CN103627088A - Reinforced and toughened anti-bacterial polypropylene composition and preparation method thereof - Google Patents
Reinforced and toughened anti-bacterial polypropylene composition and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a reinforced and toughened anti-bacterial polypropylene composition and a preparation method thereof. The composition comprises the following components in weight percent: 54% to 87.7% of polypropylene, 0.5% to 5% of a coupling-modified inorganic antimicrobial agent, 10% to 30% of ultra-high molecular weight polyethylene master batch, 1% to 8% of graft polypropylene; 0.2% to 1% of a stabilizing agent, 0.2% to 1% of a dispersing agent and 0.4% to 1% of anti-oxidant. According to the invention, ultra-high molecular weight polyethylene is prepared into ultra-high molecular weight polyethylene master batch under certain conditions, and the ultra-high molecular weight polyethylene master batch, the surface-modified inorganic antimicrobial agent, the polypropylene, the graft polypropylene and other additives are quickly mixed and extruded to be manufactured into a polypropylene composite material with high strength, high ductility and high mold resistance. Under the condition that the inorganic antimicrobial agent is added to endow excellent antibacterial activity to the polypropylene, organic very long-chain high-polymer reinforced and toughened polypropylene is added, so that the prepared polypropylene composite material not only has excellent mold resistance but also has outstanding mechanical characteristics.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to the toughness reinforcing antibacterial polypropylene composition and method of making the same of a kind of enhancing.
Background technology
Data shows that the various surface of plastic products that touch in daily life are infected with and grow multiple germ.Such as the bacterium on hotel's sitting wc pan, have intestinal bacteria, streptococcus aureus, White staphylococcus, Bacillus subtilus, tetrads etc., colony number reaches 40; The colony number of Public telephone microphone reaches 50; The colony number of the door handle at hospital, hotel even can be up to more than 200.Along with the raising of people's living standard, everybody is also more and more higher to health and healthy requirement.Since the nineties, take the developed country that Japan is representative has carried out research, the development and production work of anti-biotic material at aspects such as household electrical appliance, food product pack, toy for children, kitchen and sanitary bath equipments, to reduce because using the bacterium that plastics occur to infect.
Polypropylene is as a kind of non-toxic plastic, and the processing characteristics because density is little, price is low and good, is widely used in each fields such as household electrical appliance.But polypropylene is the same with other plastics, easily by various unwanted bacterias, polluted, in the situation of being applicable to, more easily breed bacterium.Generally adopt now interpolation antiseptic-germicide to improve polyacrylic anti-microbial property.Conventional plastic antimicrobial agent can be divided into organic antibacterial agent and inorganic antiseptic at present, and organic antibacterial agent mainly contains ethers, phenol, biphenyl ethers, quaternary ammonium salt etc., be characterized in that sterilization speed is fast, but antibacterial validity period is short, resistance toheat is poor.Inorganic antiseptic is mainly silver, zinc, titanium plasma and compound thereof, is characterized in good heat resistance, safe, antibacterial validity period length etc.For example Chinese patent CN101089038A discloses nanometer silver and adds polypropylene and obtain a kind of antibiotic rate and be greater than 99% polypropylene composite material; Chinese patent CN1699459A discloses a kind of silver-carrying nano oxide compound antibacterial polypropylene water-feeding pipes and preparation method thereof.Above-mentioned patent relates to nanometer silver, the application of silver-carrying nano oxide compound antiseptic-germicide in polypropylene, and obtains certain achievement.But silver-series antibacterial agent also exists a lot of shortcomings, as easy to change, poor heat resistance, manufactures difficulty, and cost is high, operation complexity etc. in plastics, and precious metal toxic is also disputable in addition.In mechanical properties, polypropylene, under low temperature or high strain rate, causes material impact-resistant ability, notch sensitivity strong because the striking energy absorbing has little time to transmit in time, thereby has greatly limited the application of polypropylene as engineering materials and structured material.For optimizing Properties of Polypropylene, further expand its range of application, all carried out the research and development of a large amount of polypropylene reinforced plasticized modifications both at home and abroad, aspect multiphase copolymer and blending and modifying, obtaining certain achievement.For example Chinese patent CN201110308569.0 discloses a kind of rubber sulfonation flexibilized polypropylene material that utilizes; Chinese patent CN201010214965.2 discloses a kind of styrene-butadiene rubber(SBR) toughening modifying polypropylene material and preparation method thereof that utilizes; Japanese patent laid-open 6-190991 discloses the bonding matrix material of a kind of high density polyethylene(HDPE)/polypropylene; US Patent No. 20020010241A1 discloses a kind of polyolefin compositions being comprised of polypropylene and ultrahigh molecular weight polyethylene(UHMWPE).Although above-mentioned patent report polypropylene toughness-increasing modified, in disclosed report, do not relate to the research of Mechanical Properties of PP and antibacterial two aspects.
Summary of the invention
The object of the invention is to overcome the deficiency that above-mentioned prior art exists, provide a kind of enhancing toughness reinforcing antibacterial polypropylene composition and method of making the same.When said composition utilization interpolation inorganic antiseptic is given the anti-microbial property of polypropylene excellence, by adding overlength chain polymer, polyacrylic tensile strength and notched Izod impact strength have been improved.
In polypropylene toughness-increasing modified research, the most frequently used toughness reinforcing means are introduced flexible polymer exactly in plastic substrate, when system is subject to external impacts, by cause flexible polymer around crazing and the shear yielding of matrix absorb a large amount of striking energys, thereby improve the toughness of matrix.But this method exists fatal weakness, although the toughness of polypropylene matrix has improved, often cause the reduction of tensile strength and hardness; On the other hand, for the Pp System that adds inorganic antiseptic, introduce flexible polymer and be easy to form coating layer at inorganic antiseptic particle surface, reduce the antimicrobial efficiency of inorganic antiseptic.Therefore, simply in inorganic antiseptic/Pp System, add flexible polymer, although improve to a certain extent polyacrylic toughness, the antimicrobial efficiency of sacrificial inorganic antiseptic-germicide of take is to a great extent cost.Therefore,, when guaranteeing the excellent anti-microbial property of inorganic antiseptic, how improving Mechanical Properties of PP is one of difficult point of antibacterial polypropylene material research.
