CN105367974A - Low temperature resistant TPE composition and ice cube tray prepared therefrom - Google Patents
Low temperature resistant TPE composition and ice cube tray prepared therefrom Download PDFInfo
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- CN105367974A CN105367974A CN201510795288.0A CN201510795288A CN105367974A CN 105367974 A CN105367974 A CN 105367974A CN 201510795288 A CN201510795288 A CN 201510795288A CN 105367974 A CN105367974 A CN 105367974A
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Abstract
The present invention discloses a high strength low temperature resistant TPE ice cube tray prepared from maleic anhydride-modified SEBS, maleic anhydride-modified PP, POSS grafted modified carbon fiber, chitosan-hyperbranched polyurethane composite and white oil as raw materials. The present invention also discloses a preparation method of the high strength low temperature resistant TPE ice cube tray under vacuum molding conditions.
Description
Technical field
The present invention relates to low temperature resistant TPE composition and ice tray prepared therefrom.More specifically, the present invention relates to the TPE ice tray with low temperature resistant, high strength and preparation method thereof.
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.Have 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 sulfuration, can recycle and reduce costs, both can secondary injection molding, with body material coating and bondings such as PP, PE, PC, PS, ABS, also can be shaping separately, be therefore the ideal material making ice tray.But TPE intensity at low temperatures, still needs further raising.
Therefore, be starved of by formula and the improvement of production technique, develop and a kind ofly self possess ice tray that is low temperature resistant, high-intensity performance.
Summary of the invention
In order to solve the problem, one 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 10 ~ 50 weight parts;
The POSS grafting modified carbon fiber of 1 ~ 10 weight part;
Chitosan-super branched polyurethane the mixture of 1 ~ 5 weight part; With
The white oil of 30 ~ 80 weight parts.
Wherein, described chitosan-hyperbranched polyorganosiloxane mixture carries out modification by chitosan to hyperbranched polyorganosiloxane and obtains.
In described MAH-g-SEBS, MAH percentage of grafting is 1% ~ 5%; Preferably, the percentage of grafting of MAH is 2% ~ 4%, and further preferably, the percentage of grafting of MAH is 2.5 ~ 3.5%; More preferably, the percentage of grafting of MAH is 3.2%.
In described MAH-g-PP, MAH percentage of grafting is 1.5% ~ 4.5%; Preferably, the percentage of grafting of MAH is 1.9% ~ 3.6%; Further preferably, in described MAH-g-PP, the percentage of grafting of MAH is 2.6%.
Described POSS grafting modified carbon fiber refers to that carbon fiber is first modified through anhydrides grafting compounds, then carries out grafting POSS and obtain;
Described anhydrides compound is selected from: maleic anhydride, itaconic anhydride, succinyl oxide, Pyroglutaric acid, octadecylsuccinic acid acid anhydride, 2, one or both and above combination in 2-dimethyl succinic anhydride, 2-laurylene-1-base succinyl oxide, hexafluoroglutaric anhydride, 3,3-dimethylated pentanedioic acid acid anhydrides, 3-ethyl-3-methylglutaric acid acid anhydride, anhydride diethylene glycol;
The weight ratio of described anhydrides compound and carbon fiber is 1:20 ~ 50.
In described POSS grafting modified carbon fiber, POSS comprises silane monomer to obtain in polycondensation;
Described silane monomer is selected from: methyltrimethoxy silane, Union carbide A-162, ethyl trimethoxy silane, ethyl triethoxysilane, n-propyl Trimethoxy silane, ne-butyltriethoxysilaneand, trimethoxysilane, n-pentyl triethoxyl silane, n-hexyl Trimethoxy silane, isooctyltriethoxysilane, decyl Trimethoxy silane, methyl dimethoxy oxygen base oxethyl silane, methyl diethoxy methoxy silane, phenyltrimethoxysila,e, 4-p-methoxy-phenyl Trimethoxy silane, 2-chloro-phenyl-Trimethoxy silane, phenyl triethoxysilane, 2-p-methoxy-phenyl triethoxyl silane, phenyl dimethoxyethoxy silane, one or both and above combination in diethylamino phenyl Oxymethoxy silane.
As one of the present invention preferred embodiment, in described POSS grafting modified carbon fiber, mass ratio 1:5 ~ 20 of POSS and carbon fiber.
Described chitosan-hyperbranched polyorganosiloxane mixture carries out modification by chitosan to hyperbranched polyorganosiloxane and obtains.
As one of the present invention preferred embodiment, described super branched polyurethane is reacted by vulcabond and trivalent alcohol and obtains, and the mol ratio of the isocyanato of described vulcabond and the hydroxyl of trivalent alcohol is 3:2.
