CN106883512A - A kind of PP composite material that lotus leaf effect is formed to greasy dirt and preparation method thereof - Google Patents
A kind of PP composite material that lotus leaf effect is formed to greasy dirt and preparation method thereof Download PDFInfo
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- CN106883512A CN106883512A CN201710157257.1A CN201710157257A CN106883512A CN 106883512 A CN106883512 A CN 106883512A CN 201710157257 A CN201710157257 A CN 201710157257A CN 106883512 A CN106883512 A CN 106883512A
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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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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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
- C08L23/14—Copolymers of propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/14—Copolymers of propene
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- 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
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- C08L2201/00—Properties
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/10—Peculiar tacticity
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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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/10—Peculiar tacticity
- C08L2207/14—Amorphous or atactic polypropylene
Abstract
The present invention relates to a kind of PP composite material that lotus leaf effect is formed to greasy dirt, by mass percentage, it is made up of following components：Polypropylene 60 80%, nitrile rubber 5 8%, compatilizer 2 5%, fluoride 2 8%, nanometer titanium dioxide silicon polymer composite particles 10 15%, composite antioxidant 0.2 0.5%, composite nucleating agent 0.1 0.3%.The invention further relates to the preparation method of the PP composite material.PP composite material surface of the present invention has stronger oil rub resistance, performance easy to clean, can form lotus leaf effect to greasy dirt.
Description
Technical field
The present invention relates to the technical field of modified plastics, and in particular to a kind of surface suitable for tableware forms lotus to greasy dirt
PP composite material of leaf effect and preparation method thereof.
Background technology
Polypropylene has nontoxic, tasteless, the small characteristic of density, can be five big general-purpose plastics as the manufacture raw material of tableware
One of, it is widely used in the fields such as household electrical appliances, automobile, commodity.The highly crystallized because Polypropylene structural is regular, therefore it is molten
Up to 167 DEG C of point, heat resistance is good, and polypropylene articles can be its outstanding advantage with moise-heat sterilization.And its density is 0.90g/
Cm3, is most light general-purpose plastics.Corrosion-resistant, tensile strength can reach 30MPa, and intensity, rigidity and the transparency all compare polyethylene
It is good.
Isotactic polypropylene (iPP) is the maximum kind in polypropylene, but due to only existing non-pole in isotactic polypropylene structure
Property methyl, methylene and methine structure, lack functional group, cause small molecule oil vapour that there is isotactic polypropylene stronger
Infiltration and swellability, and requirement to the resistance to permeability standard of product is improved constantly in the world, therefore isotactic polypropylene is used as obstruct
Oil resistant permeability has to be hoisted during material.
The non-disposable tablewares such as household use are a kind of packing container for being specifically used to fill food, big multiplex aluminium, stainless steel, pottery
Porcelain, plastic or other material are made.Wherein, plastic tableware material is more using food-grade isotactic polypropylene as main raw material(s).Isotactic gathers
When propylene material is used as the packing containers such as cutlery box, tableware, the oily overwhelming majority that its surface touches is vegetable oil（Such as sesame oil, dish
Oil, soya-bean oil, peanut oil, sunflower oil, corn oil, olive oil etc.）And animal oil（Such as pig, sheep, ox animal tallow are oily）, it is various
Food eats up rear remaining greasy dirt and is particularly easily mouldy animal oil can certain adhesive force and permeability to polypropylene material,
Can not immediately be washed away using clear water, have suitable greasy residues in tableware surface, can only be by days such as detergent, liquid detergents
Often decontamination product is cleaned, and is then rinsed using clear water, not only time-consuming but also take material.And common polypropylene tableware makes daily
Also it is easy to stain the spots such as flue dust and fingerprint trace during, it is difficult to scrub.
Chinese invention patent CN102485785A discloses a kind of heat-resisting, mar-proof bloom polypropylene on June 6th, 2012
Material and preparation method thereof, this composite has glossiness and heat distortion temperature higher, but the material does not possess anti-
Greasy dirt characteristic.
Chinese utility model patent CN205285395U disclosed a kind of meal of novel belt oil cleaner screen on June 8th, 2016
Box, main purpose is by filtering a certain amount of grease in daily consumption food, it is to avoid cause the oil quantity of every daily ingestion too high,
Influence people's is healthy.But this mode does not change the material composition and function of cutlery box, it is impossible to will finally remain completely
Oil removal in dish leftovers falls, and still needs to rinse cutlery box with cleaning agent hydrous water, does not reach self-cleaning effect.
