CN101148530A - Special-purpose multifunctional modified random polypropylene material for pipe and its preparing process and application - Google Patents
Special-purpose multifunctional modified random polypropylene material for pipe and its preparing process and application Download PDFInfo
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- CN101148530A CN101148530A CNA2007100300735A CN200710030073A CN101148530A CN 101148530 A CN101148530 A CN 101148530A CN A2007100300735 A CNA2007100300735 A CN A2007100300735A CN 200710030073 A CN200710030073 A CN 200710030073A CN 101148530 A CN101148530 A CN 101148530A
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Abstract
The present invention discloses one kind of multifunctional modified atactic polypropylene pipe material and its preparation process. The atactic polypropylene pipe material consists of atactic copolypropylene, environment friendly fire retardant, pre-dispersed master batch of inorganic stuffing, impact modifier, antioxidant, composite antibacterial master batch and dispersant. It is applied in building pipes, pipeline for beverage and food industry, heat supply system and farm irrigation system. It has fire retarding and antibacterial functions, less shrinkage, high low temperature impact resistance, high heat resistance, high mechanical performance and excellent heat stability.
Description
Technical field
The invention belongs to the plastic material technical field, the preparation method of particularly a kind of special-purpose multifunctional modified random polypropylene material for pipe and this PP Pipe Compound and application.
Background technology
Ethylene, propylene atactic copolymerized polypropene (PP-R) is polyacrylic a kind of, is that the copolymerization under the effect of certain temperature, pressure and catalyzer of propylene and small amount of ethylene obtains.Structural characteristics make PP-R have homo-polypropylene (PP-H) or the not available performance of block graft Co-polypropylene (PP-B), have obtained the development of advancing by leaps and bounds at aspects such as pipe applications in recent years.In the tubing system of main use at present, the advantages such as general plastic pipe light weight, intensity are good, corrosion-resistant except that having for ethylene, propylene atactic copolymerized polypropene (PP-R), long service life, installation are simple and reliable, also have safety and sanitation, heat-resisting insulation, wear-resistantly, recyclable utilize again, characteristics such as anti-bursting by freezing.
But deep day by day along with what PP-R was studied, people are to its demands for higher performance.Although PP-R has plurality of advantages, deficiency is arranged also: thermal expansivity is bigger when high temperature (95 ℃), and notched Izod impact strength is not high, and particularly aspect such as impact property does not also reach requirement during low temperature.In order to improve and improve the performance of PP-R, widen its Application Areas, must carry out modification to it, the method for modifying of PP-R has polymerization and polymerization post-modification method (comprising blend, filling, nucleation modification).
Chinese patent application CN 01129106.0 discloses a kind of special material for nano polypropylene tubing material and preparation method thereof, it is to be main raw material with Co-polypropylene and organic clay, adding lubrication dispersing agents such as silver ion antimicrobial agent, polyethylene wax forms through mixing extruding pelletization, this PP Pipe Compound has very high resistance toheat and fabulous mechanical property, and anti-microbial effect with uniqueness, the PPR raw material of the RA130E that produces with Northern Europe Chinese workers is compared, in mechanical property, vicat softening temperature, linear expansivity, vertically aspect such as shrinking percentage all has than remarkable advantages.There is following shortcoming in above-mentioned patent application technology: the low temperature notched impact property is poor, can not meet the demands under some cold working conditions, and not have anti-flaming function, is not suitable for using in the environment of fire-retardant requirement.
Summary of the invention
Deficiency at above-mentioned prior art existence, primary and foremost purpose of the present invention is to provide a kind of multifunctional modified random Co-polypropylene tubing PP Pipe Compound, by improving inorganic mixed fillers, interfacial interaction between environmental protection fire retarding agent and the atactic copolymerized polypropene and the filler dispersing uniformity in matrix, and suitably add impact modifier, make the special material for tube that obtains have the flame-proof antibiotic function, solve atactic copolymerized polypropene simultaneously and shunk big problem, have higher resistance toheat and fabulous mechanical property, and have excellent a thermostability, particularly its anti-contracility, creep resistance and Young's modulus etc. all are better than the special material for tube of production at present.
Another object of the present invention is to provide the preparation method of above-mentioned multifunctional modified random Co-polypropylene tubing PP Pipe Compound.
