficult to realize continuous operation.Therefore, preferably scorification is adopted.
Such as, prepare MAH-g-PP with scorification: by vinylbenzene and the mixing of initiator dicumyl peroxide, dissolve, be made into the styrene solution of initiator.Polypropylene and maleic anhydride are mixed into mixture, the mixture of polypropylene and maleic anhydride is inputted twin screw extruder, after its melting, by the different barrel section continuous measurement inputs of the styrene solution of initiator at twin screw extruder, carry out melting graft reaction, obtain MAH-g-PP.
In described MAH-g-PP, MAH percentage of grafting is 0.1% ~ 5%; Preferably, the percentage of grafting of MAH is 2% ~ 4%, and further preferably, the percentage of grafting of MAH is 3.3%.
In the present invention, in embodiment and comparative example, MAH percentage of grafting adopts acid base titration test.
The main process of acid base titration: take 0.5g polypropylene grafted maleic anhydride and be dissolved in the hot dimethylbenzene of 50mL, the NaOH-ethanolic soln of 10mL0.1mol/L is added until completely dissolved in system, reflux 10 minutes, anhydride group in maleic anhydride and alkali are fully reacted, after add while hot trace deionized water (50 μ l) or pyridine/DMF in system, promote anhydride hydrolyzes become carboxylic acid.Add 3 phenolphthalein indicators, rear hydrochloric acid/Virahol is titrated to terminal simultaneously.If HCl/ aqueous isopropanol concentration is C (mol/L), titration M (g) sample, consume volume V1 (mL) solution, blank titration consumes V2 (mL), and percentage of grafting G is calculated as follows:
G=C(V2-V1)×98/（2×M×1000）×100%
In formula, 98 is MAH molecular weight.
MAH-g-PP described in the present invention also can be commercially available.
MAH-g-SEBS：
In this specification sheets, term " SEBS " refers to polystyrene to be end segment, and the ethylene-butene copolymer obtained with polyhutadiene hydrogenation is the linear three block copolymer of middle spring block.Described MAH-g-SEBS refers to MAH graft modification SEBS.
The MAH-g-SEBS used in the present invention is not particularly limited, and can be that commercially available acquisition also can pass through the method synthesis well-known to those skilled in the art such as solution method, scorification, radiation method and solid phase method acquisition.
In described MAH-g-SEBS, MAH percentage of grafting is 1% ~ 4%; Preferably, the percentage of grafting of MAH is 2% ~ 3.8%, and further preferably, the percentage of grafting of MAH is 3.1%.
sulfonated SEBS:
The term " sulfonated SEBS " used in the application refers to and carries out sulfonation process to SEBS; it is made to possess certain sulfonation degree; the vitriol oil, oleum or acetyl sulfonate such as can be used as sulfonated reagent, and preferably, sulfonated SEBS can adopt following methods to prepare:
(1) under the condition of ice bath; 120mL1 is added in three-necked bottle; 2-ethylene dichloride (DEC); then add the diacetyl oxide of 0.15mol, at the uniform velocity stir, time below its temperature equilibrium to 5 DEG C; be added dropwise to the vitriol oil of 0.12mol; withdrawn ice bath after reaction 30min, rapid stirring 10min under room temperature, namely obtains fresh acetyl sulfonate.
(2) 5gSEBS is added be equipped with in the there-necked flask of 150mLDCE; fill nitrogen; 50 DEG C of water-baths; electric stirring; backflow, the hexanaphthene then adding 20mL makes it fully dissolve, until solution is transparent; the acetyl sulfonate 5-30mL adding fresh preparation subsequently carries out sulfonation reaction as sulphonating agent, adds 50mL Virahol stopped reaction after reaction 5h.
(3) mix products 40 DEG C of underpressure distillation go out mixed solvent, obtain viscous solid product, pour out after utilizing aqueous phase transfer method to precipitate, 90 DEG C are boiled a few hours subsequently, until a small amount of solvent evaporates is to the greatest extent, cools, wash and suction filtration, until filtrate is neutral, filter residue is fully dry at 40 DEG C in a vacuum, obtains.
