CN105331030A - High-elasticity weather-resistant TPE telescopic water pipe and preparation method thereof - Google Patents
High-elasticity weather-resistant TPE telescopic water pipe and preparation method thereof Download PDFInfo
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- CN105331030A CN105331030A CN201510750926.7A CN201510750926A CN105331030A CN 105331030 A CN105331030 A CN 105331030A CN 201510750926 A CN201510750926 A CN 201510750926A CN 105331030 A CN105331030 A CN 105331030A
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Abstract
A high-elasticity weather-resistant TPE telescopic water pipe is prepared from, by weight, 100 parts of MAH-g-SEBS, 30-40 parts of MAH-g-PP, 10-30 parts of white oil, 5-15 parts of modified nano titanium oxide-hyperbranched polyurethane compound and 5-10 parts of aminated graphene oxide, wherein the modified nano titanium oxide-hyperbranched polyurethane compound is prepared by modifying nano titanium oxide through an amino silane coupling agent and then compositing the nano titanium oxide with hyperbranched polyurethane. The telescopic water pipe does not break after 150 times of continuous water injection or more under the pressure of 0.8 Mpa, permanent deformation is smaller than 15%, elasticity is good, and the water pipe is not embrittled in cold places or in winter and is excellent in weather resistance.
Description
Technical field
The invention belongs to flexible water pipe field, more specifically, the present invention relates to a kind of take TPE as flexible water pipe of main raw material and preparation method thereof.
Background technology
Common flexible water pipe is generally made up of outer terylene ribbon and interior pipe, and the quality of performance depends primarily on interior pipe.Interior tubing matter comprises natural emulsion, imitative latex, TPE etc., and wherein in TPE, pipe cost performance is the highest, and market demand is maximum.TPE thermoplastic elastomer is a kind of snappiness, high strength, high resilience with rubber, and having again can the material of injection molding feature.After the flexible water pipe water-filling of TPE material, length can be extended automatically, and automatic retraction original length after cutting off the water supply is lighter compared with conventional rubber water pipe or PVC water pipe, is easy to carry and receives.The TPE water pipe that stretches is applicable to industry, agricultural, food, medical treatment, civil engineering work, fishery, aquaculture, the fields such as treegarden irrigation; The Liquid transfer of general work pressure, as gas dynamic tube, hydraulicefficiency pipe, garden water, oil transportation, water pipe, oil detection management etc.The requirement of these Application Areass to flexible water pipe is more and more higher, expects to obtain stable in properties, elasticity is high, water-resistant pressure is large, free-extension is not yielding, winter resists cold, summer is heat-resisting, the TPE of not easily hardening efflorescence stretches water pipe.
Therefore, to be starved of by arranging specific flexible water pipe formula, and by improving existing production technique, to prepare a kind of elasticity is high, good weatherability, intensity are large TPE and to stretch water pipe.
Summary of the invention
In order to solve the problem, one aspect of the present invention provides a kind of high-wearing feature and the weather-proof TPE of snappiness to stretch water pipe, and its raw materials comprises:
The MAH-g-SEBS of 100 weight parts;
The MAH-g-PP of 30 ~ 40 weight parts;
The white oil of 10 ~ 30 weight parts;
Modified Nano titanium oxide-super branched polyurethane the mixture of 5 ~ 15 weight parts; With
The amination graphene oxide of 5 ~ 10 weight parts;
Wherein said modified Nano titanium oxide-super branched polyurethane mixture uses amino silicane coupling agent to carry out modifiedly carrying out compound with super branched polyurethane again and preparing to nano-titanium oxide.
The percentage of grafting of described MAH-g-SEBS is 1.4% ~ 2.5%.
The percentage of grafting of described MAH-g-PP is 1% ~ 3%.
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 2:1.
Described vulcabond comprises isophorone diisocyanate, 4 ' 4-diphenylmethanediisocyanate, hexamethylene diisocyanate or 2,4 tolylene diisocyanates; Described trivalent alcohol comprises glycerol, TriMethylolPropane(TMP) or polyether-tribasic alcohol.
In described modified Nano titanium oxide-super branched polyurethane mixture, the weight ratio of modified Nano titanium oxide and super branched polyurethane is 1:5 ~ 10.