At present, most of cutlery boxs, the method for tableware oil rub resistance are in the coated one layer of oleophobic layer in its surface, such as, China mostly
Utility model patent CN201743117U disclosed a kind of Airline meal box on 2 16th, 2011, and the inner surface of cutlery box body is applied
There is one layer of anti-sticky removing layer, make the viscous foodstuffs such as rice be not easy to stick in cutlery box.
Chinese utility model patent CN202973294U disclosed a kind of High-efficiency anti-bacterial lampblack absorber on June 5th, 2013
With lubricating cup, lubricating cup top layer is coated with oleophobic coating, and oil is difficult to be attached on lubricating cup, it is easy to clear up.
Chinese utility model patent CN2375633 discloses a kind of surface on April 26th, 2000 with composite Nano material
The crockery product of film is expected, because composite nano materials are attached into pottery using methods such as spraying, dipping, smearing, centrifugations
In the glaze paint of porcelain tableware, the new outer surface of crockery product is constituted, so can give full play to it and bear dirty, oil rub resistance, remove
The function such as stink and sterilizing, makes product itself long-lasting cleanliness.But, oleophobic coating is not after all in itself one with tableware material
Body global formation material, repeatedly wash away in user, wash and the long-term scraping process such as spoon, knife and fork in, coating can be gradually
It is worn, oil rub resistance effect can become poorer and poorer, reflects obvious especially in polypropylene plastics dishware.
At present, electric cooker, soya-bean milk are used as the PP composite material with certain oil rub resistance and automatical cleaning ability mechanical, electrical more
The small household appliance casings such as magnetic stove, electric pressure cooking saucepan, slow cooker, material modified more due to addition, relatively costly, oil rub resistance and from clear
It is clean limited in one's ability.
Therefore, what a kind of oil rub resistance of exploitation, easy to clean and cost performance were higher can be applied to the non-disposable tableware such as household
Food-grade polypropylene composite material has suitable economic benefit and social value, and is particularly suitable for the kitchen of modern youth
Life style, market prospects are boundless.
The content of the invention
The polypropylene that lotus leaf effect is formed to greasy dirt it is an object of the invention to provide a kind of surface suitable for tableware is answered
Condensation material and preparation method thereof, this kind of PP composite material has stronger oil rub resistance, performance easy to clean, can be to greasy dirt shape
Into lotus leaf effect, to overcome weak point of the prior art.
The object of the present invention is achieved like this：
A kind of PP composite material that lotus leaf effect is formed to greasy dirt, by mass percentage, is made up of following components：
Polypropylene 60-80%,
Nitrile rubber 5-8%,
Compatilizer 2-5%,
Fluoride 2-8%,
Nanometer titanium dioxide silicon polymer composite particles 10-15%,
Composite antioxidant 0.2-0.5%,
Composite nucleating agent 0.1-0.3%.
The polyacrylic trade mark may include that HJ730L resins or a TaiWan, China platform from South Korea's Plastics Company gather
The ST868M resins of good fortune Resins Corporation or or Chinese companies Zhenghai refinery V30G, but be not limited to the product of aforementioned firm.
Had using the non-disposable tableware product surface such as the above-mentioned household of PP composite material injection moulding preferable
Oil rub resistance ability and self-cleaning performance, surface and droplets contact angle can reach more than 65o, produce " lotus leaf effect ", cleaning
Residual greasy dirt is easy to operate.
The composite antioxidant is 1 by mass ratio:1 Hinered phenols antioxidant and phosphite ester kind antioxidant composition.
Described Hinered phenols antioxidant is in the Irganox1010 and Irganox1076 of Ciba-geigy companies of the U.S.
One kind, Ultranox626 and U.S. Ciba-geigy company of the phosphite ester kind antioxidant for GE companies of the U.S.
One kind in Irganox168.
The composite nucleating agent is 3 by mass ratio:The 1 transparent nucleation of polypropylene high transparency nucleator and organic phosphate
Agent is constituted.
Described composite nucleating agent for Milliken companies of the U.S. NX8000 and Luoyang, henan in reach Chemical Co., Ltd.
Organic phosphate transparent nucleater NA-11, NX8000：NA-11 mass ratioes are 3:1.