In above-mentioned preparation method, by controlling the consumption of acetyl sulfonate, effectively can control the sulfonation degree of sulfonated SEBS, such as, when consumption is 5mL, 15mL and 30mL, the loading capacity of sulfonated SEBS is respectively 0.2,1.3 and 2.0.
In one embodiment, the loading capacity of described sulfonated SEBS is 0.3 ~ 1.0; Preferably, the loading capacity of described sulfonated SEBS is 0.5 ~ 1.0; More preferably, the loading capacity of described sulfonated SEBS is 0.7 ~ 1.0; Most preferably, the loading capacity of described sulfonated SEBS is 0.9.
Term " loading capacity " in the application refers in 1 gram of sulfonated SEBS reclaimed materials, the mmole number of sulfonic acid group.
Sulfonic acid group in sulfonated SEBS reclaimed materials both can with the amino group generation ionomer in polynite; Fu Ke-acylation reaction can be there is again with the phenyl ring of the electron rich in composition; cross-linking density increases, and improves resistance to air loss, because herein is provided Advantageous Effects of the present invention.
ultrabranching polyamide intercalated montmorillonite:
Term used in this application " ultrabranching polyamide intercalated montmorillonite " refers to have in the polynite of laminate structure, there is strong covalent linkage effect in layer, and interlayer is then a kind of weak interaction.When layer is electric neutrality, described interaction force is generally Van der Waals force; When layer be positive polarity or electronegativity time, be then weak electrostatic force.Under certain conditions, ultrabranching polyamide can overcome the reactive force between each layer of bedded substance and insert bedding void, ultrabranching polyamide intercalated montmorillonite.Polynite is called main body visually, and ultrabranching polyamide is called as object.
" ultrabranching polyamide " described in the present invention refers to carboxy blocking ultrabranching polyamide.
" ultrabranching polyamide " in the present invention be comprise diamine, the raw material of triprotic acid prepares.
In the present invention, described diamine is Isosorbide-5-Nitrae-cyclohexanediamine, isophorone diamine, 4,4 '-diaminodiphenylmethane, DDS and 1,6-one or more combinations in diamines.
Described triprotic acid is selected from: one or more combinations in golden yellow tricarboxylic acid, all benzene tricarbonic acid, 1,2,4-benzene tricarbonic acid.
In one embodiment, the mol ratio of described diamine and triprotic acid is 1.1 ~ 1.4:1.
" ultrabranching polyamide " in the present invention also can be comprise diamine, the raw material of tetraprotic acid prepares.
Described tetraprotic acid is selected from: 3,4,9,10-perylene tetracarboxylic acid, 3,3', 4,4'-bibenzene tetracarboxylic dianhydride, 1,2,3,4-ring butanetetra-carboxylic acid, 3,3', 4,4'-sulfobenzide tetracarboxylic dianhydride, 1,2,3,4-ring penta tetracarboxylic dianhydride, tetrahydrofuran (THF)-2,3,4,5-tetracarboxylic acid, 3,3', 4,4'-benzophenone tetracarboxylic, 3,3', 4,4'-diphenyl ether tetraformic, 3,3', 4,4'-ditan tetracarboxylic acid, 3,3', 4,4'-bis trifluoromethyl phenylbenzene tetracarboxylic acid, 1, any one or multiple combination in 4,5,8-naphthalenetetracarbacidic acidic.
In one embodiment, the mol ratio of described diamine and tetraprotic acid is 1.5 ~ 1.8:1.
In one embodiment, the preparation method of described ultrabranching polyamide:
The diamine mixing of the polyprotonic acid of 1 mole and 1.2 ~ 1.5 moles is dissolved in solvent, after adding catalyzer, is heated to 70 ~ 90 DEG C, heat 1 ~ 4h at 180 ~ 200 DEG C after, is warming up to 220 ~ 250 DEG C, after heating 1 ~ 3h; Be cooled to 80 ~ 90 DEG C, heating 2 ~ 3h, the sample obtained, after washing, centrifugal, drying ultrabranching polyamide.
The weight-average molecular weight of described ultrabranching polyamide is: 5000 ~ 30000.
In one embodiment, the weight-average molecular weight of described ultrabranching polyamide is: 10000 ~ 20000.