Many researchers adopts introduces overlength chain polymer in polypropylene matrix, utilize overlength molecular chain in matrix, to form the skeleton structure of physical entanglement, when material is subject to External Force Acting, in matrix, the skeleton of this entanglement absorbs and transmits striking energy, to play, strengthens toughness reinforcing effect.For example, utilize the high PE modified polypropylene of molecular weight, make itself and polypropylene fusion blend form linear interpenetrating(polymer)networks or physical cross-linked network, when material under external force, network generation gross distortion, absorbs outside energy, plays and strengthens toughness reinforcing effect.But ultrahigh molecular weight polyethylene(UHMWPE) molecular weight is very long, mutually tangle each other, even more than melting temperature, also keep elastomeric state and do not there is mobility.
It is carrier that the present invention adopts linear low density polyethylene, adds certain low-molecular-weight alkane and ultrahigh molecular weight polyethylene(UHMWPE) melt blending and generates low viscous ultrahigh molecular weight polyethylene(UHMWPE) master batch; Adopt nano zine oxide or titanium dioxide as inorganic antiseptic, then polypropylene, ultrahigh molecular weight polyethylene(UHMWPE) master batch, inorganic antiseptic, graft polypropylene and other auxiliary agent are extruded to the toughness reinforcing antibacterial polypropylene material that is enhanced by twin screw extruder melt blending.For preparation, strengthen the requirement of toughness reinforcing antibacterial polypropylene material, the present invention has following characteristic: (1) selects nano zine oxide or titanium dioxide as inorganic antiseptic; (2) ultrahigh molecular weight polyethylene(UHMWPE) of selecting to have overlength molecular chain is as organic filler, and utilizes linear low density polyethylene to extrude as carrier and ultrahigh molecular weight polyethylene(UHMWPE) melt blending, prepares ultrahigh molecular weight polyethylene(UHMWPE) master batch; (3) effectively improving under the prerequisite of polypropylene antibacterial activity and mechanical strength, use as far as possible a small amount of inorganic antiseptic and ultrahigh molecular weight polyethylene(UHMWPE) master batch.
The object of the invention is to be achieved through the following technical solutions:
First aspect, the present invention relates to the toughness reinforcing antibacterial polypropylene composition of a kind of enhancing, comprises each component of following weight percent content:
Preferably, described ultrahigh molecular weight polyethylene(UHMWPE) master batch is comprised of each component of following weight percent content:
Preferably, the weight-average molecular weight of described ultrahigh molecular weight polyethylene(UHMWPE) is 150～5,000,000.
Preferably, described linear low density polyethylene density is 0.92g/cm
3, melting index is 24g/10min.
Preferably, described inorganic powder is one or more in calcium carbonate, talcum powder, carbon fiber, glass fibre, silicon-dioxide, potassium titanate crystal whisker.
Preferably, described compatilizer is whiteruss, and number-average molecular weight is 100～200g/mol.
Preferably, described polypropylene is a kind of or composition of the two in homo-polypropylene, Co-polypropylene; Described polyacrylic melting index is 1～25g/10min.
Preferably, described coupling modified inorganic antiseptic-germicide is to utilize coupling agent to carry out the inorganic antiseptic of surface modification, and described coupling agent is one or more of silane coupling agent, titanate coupling agent, aluminate coupling agent.The object of surface modification is to increase the avidity of inorganic antiseptic and fluoropolymer resin.Silane coupling agent can be: KH550, DL602; Titanate coupling agent can be: UP-131, JW-105.
Preferably, described inorganic antiseptic is one or more in nano inorganic antimicrobial agent, composite hybridization nano inorganic antimicrobial agent.More preferably a kind of in nano zine oxide, titanium dioxide or their composition.
Preferably, described surface modification temperature is 60～70 ℃, and coupling agent consumption is 0.5～2% of inorganic antiseptic weight.
Preferably, described graft polypropylene is one or more the composition in maleic anhydride inoculated polypropylene, glycidyl methacrylate graft polypropylene.
Preferably, described dispersion agent is one or more in ethylene group bis-stearamides, glyceryl monostearate, Tristearoylglycerol.
Preferably, described stablizer is organic tin stablizer.
More preferably, described stablizer is one or more in dibutyl tin laurate, toxilic acid dibutyl tin, mercaptan dibutyl tin.
Preferably, described oxidation inhibitor comprises primary antioxidant and auxiliary anti-oxidant; Described primary antioxidant is one or more in Hinered phenols antioxidant, sulphur ester antioxidant, and described auxiliary anti-oxidant is one or more in phosphite kind antioxidant, ester kind antioxidant.Primary antioxidant can be the one or both composition in 3114,1010; Auxiliary anti-oxidant can be the composition of the one or both in 618,168.
Second aspect, the present invention relates to the preparation method of the toughness reinforcing antibacterial polypropylene composition of a kind of aforesaid enhancing, and described method comprises the steps:
A, described polypropylene, coupling modified inorganic antiseptic-germicide, ultrahigh molecular weight polyethylene(UHMWPE) master batch, graft polypropylene, dispersion agent, stablizer and oxidation inhibitor are mixed 15～20 minutes in super mixer;
B, mixed raw material is added in twin screw extruder, cooling granulation after melt extruding, obtains; Expressing technique is: 180～190 ℃ of district's temperature, two 190～200 ℃ of district's temperature 180～190 ℃， tri-district's temperature 190～200 ℃， tetra-district's temperature, five 190～200 ℃ of district's temperature, six 210～220 ℃ of district's temperature 200～210 ℃， seven district's temperature 200～210 ℃， eight district's temperature, nine 210～220 ℃ of district's temperature, 200～210 ℃ of head temperatures, 200～250 revs/min of screw speeds, pressure 18～25MPa.
Preferably, described coupling modified inorganic antiseptic-germicide is to using ethanol or Virahol as dispersion agent, adopts coupling agent inorganic antiseptic is carried out to surface modification preparation and obtain; Described surface modification temperature is 60～70 ℃, and coupling agent consumption is 0.5～2% of inorganic antiseptic weight.