The polypropylene is at least one in food-grade isotactic HOPP, atactic copolymerized polypropene.
The nitrile rubber is food grade powder nitrile rubber, and PNBR is the non-crosslinked type rubber of low temperature process production
Glue, the fine mass percent of propylene is 32 ± 3% in nitrile rubber, and ML100 DEG C of 1+4 of Mooney viscosity of nitrile rubber is 50 ± 5.
The trade mark of described PNBR includes may be from the BT-205 trades mark or Chemlgum of Butacril countries
The N3309 trades mark of the N600 trades mark or the Chemaprene country of country, but it is not limited to the product of aforementioned firm.
The compatilizer is maleic anhydride inoculated polypropylene or vinyl acetate graft polypropylene or acrylic acid-grafted poly- third
One kind in alkene.
The fluoride is food-grade polytetrafluoroethylene (PTFE)（PTFE）Micro mist, the ptfe micropowder is by food-grade four
PVF is made through telomerisation, 2-4 μm of the average grain diameter of ptfe micropowder, and specific surface area is more than 10m2/g, molecular weight
It is 1~150,000.
The trade mark of described food-grade ptfe micropowder include may be from Daikin company M111 (micro mist) or
The TF-9207 of the du pont company or L169E of Japan AGC company（Micro mist）, but it is not limited to the product of aforementioned firm.
The nanometer titanium dioxide silicon polymer composite particles are prepared from by the component of following mass percent：
Polypropylene 70%,
Gas phase nano silica 25%,
Bulking agent 5%, the grafting rate 1.84 of bulking agent, picks up from Shell Co. Ltd of the U.S..
The gas phase nano silica is oleophobic type gas phase nano silica, white powder, average grain diameter 10-
40nm, specific surface area is 200 ± 25 ㎡/g；
The trade mark of described gas phase nano silica includes may be from the LM-150 or Japan of U.S.'s Cabot (CABOT) company
The V15P of the QS-102 of moral mountain (TOKUYAMA) company or German watt gram (WACKER) companies, but it is not limited to the product of aforementioned firm
Product..
The preparation method of the nanometer titanium dioxide silicon polymer composite particles is：By above-mentioned polypropylene, gas phase nano dioxy
SiClx and bulking agent are added in high-speed mixer and are sufficiently mixed after 85 DEG C of vacuum drying 12 hours, are then squeezed in twin-screw
Go out melt blending in machine, granulation, the screw speed 300rpm of double screw extruder, four sections of temperature of machine barrel are respectively set as：180
DEG C, 190 DEG C, 200 DEG C, 210 DEG C, extruded through twin-screw melting mixing, then by it is sufficiently cool, cut using automatic high-efficiency plastics
Grain machine carries out flour milling pelletizing, is made mesh number and reaches 6000 mesh, the nanometer titanium dioxide silicon polymer composite particles of more than particle diameter 2um.
The bulking agent is that maleic anhydride is grafted hydrogenated styrene-butadiene-styrene block copolymers, and grafting rate is
1.84, pick up from Shell Co. Ltd of the U.S..
A kind of preparation method of such as foregoing PP composite material that lotus leaf effect is formed to greasy dirt, it is characterised in that bag
Include following steps：
（1）It is sufficiently mixed during polypropylene, nitrile rubber and compatilizer are added into mixer together, the time is 10-15 minutes,
Mixer rotating speed is 800-2000rpm；
（2）Fluoride, nanometer titanium dioxide silicon polymer composite particles, composite nucleating agent, composite antioxidant are added to mixer, after
Continuous to be sufficiently mixed 5-10 minutes, mixer rotating speed is 500-800rpm；
（3）By step（2）In melted, extrude, granulate in the material input parallel double-screw extruder that is well mixed, be obtained
Surface oil rub resistance PP composite material easy to clean；Wherein the barrel zone temperature of parallel double-screw extruder is 180-230 DEG C, altogether
4th area, screw speed is 400-700r/min, and the frequency of main hopper feed worm is 10~20Hz, and then by material blended melting
Extrusion granulating bar, the parallel double-screw extruder draw ratio is 48:1；
（4）Will be through step（3）The grain bar for obtaining is cooled down, air-dried, the pelletizing in plastic grain cutting machine, obtains surface to greasy dirt shape
Into the PP composite material of lotus leaf effect, the PP composite material particle diameter is 2~6mm.