A further object of the present invention is to provide the application of above-mentioned multifunctional modified random Co-polypropylene tubing PP Pipe Compound.
The objective of the invention is to be achieved through the following technical solutions: a kind of multifunctional modified random Co-polypropylene tubing PP Pipe Compound, it is characterized in that, described PP Pipe Compound is made up of atactic copolymerized polypropene, environmental protection fire retarding agent, the pre-dispersed masterbatch of mineral filler, anti-impact modifier, oxidation inhibitor, composite antibiosis masterbatch and dispersion agent, and the component of described PP Pipe Compound is counted by weight:
50～80 parts of atactic copolymerized polypropenes
5～15 parts of environmental protection fire retarding agents
10～25 parts of the pre-dispersed masterbatch of mineral filler
4～10 parts of anti-impact modifiers
0.1～0.3 part in oxidation inhibitor
2～4 parts of composite antibiosis masterbatch
0.1～3 part of dispersion agent
Described composite antibiosis masterbatch is to be composited by organic antibacterial agent and inorganic antiseptic, the organic anti-bacterial agent content is 1～30 part in the composite antibiosis masterbatch, the content of inorganic antiseptic is 1～30 part, the content of polypropylene carrier resin is 40～90 parts, described organic antibacterial agent is meant the quaternary ammonium salts antiseptic-germicide, phenolic antiseptic, organo-metallic class antiseptic-germicide, the pyridines antiseptic-germicide, imidazoles antiseptic-germicide or thiophene-based antiseptic-germicide, described inorganic antiseptic is meant nano silicon load silver ion antiseptic-germicide, nano titanium oxide load silver ion antiseptic-germicide, nano zine oxide load silver ion antiseptic-germicide or nano-stannic oxide load silver ion antiseptic-germicide
In order to realize the present invention better, the preferred melt flow rate (MFR) of described atactic copolymerized polypropene (MFR) is the atactic copolymerized polypropene of 0.3～0.6g/10min.
Described environmental protection fire retarding agent is the compound of TDE, decabromodiphynly oxide and antimonous oxide, counts by weight:
30～50 parts of TDE (TDE)
30～50 parts of decabromodiphynly oxides (PBDE)
Antimonous oxide (Sb
2O
3) 10～20 parts
Described anti-impact modifier is meant one or more in polyolefin elastomer grafted maleic anhydride (POE-g-MA), polypropylene grafted maleic anhydride (PP-g-MA), Chlorinated Polypropylene III (CPE) or the thermoplastic elastomer (SBS).
The component of the pre-dispersed masterbatch of described mineral filler is counted by weight:
70～85 parts in lime carbonate
5～10 parts of talcum powder
0.5～3 part of coupling agent
3～6 parts of macromole compatilizers
5～15 parts of homo-polypropylene
Described lime carbonate is made up of nano-calcium carbonate and water-ground limestone, and described coupling agent is meant one or more in titante coupling agent, aluminium esters of gallic acid coupling agent, Borate Ester as Coupling or the silane coupling agent.Described macromole compatilizer is meant one or more in polypropylene grafted vinylformic acid (PP-g-AA), polypropylene grafted maleic anhydride (PP-g-MA) or the ethylene-vinyl acetate copolymer grafted maleic anhydride (EVA-g-MA), and the preferred melt flow rate (MFR) of described homo-polypropylene is the homo-polypropylene of 3～10g/10min.
Preferred especially composite antibiosis masterbatch EMB-1 (20 parts of quaternary ammonium salts antiseptic-germicide+20 part nano silicon load silver ion antiseptic-germicide+60 parts of polyolefin resines), EMB-2 (20 parts of imidazoles antiseptic-germicide+20 part nano titanium oxide load silver ion antiseptic-germicide+60 parts of polyolefin resines) or EMB-3 (20 parts of pyridines antiseptic-germicide+20 part nano zine oxide load silver ion antiseptic-germicide+60 parts of polyolefin resines), above-mentioned all by weight.
Described dispersion agent is meant Poly Propylene Wax, organic silicone oil, stearic acid or is in the raw material synthetic polyester type ultra-dispersant agent one or more with 12-oxystearic acid and stearic acid.