In one embodiment, the weight-average molecular weight of described ultrabranching polyamide is: 12000.
The not special restriction of polynite for the application can be that a blanking method synthesis well-known to those skilled in the art obtains, also can by commercially available acquisition.Such as, bentonite between sliding, shellfish obtain native, lithium soap is native, polynite, na montmorillonite, bentonite, zinc soap soil, this bentonite, lithium montmorillonite, any one or a few combination in chromium polynite and copper polynite; Be preferably na montmorillonite.
Being ammonification polynite for polynite of the present invention, referring to that polynite is through compound-modifiedly obtaining containing amino.
The described compound containing amino such as, but be not limited to, the silane coupling agents such as 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, N-2-aminoethyl-3-aminopropyl trimethoxysilane, N-2-aminoethyl-3-aminopropyltriethoxy dimethoxysilane, 3-aminopropyltriethoxy diethoxy silane, anilinomethyl triethoxysilane, N-β-aminoethyl-γ-aminopropyltriethoxy dimethoxysilane, N-β-aminoethyl-γ-aminopropyltriethoxy diethoxy silane; Chitosan, quadrol, propylene diamine, hexamethylene-diamine, diethylenetriamine, Triethylenetetramine (TETA) or isophorone diamine, dicyclohexyl methyl hydride, 4 ' diamines, can also use 2-(2-aminoethylamino) ethanol, 2-hydroxyethyl ethylene diamine, 2-hydroxyethyl propylene diamine, dihydroxy ethyl quadrol or dihydroxypropyl quadrol etc. to have the amine of hydroxyl in addition.Wherein, N-2-aminoethyl-3-aminopropyl trimethoxysilane, N-2-aminoethyl-3-aminopropyltriethoxy dimethoxysilane, chitosan, isophorone diamine is preferably made.
In one embodiment, described ammonification polynite is that polynite obtains through aminosilane coupling agent modifying.
In one embodiment, in described ammonification polynite, the weight ratio of amino silicane coupling agent and polynite is 1:8 ~ 30.
In one embodiment, the preparation method of described ammonification polynite is: polynite and amino silicane coupling agent are placed in agate mortar grinding evenly by weight 1:1.Disperseed under vigorous stirring in deionized water by powder after grinding, centrifugal rear acetone extraction 48h, the coupling agent that removing is remaining and hydrolysate thereof, obtain amination nano imvite at 70 ~ 80 DEG C of vacuum-drying 12 ~ 24h.
Described ammonification polynite also can through chitin modified obtained.
Nano imvite interlamellar spacing after aminosilane coupling agent modifying strengthens, and makes amidized nano imvite surface and interlayer grafting organic molecule long-chain, effectively can hinder the reunion between polynite particle, improve the consistency of system.In addition, nano imvite surface with amino can with above-mentioned maleic anhydride modified SEBS and PP occur be cross-linked, improve cross-linking density, further increase alcohol-rejecting ability, provide beneficial effect of the present invention.
In the present invention, preparation " ultrabranching polyamide intercalated montmorillonite ", method can use: the method such as solution intercalation, in-situ inserted, emulsion intercalation, fusion intercalation and physical blending obtains.
In one embodiment, the weight ratio of described ultrabranching polyamide and polynite is 1 ~ 5:10.
In one embodiment, the preparation method of ultrabranching polyamide intercalated montmorillonite is:
150mL deionized water, 10g polynite is added in 250mL there-necked flask, be mixed with the amino montmorillonite suspension liquid of lwt%, stirring at room temperature 1h, then after adding 1 ~ 8g ultrabranching polyamide at 80 ~ 100 DEG C, vigorous stirring 48 ~ 72h, vacuum filtration also washes with water, and final product is vacuum-drying 48h at 80 DEG C, obtains combination socket one polymer.
One of the present invention preferred embodiment in, in described ultrabranching polyamide intercalated montmorillonite, it also comprises the amino POSS of 0.1 ~ 3 weight part.
In the present invention, described " amino POSS " is not special to be limited, and both can refer to the POSS containing amino monomer synthesize, also can refer to that POSS is through obtaining containing the compound-modified of amino.
