A kind of rotational moulding modified polypropene and preparation method thereofTechnical field
The present invention relates to rotational moulding materials technical fields more particularly to a kind of rotational moulding modified polypropene and preparation method thereof.
Background technique
Roll moulding shaping technology process is that powdered resin quantitatively is packed into mold, and to mold heating while mold hangs down around mutualTwo straight axial-rotations obtain product through cooling and demolding so that resin melting be made to be coated on cavity surface, relative to other atType mode, device of rotomoulding forming and mould investment are few, and product is almost without internal stress, therefore in recent years, and society is to rotomoulded articlesCognition degree it is higher and higher, rotational moulding industry rapidly develops, and industry size rapidly expands, and rotational moulding new technology, new product emerge one after another.
With the increase of social demand and increasingly mature, the present adoptable resin variety of rotational molding technique of rotational molding techniqueAlso it greatly expands, main includes the polyethylene of various specifications, polycarbonate, polystyrene, nylon etc., the wherein consumption of polyethyleneAmount is the largest, and most of is rotational molding grade linear low density polyethylene, but since there is resistance to for linear low density polyethyleneThe defects of thermal creep performance is poor, tensile strength is poor, in high performance rotational molding product direction, ability is slightly inadequate.
Compared with polyethylene, polypropylene has many advantages, such as that rigidity is good, heat-resist, resistant to environmental cracking performance is good, but itsShock resistance is poor, affects it in the application in rotomoulded articles direction, therefore, is modified to polypropylene, so that it meetsRotational molding technique requirement is that have very big Social benefit and economic benefit.
Summary of the invention
In view of the above-mentioned problems, it is an object of the invention to design to provide a kind of rotational moulding modified polypropene and its preparation sideMethod, the modified polypropene being prepared has preferable toughness and shock resistance, while being also equipped with preferable transparency, is suitble toIt is used in rotational molding technique.
The present invention solves above-mentioned technical problem by following technological means:
A kind of rotational moulding modified polypropene mainly includes following raw material: polypropylene, EP rubbers, modified additive, antioxygenAgent, crosslinking agent, assistant crosslinking agent, the modified additive are the core outer claddings 1,3 to mix silver nanoparticle silica as core:2,4- bis- (3,4- dimethyl) benzylidene sorbitol acetal layers, then be grafted 2-hydroxy-4-n-octoxybenzophenone and be made.
Rotational moulding modified polypropene of the invention, raw material include EP rubbers, and one side EP rubbers and polypropylene havePreferable compatibility, the addition of another aspect EP rubbers can improve the toughness and anti-impact of polypropylene matrix to a certain extentPerformance is hit, while the addition of crosslinking agent and assistant crosslinking agent can increase the degree of cross linking between polypropylene matrix, in conjunction with anti-oxidantAgent can increase polyacrylic service life to a certain extent.
In addition, the modified additive in the present invention is to mix silver nanoparticle silicon oxide pellets as core, first nano-silicaSiClx bead as inorganic non-metallic particle, be added in polypropylene matrix itself have increase polypropylene matrix toughness andThe effect of shock resistance, and it is doped with silver in nano silica bead, the antibacterial and mouldproof of polypropylene matrix can be increasedEffect；But the compatibility mixed between silver nanoparticle silicon oxide pellets and polypropylene matrix is bad, and mixes silver nanoparticle silicaIt is easy to happen reunion between bead, causes its poor dispersion in polypropylene matrix, therefore, is mixing silver nanoparticle silicaBead outer cladding 1,3:2,4- bis- (3,4- dimethyl) benzylidene sorbitol acetal, firstly, 1,3:2,4- bis- (3,4- dimethyl)Compatibility between benzylidene sorbitol acetal and polypropylene is preferable, can increase the phase between modified additive and polypropylene matrixCapacitive, and the agglomerating force mixed between silver nanoparticle silicon oxide pellets can be reduced, so that modified additive is in polypropylene-base bodyIt is dispersed more preferable, there is better effect, while 1,3:2,4- bis- to the raising of the toughening and shock resistance of polypropylene matrix(3,4- dimethyl) benzylidene sorbitol acetal can be used as heterogeneous nucleation agent, can reduce the crystallinity of polypropylene matrix, and byIt is good in its compatibility between polypropylene matrix, the interface between modified additive and polypropylene matrix can be obscured, thereforeThe transparency of polypropylene matrix can also be improved；In addition, being also grafted 2- hydroxyl -4- n-octyloxy hexichol on modified additiveKetone, one side 2-hydroxy-4-n-octoxybenzophenone can reduce ultraviolet light to polyacrylic old as ultraviolet absorberChange effect, while the presence of 2-hydroxy-4-n-octoxybenzophenone being capable of equilibrium modifiers additive and poly- to a certain extentAdhesion strength between polypropylene matrix prevents the excessive influence composite material of adhesive strength between modified additive and polypropylene matrixBetween brittle ductile transition, reduce to the toughening of polypropylene matrix and increase shock resistance effect.