The preparation method of above-mentioned multifunctional modified random Co-polypropylene tubing PP Pipe Compound comprises the steps:
(1) lime carbonate, talcum powder, macromole compatilizer, coupling agent and homo-polypropylene are prepared burden by said ratio, in high speed mixer, mixed 1～3 minute with 600～1000r/min speed, carry out surface activation process, in twin screw extruder, make the pre-dispersed masterbatch of mineral filler.
(2) atactic copolymerized polypropene, environmental protection fire retarding agent and anti-impact modifier are prepared burden by said ratio, in high speed mixer, mixed 2～4 minutes with 800～1000r/min speed.
(3) with step (1) and step (2) gained mixing of materials, add oxidation inhibitor, composite antibiosis masterbatch and dispersion agent again by said ratio, in high speed mixer, mixed 1～3 minute with 200～500r/min speed.
(4) material that step (3) is mixed melt extrudes granulation, drying and vacuum-packed through twin screw extruder, promptly obtains multifunctional modified random Co-polypropylene tubing PP Pipe Compound.
Special-purpose multifunctional modified random polypropylene material for pipe of the present invention can be used for producing the cold and hot water building pipe, can also be used for the irrigation system in tap water and foodstuffs industry tubing system, floor heating and traditional heat supply heating system, farmland.
The present invention compared with prior art has following advantage and beneficial effect:
The multifunctional modified random Co-polypropylene tubing PP Pipe Compound of the present invention's preparation has the flame-proof antibiotic function, solve atactic copolymerized polypropene simultaneously and shunk problem big, the low temperature impact properties difference, have higher resistance toheat and fabulous mechanical property, and have excellent thermostability, particularly its anti-contracility, low temperature and resist property etc. and all be better than the special material for tube produced at present.
Embodiment
The present invention is described in further detail below in conjunction with embodiment, but embodiments of the present invention are not limited thereto.
Following each embodiment all by weight.
Embodiment 1
50 parts of atactic copolymerized polypropenes (MFR=0.3g/10min)
Environmental protection fire retarding agent
(50 parts of TDE, 30 parts of PBDE and 20 parts of Sb
2O
3) 15 parts
25 parts of the pre-dispersed masterbatch of mineral filler (HCT-1)
10 parts of anti-impact modifier POE-g-MA
0.3 part of antioxidant 1010
3 parts of composite antibiosis masterbatch EMB-1
1 part of polyester type ultra-dispersant agent
The preparation method of multifunctional modified random Co-polypropylene tubing PP Pipe Compound comprises the steps:
(1) in the high-speed mixer of 200L, press table 1 formulation ratio, with 50 parts of 10 parts of 25 parts of nano-calcium carbonates (particle diameter is 30～65 nanometers), talcum powder (east, Liaoning occasion 1250 orders) and water-ground limestones (particle diameter is 6～10 microns), stir with 400r/min speed, be docile and obedient preface then and add 10 parts of 0.5 part of silane coupling agent (KH-550), macromole compatilizer PP-g-AA3 part and homo-polypropylene (melt flow rate (MFR) is 3g/10min), after finishing, stir with 1000r/min speed again and obtained mixture in 1 minute.Said mixture is joined in the feeding hopper of twin screw extruder, with length-to-diameter ratio be 40: 1, screw diameter be extrude in the twin screw extruder of 75mm, pelletizing, the engine speed of twin screw extruder is 250 rev/mins, 30 rev/mins of rate of feeding, the temperature of each section of forcing machine is followed successively by 150 ℃, 195 ℃, 195 ℃, 195 ℃, 195 ℃, 190 ℃, 190 ℃, 185 ℃, 180 ℃, 180 ℃, and final drying promptly obtains the pre-dispersed masterbatch HCT-1 of mineral filler.
(2) with 50 parts of atactic copolymerized polypropenes (MFR=0.3g/10min), 15 parts of environmental protection fire retarding agents (50 parts of TDE, 30 parts of PBDE and 20 parts of Sb
2O
3), the 10 parts of above-mentioned weight part meter of anti-impact modifier POE-g-MA proportion ingredients, in high speed mixer, mixed 2 minutes with 1000r/min speed.