In the present invention, amino compound can be alkane amine also can be aromatic amine.
In the present invention, described " POSS " refers to that cage-type silsesquioxane (PolyhedralOligomericSilsesquioxane is called for short POSS) is the hybrid molecule of a cage-like shape structure, and its skeleton symbol is (RSiO
1.5) n, wherein n is generally 6,8,10 or 12, and most widely used be hexahedron oligomeric silsesquioxane (T
8), namely n is the POSS molecule of 8.T
8class POSS molecule has the cubes cage structure of high degree of symmetry, and Si atom is positioned at cubical eight drift angles, is connected with O atom, the inorganic skeleton that to form with Si-O-Si nanostructure be core.T
8in class POSS, adjacent S i element spacing is 0.53nm, and organic group spacing is 1.5nm.This nanometer size effect and inorganic framework kernel, can provide good thermotolerance, oxidation-resistance, intensity and hardness for material.
In one embodiment, the preparation method of ultrabranching polyamide and the common intercalated montmorillonite of POSS is:
150mL deionized water, the amino polynite of 5g is added in 250mL there-necked flask, be mixed with the amino montmorillonite suspension liquid of lwt%, stirring at room temperature 1h, then after adding 0.05 ~ 1g super branched polyurethane, vigorous stirring 20 ~ 48h at 80 ~ 100 DEG C, add the POSS of 0.1 ~ 2g again, vigorous stirring 48 ~ 72h, vacuum filtration also washes with water, final product is vacuum-drying 48h at 80 DEG C, obtains combination socket one polymer.
Spherical carboxy blocking ultrabranching polyamide enters polynite interlayer structure, carboxyl in carboxy blocking ultrabranching polyamide and the amino in polynite produce the interaction of physics and chemistry, thus make the hyperbranched spherical polymer in middle layer and two outer polynites in conjunction with tight, present " sandwich " structure, should " sandwich " structure join in TPE system, in the white wine bottle stopper made, the diffusion admittance of blocking ethanol and water molecules can be played.Add ammonification POSS structure, the carboxyl in POSS structure and ultrabranching polyamide can be made to produce interact, further increase the tap density in " sandwich " structure middle layer, plug the diffusion admittance of ethanol and water molecules further, thus, invention effect of the present invention is provided.
white oil
The term " white oil " used in the application is by the mixture of oil gained refining liquid hydrocarbon, is mainly saturated naphthenic hydrocarbon and alkane mixture, and crude oil is through normal pressure and vacuum fractionation, solvent extraction and dewaxing, hydrofining and obtaining.White oil, mainly as lubricant, improves consistency heterogeneous in matrix material.
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 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, silicon-dioxide; Organic filler; Pigment dyestuff; Mineral dye; Inorganic antiseptic; Organic antibacterial agent etc.
In one embodiment, it also comprises the silica nanosphere of 1 ~ 3 weight part.
The nanometer sphere diameter of described silica nanosphere is 0.5 ~ 1.2nm.
The not special restriction of silica nanosphere in the present invention, can commercially availablely obtain, and also can be obtained by any one method synthesis known to those skilled in the art.
The white wine bottle stopper that another aspect of the present invention provides a kind of resistance to air loss good, it uses described TPE composition.
The preparation method of the white wine bottle stopper providing described resistance to air loss good on the other hand again of the present invention, comprising:
(1) after described raw material being mixed by weight, through double-screw extruding pelletizing;
(2) product that step (1) obtains is placed on 30 ~ 60 DEG C of hot air type hopper inner dryings 1 ~ 4 hour;
(3) by the product of step (2) gained, in 160 ~ 210 DEG C of vacuum injections in mould, and under vacuum, keep this injection temperature after 3 ~ 15 hours, then cooling curing, obtain the white wine bottle stopper that resistance to air loss is good.
In a preferred embodiment, described vacuum injection temperature is 172 DEG C.
The applicant is also surprised to find that, by vacuum injection also under vacuum, keeps pyroprocessing, can improve the cross-linking density of white wine bottle stopper further.This is because MAH-g-PP, MAH-g-SEBS are upper containing carboxyl; at high temperature and under the condition of vacuum hydro-extraction; again friedel-crafts acylation can be there is with the phenyl ring in styrene units in MAH-g-SEBS; further raising cross-linking density; improve intensity and the resistance to air loss of goods; make the white wine bottle stopper obtained have good air-tightness, Advantageous Effects of the present invention is provided.