Therefore, modified additive of the invention can not only increase the toughness and shock resistance of polypropylene matrix, moreover it is possible toIts transparency, anti-microbial property and anti-ultraviolet function are enough improved, and modified additive is that the progress of each material is compound and existingEvery kind of material exclusive use is compared, during use, the dispersion performance in polypropylene matrix is more preferable, and between materialIt can complement each other, more preferably play a role.
Further, the quality of the polypropylene, EP rubbers, modified additive, antioxidant, crosslinking agent, assistant crosslinking agentThan for (100-110): (15-20): (1-3): (0.1-0.2): (0.1-0.3): (0.1-0.3).
Further, the quality of the polypropylene, EP rubbers, modified additive, antioxidant, crosslinking agent, assistant crosslinking agentThan for 100:16:2:0.1:0.2:0.2.
Further, the antioxidant is 1,3,5- trimethyls -2,4,6- tri- (3,5- di-tert-butyl-4-hydroxyl benzyl)Benzene, crosslinking agent are cumyl peroxide, and assistant crosslinking agent is divinylbenzene.
In addition, the invention also discloses a kind of preparation method of rotational moulding modified polypropene, the preparation method include withLower step:
It weighs: according to mass ratio (100-110): (15-20): (1-3): (0.1-0.2): (0.1-0.3): (0.1-0.3)Polypropylene, EP rubbers, modified additive, antioxidant, crosslinking agent, assistant crosslinking agent are weighed respectively；
It mediates: polypropylene, EP rubbers, modified additive, the antioxidant of 25%~30% weight being taken to be placed in kneaderIt is interior, 15-20min is mediated under conditions of revolving speed is 500-950r/min, temperature is 60-70 DEG C；
Be kneaded: the product that kneading step is prepared is placed in continuous mixer, and titanate coupling agent is added, is being kneadedTemperature is 110 DEG C, extrusion temperature is 155 DEG C, die head temperature is 150 DEG C, mixing revolving speed is kneaded under conditions of being 35r/min10min obtains functional master batch；
Extruding pelletization: by the functional master batch being prepared, remaining 70%~75% weight polypropylene, crosslinking agent, help friendshipJoin agent after mixing, through double screw extruder extruding pelletization, obtains modified polypropene.
Further, the modified additive the preparation method comprises the following steps:
Cladding: it will be scattered in methyl phenyl ethers anisole solution by pretreated silver nanoparticle silicon oxide pellets of mixing, ultrasonic disperse1,3:2,4- bis- (3,4- dimethyl) benzylidene sorbitol acetal is added in 20min, is heated to 70-80 DEG C, after keeping the temperature 30min, stopsHeating is filtered, washed, dries after standing 3-4h；
Grafting: taking 2-hydroxy-4-n-octoxybenzophenone stirring and dissolving in dehydrated alcohol, and adjusting pH value is 6-7, obtainsTo reaction solution, the product that encapsulation steps are prepared is placed in plasma reactor, using ammonia as working gas, intoIt after row corona treatment 10-20s, is scattered in reaction solution, heating water bath is protected to 50-60 DEG C under the conditions of ultrasonic agitationTemperature reaction 10-12h, after the reaction was completed, be filtered, washed, dry after obtain modified additive.