Preferably, described ultrahigh molecular weight polyethylene(UHMWPE) master batch is comprised of each component of following weight percent content:
Preferably, described ultrahigh molecular weight polyethylene(UHMWPE) master batch be prepare as follows and: by described ultrahigh molecular weight polyethylene(UHMWPE), linear low density polyethylene, inorganic powder and compatilizer mix in super mixer, then by mixture through twin screw extruder extruding pelletization, expressing technique is: 190～200 ℃ of district's temperature, two 190～200 ℃ of district's temperature, three 200～210 ℃ of district's temperature, four 200～210 ℃ of district's temperature, five 200～210 ℃ of district's temperature, six 210～220 ℃ of district's temperature, seven 210～220 ℃ of district's temperature, eight 215～225 ℃ of district's temperature, nine 215～225 ℃ of district's temperature, 200～220 ℃ of head temperatures, turn/min of screw speed 200～250, melt pressure 20～25MPa.
Compare with existing antibacterial polypropylene material, the present invention has following beneficial effect: the polypropylene material that the present invention prepares is antibacterial more fast, more lasting, safer; The present invention has simultaneously used overlength chain polymer as weighting agent, has improved the mechanical property of material, has widened the range of application of antibacterial polypropylene material.
Accompanying drawing explanation
By reading the detailed description of non-limiting example being done with reference to the following drawings, it is more obvious that the other features, objects and advantages of patent of the present invention will become:
Fig. 1 is the TEM picture of KH550 modified nano zinc oxide powder in embodiment 1;
Fig. 2 is embodiment 3 polypropylene impact fracture surface SEM photos.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.Following examples will contribute to those skilled in the art further to understand the present invention, but not limit in any form the present invention.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, can also make some distortion and improvement.These all belong to protection scope of the present invention.
embodiment 1
The present embodiment relates to the toughness reinforcing antibacterial polypropylene composition of a kind of enhancing, comprises following each component: polypropylene, coupling modified inorganic antiseptic-germicide, ultrahigh molecular weight polyethylene(UHMWPE) master batch, graft polypropylene, dispersion agent, stablizer, oxidation inhibitor; Wherein, ultrahigh molecular weight polyethylene(UHMWPE) master batch is comprised of following each component: ultrahigh molecular weight polyethylene(UHMWPE), linear low density polyethylene, inorganic powder, compatilizer.
The preparation method of the toughness reinforcing antibacterial polypropylene composition of enhancing of the present embodiment comprises the steps:
1), the finishing of inorganic antiseptic
Take ethanol as dispersion medium is heated to 60 ℃, add Silane coupling agent KH550 to disperse 5min, then add inorganic antiseptic zinc oxide to disperse 30min, dry, grind, sieving obtains modified zinc oxide, wherein KH550 consumption is 0.5%.As shown in Figure 1, as shown in Figure 1, after modification, nano zine oxide reunion degree reduces the TEM photo of the Silane coupling agent KH550 modified nano zinc oxide powder of the present embodiment.
2), the preparation of ultrahigh molecular weight polyethylene(UHMWPE) master batch
By 30% ultrahigh molecular weight polyethylene(UHMWPE), 40% linear low density polyethylene, (density is 0.92g/cm
3, melting index is 24g/10min), 15% calcium carbonate, 15% whiteruss mixes in super mixer.Mixture is standby through twin screw extruder extruding pelletization, and wherein ultrahigh molecular weight polyethylene(UHMWPE) molecular weight is 1,500,000, and expressing technique is: 190 ℃ of district's temperature, two 200 ℃ of district's temperature 190 ℃， tri-district's temperature 200 ℃， tetra-district's temperature, five 200 ℃ of district's temperature, six 215 ℃ of district's temperature 210 ℃， seven district's temperature 210 ℃， eight district's temperature, nine 215 ℃ of district's temperature, 200 ℃ of head temperatures, turn/min of screw speed 200, melt pressure 20MPa.
3), strengthen the preparation of toughness reinforcing antibacterial polypropylene material
87.7% homo-polypropylene, 0.5% modified zinc oxide, 10% ultrahigh molecular weight polyethylene(UHMWPE) master batch, 1% maleic anhydride inoculated polypropylene, 0.2% glyceryl monostearate, 0.2% dibutyl tin laurate, each 0.2% primary antioxidant 3114 and auxiliary anti-oxidant 168 are mixed in super mixer, then mixture is extruded to the toughness reinforcing antibacterial polypropylene material that is enhanced through twin screw extruder.Wherein polypropylene melt index is 1g/10min, and expressing technique is: 180 ℃ of district's temperature 180 ℃， bis-district's temperature, three 190 ℃ of district's temperature, four 200 ℃ of district's temperature 190 ℃， five district's temperature 190 ℃， six district's temperature, seven 200 ℃ of district's temperature, eight 210 ℃ of district's temperature 210 ℃， nine district's temperature, 200 ℃ of head temperatures, turn/min of screw speed 200, melt pressure 18MPa.
embodiment 2
The present embodiment relates to the toughness reinforcing antibacterial polypropylene composition of a kind of enhancing, comprises following each component: polypropylene, coupling modified inorganic antiseptic-germicide, ultrahigh molecular weight polyethylene(UHMWPE) master batch, graft polypropylene, dispersion agent, stablizer, oxidation inhibitor; Wherein, ultrahigh molecular weight polyethylene(UHMWPE) master batch is comprised of following each component: ultrahigh molecular weight polyethylene(UHMWPE), linear low density polyethylene, inorganic powder, compatilizer.
The preparation method of the toughness reinforcing antibacterial polypropylene composition of enhancing of the present embodiment comprises the steps:
1), the finishing of inorganic antiseptic
Take ethanol as dispersion medium is heated to 60 ℃, add Silane coupling agent KH550 to disperse 5min, then add inorganic antiseptic zinc oxide to disperse 30min, dry, grind, sieving obtains modified zinc oxide, wherein KH550 consumption is 0.5%.
2), the preparation of ultrahigh molecular weight polyethylene(UHMWPE) master batch
50% ultrahigh molecular weight polyethylene(UHMWPE), 30% linear low density polyethylene, 10% calcium carbonate, 10% whiteruss are mixed in super mixer.Mixture is standby through twin screw extruder extruding pelletization, and wherein ultrahigh molecular weight polyethylene(UHMWPE) molecular weight is 1,500,000, and expressing technique is: 200 ℃ of district's temperature, two 210 ℃ of district's temperature 200 ℃， tri-district's temperature 210 ℃， tetra-district's temperature, five 210 ℃ of district's temperature, six 225 ℃ of district's temperature 220 ℃， seven district's temperature 220 ℃， eight district's temperature, nine 225 ℃ of district's temperature, 220 ℃ of head temperatures, turn/min of screw speed 250, melt pressure 25MPa.