Below by embodiment, the present invention is specifically described.What be necessary to herein means out is; following examples are only for the invention will be further described; limiting the scope of the invention can not be interpreted as; some nonessential improvement and adjustment that the professional and technical personnel in this field makes according to the content of the invention described above, still belong to protection scope of the present invention.
In addition, if do not have other to illustrate, raw materials used is all commercially available, Jun Gou Chemical Reagent Co., Ltd., Sinopharm Group, and following material number used is weight part.
Raw material:
A1:MAH-g-SEBS(MAH percentage of grafting 1%)
A2:MAH-g-SEBS(MAH percentage of grafting 3.1%)
A3:MAH-g-SEBS(MAH percentage of grafting 4%)
B1:MAH-g-PP(MAH percentage of grafting 0.1%)
B2:MAH-g-PP(MAH percentage of grafting 3.1%)
B3:MAH-g-PP(MAH percentage of grafting 5.0%)
C1: sulfonated SEBS (loading capacity of sulfonated SEBS is 0.3)
C2: sulfonated SEBS (loading capacity of sulfonated SEBS is 0.9)
C3: sulfonated SEBS (loading capacity of sulfonated SEBS is 1.0)
D1: the ultrabranching polyamide intercalated montmorillonite (synthesis of ultrabranching polyamide: diamine is: Isosorbide-5-Nitrae-cyclohexanediamine; Triprotic acid is: golden yellow tricarboxylic acid; Isosorbide-5-Nitrae-cyclohexanediamine and golden yellow tricarboxylic mol ratio are: 1.1:1; The weight-average molecular weight 5000 of ultrabranching polyamide; The weight ratio of ultrabranching polyamide and polynite is 1:5)
D2: the ultrabranching polyamide intercalated montmorillonite (synthesis of ultrabranching polyamide: diamine is: isophorone diamine; Triprotic acid is: 1,2,4-benzene tricarbonic acid; The mol ratio of isophorone diamine and 1,2,4-benzene tricarbonic acid is: 1.4:1; The weight-average molecular weight 10000 of ultrabranching polyamide; The weight ratio of ultrabranching polyamide and polynite is 1:6)
D3: the ultrabranching polyamide intercalated montmorillonite (synthesis of ultrabranching polyamide: diamine is: DDS; Tetraprotic acid is: 3,4,9,10-perylene tetracarboxylic acid; The mol ratio of DDS and 3,4,9,10-perylene tetracarboxylic acid is: 1.5:1; The weight-average molecular weight 12000 of ultrabranching polyamide; The weight ratio of ultrabranching polyamide and polynite is 1:7)
D4: ultrabranching polyamide and the (synthesis of ultrabranching polyamide: diamine is: 1,6-is diamines of the common intercalated montmorillonite of POSS; Tetraprotic acid is: 3,3', 4,4'-sulfobenzide tetracarboxylic dianhydride; 1,6-is diamines and 3,3', and the mol ratio of 4,4'-sulfobenzide tetracarboxylic dianhydride is: 1.6:1; The weight-average molecular weight 20000 of ultrabranching polyamide; The weight ratio of ultrabranching polyamide, polynite and POSS is 1:8:0.5)
D5: ultrabranching polyamide and the (synthesis of ultrabranching polyamide: diamine is: 1,6-is diamines of the common intercalated montmorillonite of POSS; Tetraprotic acid is: 3,3', 4,4'-diphenyl ether tetraformic; 1,6-is diamines and 3,3', and the mol ratio of 4,4'-diphenyl ether tetraformic is: 1.8:1; The weight-average molecular weight 30000 of ultrabranching polyamide; The weight ratio of ultrabranching polyamide, polynite and POSS is 1:10:3)
D6: the concrete same D4 of preparation process, difference is, it does not comprise POSS.