Using ammonia as reaction gas in the grafting the step of, to being coated with 1,3:2,4- bis- (3,4- dimethyl) benzylDuring the nano silica bead progress corona treatment for pitching sorbitol acetal, amino base is introduced on its surfaceGroup, so that 2-hydroxy-4-n-octoxybenzophenone can be preferably grafted.
Further, 1,3:2,4-, bis- (3,4- dimethyl) the benzylidene sorbitol acetal and 2- hydroxyl -4- n-octyloxy twoThe molar ratio of Benzophenone is 1:0.3.
Pass through (3,4- dimethyl) the benzylidene sorbitol acetal of 1,3:2,4- bis- and 2-hydroxy-4-n-octoxybenzophenoneMolar ratio setting, controls the grafting rate of 2-hydroxy-4-n-octoxybenzophenone, with this equilibrium modifiers additive and polypropylene-baseInterface binding intensity between body.
Further, the pretreatment are as follows: silver nanoparticle silicon oxide pellets will be mixed and be placed in reaction of low temperature plasma device, oneArgon gas is working gas, is 0.4-0.6L/s in gas flow, power carries out at low temperature plasma under conditions of being 80-90WManage 1-2min.
Low Temperature Plasma Treating is carried out as working gas using argon gas to the surface for mixing silver nanoparticle silicon oxide pellets,During the treatment, argon plasma bombardment is to the surface of silver nanoparticle silicon oxide pellets is mixed, so that mixing silver nanoparticle dioxySiClx bead surface becomes coarse, so that (3,4- dimethyl) the benzylidene sorbitol acetal of 1,3:2,4- bis- and mixing silver nanoparticle twoIt is combined between silica bead more preferable.
Further, it is described mix silver nanoparticle silica the preparation method comprises the following steps: 5ml20% is added dropwise into every liter of deionized waterAmmonium hydroxide, adjusting pH value with 0.1mol/L sodium hydroxide solution is 10-11, and silver nitrate, tetraethyl orthosilicate, anhydrous second is then addedAlcohol is protected from light after stirring 5min, is warming up to 40 DEG C, and oxalic acid solution is added dropwise, and ultrasonic agitation reaction 4-5h is filtered, the anhydrous second of filter cakeAlcohol washing, vacuum drying obtain mixing silver nanoparticle silicon oxide pellets.
Beneficial effects of the present invention:
1. a kind of rotational moulding modified polypropene of the invention, changes polypropylene by EP rubbers, modified additiveProperty, can improve the toughness and shock resistance of polypropylene matrix to a certain extent, while crosslinking agent and assistant crosslinking agent plusEnter the degree of cross linking that can be increased between polypropylene matrix, polyacrylic make can be increased to a certain extent in conjunction with antioxidantUse the service life.
2. modified additive of the invention can not only increase the toughness and shock resistance of polypropylene matrix, additionally it is possible toIts transparency, anti-microbial property and anti-ultraviolet function are improved, and modified additive is that each material is carried out to compound and existing generalEvery kind of material exclusive use is compared, and during use, the dispersion performance in polypropylene matrix is more preferable, and energy between materialIt enough complements each other, more preferably plays a role.
Specific embodiment
Below with reference to specific embodiment, the present invention is described in detail:
A kind of rotational moulding modified polypropene of the invention and preparation method thereof, joined modified additive in the feed, shouldModified additive is the core outer cladding 1,3:2 to mix silver nanoparticle silica as core, 4- bis- (3,4- dimethyl) benzal sorbAcetal layer, then be grafted 2-hydroxy-4-n-octoxybenzophenone and be made.
Embodiment one
The preparation 1 of modified additive
It mixes the preparation of silver nanoparticle silica: the ammonium hydroxide of 5ml 20% being added dropwise into every liter of deionized water, uses 0.1mol/LIt is 10 that sodium hydroxide solution, which adjusts pH value, and 5mg silver nitrate, 10g tetraethyl orthosilicate, 10g dehydrated alcohol, stirring is then addedIt after 5min, is protected from light, is warming up to 40 DEG C, ultrasonic agitation reaction is molten with the oxalic acid that 245ml 0.035g/L is added dropwise in the speed of 2d/minLiquid, while the pH value for adjusting solution is 9-10, is added dropwise to complete rear insulation reaction 2h, is filtered, filter cake is washed 3 times with dehydrated alcohol,It is dried in vacuo 12h at a temperature of 60 DEG C, obtains mixing silver nanoparticle silicon oxide pellets.