Described vulcabond is selected from: PPDI, 1, hexamethylene-diisocyanate, 1,5-naphthalene diisocyanate, 4,4-hexylmethane, O-phthalic group diisocyanate, Toluene-2,4-diisocyanate, 6-vulcabond, isophorone diisocyanate, 4 ' 4-diphenylmethanediisocyanate, hexamethylene diisocyanate, 2, the combination of one or more in 4 tolylene diisocyanates;
Described trivalent alcohol is selected from: the combination of one or more in glycerol, TriMethylolPropane(TMP) or polyether-tribasic alcohol.
As one of the present invention preferred embodiment, in described chitosan-super branched polyurethane mixture, the weight ratio of chitosan and super branched polyurethane is: 1:10 ~ 20.
As one of the present invention preferred embodiment, also comprise the antiseptic-germicide of 1 ~ 3 weight part, described antiseptic-germicide has following structural formula:
；
（1）
In formula (1), r is the integer of 1 ~ 5; S is the integer of 3 ~ 15.
Another aspect of the present invention also relates to a kind of low temperature resistant ice tray, it uses described TPE composition.
A kind of method providing again low temperature resistant TPE ice tray on the other hand of the present invention, 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 ~ 70 DEG C of hot air type hopper inner dryings 1 ~ 4 hour;
(3) by the product of step (1) gained, in 180 DEG C ~ 200 DEG C vacuum injections in mould, and under vacuum, keep this temperature after 1 ~ 20 hour, then cooling curing obtain.
In one embodiment, in the method for the low temperature resistant TPE ice tray of described preparation, vacuum injection temperature is 187 DEG C.
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.
One aspect of the present invention provides a kind of low temperature resistant TPE composition, and it comprises:
The MAH-g-SEBS of 100 weight parts;
The MAH-g-PP of 10 ~ 50 weight parts;
The POSS grafting modified carbon fiber of 1 ~ 10 weight part;
Chitosan-super branched polyurethane the mixture of 1 ~ 5 weight part; With
The white oil of 30 ~ 80 weight parts.
Wherein, described chitosan-hyperbranched polyorganosiloxane mixture carries out modification by chitosan to hyperbranched polyorganosiloxane and obtains.
In the application's book, 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.Wherein, when solution grafting carries out SEBS 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 melt grafting is adopted.
In described MAH-g-SEBS, MAH percentage of grafting is 1% ~ 5%; Preferably, the percentage of grafting of MAH is 2% ~ 4%, and further preferably, the percentage of grafting of MAH is 2.5 ~ 3.5%; More preferably, the percentage of grafting of MAH is 3.2%.
In a preferred embodiment, in described MAH-g-SEBS, the percentage of grafting of MAH is 3.2%.
MAH-g-PP：
In the application, 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 1.5% ~ 4.5%; Preferably, the percentage of grafting of MAH is 1.9% ~ 3.6%; Further preferably, in described MAH-g-PP, the percentage of grafting of MAH is 2.6%.
In the application, 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.
pOSS grafting modified carbon fiber:
POSS grafting modified carbon fiber described in the present invention refers to carbon fiber first after oxide treatment, then carries out grafting POSS and obtain.
Term " carbon fiber " described in the present invention refers to that diameter is 50 ~ 200nm, and length is 50 ~ 100 μm, and length-to-diameter ratio is the carbon fiber of 100 ~ 500.
In the present invention, the not special restriction of carbon fiber, can commercially availablely obtain, and also sputtering method, CVD can be assisted to strengthen plasma method etc. by electrochemical method well-known to those skilled in the art, hot filament and obtain.
Oxide treatment described in the present invention is that anhydrides compound obtains carbon fiber grafting process.
Described anhydrides compound, comprise maleic anhydride, itaconic anhydride, succinyl oxide, Pyroglutaric acid, octadecylsuccinic acid acid anhydride, 2,2-dimethyl succinic anhydride, 2-laurylene-1-base succinyl oxide, hexafluoroglutaric anhydride, 3,3-dimethylated pentanedioic acid acid anhydride, 3-ethyl-3-methylglutaric acid acid anhydride, anhydride diethylene glycol etc., but being not limited to them, can be any compound in the equivalency range that uses of those of ordinary skill in the art.In these compounds, single compound can be used, also can use the mixture of two or more compounds.
In one embodiment, the weight ratio of described anhydrides compound and carbon fiber is 1:20 ~ 50.