Described amination graphene oxide is obtained by amine monomers modification, described amine monomers comprises quadrol, butanediamine, 1,2-propylene diamine, 2-dimethyl-p-phenylenediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, 1,6-hexanediamine, 1,8-octamethylenediamine, 1,2-cyclohexanediamine, 1,5-naphthylene diamine, isophorone diamine.
Described amination graphene oxide is obtained by the diamines modification of side chain containing imidazole group, and wherein said side chain is selected from following at least one containing the diamines of imidazole group:
。
Described raw materials also comprises the additive of 0.5 ~ 5 weight part; Described additive comprises the silicon-dioxide of organosilicon ammonia alkane or organopolysiloxane modification; The calcium carbonate of lipid acid, fatty acid soaps, fatty acid ester modification; Anti-aging agent octyl diphenylamine; UV light absorber 2,2 '-dihydroxyl-4-methoxy benzophenone; Pigment carbon black.
Another aspect of the present invention there is provided a kind of weather-proof TPE of described snappiness for preparing and to stretch the method for water pipe, comprises the following steps:
(1) by the raw material of claim formula ratio, by weight after mixing, through twin screw extruder extruding pelletization;
(2) product that step (1) obtains is placed on 60 ~ 80 DEG C of hot air type hopper inner dryings 2 ~ 4 hours;
(3) by the product of step (2) gained, in 170 DEG C ~ 220 DEG C vacuum injections in mould, and under vacuum, keep this temperature 0.5 ~ 20 hour, then cooling curing, obtain the weather-proof TPE of snappiness and to stretch water pipe.
The present patent application provides the weather-proof TPE of a kind of snappiness and to stretch water pipe, can lengthen by automatic expansion after water being poured into this flexible water pipe under the pressure of 0.6MPa, profound to 15 meters from original 5 meters, and continuous water filling can not break for more than 150 times under the pressure of 0.8MPa, tension set is less than 15%, good springiness, can not be brittle on cold ground or winter, has excellent weather resistance.
Embodiment
The detailed description of the following preferred implementation method of the present invention of participation in the election and the embodiment comprised more easily can understand present disclosure.Can mention a large amount of term in following specification sheets and claims, these terms are defined as following implication.
During the Range Representation that equivalent, concentration or other value or parameter limit with scope, preferable range or a series of upper limit preferred value and lower preferable values, this is appreciated that all scopes specifically disclosing and formed by arbitrary pairing of any range limit or preferred value and any range lower limit or preferred value, no matter and whether this scope separately discloses.Such as, when disclosing scope " 1 to 5 ", described scope should be interpreted as comprising scope " 1 to 4 ", " 1 to 3 ", " 1-2 ", " 1-2 and 4-5 ", " 1-3 and 5 " etc.When numerical range is described in this article, unless otherwise indicated, otherwise this scope intention comprises its end value and all integers within the scope of this and mark.
One aspect of the present invention provides the weather-proof TPE of a kind of snappiness and to stretch water pipe, and its raw materials comprises:
The MAH-g-SEBS of 100 weight parts;
The MAH-g-PP of 30 ~ 40 weight parts;
The white oil of 10 ~ 30 weight parts;
Modified Nano titanium oxide-super branched polyurethane the mixture of 5 ~ 15 weight parts; With
The amination graphene oxide of 5 ~ 10 weight parts;
Wherein said modified Nano titanium oxide-super branched polyurethane mixture uses amino silicane coupling agent to carry out modifiedly carrying out compound with super branched polyurethane again and preparing to nano-titanium oxide.
MAH-g-SEBS：
The term " SEBS " used in the application 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 maleic anhydride modified SEBS, namely uses maleic anhydride to carry out graft modification to SEBS, can adopt solution graft copolymerization and fusion-grafting two kinds of method preparations, wherein, when solution grafting carries out SEBS grafting MAH, the graft reaction time is long, and grafting efficiency is low, need to consume poisonous, flammable solvent in a large number, production cost is high, large to human injury, contaminate environment, take up an area large, be difficult to realize continuous operation.Therefore, preferably melt grafting is adopted.
Be not particularly limited as the MAH-g-SEBS used in the present invention, can be commercially available or experiment synthesis, wherein, the percentage of grafting of maleic anhydride can be 1.4% ~ 2.5%; Preferably, in described MAH-g-SEBS, the percentage of grafting of MAH is 1.8%.