Cladding: will mix silver nanoparticle silicon oxide pellets and be placed in reaction of low temperature plasma device, using argon gas as working gas,It is 0.6L/s in gas flow, power carries out Low Temperature Plasma Treating 1min under conditions of being 90W, is then according to solid-to-liquid ratio30g/L is scattered in methyl phenyl ethers anisole solution, and ultrasonic disperse 20min obtains suspension, and 18g 1,3:2,4- bis- is added in every liter of suspension(3,4- dimethyl) benzylidene sorbitol acetal is heated to 70 DEG C, after keeping the temperature 30min, stops heating, after standing 4h, filtering, and filter cakeIt is washed with ethyl acetate and sodium carbonate to being in neutrality, is dried at a temperature of 40 DEG C.
Grafting: take 2-hydroxy-4-n-octoxybenzophenone stirring and dissolving in etc. quality dehydrated alcohol in, use 1mol/LIt is 6-7 that sodium hydroxide solution, which adjusts pH value, obtains reaction solution, it is anti-that the product that encapsulation steps are prepared is placed in plasmaIt answers in device, is 8Pa in pressure, power carries out corona treatment 15s under conditions of being 110W using ammonia as working gasAfterwards, it is scattered in reaction solution according to the solid-to-liquid ratio of 25g/L, heating water bath is to 50 DEG C under the conditions of ultrasonic agitation, insulation reaction12h, after the reaction was completed, filtering, filter cake acetone washing obtain modified additive after being dried in vacuo at a temperature of 40 DEG C.
Embodiment two
The preparation 2 of modified additive
It mixes the preparation of silver nanoparticle silica: the ammonium hydroxide of 5ml 20% being added dropwise into every liter of deionized water, uses 0.1mol/LIt is 11 that sodium hydroxide solution, which adjusts pH value, and 5mg silver nitrate, 10g tetraethyl orthosilicate, 10g dehydrated alcohol, stirring is then addedIt after 5min, is protected from light, is warming up to 40 DEG C, ultrasonic agitation reaction is molten with the oxalic acid that 245ml 0.035g/L is added dropwise in the speed of 2d/minLiquid, while the pH value for adjusting solution is 9-10, is added dropwise to complete rear insulation reaction 1, is filtered, filter cake is washed 3 times with dehydrated alcohol, inIt is dried in vacuo 12h at a temperature of 60 DEG C, obtains mixing silver nanoparticle silicon oxide pellets.
Cladding: will mix silver nanoparticle silicon oxide pellets and be placed in reaction of low temperature plasma device, using argon gas as working gas,It is 0.4L/s in gas flow, power carries out Low Temperature Plasma Treating 2min under conditions of being 80W, is then according to solid-to-liquid ratio30g/L is scattered in methyl phenyl ethers anisole solution, and ultrasonic disperse 20min obtains suspension, and 18g 1,3:2,4- bis- is added in every liter of suspension(3,4- dimethyl) benzylidene sorbitol acetal is heated to 75 DEG C, after keeping the temperature 30min, stops heating, after standing 3h, filtering, and filter cakeIt is washed with ethyl acetate and sodium carbonate to being in neutrality, is dried at a temperature of 40 DEG C.
Grafting: take 2-hydroxy-4-n-octoxybenzophenone stirring and dissolving in etc. quality dehydrated alcohol in, use 1mol/LIt is 6-7 that sodium hydroxide solution, which adjusts pH value, obtains reaction solution, it is anti-that the product that encapsulation steps are prepared is placed in plasmaIt answers in device, is 8Pa in pressure, power carries out corona treatment 20s under conditions of being 110W using ammonia as working gasAfterwards, it is scattered in reaction solution according to the solid-to-liquid ratio of 25g/L, heating water bath is to 60 DEG C under the conditions of ultrasonic agitation, insulation reaction10h, after the reaction was completed, filtering, filter cake acetone washing obtain modified additive after being dried in vacuo at a temperature of 40 DEG C.