Application of the above-mentioned PP composite material in household field of tableware, can be used in particular for the clear of tableware surface greasy dirt
Wash.
Beneficial effects of the present invention are as follows：
Present invention adds three kinds of materials for promoting polypropylene to improve oil resistivity, including nitrile rubber, polytetrafluoroethylene (PTFE), nanometer two
Silica, and be all food-grade, it is ensured that can be in the application in household tableware.Compared to existing technology, household tableware surface
Resistance to oil stains be greatly improved.At present, the information for obtaining is polypropylene modified material surface with the contact angle of oil droplet most
Big reaches 45o, it is clear that be not reaching to " lotus leaf effect " that the present invention should possess.According to practical application and experiment experience, when
When material surface reaches more than 60o with the contact angle of oil droplet, the effect of similar " lotus leaf effect " could be produced, formation is real not
Oily effect is stained with, such contact angle can more easily be removed the greasy dirt on surface, without by detergent by clear water by impulse force
Or the similar auxiliary cleaning product such as cleaning agent.And present invention introduces three kinds of materials that can improve polypropylene oil resistivity, and
It is not simply to increase its oil resistance, but imitates the oil resistant that its modified polypropylene material surface forms " lotus leaf effect "
Really, material surface is made to reach 65o with the contact angle of oil droplet, even more high enables household tableware user clear not by auxiliary
The bio oil on surface is washed off in the case of washing class product by clear water, to reach the convenient effect for using.
The present invention adds nitrile rubber, and it has excellent oil resistivity, heat resistance, ageing-resistant and good processing characteristics,
Compatilizer is added, can well improve the interface compatibility of polypropylene and nitrile rubber, and, by adjusting certain recipe ratio
Example, be allowed to the fluoride and nanometer titanium dioxide silicon polymer composite particles for subsequently adding double screw extruder set it is same
There is good blending, it is ensured that the performance high matched of blending fusions so that the material energy of addition under temperature range
It is enough to play maximum oil resistivity advantage.
The present invention adds polytetrafluorethylepowder powder, and with polypropylene powder resin and nitrile rubber powder, physical state is similar,
Can be good at mixing.Polytetrafluoroethylene (PTFE) has good oil resistant characteristic, after addition, so that the polypropylene for preparing is answered
The surface of condensation material can reduce, and form to oily matter the special property for being difficult to soak, be difficult attachment including bio oil etc., from
And make the PP composite material of preparation that there is excellent oil resistivity.
The present invention adds gas phase nano silica after treatment, and gas phase nano silica is in itself with hydrophilic oleophobic
Characteristic, the purpose required for by reaching the present invention, oleophobic property is good, can be infiltrated by clear water again, developing result more preferably, so as to
Meet the requirement of contemporary household tableware surface resistance to greasy dirt higher, preferably increased the automatical cleaning ability of material.
The antioxidant that the present invention is used is composite antioxidant, and two kinds or more of antioxidant produces collaboration effect by compounding
Answer and given play to superior function, composite antioxidant oxidation activity is high, and volatility is low, is particularly well-suited to high temperature process, is good
Plastic antioxidants and hydrolysis stabilizer.The addition of Hinered phenols antioxidant and phosphite ester kind antioxidant compound antioxidant, not
Being simply mixed for two kind antioxidants is confined to, but by adding the stable component of capture Ionization Potential of C-Centered Radicals, to reduce phenols
The pressure of antioxidant improves the stablizing effect of its antioxygen, is a kind of collaboration synergistic effect.
The nucleator that the present invention is used is composite nucleating agent, using the synergy between different antioxidant, by inhomogeneity
The nucleator of type carries out chemical compounding, obtains the unexistent novel high-performance composite nucleating agent of single auxiliary agent so that polypropylene is multiple
The nucleation performance of condensation material is more preferably.
PP composite material surface has stronger oil rub resistance, performance easy to clean, can form lotus leaf effect to greasy dirt,
The non-disposable tableware product surface such as the household using this kind of PP composite material injection moulding has preferable oil rub resistance energy
Power and self-cleaning performance, surface can reach more than 65o with droplets contact angle, produce " lotus leaf effect ", cleaning residual greasy dirt behaviour
Facilitate.
Specific embodiment
With reference to embodiment, the invention will be further described.
