CN110157099A - A kind of rotational moulding modified polypropene and preparation method thereof - Google Patents
A kind of rotational moulding modified polypropene and preparation method thereof Download PDFInfo
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- CN110157099A CN110157099A CN201910507389.1A CN201910507389A CN110157099A CN 110157099 A CN110157099 A CN 110157099A CN 201910507389 A CN201910507389 A CN 201910507389A CN 110157099 A CN110157099 A CN 110157099A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
Abstract
The invention discloses a kind of rotational moulding modified polypropenes and preparation method thereof, it is related to rotational moulding materials technical field, a kind of rotational moulding modified polypropene mainly includes following raw material: polypropylene, EP rubbers, modified additive, antioxidant, crosslinking agent, assistant crosslinking agent, wherein, modified additive is to mix silver nanoparticle silica as core, core outer cladding 1,3:2,4- bis- (3,4- dimethyl) benzylidene sorbitol acetal layer, then be grafted 2-hydroxy-4-n-octoxybenzophenone and be made.A kind of rotational moulding modified polypropene of the invention and preparation method thereof, the modified polypropene being prepared has preferable toughness and shock resistance, while being also equipped with preferable transparency, is suitable for rotational molding technique use.
Description
Technical 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 mutual
Two straight axial-rotations obtain product through cooling and demolding so that resin melting be made to be coated on cavity surface, relative to other at
Type 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 articles
Cognition 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 technique
Also it greatly expands, main includes the polyethylene of various specifications, polycarbonate, polystyrene, nylon etc., the wherein consumption of polyethylene
Amount is the largest, and most of is rotational molding grade linear low density polyethylene, but since there is resistance to for linear low density polyethylene
The 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 its
Shock resistance is poor, affects it in the application in rotomoulded articles direction, therefore, is modified to polypropylene, so that it meets
Rotational 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 side
Method, the modified polypropene being prepared has preferable toughness and shock resistance, while being also equipped with preferable transparency, is suitble to
It 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, antioxygen
Agent, 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 have
Preferable compatibility, the addition of another aspect EP rubbers can improve the toughness and anti-impact of polypropylene matrix to a certain extent
Performance 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-oxidant
Agent 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-silica
SiClx bead as inorganic non-metallic particle, be added in polypropylene matrix itself have increase polypropylene matrix toughness and
The effect of shock resistance, and it is doped with silver in nano silica bead, the antibacterial and mouldproof of polypropylene matrix can be increased
Effect；But the compatibility mixed between silver nanoparticle silicon oxide pellets and polypropylene matrix is bad, and mixes silver nanoparticle silica
It is easy to happen reunion between bead, causes its poor dispersion in polypropylene matrix, therefore, is mixing silver nanoparticle silica
Bead 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 matrix
Capacitive, and the agglomerating force mixed between silver nanoparticle silicon oxide pellets can be reduced, so that modified additive is in polypropylene-base body
It 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 by
It is good in its compatibility between polypropylene matrix, the interface between modified additive and polypropylene matrix can be obscured, therefore
The transparency of polypropylene matrix can also be improved；In addition, being also grafted 2- hydroxyl -4- n-octyloxy hexichol on modified additive
Ketone, one side 2-hydroxy-4-n-octoxybenzophenone can reduce ultraviolet light to polyacrylic old as ultraviolet absorber
Change effect, while the presence of 2-hydroxy-4-n-octoxybenzophenone being capable of equilibrium modifiers additive and poly- to a certain extent
Adhesion strength between polypropylene matrix prevents the excessive influence composite material of adhesive strength between modified additive and polypropylene matrix
Between 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 to
Its transparency, anti-microbial property and anti-ultraviolet function are enough improved, and modified additive is that the progress of each material is compound and existing
Every kind of material exclusive use is compared, during use, the dispersion performance in polypropylene matrix is more preferable, and between material
It can complement each other, more preferably play a role.