MAH-g-PP：
Described MAH-g-PP refers to maleic anhydride modified polypropylene, the maleic anhydride modified PP(MAH-g-PP as using in the present invention) be not particularly limited, can be commercially available or experiment synthesis, wherein, MAH percentage of grafting here can be 1% ~ 3%; Preferably, the percentage of grafting of MAH is 2%.
white oil:
White oil 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 two-phase consistency.
The application is not particularly limited white oil, can commercially availablely obtain.Preferably, the white oil of conformance with standard Q/MSH32-2009.
modified Nano titanium oxide-super branched polyurethane mixture:
The term " modified Nano titanium oxide-super branched polyurethane mixture " used in the application uses amino silicane coupling agent to carry out modifiedly carrying out compound with super branched polyurethane again and preparing to nano-titanium oxide.
In one embodiment, described super branched polyurethane preparation method 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 10 ~ 30%; Wherein, vulcabond is 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 9:8 ~ 3:1; After vulcabond has added, reaction system insulation reaction 10 ~ 30h; Then in reaction system, add protective material, at 30 ~ 100 DEG C, continue reaction 5 ~ 10h;
(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 ~ 24h at 50 ~ 140 DEG C, obtains the super branched polyurethane containing isocyanato of purifying.
Preferably, the mol ratio of the isocyanato-NCO of described vulcabond and the hydroxyl-OH of trivalent alcohol is 2:1.
In one embodiment, the preparation method of modified Nano titanium oxide-super branched polyurethane mixture is:
(1) aminosilane coupling agent modifying nano-titanium oxide:
60g toluene and 1g nano-titanium oxide is added in there-necked flask, ultrasonic disperse 30min, vigorous stirring, add 0.5 ~ 1g amino silicane coupling agent, the deionized water 10ml containing 1ml triethylamine, 110 DEG C of back flow reaction 4h, filter, with absolute ethanol washing, extraction three times, at the dry 24h of vacuum drying oven, obtain aminosilane coupling agent modifying nano-titanium oxide.
(2) modified Nano titanium oxide-super branched polyurethane mixture:
Aminosilane coupling agent modifying nano-titanium oxide 0.1g, super branched polyurethane 0.2 ~ 2g and the DMF 50ml of above-mentioned synthesis is added, after stirred at ambient temperature is even in there-necked flask; React after 8 ~ 24 hours at 30 ~ 60 DEG C, sedimentation and filtration in methyl alcohol, obtain modified Nano titanium oxide-super branched polyurethane mixture.
Amino silicane coupling agent comprises 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, N-2-aminoethyl-3-aminopropyl trimethoxysilane, N-2-aminoethyl-3-aminopropyltriethoxy dimethoxysilane, 3-aminopropyltriethoxy diethoxy silane, anilinomethyl triethoxysilane.
In one embodiment, in modified Nano titanium oxide-amidized super branched polyurethane mixture, the weight ratio of modified Nano titanium oxide and amidized super branched polyurethane is 1:5 ~ 10.
Super branched polyurethane has the spheroidal molecular structure of class, and intermolecular chain entanglement is less, the ester group in molecular chain can be embedded in highly branched structure, and then stops the contact with moisture in ester group and air, reduces hydrolysis probability, effectively improves weather resistance.In addition, the nano titania particle surface of aminosilane coupling agent modifying will with amino, can be interconnected by chemical action with the super branched polyurethane of isocyanato end-blocking, macromolecular complex effectively can avoid the reunion of nano particle, better self photolytic activity of performance nano-titanium oxide and anti-microbial property, improve ultra-violet resistance energy and the water tolerance of flexible water pipe, homodisperse nano oxidized titanium particle can also improve the density of whole material, and then improves the intensity of flexible water pipe.
amination graphene oxide:
" amination graphene oxide " in the application refers to the method by modification or grafting, makes in graphene oxide containing active amino.Containing the amino in amino group Graphene, can react with the anhydride group in MAH-g-SEBS, thus form crosslinking structure, to improve cross-linking density, thus provide Advantageous Effects of the present invention.