3), strengthen the preparation of toughness reinforcing antibacterial polypropylene material
67.7% homo-polypropylene, 0.5% modified zinc oxide, 30% ultrahigh molecular weight polyethylene(UHMWPE) master batch, 1% maleic anhydride inoculated polypropylene, 0.2% glyceryl monostearate, 0.2% dibutyl tin laurate, each 0.2% primary antioxidant 3114 and auxiliary anti-oxidant 168 are mixed in super mixer, then mixture is extruded to the toughness reinforcing antibacterial polypropylene material that is enhanced through twin screw extruder.Wherein polypropylene melt index is 1g/10min, and expressing technique is: 190 ℃ of district's temperature 190 ℃， bis-district's temperature, three 200 ℃ of district's temperature, four 210 ℃ of district's temperature 200 ℃， five district's temperature 200 ℃， six district's temperature, seven 210 ℃ of district's temperature, eight 220 ℃ of district's temperature 220 ℃， nine district's temperature, 210 ℃ of head temperatures, turn/min of screw speed 230, melt pressure 20MPa.
embodiment 3
The present embodiment relates to the toughness reinforcing antibacterial polypropylene composition of a kind of enhancing, comprises following each component: polypropylene, coupling modified inorganic antiseptic-germicide, ultrahigh molecular weight polyethylene(UHMWPE) master batch, graft polypropylene, dispersion agent, stablizer, oxidation inhibitor; Wherein, ultrahigh molecular weight polyethylene(UHMWPE) master batch is comprised of following each component: ultrahigh molecular weight polyethylene(UHMWPE), linear low density polyethylene, inorganic powder, compatilizer.
The preparation method of the toughness reinforcing antibacterial polypropylene composition of enhancing of the present embodiment comprises the steps:
1), the finishing of inorganic antiseptic
Take Virahol as dispersion medium is heated to 70 ℃, add silane coupling agent DL602 to disperse 5min, then add inorganic antiseptic zinc oxide to disperse 30min, dry, grind, sieving obtains modified zinc oxide, wherein DL602 consumption is 2%.
2), the preparation of ultrahigh molecular weight polyethylene(UHMWPE) master batch
30% ultrahigh molecular weight polyethylene(UHMWPE), 40% linear low density polyethylene, 15% talcum powder, 15% whiteruss are mixed in super mixer.Mixture is standby through twin screw extruder extruding pelletization, and wherein ultrahigh molecular weight polyethylene(UHMWPE) molecular weight is 1,500,000, and expressing technique is: 190 ℃ of district's temperature, two 200 ℃ of district's temperature 190 ℃， tri-district's temperature 200 ℃， tetra-district's temperature, five 200 ℃ of district's temperature, six 215 ℃ of district's temperature 210 ℃， seven district's temperature 210 ℃， eight district's temperature, nine 215 ℃ of district's temperature, 200 ℃ of head temperatures, turn/min of screw speed 200, melt pressure 20MPa.
3), strengthen the preparation of toughness reinforcing antibacterial polypropylene material
64.4% homo-polypropylene, 5% modified zinc oxide, 20% ultrahigh molecular weight polyethylene(UHMWPE) master batch, 8% maleic anhydride inoculated polypropylene, 1% glyceryl monostearate, 1% dibutyl tin laurate, each 0.3% primary antioxidant 3114 and auxiliary anti-oxidant 168 are mixed in super mixer, then mixture is extruded to the toughness reinforcing antibacterial polypropylene material that is enhanced through twin screw extruder.Wherein polypropylene melt index is 1g/10min, and expressing technique is: 180 ℃ of district's temperature 180 ℃， bis-district's temperature, three 190 ℃ of district's temperature, four 200 ℃ of district's temperature 190 ℃， five district's temperature 190 ℃， six district's temperature, seven 200 ℃ of district's temperature, eight 210 ℃ of district's temperature 210 ℃， nine district's temperature, 200 ℃ of head temperatures, turn/min of screw speed 200, melt pressure 20MPa.
As shown in Figure 2, as shown in Figure 2, nano zine oxide is uniformly dispersed the SEM photo of the toughness reinforcing antibacterial polypropylene material impact fracture surface of enhancing of the present embodiment in polypropylene.
embodiment 4
The present embodiment relates to the toughness reinforcing antibacterial polypropylene composition of a kind of enhancing, comprises following each component: polypropylene, coupling modified inorganic antiseptic-germicide, ultrahigh molecular weight polyethylene(UHMWPE) master batch, graft polypropylene, dispersion agent, stablizer, oxidation inhibitor; Wherein, ultrahigh molecular weight polyethylene(UHMWPE) master batch is comprised of following each component: ultrahigh molecular weight polyethylene(UHMWPE), linear low density polyethylene, inorganic powder, compatilizer.
The preparation method of the toughness reinforcing antibacterial polypropylene composition of enhancing of the present embodiment comprises the steps:
1), the finishing of inorganic antiseptic
Take ethanol as dispersion medium is heated to 70 ℃, add titanate coupling agent UP-131 to disperse 5min, then add inorganic antiseptic zinc oxide to disperse 30min, dry, grind, sieving obtains modified zinc oxide, wherein UP-131 consumption is 1%.
2), the preparation of ultrahigh molecular weight polyethylene(UHMWPE) master batch
50% ultrahigh molecular weight polyethylene(UHMWPE), 30% linear low density polyethylene, 10% potassium titanate crystal whisker, 10% whiteruss are mixed in super mixer.Mixture is standby through twin screw extruder extruding pelletization, and wherein ultrahigh molecular weight polyethylene(UHMWPE) molecular weight is 1,500,000, and expressing technique is: 200 ℃ of district's temperature, two 210 ℃ of district's temperature 200 ℃， tri-district's temperature 210 ℃， tetra-district's temperature, five 210 ℃ of district's temperature, six 225 ℃ of district's temperature 220 ℃， seven district's temperature 220 ℃， eight district's temperature, nine 225 ℃ of district's temperature, 220 ℃ of head temperatures, turn/min of screw speed 250, melt pressure 25MPa.