Embodiment three
The preparation 3 of modified additive
It mixes the preparation of silver nanoparticle silica: the ammonium hydroxide of 5ml 20% being added dropwise into every liter of deionized water, uses 0.1mol/LIt is 10 that sodium hydroxide solution, which adjusts pH value, and 5mg silver nitrate, 10g tetraethyl orthosilicate, 10g dehydrated alcohol, stirring is then addedIt after 5min, is protected from light, is warming up to 40 DEG C, ultrasonic agitation reaction is molten with the oxalic acid that 245ml 0.035g/L is added dropwise in the speed of 2d/minLiquid, while the pH value for adjusting solution is 9-10, is added dropwise to complete rear insulation reaction 2h, is filtered, filter cake is washed 3 times with dehydrated alcohol,It is dried in vacuo 12h at a temperature of 60 DEG C, obtains mixing silver nanoparticle silicon oxide pellets.
Cladding: will mix silver nanoparticle silicon oxide pellets and be placed in reaction of low temperature plasma device, using argon gas as working gas,It is 0.5L/s in gas flow, power carries out Low Temperature Plasma Treating 1min under conditions of being 85W, is then according to solid-to-liquid ratio30g/L is scattered in methyl phenyl ethers anisole solution, and ultrasonic disperse 20min obtains suspension, and 18g 1,3:2,4- bis- is added in every liter of suspension(3,4- dimethyl) benzylidene sorbitol acetal is heated to 80 DEG C, after keeping the temperature 30min, stops heating, after standing 4h, filtering, and filter cakeIt is washed with ethyl acetate and sodium carbonate to being in neutrality, is dried at a temperature of 40 DEG C.
Grafting: take 2-hydroxy-4-n-octoxybenzophenone stirring and dissolving in etc. quality dehydrated alcohol in, use 1mol/LIt is 6-7 that sodium hydroxide solution, which adjusts pH value, obtains reaction solution, it is anti-that the product that encapsulation steps are prepared is placed in plasmaIt answers in device, is 8Pa in pressure, power carries out corona treatment 10s under conditions of being 110W using ammonia as working gasAfterwards, it is scattered in reaction solution according to the solid-to-liquid ratio of 25g/L, heating water bath is to 55 DEG C under the conditions of ultrasonic agitation, insulation reaction11h, after the reaction was completed, filtering, filter cake acetone washing obtain modified additive after being dried in vacuo at a temperature of 40 DEG C.
Example IV
The preparation 1 of modified polypropene
The present embodiment selects embodiment one to prepare resulting modified additive, the specific steps are as follows:
It weighs: being that 100:16:2:0.1:0.2:0.2 weighs polypropylene, EP rubbers, modified addition respectively according to mass ratioAgent, antioxidant, crosslinking agent, assistant crosslinking agent.
It mediates: taking polypropylene, EP rubbers, modified additive, the antioxidant 1,3 of 25%~30% weight, 5- front threeBase -2,4,6- tri- (3,5- di-tert-butyl-4-hydroxyl benzyl) benzene are placed in kneader, revolving speed be 950r/min, temperature 6015min is mediated under conditions of DEG C.
Be kneaded: the product that kneading step is prepared is placed in continuous mixer, and titanate coupling agent is added, is being kneadedTemperature is 110 DEG C, and extrusion temperature is 155 DEG C, and die head temperature is 150 DEG C, is kneaded under conditions of revolving speed is 35r/min and is kneaded10min obtains functional master batch.
Extruding pelletization: by the functional master batch being prepared, the polypropylene of remaining 70%~75% weight, crosslinking agent peroxidatingDiisopropylbenzene (DIPB), assistant crosslinking agent divinylbenzene after mixing, are placed in double screw extruder, are 150r/min in screw speed, intoMaterial mouth temperature is 130 DEG C, and interlude temperature is 165 DEG C, and head temperature is 175 DEG C, and the condition extrusion that die head temperature is 165 DEG C is madeGrain, obtains modified polypropene.