In one embodiment, described amination graphene oxide is obtained by amine monomers modification, described amine monomers comprises quadrol, butanediamine, 1,2-propylene diamine, 2-dimethyl-p-phenylenediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, 1,6-hexanediamine, 1,8-octamethylenediamine, 1,2-cyclohexanediamine, 1,5-naphthylene diamine, isophorone diamine.
In one embodiment, described amination graphene oxide is obtained by the amine modification of side chain containing imidazole group, and wherein said side chain is selected from following at least one containing the diamines of imidazole group:
。
In one embodiment, the preparation method of amination modified graphene oxide is:
(1) in there-necked flask, add DMF 100ml and graphene oxide 100mg, ultrasonic mixing 2 ~ 3h, obtain graphene oxide uniform dispersion;
(2) add 20 ~ 30g amine monomers again, condensing agent Dicyclohexylcarbodiimide 5 ~ 7g, ultrasonic mixing 5 ~ 10min, at 100 ~ 120 DEG C of reaction 30 ~ 48h, add 50 ~ 80ml dehydrated alcohol, leave standstill 24h;
(3) remove supernatant liquid, by tetrafluoroethylene membrane filtration lower sediment, and with dehydrated alcohol, deionized water wash, by the sample vacuum-drying 24h at 30 ~ 50 DEG C obtained, obtain amination modified graphene oxide.
Through great many of experiments, applicant is surprised to find that, by under vacuum injection condition, keeps pyroprocessing, can improve the cross-linking density of flexible water pipe further.This is due to graphene oxide containing a large amount of carboxyls; 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, improve the tensile strength of whole matrix material.In addition, the imidazole group introduced in preferred version effectively can improve oxidation-resistance, to provide Advantageous Effects of the present invention.
In one embodiment, the weight ratio of described modified Nano titanium oxide-super branched polyurethane mixture and amination graphene oxide is 1 ~ 1.4:1.
other stopping composition and additive:
Stretch in water pipe raw material at the weather-proof TPE of snappiness of the present invention, suitably can coordinate weighting agent to use as required.As packing material, be not particularly limited, can enumerate, the enhancement packing material that wood powder, paper pulp, cotton sheet, asbestos, glass fibre, carbon fiber, mica, walnut shell flour, powdered rice hulls, graphite, diatomite, terra alba, silicon-dioxide (Fumed Silica, settleability silicon-dioxide, crystallinity silicon-dioxide, fused silica, rhombspar, anhydrous silicic acid, moisture silicic acid etc.), carbon black are such; The packing material that water-ground limestone, calcene, magnesiumcarbonate, diatomite, calcined clay, clay, talcum, wilkinite, organobentonite, ferric oxide, red iron oxide, aluminium powder form, flint powder, zinc oxide, active zinc flower, zinc powder, zinc carbonate and natural glass matter hollow microsphere etc. are such; The fibrous filler material etc. that asbestos, glass fibre and glass yarn, carbon fiber, yaruru fiber, polyethylene fibre etc. are such.
When packing material is silicon-dioxide, its surface can be used to have carried out the silicon-dioxide of hydrophobic treatment with silicoorganic compound such as organosilane or organic silazane, diorganopolysiloxanecompositions in advance.In addition, calcium carbonate can use the organism such as lipid acid, fatty acid soaps, fatty acid ester or various tensio-active agent and the surface treatment agents such as various couplers such as silane coupling agent or titanic acid ester coupler to implement surface-treated calcium carbonate.
The weather-proof TPE of snappiness of the present invention stretches in water pipe raw material, to adjust for the purpose of raw material and the various physical property of flexible water pipe that obtain, optionally can also add various additive other than the above.As such additive, stablizer, softening agent, softness-conferring agent, fire retardant, pigment, antistatic agent, antibacterial mould resistant etc. can be added.
Such as, as anti-aging agent, can enumerate, phenyl-a-naphthylamine, octyl diphenylamine, N, N '-diphenyl-para-phenylene diamine, N, N '-two-betanaphthyl Ursol D.In addition, as photostabilizer or UV light absorber, can enumerate, 4-tert-butylphenyl salicylate acid esters, 2,4-dihydroxy benaophenonel, 2,2 '-dihydroxyl-4-methoxy benzophenone, ethyl-2-cyano group-3,3 ' diphenylacrylate ester, 2-ethylhexyl-2-cyano group-3,3 '-diphenylacrylate ester, 2-hydroxyl-5-chlorobenzophenone, ESCALOL 567,2-hydroxyl-4-octyloxybenzophenone, Whitfield's ointment monoethylene glycol ester, oxamide, 2,2 ', 4,4 '-tetrahydroxybenzophenone etc.As above-mentioned pigment, can enumerate compound below, but be not particularly limited, can enumerate, carbon black, zinc sulphide, zinc oxide etc., these can be used alone, and also can combine multiple use.