In addition, described oxidation treatment method also comprises strong acid oxide treatment, plasma treatment and high-energy photoelectron irradiation etc.
" POSS " described in the present invention 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, its periphery is surrounded by organic group R.In the present invention, described R is the active group comprising at least one amino, and described active group can be alkane amine also can be aromatic amine.
In the present invention, described POSS structure under the existence of polycondensation catalyst, polycondensation occurs by silane monomer and obtains.
Can list silane monomer is methyltrimethoxy silane, Union carbide A-162, ethyl trimethoxy silane, ethyl triethoxysilane, n-propyl Trimethoxy silane, ne-butyltriethoxysilaneand, trimethoxysilane, n-pentyl triethoxyl silane, n-hexyl Trimethoxy silane, isooctyltriethoxysilane, decyl Trimethoxy silane, methyl dimethoxy oxygen base oxethyl silane, methyl diethoxy methoxy silane etc.
Can list that fragrant silane monomer is phenyltrimethoxysila,e, 4-p-methoxy-phenyl Trimethoxy silane, 2-chloro-phenyl-Trimethoxy silane, phenyl triethoxysilane, 2-p-methoxy-phenyl triethoxyl silane, phenyl dimethoxyethoxy silane, diethylamino phenyl Oxymethoxy silane etc. can have substituent aryltrialkoxysilane compounds etc.
As used polycondensation catalyst, be just not particularly limited as long as above-mentioned POSS structure can be obtained, the mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid can be listed; The organic acids etc. such as methylsulfonic acid, trifluoromethanesulfonic acid, Phenylsulfonic acid, tosic acid, acetic acid, trifluoroacetic acid, citric acid.
The solvent used suitably can be selected according to the kind of silane monomer, polycondensation catalyst, consumption etc.Such as water can be listed; Benzene,toluene,xylenes etc. are aromatic hydrocarbon based; The ester classes such as methyl acetate, ethyl acetate, propyl acetate, methyl propionate; The ketones such as acetone, methylethylketone, methyl iso-butyl ketone (MIBK), pimelinketone; The alcohols etc. such as methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol.These solvents can be used alone one, or mix two or more use.
Temperature when making silane monomer generation polycondensation, reaction times are selected according to the kind, consumption etc. of used silane monomer, polycondensation catalyst and solvent.
Temperature of reaction is generally temperature range till the 0 DEG C ~ boiling point of solvent that uses, is preferably the scope of 20 DEG C ~ 100 DEG C.When temperature of reaction is too low, the propelling of condensation reaction sometimes becomes insufficient.On the other hand, when temperature of reaction becomes too high, be difficult to suppress gelation.Reaction times is generally 30 minutes ~ 10 hours.
As a kind of preferred implementation of the present invention, such as, when using phenyl triethoxysilane (10.2g) and trimethoxysilane (8.9g) as silane monomer, be the catalyzer citric acid of 10% relative to silane monomer quality by use, use second alcohol and water as mixed solvent, with the scope of 50 DEG C ~ 75 DEG C reaction 2 ~ 5.5 hours, obtain POSS compound.
As a kind of preferred implementation of the present invention, described POSS obtains containing amino silane compounds graft modification at least comprising one, and this Graft Method is obtained by the method known by those skilled in the art.
Described amino silane compounds such as, but be not limited to, N-2-(amino-ethyl)-3-amino propyl methyl dimethoxysilane, N-2-(amino-ethyl)-3-TSL 8330, N-2-(amino-ethyl)-APTES, 3-TSL 8330, APTES, 3-triethoxysilyl-N-(1,3-dimethyl butyrate fork base) propylamine, N-phenyl-3-TSL 8330, any one or two kinds and above combination in γ-anilino propyl trimethoxy silicane.
Not containing amino silane compounds such as, but be not limited to, 2-(3, 4-expoxycyclohexyl) ethyl trimethoxy silane, 2-(3, 4-expoxycyclohexyl) ethyl triethoxysilane, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxypropyl group triethoxyl silane, 3-glycidoxypropyl dimethoxysilane, 3-glycidoxypropyl diethoxy silane, (trimethylene oxide-3-base) methyltrimethoxy silane, (trimethylene oxide-3-base) Union carbide A-162, (trimethylene oxide-3-base) methyl dimethoxysilane, (trimethylene oxide-3-base) methylethyl dimethoxysilane, (trimethylene oxide-3-base) methylethyl diethoxy silane, (trimethylene oxide-3-base) aminomethyl phenyl diethoxy silane, 2-(trimethylene oxide-3 '-Ji) ethyl trimethoxy silane etc. has the silane compound of epoxy group(ing), 2-trimethoxysilylethylgroup group succinyl oxide, 3-triethoxysilylpropyltetrasulfide succinyl oxide etc. have the silane compound of acid anhydride structure, two (triethoxysilylpropyltetrasulfide) tetrasulfide, octadecyldimethyl (3-(trimethoxysilyl) propyl group) muriate etc.