3), strengthen the preparation of toughness reinforcing antibacterial polypropylene material
54% homo-polypropylene, 5% modified zinc oxide, 30% ultrahigh molecular weight polyethylene(UHMWPE) master batch, 8% maleic anhydride inoculated polypropylene, 1% glyceryl monostearate, 1% dibutyl tin laurate, each 0.5% primary antioxidant 1010 and auxiliary anti-oxidant 168 are mixed in super mixer, then mixture is extruded to the toughness reinforcing antibacterial polypropylene material that is enhanced through twin screw extruder.Wherein polypropylene melt index is 1g/10min, and expressing technique is: 190 ℃ of district's temperature 190 ℃， bis-district's temperature, three 200 ℃ of district's temperature, four 210 ℃ of district's temperature 200 ℃， five district's temperature 200 ℃， six district's temperature, seven 210 ℃ of district's temperature, eight 220 ℃ of district's temperature 220 ℃， nine district's temperature, 210 ℃ of head temperatures, turn/min of screw speed 250, melt pressure 25MPa.
embodiment 5
The present embodiment relates to the toughness reinforcing antibacterial polypropylene composition of a kind of enhancing, comprises following each component: polypropylene, coupling modified inorganic antiseptic-germicide, ultrahigh molecular weight polyethylene(UHMWPE) master batch, graft polypropylene, dispersion agent, stablizer, oxidation inhibitor; Wherein, ultrahigh molecular weight polyethylene(UHMWPE) master batch is comprised of following each component: ultrahigh molecular weight polyethylene(UHMWPE), linear low density polyethylene, inorganic powder, compatilizer.
The preparation method of the toughness reinforcing antibacterial polypropylene composition of enhancing of the present embodiment comprises the steps:
1), the finishing of inorganic antiseptic
Take ethanol as dispersion medium is heated to 60 ℃, add Silane coupling agent KH550 to disperse 5min, then add inorganic antiseptic titanium dioxide to disperse 30min, dry, grind, sieving obtains modifying titanium dioxide, wherein KH550 consumption is 0.5%.
2), the preparation of ultrahigh molecular weight polyethylene(UHMWPE) master batch
40% ultrahigh molecular weight polyethylene(UHMWPE), 34% linear low density polyethylene, 13% calcium carbonate, 13% whiteruss are mixed in super mixer.Mixture is standby through twin screw extruder extruding pelletization, and wherein ultrahigh molecular weight polyethylene(UHMWPE) molecular weight is 1,500,000, and expressing technique is: 190 ℃ of district's temperature, two 200 ℃ of district's temperature 190 ℃， tri-district's temperature 200 ℃， tetra-district's temperature, five 200 ℃ of district's temperature, six 215 ℃ of district's temperature 210 ℃， seven district's temperature 210 ℃， eight district's temperature, nine 215 ℃ of district's temperature, 200 ℃ of head temperatures, turn/min of screw speed 200, melt pressure 20MPa.
3), strengthen the preparation of toughness reinforcing antibacterial polypropylene material
87.7% homo-polypropylene, 0.5% modifying titanium dioxide, 10% ultrahigh molecular weight polyethylene(UHMWPE) master batch, 1% maleic anhydride inoculated polypropylene, 0.2% glyceryl monostearate, 0.2% dibutyl tin laurate, each 0.2% primary antioxidant 3114 and auxiliary anti-oxidant 168 are mixed in super mixer, then mixture is extruded to the toughness reinforcing antibacterial polypropylene material that is enhanced through twin screw extruder.Wherein polypropylene melt index is 1g/10min, and expressing technique is: 180 ℃ of district's temperature 180 ℃， bis-district's temperature, three 190 ℃ of district's temperature, four 200 ℃ of district's temperature 190 ℃， five district's temperature 190 ℃， six district's temperature, seven 200 ℃ of district's temperature, eight 210 ℃ of district's temperature 210 ℃， nine district's temperature, 200 ℃ of head temperatures, turn/min of screw speed 200, melt pressure 18MPa.
embodiment 6
The present embodiment relates to the toughness reinforcing antibacterial polypropylene composition of a kind of enhancing, comprises following each component: polypropylene, coupling modified inorganic antiseptic-germicide, ultrahigh molecular weight polyethylene(UHMWPE) master batch, graft polypropylene, dispersion agent, stablizer, oxidation inhibitor; Wherein, ultrahigh molecular weight polyethylene(UHMWPE) master batch is comprised of following each component: ultrahigh molecular weight polyethylene(UHMWPE), linear low density polyethylene, inorganic powder, compatilizer.
The preparation method of the toughness reinforcing antibacterial polypropylene composition of enhancing of the present embodiment comprises the steps:
1), the finishing of inorganic antiseptic
Take Virahol as dispersion medium is heated to 65 ℃, add titanate coupling agent UP-131 to disperse 5min, then add inorganic antiseptic titanium dioxide to disperse 30min, dry, grind, sieving obtains modifying titanium dioxide, wherein UP-131 consumption is 2%.
2), the preparation of ultrahigh molecular weight polyethylene(UHMWPE) master batch
50% ultrahigh molecular weight polyethylene(UHMWPE), 30% linear low density polyethylene, 10% talcum powder, 10% whiteruss are mixed in super mixer.Mixture is standby through twin screw extruder extruding pelletization, and wherein ultrahigh molecular weight polyethylene(UHMWPE) molecular weight is 5,000,000, and expressing technique is: 200 ℃ of district's temperature, two 210 ℃ of district's temperature 200 ℃， tri-district's temperature 210 ℃， tetra-district's temperature, five 210 ℃ of district's temperature, six 225 ℃ of district's temperature 220 ℃， seven district's temperature 220 ℃， eight district's temperature, nine 225 ℃ of district's temperature, 220 ℃ of head temperatures, turn/min of screw speed 250, melt pressure 25MPa.