(3) with the pre-dispersed masterbatch HCT-1 of 25 parts of mineral fillers and step (2) the gained mixing of materials of step (1), the 3 parts of composite antibiosis masterbatch EMB-1 (20 parts of poly-(4-vinylpridine quaternary ammonium salt-acrylamide) antiseptic-germicide+20 part nano silicon load silver ion antiseptic-germicide+60 parts of acrylic resins) and the 0.3 part of antioxidant 1010,1 that add above-mentioned weight part meter proportioning again, 2-hydroxystearic acid and stearic acid are 1 part of raw material synthetic polyester type ultra-dispersant agent, mix 1 minute with 500r/min speed in high speed mixer.
(4) be that 40: 1, screw diameter are that the twin screw extruder of 75mm melt extrudes granulation, drying and vacuum-packed with the material that mixes through length-to-diameter ratio, obtain multifunctional modified random Co-polypropylene tubing PP Pipe Compound PPM-1.The performance index of PPM-1 are as shown in table 2.
Embodiment 2
60 parts of atactic copolymerized polypropenes (MFR=0.6g/10min)
Environmental protection fire retarding agent
(30 parts of TDE, 30 parts of PBDE and 10 parts of Sb
2O
3) 10 parts
20 parts of the pre-dispersed masterbatch of mineral filler (HCT-1)
10 parts of anti-impact modifiers (CPE)
1,098 0.2 parts in oxidation inhibitor
2 parts of composite antibiosis masterbatch EMB-1
1 part of Poly Propylene Wax
(1) in the high-speed mixer of 200L, press table 1 formulation ratio, with 50 parts of 10 parts of 25 parts of nano-calcium carbonates (particle diameter is 30～65 nanometers), talcum powder (east, Liaoning occasion 1250 orders) and water-ground limestones (particle diameter is 6～10 microns), stir with 400r/min speed, be docile and obedient preface then and add 10 parts of 0.5 part of silane coupling agent, 3 parts of macromole compatilizer PP-g-AA and homo-polypropylene (melt flow rate (MFR) is 10g/10min), after finishing, stir with 1000r/min speed again and obtained mixture in 1 minute.Said mixture is joined in the feeding hopper of twin screw extruder, with length-to-diameter ratio be 40: 1, screw diameter be extrude in the twin screw extruder of 75mm, pelletizing, the engine speed of twin screw extruder is 250 rev/mins, 30 rev/mins of rate of feeding, the temperature of each section of forcing machine is followed successively by 150 ℃, 195 ℃, 195 ℃, 195 ℃, 195 ℃, 190 ℃, 190 ℃, 185 ℃, 180 ℃, 180 ℃, and final drying promptly obtains the pre-dispersed masterbatch HCT-1 of mineral filler.
(2) with 60 parts of atactic copolymerized polypropenes (MFR=0.6g/10min), 10 parts of environmental protection fire retarding agents (30 parts of TDE, 30 parts of PBDE and 10 parts of Sb
2O
3), the 10 parts of above-mentioned weight part meter of anti-impact modifier CPE proportion ingredients, in high speed mixer, mixed 4 minutes with 800r/min speed.
(3) with the pre-dispersed masterbatch HCT-1 of 20 parts of mineral fillers and step (2) the gained mixing of materials of step (1), add 2 parts of composite antibiosis masterbatch EMB-1 (20 parts of poly-(4-vinylpridine quaternary ammonium salt-acrylamide) antiseptic-germicide+20 part nano silicon load silver ion antiseptic-germicide+60 parts of acrylic resins) and 1098,1 part of Poly Propylene Wax of 0.2 part of oxidation inhibitor of above-mentioned weight part meter proportioning again, in high speed mixer, mixed 3 minutes with 200r/min speed.
(4) be that 40: 1, screw diameter are that the twin screw extruder of 75mm melt extrudes granulation, drying and vacuum-packed with the material that mixes through length-to-diameter ratio, obtain multifunctional modified random Co-polypropylene tubing PP Pipe Compound PPM-2.The performance index of PPM-2 are as shown in table 2.