In the present invention, POSS grafting modified carbon fiber produces chemical action by the carboxylic group on the amino on POSS and treated carbon fiber surface.In addition, the nitrogen element contained in POSS structure can also produce hydrogen bond action with the active group on the surface of carbon fiber, and then realizes POSS grafting modified carbon fiber.Because carbon fiber has the material of high strength, high-modulus, add in this TPE system, substantially increase the resistance to low temperature in TPE system.But the toughness of carbon fiber is poor, well improve the toughness of carbon fiber on the one hand through POSS grafting modified carbon fiber; On the other hand, the consistency of carbon fiber and TPE system is added.
chitosan-super branched polyurethane mixture:
In the application, described " chitosan-super branched polyurethane mixture " carries out modification by chitosan to super branched polyurethane and obtains.
In the application, the not special restriction of described chitosan, can commercially availablely obtain, and also can be obtained by a blanking method synthesis known in the art.
In the application, described super branched polyurethane by adopting A2+B3 legal system standby, and obtains isocyanate-terminated polymkeric substance, and concrete grammar is:
(1) vulcabond and trivalent alcohol are dissolved in respectively in polar solvent, obtain diisocyanate solution and trivalent alcohol solution respectively, controlling its mass concentration is 15 ~ 35%; Wherein, vulcabond is PPDI, 1, hexamethylene-diisocyanate, 1,5-naphthalene diisocyanate, 4,4-hexylmethane, O-phthalic group diisocyanate, Toluene-2,4-diisocyanate, 6-vulcabond, isophorone diisocyanate, 4 ' 4-diphenylmethanediisocyanate, hexamethylene diisocyanate or 2,4 tolylene diisocyanates; Described trivalent alcohol is glycerol, TriMethylolPropane(TMP) or polyether-tribasic alcohol;
(2) 30 ~ 100 DEG C, under protective atmosphere, limit is stirred, and be added to by diisocyanate solution in trivalent alcohol solution, wherein the mol ratio of the isocyanato of vulcabond and the hydroxyl of trivalent alcohol is 9:7 ~ 3:1; After vulcabond has added, reaction system insulation reaction 5 ~ 30h; Then in reaction system, add protective material hexanolactam, at 30 ~ 100 DEG C, continue reaction 5 ~ 15h;
(3) after reaction terminates, after underpressure distillation goes out solvent, dissolved by gained material through tetrahydrofuran (THF), sedimentation and after filtering in methyl alcohol, by its vacuum-drying 10 ~ 20h at 60 ~ 140 DEG C, obtains the super branched polyurethane containing isocyanato of purifying;
Preferably, the mol ratio of the isocyanato of described vulcabond and the hydroxyl of trivalent alcohol is 3:2.
In one embodiment, the solvent that described diisocyanate solution, trivalent alcohol solution adopt is dimethyl sulfoxide (DMSO), N, the mixing of one or more in N-N,N-DIMETHYLACETAMIDE, DMF, N, N-dimethyl pyrrolidone, tetrahydrofuran (THF) or toluene.
Chitosan-super branched polyurethane mixture for the application can obtain especially by following methods:
In 100mL three-necked bottle, add chitosan 0.1 gram, super branched polyurethane 1 ~ 2 gram and DMF 50mL, after stirred at ambient temperature is even; React after 10 ~ 24 hours at 30 ~ 60 DEG C, sedimentation and filtration in methyl alcohol, obtain chitosan-super branched polyurethane mixture;
Preferably, the weight ratio of described chitosan and super branched polyurethane is 1:10 ~ 20.
Chitosan-super branched polyurethane mixture add the intensity can improving on the one hand carbon fiber, and play to act synergistically with POSS grafting modified carbon fiber and strengthen the effect of intensity under TPE low temperature.On the other hand, also under the prerequisite not affecting processing characteristics, certain crosslinked action can be played, improve the intensity of TPE system, in addition, special hyperbranched globosity can also ensure the consistency good with SEBS and provide toughness more carefully, because herein is provided Advantageous Effects of the present invention.
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.
The application is not particularly limited white oil, can commercially availablely obtain.Preferably, the white oil of conformance with standard Q/MSH32-2009.
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 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 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.