3), strengthen the preparation of toughness reinforcing antibacterial polypropylene material
54% Co-polypropylene, 5% modifying titanium dioxide, 30% ultrahigh molecular weight polyethylene(UHMWPE) master batch, 8% glycidyl methacrylate graft polypropylene, 1% Tristearoylglycerol, 1% toxilic acid dibutyl tin, each 0.5% primary antioxidant 1010 and auxiliary anti-oxidant 618 are mixed in super mixer, then mixture is extruded to the toughness reinforcing antibacterial polypropylene material that is enhanced through twin screw extruder.Wherein polypropylene melt index is 25g/10min, and expressing technique is: 190 ℃ of district's temperature 190 ℃， bis-district's temperature, three 200 ℃ of district's temperature, four 210 ℃ of district's temperature 200 ℃， five district's temperature 200 ℃， six district's temperature, seven 210 ℃ of district's temperature, eight 220 ℃ of district's temperature 220 ℃， nine district's temperature, 210 ℃ of head temperatures, turn/min of screw speed 250, melt pressure 25MPa.
embodiment 7
The present embodiment relates to the toughness reinforcing antibacterial polypropylene composition of a kind of enhancing, comprises following each component: polypropylene, coupling modified inorganic antiseptic-germicide, ultrahigh molecular weight polyethylene(UHMWPE) master batch, graft polypropylene, dispersion agent, stablizer, oxidation inhibitor; Wherein, ultrahigh molecular weight polyethylene(UHMWPE) master batch is comprised of following each component: ultrahigh molecular weight polyethylene(UHMWPE), linear low density polyethylene, inorganic powder, compatilizer.
The preparation method of the toughness reinforcing antibacterial polypropylene composition of enhancing of the present embodiment comprises the steps:
1), the finishing of inorganic antiseptic
Take ethanol as dispersion medium is heated to 60 ℃, add Silane coupling agent KH550 to disperse 5min, then add inorganic antiseptic zinc oxide to disperse 30min, dry, grind, sieving obtains modified zinc oxide, wherein KH550 consumption is 0.5%.Same method, obtains titanate coupling agent UP-131 modifying titanium dioxide.
2), the preparation of ultrahigh molecular weight polyethylene(UHMWPE) master batch
30% ultrahigh molecular weight polyethylene(UHMWPE), 40% linear low density polyethylene, 15% calcium carbonate, 15% whiteruss are mixed in super mixer.Mixture is standby through twin screw extruder extruding pelletization, and wherein ultrahigh molecular weight polyethylene(UHMWPE) molecular weight is 2,500,000, and expressing technique is: 190 ℃ of district's temperature, two 200 ℃ of district's temperature 190 ℃， tri-district's temperature 200 ℃， tetra-district's temperature, five 200 ℃ of district's temperature, six 215 ℃ of district's temperature 210 ℃， seven district's temperature 210 ℃， eight district's temperature, nine 215 ℃ of district's temperature, 200 ℃ of head temperatures, turn/min of screw speed 200, melt pressure 20MPa.
3), strengthen the preparation of toughness reinforcing antibacterial polypropylene material
85% Co-polypropylene, each 0.5% modified zinc oxide and titanium dioxide, 10% ultrahigh molecular weight polyethylene(UHMWPE) master batch, 2% maleic anhydride inoculated polypropylene, 0.5% glyceryl monostearate, 0.5% dibutyl tin laurate, each 0.5% primary antioxidant 3114 and auxiliary anti-oxidant 168 are mixed in super mixer, then mixture is extruded to the toughness reinforcing antibacterial polypropylene material that is enhanced through twin screw extruder.Wherein polypropylene melt index is 25g/10min, and expressing technique is: 180 ℃ of district's temperature 180 ℃， bis-district's temperature, three 190 ℃ of district's temperature, four 200 ℃ of district's temperature 190 ℃， five district's temperature 190 ℃， six district's temperature, seven 200 ℃ of district's temperature, eight 210 ℃ of district's temperature 210 ℃， nine district's temperature, 200 ℃ of head temperatures, turn/min of screw speed 200, melt pressure 18MPa.
embodiment 8
The present embodiment relates to the toughness reinforcing antibacterial polypropylene composition of a kind of enhancing, comprises following each component: polypropylene, coupling modified inorganic antiseptic-germicide, ultrahigh molecular weight polyethylene(UHMWPE) master batch, graft polypropylene, dispersion agent, stablizer, oxidation inhibitor; Wherein, ultrahigh molecular weight polyethylene(UHMWPE) master batch is comprised of following each component: ultrahigh molecular weight polyethylene(UHMWPE), linear low density polyethylene, inorganic powder, compatilizer.
The preparation method of the toughness reinforcing antibacterial polypropylene composition of enhancing of the present embodiment comprises the steps:
1), the finishing of inorganic antiseptic
Take Virahol as dispersion medium is heated to 70 ℃, add silane coupling agent DL602 to disperse 5min, then add inorganic antiseptic zinc oxide to disperse 30min, dry, grind, sieving obtains modified zinc oxide, wherein DL602 consumption is 2%.Same method, obtains titanate coupling agent JW-105 modifying titanium dioxide.
2), the preparation of ultrahigh molecular weight polyethylene(UHMWPE) master batch
50% ultrahigh molecular weight polyethylene(UHMWPE), 30% linear low density polyethylene, 10% potassium titanate crystal whisker, 10% whiteruss are mixed in super mixer.Mixture is standby through twin screw extruder extruding pelletization, and wherein ultrahigh molecular weight polyethylene(UHMWPE) molecular weight is 2,500,000, and expressing technique is: 190 ℃ of district's temperature, two 200 ℃ of district's temperature 190 ℃， tri-district's temperature 200 ℃， tetra-district's temperature, five 200 ℃ of district's temperature, six 220 ℃ of district's temperature 210 ℃， seven district's temperature 210 ℃， eight district's temperature, nine 220 ℃ of district's temperature, 210 ℃ of head temperatures, turn/min of screw speed 250, melt pressure 25MPa.