Further, the quality of the polypropylene, EP rubbers, modified additive, antioxidant, crosslinking agent, assistant crosslinking agent
Than 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 agent
Than 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 with
Lower 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 kneader
It 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 kneaded
Temperature 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/min
10min obtains functional master batch；
Extruding pelletization: by the functional master batch being prepared, remaining 70%~75% weight polypropylene, crosslinking agent, help friendship
Join 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 disperse
1,3:2,4- bis- (3,4- dimethyl) benzylidene sorbitol acetal is added in 20min, is heated to 70-80 DEG C, after keeping the temperature 30min, stops
Heating 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, obtains
To reaction solution, the product that encapsulation steps are prepared is placed in plasma reactor, using ammonia as working gas, into
It 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 agitation
Temperature 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) benzyl
During the nano silica bead progress corona treatment for pitching sorbitol acetal, amino base is introduced on its surface
Group, 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 two
The 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-octoxybenzophenone
Molar ratio setting, controls the grafting rate of 2-hydroxy-4-n-octoxybenzophenone, with this equilibrium modifiers additive and polypropylene-base
Interface 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, one
Argon gas is working gas, is 0.4-0.6L/s in gas flow, power carries out at low temperature plasma under conditions of being 80-90W
Manage 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 dioxy
SiClx bead surface becomes coarse, so that (3,4- dimethyl) the benzylidene sorbitol acetal of 1,3:2,4- bis- and mixing silver nanoparticle two
It 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 water
Ammonium hydroxide, adjusting pH value with 0.1mol/L sodium hydroxide solution is 10-11, and silver nitrate, tetraethyl orthosilicate, anhydrous second is then added
Alcohol 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 cake
Alcohol 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 additive
Property, can improve the toughness and shock resistance of polypropylene matrix to a certain extent, while crosslinking agent and assistant crosslinking agent plus
Enter the degree of cross linking that can be increased between polypropylene matrix, polyacrylic make can be increased to a certain extent in conjunction with antioxidant
Use 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 to
Its transparency, anti-microbial property and anti-ultraviolet function are improved, and modified additive is that each material is carried out to compound and existing general
Every kind of material exclusive use is compared, and during use, the dispersion performance in polypropylene matrix is more preferable, and energy between material
It 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, should
Modified additive is the core outer cladding 1,3:2 to mix silver nanoparticle silica as core, 4- bis- (3,4- dimethyl) benzal sorb
Acetal 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/L
It is 10 that sodium hydroxide solution, which adjusts pH value, and 5mg silver nitrate, 10g tetraethyl orthosilicate, 10g dehydrated alcohol, stirring is then added
It 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/min
Liquid, 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 ratio
30g/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 cake
It 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/L
It 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 plasma
It answers in device, is 8Pa in pressure, power carries out corona treatment 15s under conditions of being 110W using ammonia as working gas
Afterwards, 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 reaction
12h, 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/L
It is 11 that sodium hydroxide solution, which adjusts pH value, and 5mg silver nitrate, 10g tetraethyl orthosilicate, 10g dehydrated alcohol, stirring is then added
It 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/min
Liquid, 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, in
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 0.4L/s in gas flow, power carries out Low Temperature Plasma Treating 2min under conditions of being 80W, is then according to solid-to-liquid ratio
30g/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 cake
It 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/L
It 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 plasma
It answers in device, is 8Pa in pressure, power carries out corona treatment 20s under conditions of being 110W using ammonia as working gas
Afterwards, 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 reaction
10h, 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/L
It is 10 that sodium hydroxide solution, which adjusts pH value, and 5mg silver nitrate, 10g tetraethyl orthosilicate, 10g dehydrated alcohol, stirring is then added
It 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/min
Liquid, 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 ratio
30g/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 cake
It 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/L
It 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 plasma
It answers in device, is 8Pa in pressure, power carries out corona treatment 10s under conditions of being 110W using ammonia as working gas
Afterwards, 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 reaction
11h, 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 ratio
Agent, antioxidant, crosslinking agent, assistant crosslinking agent.