In a preferred embodiment, described TPE composition also comprises a kind of antiseptic-germicide, and described antiseptic-germicide has following structure:
；
（1）
In formula (1), r is the integer of 1 ~ 5; S is the integer of 3 ~ 15.
In a preferred embodiment, the preparation method of described antiseptic-germicide is as follows:
In 100ml three-necked bottle, add Isosorbide-5-Nitrae-lupetazin 0.08mol, the pentamethylene bromide of 0.1 ~ 0.3mol and solvent DMF 50ml, react after 10 ~ 24 hours at 40 ~ 60 DEG C, underpressure distillation is removed solvent and is obtained antiseptic-germicide.
Another aspect of the present invention provides a kind of low temperature resistant TPE ice tray, it uses described TPE composition.
A kind of method providing again low temperature resistant TPE ice tray on the other hand of the present invention, 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 ~ 70 DEG C of hot air type hopper inner dryings 1 ~ 4 hour;
(3) by the product of step (1) gained, in 180 DEG C ~ 200 DEG C vacuum injections in mould, and under vacuum, keep this temperature after 1 ~ 20 hour, then cooling curing obtain.
In one embodiment, in the method for the low temperature resistant TPE ice tray of described preparation, vacuum injection temperature is 187 DEG C.
Applicant is surprised to find that, by vacuum injection also under vacuum, keeps pyroprocessing, can improve the cross-linking density of TPE system further.This is the carboxyl due to chitosan containing, and at high temperature and under the condition of vacuum hydro-extraction, can with the phenyl ring generation friedel-crafts acylation on styrene units in MAH-g-SEBS, thus occur further crosslinked, to provide Advantageous Effects of the present invention.
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 3.2%)
A3:MAH-g-SEBS(MAH percentage of grafting 5%)
B1:MAH-g-PP(MAH percentage of grafting 1.5%)
B2:MAH-g-PP(MAH percentage of grafting 2.6%)
B3:MAH-g-PP(MAH percentage of grafting 4.5%)
C1: carbon fiber (being purchased from Zhongfu Shenying Carbon Fiber Limited Liability Company)
C2:POSS grafting modified carbon fiber
(1) using methyltrimethoxy silane 10.7g, dimethyldimethoxysil,ne 12.2g, ethanol 3.3g, water 8.1g, to add in sealable container as the methanol solution 4.8g of the trifluoroacetic acid of catalyzer and mix, airtight and limit agitator stirs after the limit warm water bath of 50 DEG C heats 5 hours, return to room temperature, obtain hydrolytie polycondensation liquid, then, with rotatory evaporator carry out concentrated after, vacuum-drying is carried out to enriched material, thus obtains POSS structural polymer.
(2) by described 5gPOSS structural polymer with join pre-dispersed 10min in dehydrated alcohol, then the N-2-(amino-ethyl of 0.5g is slowly added)-3-amino propyl methyl dimethoxysilane, then at 80 DEG C of stirred in water bath 30min, after fully reacting, washing, oven dry, grinding, collect sample and obtain.
(3) by the maleic anhydride modified carbon fiber of amino modified for 1g POSS and 5g, take DCM as solvent, triethylamine is alkali, and after the 3h that refluxes under room temperature, through suction filtration, filtrate evaporate to dryness can obtain POSS grafting modified carbon fiber.
C3:POSS grafting modified carbon fiber
(1) using phenyl triethoxysilane 10.2g, trimethoxysilane 8.9g, ethanol 3.3g, water 8.1g, to add in sealable container as the methanol solution 5.1g of catalyzer citric acid and mix, airtight and limit agitator stirs after the limit warm water bath of 50 DEG C heats 5 hours, return to room temperature, obtain hydrolytie polycondensation liquid, then, with rotatory evaporator carry out concentrated after, vacuum-drying is carried out to enriched material, thus obtains POSS structural polymer.
(2) by described 5gPOSS structural polymer with join pre-dispersed 10min in dehydrated alcohol, then the N-2-(amino-ethyl of 0.5g is slowly added)-3-TSL 8330, then at 80 DEG C of stirred in water bath 30min, after fully reacting, washing, oven dry, grinding, collect sample and obtain.
(3) by the maleic anhydride modified carbon fiber of amino modified for 1g POSS and 10g, (weight ratio of maleic anhydride and carbon fiber is: 1:30), take DCM as solvent, triethylamine is alkali, after the 3h that refluxes under room temperature, through suction filtration, filtrate evaporate to dryness can obtain POSS grafting modified carbon fiber.