3), strengthen the preparation of toughness reinforcing antibacterial polypropylene material
57% Co-polypropylene, each 2% modified zinc oxide and titanium dioxide, 30% ultrahigh molecular weight polyethylene(UHMWPE) master batch, 6% glycidyl methacrylate graft polypropylene, 1% Tristearoylglycerol, 1% toxilic acid dibutyl tin, each 0.5% primary antioxidant 1010 and auxiliary anti-oxidant 618 are mixed in super mixer, then mixture is extruded to the toughness reinforcing antibacterial polypropylene material that is enhanced through twin screw extruder.Wherein polypropylene melt index is 25g/10min, and expressing technique is: 180 ℃ of district's temperature 180 ℃， bis-district's temperature, three 190 ℃ of district's temperature, four 200 ℃ of district's temperature 190 ℃， five district's temperature 190 ℃， six district's temperature, seven 200 ℃ of district's temperature, eight 210 ℃ of district's temperature 210 ℃， nine district's temperature, 200 ℃ of head temperatures, turn/min of screw speed 250, melt pressure 25MPa.
comparative example 1
This comparative example relates to a kind of antibacterial polypropylene composition; Its preparation method comprises the steps:
Take ethanol as dispersion medium is heated to 60 ℃, add Silane coupling agent KH550 to disperse 5min, then add inorganic antiseptic zinc oxide to disperse 30min, dry, grind, sieving obtains modified zinc oxide, wherein KH550 consumption is 0.5%.97.7% homo-polypropylene, 0.5% modified zinc oxide, 1% maleic anhydride inoculated polypropylene, 0.2% glyceryl monostearate, 0.2% dibutyl tin laurate, each 0.2% primary antioxidant 3114 and auxiliary anti-oxidant 168 are mixed in super mixer, then mixture is extruded and obtained antibacterial polypropylene material through twin screw extruder.Wherein polypropylene melt index is 1g/10min, and expressing technique is: 190 ℃ of district's temperature 190 ℃， bis-district's temperature, three 200 ℃ of district's temperature, four 210 ℃ of district's temperature 200 ℃， five district's temperature 200 ℃， six district's temperature, seven 210 ℃ of district's temperature, eight 220 ℃ of district's temperature 220 ℃， nine district's temperature, 210 ℃ of head temperatures, turn/min of screw speed 230, melt pressure 20MPa.
comparative example 2
This comparative example relates to a kind of antibacterial polypropylene composition; Its preparation method comprises the steps:
Take Virahol as dispersion medium is heated to 65 ℃, add titanate coupling agent UP-131 to disperse 5min, then add inorganic antiseptic titanium dioxide to disperse 30min, dry, grind, sieving obtains modifying titanium dioxide, wherein UP-131 consumption is 2%.Subsequently by 84% Co-polypropylene, 5% modifying titanium dioxide, 8% glycidyl methacrylate graft polypropylene, 1% Tristearoylglycerol, 1% toxilic acid dibutyl tin, each 0.5% primary antioxidant 1010 and auxiliary anti-oxidant 618 mix in super mixer, then mixture are extruded and are obtained titania modified polypropylene material through twin screw extruder.Wherein polypropylene melt index is 25g/10min, and expressing technique is: 190 ℃ of district's temperature 190 ℃， bis-district's temperature, three 200 ℃ of district's temperature, four 210 ℃ of district's temperature 200 ℃， five district's temperature 200 ℃， six district's temperature, seven 210 ℃ of district's temperature, eight 220 ℃ of district's temperature 220 ℃， nine district's temperature, 210 ℃ of head temperatures, turn/min of screw speed 250, melt pressure 25MPa.
comparative example 3
This comparative example relates to a kind of antibacterial polypropylene composition; Its preparation method comprises the steps:
50% ultrahigh molecular weight polyethylene(UHMWPE), 30% linear low density polyethylene, 10% potassium titanate crystal whisker, 10% whiteruss are mixed in super mixer.Mixture is standby through twin screw extruder extruding pelletization, and wherein ultrahigh molecular weight polyethylene(UHMWPE) molecular weight is 2,500,000, and expressing technique is: 190 ℃ of district's temperature, two 200 ℃ of district's temperature 190 ℃， tri-district's temperature 200 ℃， tetra-district's temperature, five 200 ℃ of district's temperature, six 220 ℃ of district's temperature 210 ℃， seven district's temperature 210 ℃， eight district's temperature, nine 220 ℃ of district's temperature, 210 ℃ of head temperatures, turn/min of screw speed 250, melt pressure 25MPa.Subsequently 61% Co-polypropylene, 30% ultrahigh molecular weight polyethylene(UHMWPE) master batch, 6% glycidyl methacrylate graft polypropylene, 1% Tristearoylglycerol, 1% toxilic acid dibutyl tin, each 0.5% primary antioxidant 1010 and auxiliary anti-oxidant 618 are mixed in super mixer, then mixture is extruded and obtained antibacterial polypropylene material through twin screw extruder.Wherein polypropylene melt index is 25g/10min, and expressing technique is: 180 ℃ of district's temperature 180 ℃， bis-district's temperature, three 190 ℃ of district's temperature, four 200 ℃ of district's temperature 190 ℃， five district's temperature 190 ℃， six district's temperature, seven 200 ℃ of district's temperature, eight 210 ℃ of district's temperature 210 ℃， nine district's temperature, 200 ℃ of head temperatures, turn/min of screw speed 250, melt pressure 25MPa.
The composition of above embodiment 1～8 and comparative example 1～3 is carried out to performance test, and test result is as shown in table 1; Specific performance evaluation method and implementation standard are as follows:
By the particle of preparing as stated above, dry 5～6h in the convection oven of 80～90 ℃, and then dried particle is carried out in injector to injection molding sample preparation.
Tensile property test: undertaken by GB/T1040-2006 standard, specimen size is 170mm*10mm*4mm, and rate of extension is 50mm/min.
Bending property test: undertaken by GB/T9341-2000 standard, specimen size is 80mm*10mm*4mm, and rate of bending is 2mm/min.
Simply supported beam notched Izod impact strength test: GB/T1043.1-2008 standard is carried out, and pattern is of a size of 60mm*10mm*4mm.
Anti-microbial property detects with reference to the light industry standard QB/T2591-2003 of People's Republic of China (PRC) film applicator coating, investigates the bacteriostasis rate of sample 24h, and the mensuration of total number of bacterial colony is counted with reference to QB/T4789.2-2003.The antibacterial model of injection formed is made to 50mm*50mm.The calculating formula of antibiotic rate is as follows:
Wherein, B represents the average bacterial count recovered of control sample, cfu/ sheet; C represents antibiotic plastic sample average bacterial count recovered, cfu/ sheet.
Table 1 mechanics and anti-microbial property data
As shown in Table 1, coupling modified Nano inorganic antiseptic and ultrahigh molecular weight polyethylene(UHMWPE) master batch filled modified polypropylene have significantly improved antimicrobial efficiency and the mechanical property of polypropylene material, and then have widened the range of application of polypropylene material.
Above specific embodiments of the invention are described.It will be appreciated that, the present invention is not limited to above-mentioned specific implementations, and those skilled in the art can make various distortion or modification within the scope of the claims, and this does not affect flesh and blood of the present invention.