It mediates: taking polypropylene, EP rubbers, modified additive, the antioxidant 1,3 of 25%~30% weight, 5- front three
Base -2,4,6- tri- (3,5- di-tert-butyl-4-hydroxyl benzyl) benzene are placed in kneader, revolving speed be 950r/min, temperature 60
15min 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 kneaded
Temperature 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 kneaded
10min obtains functional master batch.
Extruding pelletization: by the functional master batch being prepared, the polypropylene of remaining 70%~75% weight, crosslinking agent peroxidating
Diisopropylbenzene (DIPB), assistant crosslinking agent divinylbenzene after mixing, are placed in double screw extruder, are 150r/min in screw speed, into
Material 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 made
Grain, 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 ratio
Agent, antioxidant, crosslinking agent, assistant crosslinking agent.
It mediates: taking polypropylene, EP rubbers, modified additive, the antioxidant 1,3 of 25%~30% weight, 5- front three
Base -2,4,6- tri- (3,5- di-tert-butyl-4-hydroxyl benzyl) benzene are placed in kneader, revolving speed be 750r/min, temperature 65
18min 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 kneaded
Temperature 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 kneaded
10min obtains functional master batch.
Extruding pelletization: by the functional master batch being prepared, the polypropylene of remaining 70%~75% weight, crosslinking agent peroxidating
Diisopropylbenzene (DIPB), assistant crosslinking agent divinylbenzene after mixing, are placed in double screw extruder, are 150r/min in screw speed, into
Material 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 made
Grain, 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 ratio
Agent, antioxidant, crosslinking agent, assistant crosslinking agent
It mediates: taking polypropylene, EP rubbers, modified additive, the antioxidant 1,3 of 25%~30% weight, 5- front three
Base -2,4,6- tri- (3,5- di-tert-butyl-4-hydroxyl benzyl) benzene are placed in kneader, revolving speed be 500r/min, temperature 70
15min 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 kneaded
Temperature 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 kneaded
10min obtains functional master batch.
Extruding pelletization: by the functional master batch being prepared, the polypropylene of remaining 70%~75% weight, crosslinking agent peroxidating
Diisopropylbenzene (DIPB), assistant crosslinking agent divinylbenzene after mixing, are placed in double screw extruder, are 150r/min in screw speed, into
Material 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 made
Grain, 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 prepare
Required 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-impact
Hit 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 table
It 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 raising
It 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 hair
It is bright to be described in detail, those skilled in the art should understand that, it can modify to technical solution of the present invention
Or equivalent replacement should all cover without departing from the objective and range of technical solution of the present invention in claim of the invention
In range.Technology not described in detail in the present invention, shape, construction portion are well-known technique.
Claims (9)
1. a kind of rotational moulding modified polypropene, which is characterized in that mainly include following raw material: polypropylene, EP rubbers, modification add
Add agent, antioxidant, crosslinking agent, assistant crosslinking agent, the modified additive is to mix silver nanoparticle silica as core, outside core
1,3:2,4- bis- (3,4- dimethyl) benzylidene sorbitol acetal layer is coated, then is grafted 2-hydroxy-4-n-octoxybenzophenone system
?.
2. a kind of rotational moulding modified polypropene according to claim 1, which is characterized in that the polypropylene, EP rubbers,
Modified additive, antioxidant, crosslinking agent, assistant crosslinking agent mass ratio be (100-110): (15-20): (1-3): (0.1-
0.2):(0.1-0.3):(0.1-0.3)。
3. a kind of rotational moulding modified polypropene according to claim 2, which is characterized in that the polypropylene, EP rubbers,
Modified additive, antioxidant, crosslinking agent, assistant crosslinking agent mass ratio be 100:16:2:0.1:0.2:0.2.