Another aspect of the present invention there is provided a kind of weather-proof TPE of described snappiness for preparing and to stretch the method for water pipe, comprises the following steps:
(1) by the raw material of claim formula ratio, by weight after mixing, through twin screw extruder extruding pelletization;
(2) product that step (1) obtains is placed on 60 ~ 80 DEG C of hot air type hopper inner dryings 2 ~ 4 hours;
(3) by the product of step (2) gained, in 170 DEG C ~ 220 DEG C vacuum injections in mould, and under vacuum, keep this temperature 0.5 ~ 20 hour, then cooling curing, obtain the weather-proof TPE of snappiness and to stretch water pipe.
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 there is no other explanation, raw materials used is all commercially available, nano titanium oxide (median size 10nm) is purchased from Nanjing nanometer Haitai company limited, graphene oxide is purchased from Nanjing Xian Feng Nono-material Science & Technology Ltd., other raw materials are purchased from Sigma-Aldrich company, and following material number used is weight part.
Raw material:
A1:MAH-g-SEBS(MAH percentage of grafting 1.4%)
A2:MAH-g-SEBS(MAH percentage of grafting 1.8%)
A3:MAH-g-SEBS(MAH percentage of grafting 2.5%)
B1:MAH-g-PP(MAH percentage of grafting 1%)
B2:MAH-g-PP(MAH percentage of grafting 2%)
B3:MAH-g-PP(MAH percentage of grafting 3%)
C1: white oil
D1: modified Nano titanium oxide-super branched polyurethane mixture
(1) super branched polyurethane is prepared:
The isophorone diisocyanate of 0.03mol is dissolved in the toluene of 20mL, obtain diisocyanate solution, then 0.015mol glycerol is dissolved in 20mL dimethyl sulphoxide solution, obtain trivalent alcohol solution, then described trivalent alcohol solution is joined in the there-necked flask of band magnetic agitation and reflux, 40 DEG C, under nitrogen protection, slowly add the toluene solution of described isophorone diisocyanate under stirring wherein;
After dripping, system continues to react 10h at 40 DEG C, in reaction medium, then add the phenol of 0.002mol, and heating, reacts 5h at 100 DEG C;
After reaction terminates, underpressure distillation goes out solvent; Products therefrom methyl alcohol-tetrahydrofuran (THF) (volume ratio 1:10) dissolving, sedimentation 3 times, filter, 60 DEG C of vacuum-drying 24h, obtain super branched polyurethane.
(2) aminosilane coupling agent modifying nano-titanium oxide:
60g toluene and 1g nano-titanium oxide is added in there-necked flask, ultrasonic disperse 30min, vigorous stirring, add 0.5g3-aminopropyl triethoxysilane, the deionized water 10ml containing 1ml triethylamine, 110 DEG C of back flow reaction 4h, filter, with absolute ethanol washing, extraction three times, at the dry 24h of vacuum drying oven, obtain aminosilane coupling agent modifying nano-titanium oxide.
(3) modified Nano titanium oxide-super branched polyurethane mixture:
Aminosilane coupling agent modifying nano-titanium oxide 0.1g, super branched polyurethane 0.2g and the DMF 50ml of above-mentioned synthesis is added, after stirred at ambient temperature is even in there-necked flask; React after 10 hours at 30 DEG C, sedimentation and filtration in methyl alcohol, obtain modified Nano titanium oxide-super branched polyurethane mixture.
D2: modified Nano titanium oxide-super branched polyurethane mixture
(1) super branched polyurethane is prepared: identical with D1 preparation process.
(2) aminosilane coupling agent modifying nano-titanium oxide:
60g toluene and 1g nano-titanium oxide is added in there-necked flask, ultrasonic disperse 30min, vigorous stirring, add 0.7g3-aminopropyl trimethoxysilane, the deionized water 10ml containing 1ml triethylamine, 110 DEG C of back flow reaction 4h, filter, with absolute ethanol washing, extraction three times, at the dry 24h of vacuum drying oven, obtain aminosilane coupling agent modifying nano-titanium oxide.