E1: polynite (being purchased from Shandong Heng Yang balsamum powder factory)
F1: ammonification polynite
Preparation method: polynite and 3-aminopropyl triethoxysilane are placed in agate mortar grinding evenly by weight 1:1.Disperseed under vigorous stirring in deionized water by powder after grinding, centrifugal rear acetone extraction 48h, the coupling agent that removing is remaining and hydrolysate thereof, obtain amination nano imvite at 70 DEG C of vacuum-drying 24h.
G1: quaternary ammonium salts polynite (the same CN102978301A of preparation method)
H1: silica nanosphere (being purchased from Shanghai Lian Kai daily-use chemical industry company limited)
J1: white oil
embodiment 1 ~ 9 and comparative example 1 ~ 5:
High strength is prepared, preparation method's following (consumption of following component is parts by weight) according in the formula in following table:
Embodiment 1: each component proportioning by weight, after double-screw extruding pelletizing, 30 DEG C of hot air type hopper inner dryings 4 hours, in 160 DEG C of vacuum injections in mould, keep this temperature after 15 hours, then cooling curing obtain preliminary goods;
Embodiment 2: each component proportioning by weight, after double-screw extruding pelletizing, 60 DEG C of hot air type hopper inner dryings 1 hour, in 210 DEG C of vacuum injections in mould, keep this temperature after 3 hours, then cooling curing obtain preliminary goods;
Embodiment 3: each component proportioning by weight, after double-screw extruding pelletizing, 40 DEG C of hot air type hopper inner dryings 3 hours, in 190 DEG C of vacuum injections in mould, keep this temperature after 10 hours, then cooling curing obtain preliminary goods;
Embodiment 4: each component proportioning by weight, after double-screw extruding pelletizing, 50 DEG C of hot air type hopper inner dryings 3 hours, in 172 DEG C of vacuum injections in mould, keep this temperature after 11 hours, then cooling curing obtain preliminary goods;
Embodiment 5: each component proportioning by weight, after double-screw extruding pelletizing, 40 DEG C of hot air type hopper inner dryings 2 hours, in 172 DEG C of vacuum injections in mould, keep this temperature after 11 hours, then cooling curing obtain preliminary goods;
Embodiment 6: each component proportioning by weight, after double-screw extruding pelletizing, 40 DEG C of hot air type hopper inner dryings 2 hours, in 172 DEG C of vacuum injections in mould, keep this temperature after 8 hours, then cooling curing obtain preliminary goods;
Embodiment 7: each component proportioning by weight, after double-screw extruding pelletizing, 35 DEG C of hot air type hopper inner dryings 2 hours, 172 DEG C of vacuum injections, in mould, keep this temperature after 10 hours, then cooling curing obtain preliminary goods;
Embodiment 8: each component proportioning by weight, after double-screw extruding pelletizing, 45 DEG C of hot air type hopper inner dryings 3 hours, in 172 DEG C of vacuum injections in mould, keep this temperature after 12 hours, then cooling curing obtain preliminary goods;
Embodiment 9: each component proportioning by weight, after double-screw extruding pelletizing, 45 DEG C of hot air type hopper inner dryings 3 hours, in 172 DEG C of vacuum injections in mould, keep this temperature after 9 hours, then cooling curing obtain preliminary goods;
Comparative example 1: each component proportioning by weight, after double-screw extruding pelletizing, 30 DEG C of hot air type hopper inner dryings 2 hours, in 172 DEG C of vacuum injections in mould, keep this temperature after 8 hours, then cooling curing obtain preliminary goods;
Comparative example 2: each component proportioning by weight, after double-screw extruding pelletizing, 30 DEG C of hot air type hopper inner dryings 2 hours, in 172 DEG C of vacuum injections in mould, keep this temperature after 8 hours, then cooling curing obtain preliminary goods;
Comparative example 3: each component proportioning by weight, after double-screw extruding pelletizing, 30 DEG C of hot air type hopper inner dryings 2 hours, in 172 DEG C of vacuum injections in mould, keep this temperature after 10 hours, then cooling curing obtain preliminary goods;
Comparative example 4: each component proportioning by weight, after double-screw extruding pelletizing, 40 DEG C of hot air type hopper inner dryings 2 hours, in 172 DEG C of vacuum injections in mould, keep this temperature after 14 hours, then cooling curing obtain preliminary goods;
Comparative example 5: each component proportioning by weight, after double-screw extruding pelletizing, 30 DEG C of hot air type hopper inner dryings 2 hours, in 172 DEG C of vacuum injections in mould, keep this temperature after 8 hours, then cooling curing obtain preliminary goods;
Comparative example 6: each component proportioning by weight, after double-screw extruding pelletizing, 30 DEG C of hot air type hopper inner dryings 2 hours, in 172 DEG C of vacuum injections in mould, keep this temperature after 8 hours, then cooling curing obtain preliminary goods;
Comparative example 7: each component proportioning by weight, after double-screw extruding pelletizing, 40 DEG C of hot air type hopper inner dryings 3 hours, cooling curing obtains preliminary goods.