C4:POSS grafting modified carbon fiber
(1) using decyl Trimethoxy silane 11.2g, phenyl triethoxysilane 9.5g, ethanol 3.5g, water 8.1g, to add in sealable container as the methanol solution 5.0g of catalyzer phosphoric acid and mix, airtight and limit agitator stirs after the limit warm water bath of 50 DEG C heats 5 hours, return to room temperature, obtain hydrolytie polycondensation liquid, then, with rotatory evaporator carry out concentrated after, vacuum-drying is carried out to enriched material, thus obtains POSS structural polymer.
(2) by described 5gPOSS structural polymer with join pre-dispersed 10min in dehydrated alcohol, then the N-2-(amino-ethyl of 0.2g is slowly added) 2-(3 of-APTES and 0.7g, 4-expoxycyclohexyl) ethyl trimethoxy silane, then at 80 DEG C of stirred in water bath 30min, after fully reacting, washing, oven dry, grinding, collect sample and obtain.
(3) by the succinic anhydride modified carbon fiber of amino modified for 1g POSS and 15g, (weight ratio of succinyl oxide and carbon fiber is: 1:20), take DCM as solvent, triethylamine is alkali, after the 3h that refluxes under room temperature, through suction filtration, filtrate evaporate to dryness can obtain POSS grafting modified carbon fiber.
C5:POSS grafting modified carbon fiber
(1) using trimethoxysilane 13.2g, 2-chloro-phenyl-Trimethoxy silane 9.5g, ethanol 3.0g, water 8.1g, to add in sealable container as the methanol solution 5.0g of catalyzer boric acid and mix, airtight and limit agitator stirs after the limit warm water bath of 50 DEG C heats 5 hours, return to room temperature, obtain hydrolytie polycondensation liquid, then, with rotatory evaporator carry out concentrated after, vacuum-drying is carried out to enriched material, thus obtains POSS structural polymer.
(2) by described 10gPOSS structural polymer with join pre-dispersed 10min in dehydrated alcohol, then the 3-TSL 8330 of 1g and the 2-trimethoxysilylethylgroup group succinyl oxide of 1g is slowly added, then at 80 DEG C of stirred in water bath 30min, after fully reacting, washing, oven dry, grinding, collect sample and obtain.
(3) by the itaconic anhydride modified carbon fiber of amino modified for 1g POSS and 20g, (weight ratio of itaconic anhydride and carbon fiber is: 1:50), take DCM as solvent, triethylamine is alkali, after the 3h that refluxes under room temperature, through suction filtration, filtrate evaporate to dryness can obtain POSS grafting modified carbon fiber.
D1: super branched polyurethane
Preparation method:
50 DEG C, under protective atmosphere, limit is stirred, and be added to by hexamethylene diisocyanate in the dimethyl sulphoxide solution of glycerol, wherein the mol ratio of the isocyanato of hexamethylene diisocyanate and the hydroxyl of glycerol is 9:7; After hexamethylene diisocyanate has added, reaction system insulation reaction 20h; Then in reaction system, add protective material hexanolactam, at 60 DEG C, continue reaction 15h; After reaction terminates, after underpressure distillation goes out solvent, dissolved by gained material through tetrahydrofuran (THF), sedimentation and after filtering in methyl alcohol, by its vacuum-drying 20h at 60 DEG C, obtains the super branched polyurethane of purifying.
D2: chitosan-super branched polyurethane mixture
(1) super branched polyurethane: 50 DEG C, under protective atmosphere, limit is stirred, PPDI be added in the N,N-dimethylacetamide solution of TriMethylolPropane(TMP), wherein the mol ratio of the isocyanato of PPDI and the hydroxyl of TriMethylolPropane(TMP) is 9:5; After PPDI has added, reaction system insulation reaction 20h; Then in reaction system, add protective material hexanolactam, at 60 DEG C, continue reaction 15h; After reaction terminates, after underpressure distillation goes out solvent, dissolved by gained material through tetrahydrofuran (THF), sedimentation and after filtering in methyl alcohol, by its vacuum-drying 20h at 60 DEG C, obtains the super branched polyurethane of purifying.
(2) chitosan-super branched polyurethane mixture: in 100mL three-necked bottle, adds chitosan 0.1 gram, super branched polyurethane 1 gram and DMF 50mL, after stirred at ambient temperature is even; React after 14 hours at 50 DEG C, sedimentation and filtration in methyl alcohol, obtain chitosan-super branched polyurethane mixture;
D3: chitosan-super branched polyurethane mixture
The same D2 of concrete preparation process, its difference is, in the synthesis of (1) super branched polyurethane, vulcabond is chosen as: 4,4-hexylmethane; Trivalent alcohol is chosen as: polyether-tribasic alcohol; Wherein the mol ratio of the isocyanato of 4,4-hexylmethane and the hydroxyl of trivalent alcohol is 3:1;
(2), in chitosan-super branched polyurethane mixture, the weight ratio of chitosan and super branched polyurethane is: 1:15.