4. a kind of rotational moulding modified polypropene according to claim 1, which is characterized in that the antioxidant is 1,3,5-
Trimethyl -2,4,6- tri- (3,5- di-tert-butyl-4-hydroxyl benzyl) benzene, crosslinking agent is cumyl peroxide, and assistant crosslinking agent is
Divinylbenzene.
5. a kind of preparation method of rotational moulding modified polypropene, which is characterized in that the preparation method comprises the following steps:
It weighs: according to mass ratio (100-110): (15-20): (1-3): (0.1-0.2): (0.1-0.3): (0.1-0.3) difference
Weigh polypropylene, EP rubbers, modified additive, antioxidant, crosslinking agent, assistant crosslinking agent；
It mediates: polypropylene, EP rubbers, modified additive, the antioxidant of 25%~30% weight being taken to be placed in kneader,
Revolving speed is 500-950r/min, temperature mediates 15-20min under conditions of being 60-70 DEG C；
Be kneaded: the product that kneading step is prepared is placed in continuous mixer, titanate coupling agent is added, in melting temperature
Be 155 DEG C for 110 DEG C, extrusion temperature, die head temperature is 150 DEG C, is kneaded revolving speed be 35r/min under conditions of be kneaded 10min, obtain
To functional master batch；
Extruding pelletization: by the functional master batch being prepared, polypropylene, crosslinking agent, the assistant crosslinking agent of remaining 70%~75% weight
After mixing, through double screw extruder extruding pelletization, modified polypropene is obtained.
6. a kind of preparation method of rotational moulding modified polypropene according to claim 5, which is characterized in that the modification adds
Add agent the preparation method comprises the following steps:
Cladding: will be scattered in methyl phenyl ethers anisole solution, ultrasonic disperse 20min by pretreated silver nanoparticle silicon oxide pellets of mixing,
1,3:2,4- bis- (3,4- dimethyl) benzylidene sorbitol acetal is added, is heated to 70-80 DEG C, after keeping the temperature 30min, stops heating,
After standing 3-4h, it is filtered, washed, dries；
Grafting: taking 2-hydroxy-4-n-octoxybenzophenone stirring and dissolving in dehydrated alcohol, and adjusting pH value is 6-7, obtains anti-
Solution is answered, the product that encapsulation steps are prepared is placed in plasma reactor, using ammonia as working gas, carry out etc.
It after gas ions handle 10-20s, is scattered in reaction solution, for heating water bath to 50-60 DEG C, heat preservation is anti-under the conditions of ultrasonic agitation
Answer 10-12h, after the reaction was completed, be filtered, washed, dry after obtain modified additive.
7. a kind of preparation method of rotational moulding modified polypropene according to claim 6, which is characterized in that described 1,3:2,
The molar ratio of (3,4- dimethyl) the benzylidene sorbitol acetal of 4- bis- and 2-hydroxy-4-n-octoxybenzophenone is 1:0.3.
8. a kind of preparation method of rotational moulding modified polypropene according to claim 7, which is characterized in that the pretreatment
Are as follows: silver nanoparticle silicon oxide pellets will be mixed and be placed in reaction of low temperature plasma device, using argon gas as working gas, in gas flow
For 0.4-0.6L/s, power carries out Low Temperature Plasma Treating 1-2min under conditions of being 80-90W.
9. a kind of preparation method of rotational moulding modified polypropene according to claim 8, which is characterized in that described to mix Yin Na
Rice silica the preparation method comprises the following steps: into every liter of deionized water be added dropwise 5ml20% ammonium hydroxide, it is molten with 0.1mol/L sodium hydroxide
It is 10-11 that liquid, which adjusts pH value, and silver nitrate, tetraethyl orthosilicate, dehydrated alcohol is then added, and after stirring 5min, is protected from light, is warming up to
40 DEG C, oxalic acid solution is added dropwise, ultrasonic agitation reaction 4-5h is filtered, and filter cake is washed with dehydrated alcohol, is dried in vacuo, is obtained mixing silver
Nano silica bead.
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Application publication date: 20190823 |