(3) modified Nano titanium oxide-super branched polyurethane mixture:
Aminosilane coupling agent modifying nano-titanium oxide 0.1g, super branched polyurethane 0.5g and the DMF 50ml of above-mentioned synthesis is added, after stirred at ambient temperature is even in there-necked flask; React after 10 hours at 30 DEG C, sedimentation and filtration in methyl alcohol, obtain modified Nano titanium oxide-super branched polyurethane mixture.
D3: modified Nano titanium oxide-super branched polyurethane mixture
(1) super branched polyurethane is prepared:
4 ' of 0.09mol 4-diphenylmethanediisocyanate is dissolved in the toluene of 20mL, obtain diisocyanate solution, then 0.08mol TriMethylolPropane(TMP) is dissolved in 20mL dimethyl sulphoxide solution, obtain three ethanolic solns, then described three ethanolic solns are joined in the there-necked flask of band magnetic agitation and reflux, 50 DEG C, under nitrogen protection, slowly add the toluene solution of 4 ' described 4-diphenylmethanediisocyanate under stirring wherein;
After dripping, system continues to react 20h at 35 DEG C, in reaction medium, then add the phenol of 0.002mol, and heating, reacts 7h at 80 DEG C;
After reaction terminates, underpressure distillation goes out solvent; Products therefrom methyl alcohol-tetrahydrofuran (THF) (volume ratio 1:10) dissolving, sedimentation 3 times, filter, 80 DEG C of vacuum-drying 18h, obtain super branched polyurethane.
(2) aminosilane coupling agent modifying nano-titanium oxide:
60g toluene and 1g nano-titanium oxide is added in there-necked flask, ultrasonic disperse 30min, vigorous stirring, add 1.0g3-aminopropyltriethoxy diethoxy silane, the deionized water 10ml containing 1ml triethylamine, 110 DEG C of back flow reaction 4h, filter, with absolute ethanol washing, extraction three times, at the dry 24h of vacuum drying oven, obtain aminosilane coupling agent modifying nano-titanium oxide.
(3) modified Nano titanium oxide-super branched polyurethane mixture:
Aminosilane coupling agent modifying nano-titanium oxide 0.1g, super branched polyurethane 0.5g and the DMF 50ml of above-mentioned synthesis is added, after stirred at ambient temperature is even in there-necked flask; React after 16 hours at 45 DEG C, sedimentation and filtration in methyl alcohol, obtain modified Nano titanium oxide-super branched polyurethane mixture.
D4: modified Nano titanium oxide-super branched polyurethane mixture
Be with the difference of D2:
The vulcabond used in step (1) is 2,4 tolylene diisocyanates, and trivalent alcohol is glycerol; And the mol ratio of 2,4 tolylene diisocyanates and glycerol is 3:1;
In step (3), aminosilane coupling agent modifying nano-titanium oxide and super branched polyurethane weight ratio are 1:10.
E1: amination graphene oxide
(1) in there-necked flask, add DMF 100ml and graphene oxide 100mg, ultrasonic mixing 2h, obtain graphene oxide uniform dispersion;
(2) add 20g butanediamine, condensing agent Dicyclohexylcarbodiimide 5g, ultrasonic mixing 5min, at 100 DEG C of reaction 40h, add 50ml dehydrated alcohol, leave standstill 24h;
(3) removing step (2) obtains the supernatant liquid of solution, by tetrafluoroethylene membrane filtration lower sediment, and with dehydrated alcohol, deionized water wash, by the sample vacuum-drying 24h at 45 DEG C obtained, obtains amination modified graphene oxide.
E2: amination graphene oxide
Be with E1 difference: in step (2), add 25g1,5-naphthylene diamine, condensing agent Dicyclohexylcarbodiimide 7g, ultrasonic mixing 10min, at 120 DEG C of reaction 30h, add 80ml dehydrated alcohol, leave standstill 24h.
E3: amination graphene oxide
Be with E1 difference: 1,5-naphthylene diamine is replaced with 25g following formula diamine monomer
，
Coordinate condensing agent Dicyclohexylcarbodiimide 7g, ultrasonic mixing 10min, at 120 DEG C of reaction 48h, add 80ml dehydrated alcohol, leave standstill 24h.