D4: chitosan-super branched polyurethane mixture
The same D2 of concrete preparation process, its difference is, in the synthesis of (1) super branched polyurethane, vulcabond is chosen as: isophorone diisocyanate; Trivalent alcohol is chosen as: polyether-tribasic alcohol; Wherein the mol ratio of the isocyanato of isophorone diisocyanate and the hydroxyl of trivalent alcohol is 3:2;
(2), in chitosan-super branched polyurethane mixture, the weight ratio of chitosan and super branched polyurethane is: 1:20.
D5: chitosan-super branched polyurethane mixture
The same D2 of concrete preparation process, its difference is, in the synthesis of (1) super branched polyurethane, vulcabond is chosen as: O-phthalic group diisocyanate; Trivalent alcohol is chosen as: TriMethylolPropane(TMP); Wherein the mol ratio of the isocyanato of isophorone diisocyanate and the hydroxyl of trivalent alcohol is 3:2;
(2), in chitosan-super branched polyurethane mixture, the weight ratio of chitosan and super branched polyurethane is: 1:15.
E1: antiseptic-germicide
Preparation method:
In 100ml three-necked bottle, add pentamethylene bromide and the solvent DMF 50ml of Isosorbide-5-Nitrae-lupetazin 0.08mol, 0.15mol, react after 20 hours at 50 DEG C, underpressure distillation is removed solvent and is obtained antiseptic-germicide.
F1: 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 180 DEG C of vacuum injections in mould, keep this temperature after 20 hours, then cooling curing obtain preliminary goods;
Embodiment 2: each component proportioning by weight, after double-screw extruding pelletizing, 70 DEG C of hot air type hopper inner dryings 1 hour, in 200 DEG C of vacuum injections in mould, keep this temperature after 1 hour, 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 1 hour, then cooling curing obtain preliminary goods;
Embodiment 4: each component proportioning by weight, after double-screw extruding pelletizing, 30 DEG C of hot air type hopper inner dryings 2 hours, in 187 DEG C of vacuum injections in mould, keep this temperature after 8 hours, then cooling curing obtain preliminary goods;
Embodiment 5: each component proportioning by weight, after double-screw extruding pelletizing, 30 DEG C of hot air type hopper inner dryings 2 hours, in 187 DEG C of vacuum injections in mould, keep this temperature after 8 hours, then cooling curing obtain preliminary goods;
Embodiment 6: each component proportioning by weight, after double-screw extruding pelletizing, 30 DEG C of hot air type hopper inner dryings 2 hours, in 187 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, 30 DEG C of hot air type hopper inner dryings 2 hours, in 187 DEG C of vacuum injections in mould, keep this temperature after 8 hours, then cooling curing obtain preliminary goods;
Embodiment 8: each component proportioning by weight, after double-screw extruding pelletizing, 30 DEG C of hot air type hopper inner dryings 2 hours, in 187 DEG C of vacuum injections in mould, keep this temperature after 8 hours, then cooling curing obtain preliminary goods;
Embodiment 9: each component proportioning by weight, after double-screw extruding pelletizing, 30 DEG C of hot air type hopper inner dryings 2 hours, in 187 DEG C of vacuum injections in mould, keep this temperature after 8 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 187 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 187 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 187 DEG C of vacuum injections in mould, keep this temperature after 8 hours, then cooling curing obtain preliminary goods;
Comparative example 4: each component proportioning by weight, after double-screw extruding pelletizing, 30 DEG C of hot air type hopper inner dryings 2 hours, in 187 DEG C of vacuum injections in mould, keep this temperature after 8 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 187 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, cooling curing obtains preliminary goods.
testing method:
Test the TPE ice tray that above-described embodiment 1 ~ 9 and comparative example 1 ~ 6 obtain, testing method is as follows:
After determinand being placed in-30 DEG C of freezing treatment 12h, carry out mensuration tensile strength according to JISK6251.
The table low temperature resistant composition material formula of 1TPE and consumption (parts by weight)
Can be found out by above data and compare, with the Compound Phase ratio not using POSS grafting modified carbon fiber and chitosan-super branched polyurethane mixture, the low temperature resistant ice tray that TPE of the present invention makes has better 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 low temperature resistant TPE composition, is characterized in that, is prepared from by comprising following raw material:
The MAH-g-SEBS of 100 weight parts;
The MAH-g-PP of 10 ~ 50 weight parts;
The POSS grafting modified carbon fiber of 1 ~ 10 weight part;
Chitosan-super branched polyurethane the mixture of 1 ~ 5 weight part; With
The white oil of 30 ~ 80 weight parts.