A kind of PP composite material that lotus leaf effect is formed to greasy dirt, by mass percentage, is made up of following components：
Polypropylene 60-80%,
Nitrile rubber 5-8%,
Compatilizer 2-5%,
Fluoride 2-8%,
Nanometer titanium dioxide silicon polymer composite particles 10-15%,
Composite antioxidant 0.2-0.5%,
Composite nucleating agent 0.1-0.3%.
The polyacrylic trade mark may include that HJ730L resins or a TaiWan, China platform from South Korea's Plastics Company gather
The ST868M resins of good fortune Resins Corporation or or Chinese companies Zhenghai refinery V30G, but be not limited to the product of aforementioned firm.
Had using the non-disposable tableware product surface such as the above-mentioned household of PP composite material injection moulding preferable
Oil rub resistance ability and self-cleaning performance, surface and droplets contact angle can reach more than 65o, produce " lotus leaf effect ", cleaning
Residual greasy dirt is easy to operate.
The composite antioxidant is 1 by mass ratio:1 Hinered phenols antioxidant and phosphite ester kind antioxidant composition.
Described Hinered phenols antioxidant is in the Irganox1010 and Irganox1076 of Ciba-geigy companies of the U.S.
One kind, Ultranox626 and U.S. Ciba-geigy company of the phosphite ester kind antioxidant for GE companies of the U.S.
One kind in Irganox168.
The composite nucleating agent is 3 by mass ratio:The 1 transparent nucleation of polypropylene high transparency nucleator and organic phosphate
Agent is constituted.
Described composite nucleating agent for Milliken companies of the U.S. NX8000 and Luoyang, henan in reach Chemical Co., Ltd.
Organic phosphate transparent nucleater NA-11, NX8000：NA-11 mass ratioes are 3:1.
The polypropylene is at least one in food-grade isotactic HOPP, atactic copolymerized polypropene.
The nitrile rubber is food grade powder nitrile rubber, and PNBR is the non-crosslinked type rubber of low temperature process production
Glue, the fine mass percent of propylene is 32 ± 3% in nitrile rubber, and ML100 DEG C of 1+4 of Mooney viscosity of nitrile rubber is 50 ± 5.
The trade mark of described PNBR includes may be from the BT-205 trades mark or Chemlgum of Butacril countries
The N3309 trades mark of the N600 trades mark or the Chemaprene country of country, but it is not limited to the product of aforementioned firm.
The compatilizer is maleic anhydride inoculated polypropylene or vinyl acetate graft polypropylene or acrylic acid-grafted poly- third
One kind in alkene.
The fluoride is food-grade polytetrafluoroethylene (PTFE)（PTFE）Micro mist, the ptfe micropowder is by food-grade four
PVF is made through telomerisation, 2-4 μm of the average grain diameter of ptfe micropowder, and specific surface area is more than 10m2/g, molecular weight
It is 1~150,000.
The trade mark of described food-grade ptfe micropowder include may be from Daikin company M111 (micro mist) or
The TF-9207 of the du pont company or L169E of Japan AGC company（Micro mist）, but it is not limited to the product of aforementioned firm.
The nanometer titanium dioxide silicon polymer composite particles are prepared from by the component of following mass percent：
Polypropylene 70%,
Gas phase nano silica 25%,
Bulking agent 5%, the grafting rate 1.84 of bulking agent, picks up from Shell Co. Ltd of the U.S..
The gas phase nano silica is oleophobic type gas phase nano silica, white powder, average grain diameter 10-
40nm, specific surface area is 200 ± 25 ㎡/g；
The trade mark of described gas phase nano silica includes may be from the LM-150 or Japan of U.S.'s Cabot (CABOT) company
The V15P of the QS-102 of moral mountain (TOKUYAMA) company or German watt gram (WACKER) companies, but it is not limited to the product of aforementioned firm
Product..
The preparation method of the nanometer titanium dioxide silicon polymer composite particles is：By above-mentioned polypropylene, gas phase nano dioxy
SiClx and bulking agent are added in high-speed mixer and are sufficiently mixed after 85 DEG C of vacuum drying 12 hours, are then squeezed in twin-screw
Go out melt blending in machine, granulation, the screw speed 300rpm of double screw extruder, four sections of temperature of machine barrel are respectively set as：180
DEG C, 190 DEG C, 200 DEG C, 210 DEG C, extruded through twin-screw melting mixing, then by it is sufficiently cool, cut using automatic high-efficiency plastics
Grain machine carries out flour milling pelletizing, is made mesh number and reaches 6000 mesh, the nanometer titanium dioxide silicon polymer composite particles of more than particle diameter 2um.