E4: amination graphene oxide
Be with E1 difference: 1,5-naphthylene diamine is replaced with 30g following formula diamine monomer
，
Coordinate condensing agent Dicyclohexylcarbodiimide 7g, ultrasonic mixing 10min, at 110 DEG C of reaction 45h, add 70ml dehydrated alcohol, leave standstill 24h.
F: additive
3-aminopropyltriethoxy diethoxy silane improved silica, oleic acid modified calcium carbonate, octyl diphenylamine, 2,2 '-dihydroxyl-4-methoxy benzophenone, carbon black; Weight ratio is 0.5:0.5:1:1:1.2
embodiment:
The composition of raw materials that table 1 is the flexible water pipe of preparation and consumption (parts by weight)
Table 1 embodiment (example) 1 ~ 9, comparative example (to) preparation method of 1 ~ 4 is as follows:
(1) after the raw material of each example being mixed by weight, through twin screw extruder extruding pelletization;
(2) product that step (1) obtains is placed on 80 DEG C of hot air type hopper inner dryings 3 hours;
(3) by the product of step (2) gained, in 195 DEG C of vacuum injections in mould, and under vacuum, keep this temperature 10 hours, then cooling curing, obtain the weather-proof TPE of snappiness and to stretch water pipe.
Comparative example 5(is to 5):
Use without 100 maleic anhydride modified weight part SEBS and 50 weight part PP as main raw material, be other composition of raw materials and the consumption of the flexible water pipe of preparation according to embodiment 9 in upper table 1, preparation method is as follows:
(1) by the raw material of claim formula ratio, by weight after mixing, through twin screw extruder extruding pelletization;
(2) product that step (1) obtains is placed on 80 DEG C of hot air type hopper inner dryings 3 hours;
(3) by the product of step (2) gained, in 200 DEG C of vacuum injections in mould, and under vacuum, keep this temperature 12 hours, then cooling curing, obtain the weather-proof TPE of snappiness and to stretch water pipe.
Comparative example 6(is to 6):
According to composition of raw materials and consumption that embodiment 9 in upper table 1 is the flexible water pipe of preparation, preparation method is as follows:
(1) by the raw material of claim formula ratio, by weight after mixing, through twin screw extruder extruding pelletization;
(2) by the product of step (1) gained, be injected in mould in 220 DEG C, keep this temperature 12 hours, then cooling curing, obtain the weather-proof TPE of snappiness and to stretch water pipe.
testing method
Test the flexible water pipe that above-described embodiment 1 ~ 9 and comparative example 1 ~ 6 obtain, testing method is as follows:
Tensile property: tensile strength and elongation at break measure according to JISK6251.
Weather resistance: according to the program of the SA method of JISK6266, carries out degeneration experiment to flexible water pipe.By the outside surface structure-oriented carbon lamp light source of flexible water pipe, experimental temperature 63 DEG C, this light of continuous irradiation, and water is sprayed on the outside surface of the flexible water pipe of pad, circulation in every 102 minutes 18 minutes.Annealing time is 48 hours, 96 hours and 168 hours.Constant strain fatigue experiment is carried out to each the flexible water pipe sample after experiment of degenerating, at 20 DEG C, with the circulation of 6.7Hz, 40% is applied to sample repeat elongation strain, and evaluate its endurance quality.The terminal evaluated is considered to when splitting in the surface of flexible water pipe.Repeat fatigue and cyclic with 1,000 ten thousand times to stop evaluating.
Test result is in table 2.
Table 2 test result
As can be seen from the above data, with do not use modified Nano titanium oxide-super branched polyurethane mixture, amination graphene oxide and do not adopt preparation method provided by the present invention to prepare product compared with, flexible water pipe prepared by the present invention is while having better tensile strength, also have excellent weather resistance concurrently, because herein is provided Advantageous Effects of the present invention.
Aforesaid example is only illustrative, for explaining some features of feature of the present disclosure.Appended claim is intended to the scope wide as far as possible that requirement it is contemplated that, and the embodiment presented herein is only the explanation of the embodiment of the selection of combination according to all possible embodiment.Therefore, the purpose of applicant is the selectional restriction that appended claim is not illustrated the example of feature of the present invention.And progress in science and technology is not replaced to be formed due to the inaccurate reason of language performance by the possible equivalent considered at present or son, and these changes also should be interpreted as being covered by appended claim in the conceived case.