Wherein, described chitosan-hyperbranched polyorganosiloxane mixture carries out modification by chitosan to hyperbranched polyorganosiloxane and obtains.
2. low temperature resistant TPE composition as claimed in claim 1, it is characterized in that, described POSS grafting modified carbon fiber is that carbon fiber is first modified through anhydrides grafting compounds, then carries out grafting POSS and obtain;
Described anhydrides compound is selected from: maleic anhydride, itaconic anhydride, succinyl oxide, Pyroglutaric acid, octadecylsuccinic acid acid anhydride, 2, one or both and above combination in 2-dimethyl succinic anhydride, 2-laurylene-1-base succinyl oxide, hexafluoroglutaric anhydride, 3,3-dimethylated pentanedioic acid acid anhydrides, 3-ethyl-3-methylglutaric acid acid anhydride, anhydride diethylene glycol;
The weight ratio of described anhydrides compound and carbon fiber is 1:20 ~ 50.
3. low temperature resistant TPE composition as claimed in claim 1, it is characterized in that, in described POSS grafting modified carbon fiber, POSS comprises silane monomer to obtain in polycondensation;
Described silane monomer is selected from: methyltrimethoxy silane, Union carbide A-162, ethyl trimethoxy silane, ethyl triethoxysilane, n-propyl Trimethoxy silane, ne-butyltriethoxysilaneand, trimethoxysilane, n-pentyl triethoxyl silane, n-hexyl Trimethoxy silane, isooctyltriethoxysilane, decyl Trimethoxy silane, methyl dimethoxy oxygen base oxethyl silane, methyl diethoxy methoxy silane, phenyltrimethoxysila,e, 4-p-methoxy-phenyl Trimethoxy silane, 2-chloro-phenyl-Trimethoxy silane, phenyl triethoxysilane, 2-p-methoxy-phenyl triethoxyl silane, phenyl dimethoxyethoxy silane, one or both and above combination in diethylamino phenyl Oxymethoxy silane.
4. low temperature resistant TPE composition as claimed in claim 1, is characterized in that, in described POSS grafting modified carbon fiber, and mass ratio 1:5 ~ 20 of POSS and carbon fiber.
5. low temperature resistant TPE composition as claimed in claim 1, is characterized in that, described super branched polyurethane is reacted by vulcabond and trivalent alcohol and obtains, and the mol ratio of the isocyanato of described vulcabond and the hydroxyl of trivalent alcohol is 3:2.
6. low temperature resistant TPE composition as claimed in claim 5, it is characterized in that, described vulcabond is selected from: PPDI, 1, hexamethylene-diisocyanate, 1,5-naphthalene diisocyanate, 4,4-hexylmethane, O-phthalic group diisocyanate, Toluene-2,4-diisocyanate, 6-vulcabond, isophorone diisocyanate, 4 ' 4-diphenylmethanediisocyanate, hexamethylene diisocyanate, 2, the combination of one or more in 4 tolylene diisocyanates;
Described trivalent alcohol is selected from: the combination of one or more in glycerol, TriMethylolPropane(TMP) or polyether-tribasic alcohol.
7. low temperature resistant TPE composition as claimed in claim 1, it is characterized in that, in described chitosan-super branched polyurethane mixture, the weight ratio of chitosan and super branched polyurethane is 1:10 ~ 20.
8. low temperature resistant TPE composition as claimed in claim 1, it is characterized in that, also comprise the antiseptic-germicide of 1 ~ 3 weight part, described antiseptic-germicide has following structural formula:
；
（1）
In formula (1), r is the integer of 1 ~ 5; S is the integer of 3 ~ 15.
9. a low temperature resistant ice tray, it uses the TPE composition of any one of claim 1 ~ 8.
10. a preparation method for low temperature resistant ice tray, 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 ~ 70 DEG C of hot air type hopper inner dryings 1 ~ 4 hour;
(3) by the product of step (1) gained, in 180 DEG C ~ 200 DEG C vacuum injections in mould, and under vacuum, keep this temperature after 1 ~ 20 hour, then cooling curing obtain.
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| CN108084379A (en) * | 2017-12-21 | 2018-05-29 | 西安交通大学 | For the preparation method of POSS Quito arm block copolymer of historical relic bonding protection |
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