Embodiment five
The preparation 2 of modified polypropene
The present embodiment selects embodiment two to prepare resulting modified additive, the specific steps are as follows:
It weighs: being that 110:20:3:0.1:0.1:0.3 weighs polypropylene, EP rubbers, modified addition respectively according to mass ratioAgent, antioxidant, crosslinking agent, assistant crosslinking agent.
It mediates: taking polypropylene, EP rubbers, modified additive, the antioxidant 1,3 of 25%~30% weight, 5- front threeBase -2,4,6- tri- (3,5- di-tert-butyl-4-hydroxyl benzyl) benzene are placed in kneader, revolving speed be 750r/min, temperature 6518min is mediated under conditions of DEG C.
Be kneaded: the product that kneading step is prepared is placed in continuous mixer, and titanate coupling agent is added, is being kneadedTemperature is 110 DEG C, and extrusion temperature is 155 DEG C, and die head temperature is 150 DEG C, is kneaded under conditions of revolving speed is 35r/min and is kneaded10min obtains functional master batch.
Extruding pelletization: by the functional master batch being prepared, the polypropylene of remaining 70%~75% weight, crosslinking agent peroxidatingDiisopropylbenzene (DIPB), assistant crosslinking agent divinylbenzene after mixing, are placed in double screw extruder, are 150r/min in screw speed, intoMaterial mouth temperature is 130 DEG C, and interlude temperature is 165 DEG C, and head temperature is 175 DEG C, and the condition extrusion that die head temperature is 165 DEG C is madeGrain, obtains modified polypropene.
Embodiment six
The preparation 3 of modified polypropene
The present embodiment selects embodiment three to prepare resulting modified additive, the specific steps are as follows:
It weighs: being that 105:15:1:0.2:0.3:0.1 weighs polypropylene, EP rubbers, modified addition respectively according to mass ratioAgent, antioxidant, crosslinking agent, assistant crosslinking agent
It mediates: taking polypropylene, EP rubbers, modified additive, the antioxidant 1,3 of 25%~30% weight, 5- front threeBase -2,4,6- tri- (3,5- di-tert-butyl-4-hydroxyl benzyl) benzene are placed in kneader, revolving speed be 500r/min, temperature 7015min is mediated under conditions of DEG C.
Be kneaded: the product that kneading step is prepared is placed in continuous mixer, and titanate coupling agent is added, is being kneadedTemperature is 110 DEG C, and extrusion temperature is 155 DEG C, and die head temperature is 150 DEG C, is kneaded under conditions of revolving speed is 35r/min and is kneaded10min obtains functional master batch.
Extruding pelletization: by the functional master batch being prepared, the polypropylene of remaining 70%~75% weight, crosslinking agent peroxidatingDiisopropylbenzene (DIPB), assistant crosslinking agent divinylbenzene after mixing, are placed in double screw extruder, are 150r/min in screw speed, intoMaterial mouth temperature is 130 DEG C, and interlude temperature is 165 DEG C, and head temperature is 175 DEG C, and the condition extrusion that die head temperature is 165 DEG C is madeGrain, obtains modified polypropene.
Embodiment seven
The present embodiment and example IV the difference is that, do not add modified additive in the present embodiment, will prepareRequired nano silica bead in modified additive, 1,3:2,4- bis- (3,4- dimethyl) benzylidene sorbitol acetal, 2-Hydroxyl -4- oxy-octyl benzophenone is directly added into.
The stretching yield stress for the modified polypropene that example IV~embodiment seven is prepared, bending modulus, anti-impactHit performance, transparency is tested, test result is as follows shown in table:
It can be seen that the modified polypropene being prepared using inventive formulation, toughness and shock resistance by upper tableIt is all improved, while the modified additive that adds of the present invention is composite material, relative to the existing mode individually added,The effect of toughening and raising shock resistance to polypropylene matrix is more preferable, and more to the effect of polypropylene matrix transparency raisingIt is good.
The above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to preferred embodiment to this hairIt is bright to be described in detail, those skilled in the art should understand that, it can modify to technical solution of the present inventionOr equivalent replacement should all cover without departing from the objective and range of technical solution of the present invention in claim of the inventionIn range.Technology not described in detail in the present invention, shape, construction portion are well-known technique.