The bulking agent is that maleic anhydride is grafted hydrogenated styrene-butadiene-styrene block copolymers, and grafting rate is
1.84, pick up from Shell Co. Ltd of the U.S..
A kind of preparation method of such as foregoing PP composite material that lotus leaf effect is formed to greasy dirt, it is characterised in that bag
Include following steps：
（1）It is sufficiently mixed during polypropylene, nitrile rubber and compatilizer are added into mixer together, the time is 10-15 minutes,
Mixer rotating speed is 800-2000rpm；
（2）Fluoride, nanometer titanium dioxide silicon polymer composite particles, composite nucleating agent, composite antioxidant are added to mixer, after
Continuous to be sufficiently mixed 5-10 minutes, mixer rotating speed is 500-800rpm；
（3）By step（2）In melted, extrude, granulate in the material input parallel double-screw extruder that is well mixed, be obtained
Surface oil rub resistance PP composite material easy to clean；Wherein the barrel zone temperature of parallel double-screw extruder is 180-230 DEG C, spiral shell
Bar rotating speed is 400-700r/min, and the frequency of main hopper feed worm is 10~20Hz, and then material blended melting is extruded into
Grain bar, the parallel double-screw extruder draw ratio is 48:1；
（4）Will be through step（3）The grain bar for obtaining is cooled down, air-dried, the pelletizing in plastic grain cutting machine, obtains surface to greasy dirt shape
Into the PP composite material of lotus leaf effect, the PP composite material particle diameter is 2~6mm.
The first embodiment of present invention application：
Isotactic food-grade polypropylene resin HJ730L --- 75%
Nitrile rubber（NBR）N600——8%
Compatilizer maleic anhydride inoculated polypropylene --- 3%
Fluoride polytetrafluoroethylene (PTFE) M111 (micro mist) --- 5%
Nanometer titanium dioxide silicon polymer composite particles（Wherein, the nano silicon trade mark is U.S.'s Cabot (CABOT) company
LM-150）——10%
Composite antioxidant Irganox1010：Ultranox626（1:1）——0.3%
Composite nucleating agent NX8000：NA-11（3:1）——0.2%
Specific preparation method is as follows：
（1）By proportioning, by above-mentioned isotactic food-grade polypropylene resin HJ730L, nitrile rubber（NBR）N600 and compatilizer Malaysia
Anhydride-grafted polypropylene in adding mixer together be sufficiently mixed 10 minutes, and mixer rotating speed is 800rpm；
（2）By proportioning, above-mentioned fluoride polytetrafluoroethylene (PTFE) M111 (micro mist), nanometer titanium dioxide silicon polymer is added to mixer
Composite particles, composite nucleating agent, composite antioxidant, continue to be sufficiently mixed 5 minutes, and mixer rotating speed is 500rpm；
（3）By step（2）In melted, extrude, granulate in the material input parallel double-screw extruder that is well mixed, be obtained
Surface oil rub resistance PP composite material easy to clean；Wherein the barrel zone temperature of parallel double-screw extruder is 180-230 DEG C, spiral shell
Bar rotating speed is 500r/min, and the frequency of main hopper feed worm is 15Hz, and then material blended melting is extruded into granulating bar；
（4）Will be through step（3）The grain bar for obtaining is cooled down, air-dried, the pelletizing in plastic grain cutting machine, obtains surface to greasy dirt shape
Into the PP composite material of lotus leaf effect.