Claims (19)
1. strengthen a toughness reinforcing antibacterial polypropylene composition, it is characterized in that, comprise each component of following weight percent content:
2. the toughness reinforcing antibacterial polypropylene composition of enhancing as claimed in claim 1, is characterized in that, described ultrahigh molecular weight polyethylene(UHMWPE) master batch is comprised of each component of following weight percent content:
3. the toughness reinforcing antibacterial polypropylene composition of enhancing as claimed in claim 2, is characterized in that, the weight-average molecular weight of described ultrahigh molecular weight polyethylene(UHMWPE) is 150～5,000,000.
4. the toughness reinforcing antibacterial polypropylene composition of enhancing as claimed in claim 2, is characterized in that, described linear low density polyethylene density is 0.92g/cm
3, melting index is 24g/10min.
5. the toughness reinforcing antibacterial polypropylene composition of enhancing as claimed in claim 2, is characterized in that, described inorganic powder is one or more in calcium carbonate, talcum powder, carbon fiber, glass fibre, silicon-dioxide, potassium titanate crystal whisker.
6. the toughness reinforcing antibacterial polypropylene composition of enhancing as claimed in claim 2, is characterized in that, described compatilizer is whiteruss, and number-average molecular weight is 100～200g/mol.
7. the toughness reinforcing antibacterial polypropylene composition of the enhancing as described in any one in claim 1～6, is characterized in that, described polypropylene is a kind of or composition of the two in homo-polypropylene, Co-polypropylene; Described polyacrylic melting index is 1～25g/10min.
8. the toughness reinforcing antibacterial polypropylene composition of the enhancing as described in any one in claim 1～6, it is characterized in that, described coupling modified inorganic antiseptic-germicide is to adopt coupling agent to carry out the inorganic antiseptic of surface modification, and described coupling agent is one or more of silane coupling agent, titanate coupling agent, aluminate coupling agent.
9. the toughness reinforcing antibacterial polypropylene composition of enhancing as claimed in claim 8, is characterized in that, described inorganic antiseptic is one or more in nano inorganic antimicrobial agent, composite hybridization nano inorganic antimicrobial agent.
10. the toughness reinforcing antibacterial polypropylene composition of enhancing as claimed in claim 8, is characterized in that, described surface modification temperature is 60～70 ℃, and coupling agent consumption is 0.5～2% of inorganic antiseptic weight.
11. toughness reinforcing antibacterial polypropylene compositions of enhancing as described in any one in claim 1～6, is characterized in that, described graft polypropylene is one or more the composition in maleic anhydride inoculated polypropylene, glycidyl methacrylate graft polypropylene.
12. toughness reinforcing antibacterial polypropylene compositions of enhancing as described in any one in claim 1～6, is characterized in that, described dispersion agent is one or more in ethylene group bis-stearamides, glyceryl monostearate, Tristearoylglycerol.
13. toughness reinforcing antibacterial polypropylene compositions of enhancing as described in any one in claim 1～6, is characterized in that, described stablizer is organic tin stablizer.
The toughness reinforcing antibacterial polypropylene composition of 14. enhancing as claimed in claim 13, is characterized in that, described stablizer is one or more in dibutyl tin laurate, toxilic acid dibutyl tin, mercaptan dibutyl tin.
15. toughness reinforcing antibacterial polypropylene compositions of enhancing as described in any one in claim 1～6, is characterized in that, described oxidation inhibitor comprises primary antioxidant and auxiliary anti-oxidant; Described primary antioxidant is one or more in Hinered phenols antioxidant, sulphur ester antioxidant, and described auxiliary anti-oxidant is one or more in phosphite kind antioxidant, ester kind antioxidant.
The preparation method of 16. 1 kinds of toughness reinforcing antibacterial polypropylene compositions of enhancing as claimed in claim 1, is characterized in that, described method comprises the steps:
A, described polypropylene, coupling modified inorganic antiseptic-germicide, ultrahigh molecular weight polyethylene(UHMWPE) master batch, graft polypropylene, dispersion agent, stablizer and oxidation inhibitor are mixed 15～20 minutes in super mixer;
B, mixed raw material is added in twin screw extruder, cooling granulation after melt extruding, obtains; Expressing technique is: 180～190 ℃ of district's temperature, two 190～200 ℃ of district's temperature 180～190 ℃， tri-district's temperature 190～200 ℃， tetra-district's temperature, five 190～200 ℃ of district's temperature, six 210～220 ℃ of district's temperature 200～210 ℃， seven district's temperature 200～210 ℃， eight district's temperature, nine 210～220 ℃ of district's temperature, 200～210 ℃ of head temperatures, 200～250 revs/min of screw speeds, pressure 18～25MPa.
The preparation method of the toughness reinforcing antibacterial polypropylene composition of 17. enhancing as claimed in claim 16, it is characterized in that, described coupling modified inorganic antiseptic-germicide is to using ethanol or Virahol as dispersion agent, adopts coupling agent inorganic antiseptic is carried out to surface modification preparation and obtain; Described surface modification temperature is 60～70 ℃, and coupling agent consumption is 0.5～2% of inorganic antiseptic weight.
The preparation method of the toughness reinforcing antibacterial polypropylene composition of 18. enhancing as claimed in claim 16, is characterized in that, described ultrahigh molecular weight polyethylene(UHMWPE) master batch is comprised of each component of following weight percent content:
The preparation method of the toughness reinforcing antibacterial polypropylene composition of 19. enhancing as claimed in claim 18, it is characterized in that, described ultrahigh molecular weight polyethylene(UHMWPE) master batch be prepare as follows and: by described ultrahigh molecular weight polyethylene(UHMWPE), linear low density polyethylene, inorganic powder and compatilizer mix in super mixer, then by mixture through twin screw extruder extruding pelletization, expressing technique is: 190～200 ℃ of district's temperature, two 190～200 ℃ of district's temperature, three 200～210 ℃ of district's temperature, four 200～210 ℃ of district's temperature, five 200～210 ℃ of district's temperature, six 210～220 ℃ of district's temperature, seven 210～220 ℃ of district's temperature, eight 215～225 ℃ of district's temperature, nine 215～225 ℃ of district's temperature, 200～220 ℃ of head temperatures, turn/min of screw speed 200～250, melt pressure 20～25MPa.
Priority Applications (1)
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