Claims (10)
1. the weather-proof TPE of snappiness stretches a water pipe, and its raw materials comprises:
The MAH-g-SEBS of 100 weight parts;
The MAH-g-PP of 30 ~ 40 weight parts;
The white oil of 10 ~ 30 weight parts;
Modified Nano titanium oxide-super branched polyurethane the mixture of 5 ~ 15 weight parts; With
The amination graphene oxide of 5 ~ 10 weight parts;
Wherein said modified Nano titanium oxide-super branched polyurethane mixture uses amino silicane coupling agent to carry out modifiedly carrying out compound with super branched polyurethane again and preparing to nano-titanium oxide.
2. the weather-proof TPE of snappiness according to claim 1 stretches water pipe, and it is characterized in that, the percentage of grafting of described MAH-g-SEBS is 1.4% ~ 2.5%.
3. the weather-proof TPE of snappiness according to claim 1 stretches water pipe, and it is characterized in that, the percentage of grafting of described MAH-g-PP is 1% ~ 3%.
4. the weather-proof TPE of snappiness according to claim 1 stretches water pipe, it 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 2:1.
5. the weather-proof TPE of snappiness according to claim 4 stretches water pipe, and it is characterized in that, described vulcabond comprises isophorone diisocyanate, 4 ' 4-diphenylmethanediisocyanate, hexamethylene diisocyanate or 2,4 tolylene diisocyanates; Described trivalent alcohol comprises glycerol, TriMethylolPropane(TMP) or polyether-tribasic alcohol.
6. the weather-proof TPE of snappiness according to claim 1 stretches water pipe, and it is characterized in that, in described modified Nano titanium oxide-super branched polyurethane mixture, the weight ratio of modified Nano titanium oxide and super branched polyurethane is 1:5 ~ 10.
7. the weather-proof TPE of snappiness according to claim 1 stretches water pipe, it is characterized in that, described amination graphene oxide is obtained by amine monomers modification, described amine monomers comprises quadrol, butanediamine, 1,2-propylene diamine, 2-dimethyl-p-phenylenediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, 1,6-hexanediamine, 1,8-octamethylenediamine, 1,2-cyclohexanediamine, 1,5-naphthylene diamine, isophorone diamine.
8. the weather-proof TPE of snappiness according to claim 1 stretches water pipe, and it is characterized in that, described amination graphene oxide is obtained by the diamines modification of side chain containing imidazole group, and wherein said side chain is selected from following at least one containing the diamines of imidazole group:
。
9. the weather-proof TPE of snappiness according to claim 1 stretches water pipe, and it is characterized in that, described raw materials also comprises the additive of 0.5 ~ 5 weight part; Described additive comprises the silicon-dioxide of organosilicon ammonia alkane or organopolysiloxane modification; The calcium carbonate of lipid acid, fatty acid soaps, fatty acid ester modification; Anti-aging agent octyl diphenylamine; UV light absorber 2,2 '-dihydroxyl-4-methoxy benzophenone; Pigment carbon black.
10. prepare the weather-proof TPE of snappiness to stretch the method for water pipe, it is characterized in that,
(1) by the raw material described in claim any one of claim 1 ~ 9, by weight after mixing, through double-screw extruding pelletizing;
(2) product that step (1) obtains is placed on 60 ~ 80 DEG C of hot air type hopper inner dryings 2 ~ 4 hours;
(3) by the product of step (2) gained, in 170 DEG C ~ 220 DEG C vacuum injections in mould, and under vacuum, keep this temperature 0.5 ~ 20 hour, then cooling curing, obtain the weather-proof TPE of snappiness and to stretch water pipe.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510750926.7A CN105331030A (en) | 2015-11-06 | 2015-11-06 | High-elasticity weather-resistant TPE telescopic water pipe and preparation method thereof |
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| CN201510750926.7A CN105331030A (en) | 2015-11-06 | 2015-11-06 | High-elasticity weather-resistant TPE telescopic water pipe and preparation method thereof |
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| CN105331030A true CN105331030A (en) | 2016-02-17 |
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