The second embodiment of present invention application：
Random copolymerization food-grade polypropylene resin ST868M --- 70%
Nitrile rubber（NBR）BT-205——8%
Compatilizer vinyl acetate graft polypropylene --- 4%
Fluoride polytetrafluoroethylene (PTFE) L169E（Micro mist）——7%
Nanometer titanium dioxide silicon polymer composite particles（Wherein, the nano silicon trade mark is day Bender mountain (TOKUYAMA) company
QS-102）——15%
Composite antioxidant Irganox1076：Ultranox626（1:1）——0.2%
Composite nucleating agent NX8000：NA-11（3:1）——0.3%
Specific preparation method is as follows：
（1）By proportioning, by above-mentioned random copolymerization food-grade polypropylene resin ST868M, nitrile rubber（NBR）BT-205 and compatible
Agent vinyl acetate graft polypropylene in adding mixer together be sufficiently mixed 12 minutes, and mixer rotating speed is 1200rpm；
（2）By proportioning, above-mentioned fluoride polytetrafluoroethylene (PTFE) L169E is added to mixer（Micro mist）, nanometer titanium dioxide silicon polymer
Composite particles, composite nucleating agent, composite antioxidant, continue to be sufficiently mixed 8 minutes, and mixer rotating speed is 600rpm；
（3）By step（2）In melted, extrude, granulate in the material input parallel double-screw extruder that is well mixed, be obtained
Surface oil rub resistance PP composite material easy to clean；Wherein the barrel zone temperature of parallel double-screw extruder is 180-230 DEG C, institute
The parallel double-screw extruder bucket for using is divided into 4 intervals, i.e. feed zone, transportation section, engaged section, four regions of exhaust section, often
The technological parameter of individual region setting（Temperature）Can be different, screw speed is 600r/min, the frequency of main hopper feed worm
It is 12Hz, and then material blended melting is extruded into granulating bar；
（4）Will be through step（3）The grain bar for obtaining is cooled down, air-dried, the pelletizing in plastic grain cutting machine, obtains surface to greasy dirt shape
Into the PP composite material of lotus leaf effect.
The 3rd embodiment of present invention application
Isotactic copolymerization food-grade polypropylene resin（Zhenghai refinery V30G）—— 80%
Nitrile rubber（NBR）N3309——5%
Compatilizer acrylic acid-grafted polypropylene --- 3%
Fluoride polytetrafluoroethylene (PTFE) TF-9207 --- 3%
Nanometer titanium dioxide silicon polymer composite particles（Wherein, the nano silicon trade mark is German watt gram (WACKER) company
V15P）——10%
Composite antioxidant Irganox1076：Ultranox626（1:1）——0.4%
Composite nucleating agent NX8000：NA-11（3:1）——0.2%
Specific preparation method is as follows：
（1）By proportioning, by above-mentioned isotactic copolymerization food-grade polypropylene resin, nitrile rubber（NBR）N3309 and compatilizer acrylic acid
Graft polypropylene in adding mixer together be sufficiently mixed 14 minutes, and mixer rotating speed is 1500rpm；
（2）Above-mentioned fluoride polytetrafluoroethylene (PTFE) TF-9207, nanometer titanium dioxide silicon polymer composite particles are added to mixer, answer
Synthetic kernel agent, composite antioxidant, continue to be sufficiently mixed 6 minutes, and mixer rotating speed is 800rpm；
（3）By step（2）In melted, extrude, granulate in the material input parallel double-screw extruder that is well mixed, be obtained
Surface oil rub resistance PP composite material easy to clean；Wherein the barrel zone temperature of parallel double-screw extruder is 180-230 DEG C, altogether
4th area, screw speed is 650r/min, and the frequency of main hopper feed worm is 19Hz, and then material blended melting is extruded into granulating
Bar；
（4）Will be through step（3）The grain bar for obtaining is cooled down, air-dried, the pelletizing in plastic grain cutting machine, obtains surface to greasy dirt shape
Into the PP composite material of lotus leaf effect.
The embodiment of use above is only several in several preferred embodiment of the invention, the invention is not restricted to above-mentioned
Embodiment；For the person of ordinary skill of the art, the technical scheme described in previous embodiment can still be carried out
Modification, or equivalent is carried out to which part technical characteristic, or improve；And these modifications, replacement or improvement, do not make
The essence of appropriate technical solution departs from the spirit and scope of claimed technical solution of the invention.
Claims (10)
1. it is a kind of to greasy dirt formed lotus leaf effect PP composite material, it is characterised in that by mass percentage, by following
Component is made：
Polypropylene 60-80%,
Nitrile rubber 5-8%,
Compatilizer 2-5%,
Fluoride 2-8%,
Nanometer titanium dioxide silicon polymer composite particles 10-15%,
Composite antioxidant 0.2-0.5%,
Composite nucleating agent 0.1-0.3%.
2. it is according to claim 1 to greasy dirt formed lotus leaf effect PP composite material, it is characterised in that it is described multiple
It is 1 that antioxidant is closed by mass ratio:1 Hinered phenols antioxidant and phosphite ester kind antioxidant composition.