testing method:
Fill in row test to the TPE White Spirit Bottle that above-described embodiment 1 ~ 9 and comparative example 1 ~ 6 obtain, testing method is as follows:
1, tensile strength carries out mensuration tensile strength according to JISK6251.
2, air-tightness test
Test process: after being mated with vial by bottle stopper, whether tight lid is placed in the container with air extractor, does not have, be evacuated down to 30KPa with water logging, maintains 2min, observe in bottle and have into water or bubbling phenomenon.Occur that bubbling represents with zero; Do not occur bubbling with × represent.
The table low temperature resistant composition material formula of 1TPE and consumption (parts by weight)
Above data can be found out, compared with the product not using ultrabranching polyamide intercalated montmorillonite and do not adopt vacuum injection, the white wine bottle stopper that TPE composition of the present invention is made has good resistance to air loss and tensile strength, 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. a TPE composition, is characterized in that, is prepared from by the raw material comprising following weight part:
The MAH-g-SEBS of 100 weight parts;
The MAH-g-PP of 40 ~ 80 weight parts;
The sulfonated SEBS of 10 ~ 20 weight parts;
The ultrabranching polyamide intercalated montmorillonite of 1 ~ 15 weight part; With
The white oil of 30 ~ 50 weight parts;
Wherein, described ultrabranching polyamide is the spherical ultrabranching polyamide of carboxy blocking, and described polynite is amination polynite.
2. TPE composition as claimed in claim 1, is characterized in that, the loading capacity 0.3 ~ 1.0 of described sulfonated SEBS.
3. TPE composition as claimed in claim 1, it is characterized in that, in described ultrabranching polyamide intercalated montmorillonite, the weight ratio of ultrabranching polyamide and polynite is 1 ~ 5:10.
4. TPE composition as claimed in claim 1, it is characterized in that, the weight-average molecular weight of described ultrabranching polyamide is: 5000 ~ 30000.
5. TPE composition as claimed in claim 1, it is characterized in that, the weight-average molecular weight of described ultrabranching polyamide is: 10000 ~ 20000.
6. TPE composition as claimed in claim 1, it is characterized in that, the weight-average molecular weight of described ultrabranching polyamide is: 12000.
7. TPE composition as claimed in claim 1, is characterized in that, in described ultrabranching polyamide intercalated montmorillonite, it also comprises containing amino POSS; The weight ratio of described ultrabranching polyamide, polynite and POSS is 1 ~ 5:10:0.5 ~ 3.
8. TPE composition as claimed in claim 1, it is characterized in that, it also comprises the silica nanosphere of 1 ~ 3 weight part; The nanometer sphere diameter of described silica nanosphere is 0.5 ~ 1.2nm.
9. a white wine bottle stopper, the TPE composition according to any one of claim 1 ~ 8 prepares.
10. a preparation method for white wine bottle stopper, comprises the following steps:
(1) after described raw material being mixed by weight, through double-screw extruding pelletizing;
(2) product that step (1) obtains is placed on 30 ~ 60 DEG C of hot air type hopper inner dryings 1 ~ 4 hour;
(3) by the product of step (2) gained, in 160 ~ 210 DEG C of vacuum injections in mould, and under vacuum, keep this injection temperature after 3 ~ 15 hours, then cooling curing, obtain the white wine bottle stopper that resistance to air loss is good.
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