3. it is according to claim 1 to greasy dirt formed lotus leaf effect PP composite material, it is characterised in that it is described multiple
Synthetic kernel agent is 3 by mass ratio:1 polypropylene high transparency nucleator and organic phosphate transparent nucleater composition.
4. the PP composite material that lotus leaf effect is formed to greasy dirt according to claim 1, it is characterised in that described poly-
Propylene is at least one in food-grade isotactic HOPP, atactic copolymerized polypropene.
5. it is according to claim 1 to greasy dirt formed lotus leaf effect PP composite material, it is characterised in that the fourth
Nitrile rubber is food grade powder nitrile rubber, and PNBR is the non-crosslinked type rubber of low temperature process production, in nitrile rubber
The fine mass percent of propylene is 32 ± 3%, and ML100 DEG C of 1+4 of Mooney viscosity of nitrile rubber is 50 ± 5.
6. it is according to claim 1 to greasy dirt formed lotus leaf effect PP composite material, it is characterised in that the phase
It is the one kind in maleic anhydride inoculated polypropylene or vinyl acetate graft polypropylene or acrylic acid-grafted polypropylene to hold agent.
7. it is according to claim 1 to greasy dirt formed lotus leaf effect PP composite material, it is characterised in that the fluorine
Compound is food-grade ptfe micropowder, and the ptfe micropowder is by food-grade tetrafluoroethene through telomerisation system
Into 2-4 μm of the average grain diameter of ptfe micropowder, specific surface area is more than 10m2/ g, molecular weight is 1~150,000.
8. it is according to claim 1 to greasy dirt formed lotus leaf effect PP composite material, it is characterised in that it is described to receive
Rice silica polymer composite particles are prepared from by the component of following mass percent：
Polypropylene 70%,
Gas phase nano silica 25%,
Bulking agent 5%,
The gas phase nano silica be oleophobic type gas phase nano silica, white powder, average grain diameter 10-40nm,
Specific surface area is 200 ± 25 ㎡/g；
The preparation method of the nanometer titanium dioxide silicon polymer composite particles is：By above-mentioned polypropylene, gas phase nano silica
With bulking agent after 85 DEG C of vacuum drying 12 hours, it is added in high-speed mixer and is sufficiently mixed, then in double screw extruder
Middle melt blending, granulation, the screw speed 300rpm of double screw extruder, four sections of temperature of machine barrel are respectively set as：180℃、190
DEG C, 200 DEG C, 210 DEG C, extruded through twin-screw melting mixing, then by it is sufficiently cool, entered using automatic high-efficiency plastic grain cutting machine
Row flour milling pelletizing, is made mesh number and reaches 6000 mesh, the nanometer titanium dioxide silicon polymer composite particles of more than particle diameter 2um.
9. it is according to claim 8 to greasy dirt formed lotus leaf effect PP composite material, it is characterised in that the increasing
It is that maleic anhydride is grafted hydrogenated styrene-butadiene-styrene block copolymers to hold agent.
10. the preparation of a kind of PP composite material that lotus leaf effect is formed to greasy dirt as described in claim any one of 1-9
Method, it is characterised in that comprise the following steps：
（1）It is sufficiently mixed during polypropylene, nitrile rubber and compatilizer are added into mixer together, the time is 10-15 minutes,
Mixer rotating speed is 800-2000rpm；
（2）Fluoride, nanometer titanium dioxide silicon polymer composite particles, composite nucleating agent, composite antioxidant are added to mixer, after
Continuous to be sufficiently mixed 5-10 minutes, mixer rotating speed is 500-800rpm；
（3）By step（2）In melted, extrude, granulate in the material input parallel double-screw extruder that is well mixed, be obtained
Surface oil rub resistance PP composite material easy to clean；Wherein the barrel zone temperature of parallel double-screw extruder is 180-230 DEG C, spiral shell
Bar rotating speed is 400-700r/min, and the frequency of main hopper feed worm is 10~20Hz, and then material blended melting is extruded into
Grain bar, the parallel double-screw extruder draw ratio is 48:1；
（4）Will be through step（3）The grain bar for obtaining is cooled down, air-dried, the pelletizing in plastic grain cutting machine, obtains surface to greasy dirt shape
Into the PP composite material of lotus leaf effect, the PP composite material particle diameter is 2~6mm.
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Application publication date: 20170623 |