Embodiment 3
70 parts of atactic copolymerized polypropenes (MFR=0.4g/10min)
Environmental protection fire retarding agent
(40 parts of TDE, 50 parts of PBDE and 15 parts of Sb
2O
3) 5 parts
15 parts of the pre-dispersed masterbatch of mineral filler (HCT-2)
10 parts of anti-impact modifiers (POE-g-MA)
0.1 part in oxidation inhibitor (B-215)
3 parts of composite antibiosis masterbatch EMB-2
3 parts of organic silicone oils
(1) in the high-speed mixer of 200L, press table 1 formulation ratio, with 75 parts of 5 parts of 10 parts of nano-calcium carbonates (particle diameter is 30～65 nanometers), talcum powder (east, Liaoning occasion 1250 orders) and water-ground limestones (particle diameter is 6～10 microns), stir with 400r/min speed, be docile and obedient 5 parts of 2 parts of preface adding aluminium esters of gallic acid coupling agents and 6 parts of macromole compatilizer PP-g-MA and homo-polypropylene (melt flow rate (MFR) is 8g/10min) then, after finishing, stir with 600r/min speed again and obtained mixture in 3 minutes.Said mixture is joined in the feeding hopper of twin screw extruder, with length-to-diameter ratio be 40: 1, screw diameter be extrude in the twin screw extruder of 75mm, pelletizing, the engine speed of twin screw extruder is 250 rev/mins, 30 rev/mins of rate of feeding, the temperature of each section of forcing machine is followed successively by 150 ℃, 195 ℃, 195 ℃, 195 ℃, 195 ℃, 190 ℃, 190 ℃, 185 ℃, 180 ℃, 180 ℃, and final drying promptly obtains the pre-dispersed masterbatch HCT-2 of mineral filler.
(2) with 70 parts of atactic copolymerized polypropenes (MFR=0.4g/10min), 5 parts of environmental protection fire retarding agents (40 parts of TDE, 50 parts of PBDE and 15 parts of Sb
2O
3), the 10 parts of above-mentioned weight part meter of anti-impact modifier POE-g-MA proportion ingredients, in high speed mixer, mixed 3 minutes with 900r/min speed.
(3) with the pre-dispersed masterbatch HCT-2 of 15 parts of mineral fillers and step (2) the gained mixing of materials of step (1), add 3 parts of composite antibiosis masterbatch EMB-2 (20 parts of benzoglyoxaline antiseptic-germicide+20 part nano titanium oxide load silver ion antiseptic-germicide+60 parts of acrylic resins) of above-mentioned weight part meter proportioning and 0.1 part of oxidation inhibitor (B-215), 3 parts of organic silicone oils again, in high speed mixer, mixed 2 minutes with 300r/min speed.
(4) be that 40: 1, screw diameter are that the twin screw extruder of 75mm melt extrudes granulation, drying and vacuum-packed with the material that mixes through length-to-diameter ratio, obtain multifunctional modified random Co-polypropylene tubing PP Pipe Compound PPM-3.The performance index of PPM-3 are as shown in table 2.
Embodiment 4
80 parts of atactic copolymerized polypropenes (MFR=0.6g/10min)
Environmental protection fire retarding agent
(50 parts of TDE, 40 parts of PBDE and 20 parts of Sb
2O
3) 5 parts
10 parts of the pre-dispersed masterbatch of mineral filler (HCT-2)
5 parts of anti-impact modifiers (SBS)
0.3 part of antioxidant 1010
4 parts of composite antibiosis masterbatch EMB-3
1 part of polyester type ultra-dispersant agent
(1) in the high-speed mixer of 200L, press table 1 formulation ratio, with 75 parts of 5 parts of 10 parts of nano-calcium carbonates (particle diameter is 30～65 nanometers), talcum powder (east, Liaoning occasion 1250 orders) and water-ground limestones (particle diameter is 6～10 microns), stir with 400r/min speed, be docile and obedient 5 parts of 2 parts of preface adding aluminium esters of gallic acid coupling agents and 6 parts of macromole compatilizer PP-g-MA and homo-polypropylene (melt flow rate (MFR) is 3g/10min) then, after finishing, stir with 600r/min speed again and obtained mixture in 3 minutes.Said mixture is joined in the feeding hopper of twin screw extruder, with length-to-diameter ratio be 40: 1, screw diameter be extrude in the twin screw extruder of 75mm, pelletizing, the engine speed of twin screw extruder is 250 rev/mins, 30 rev/mins of rate of feeding, the temperature of each section of forcing machine is followed successively by 150 ℃, 195 ℃, 195 ℃, 195 ℃, 195 ℃, 190 ℃, 190 ℃, 185 ℃, 180 ℃, 180 ℃, and final drying promptly obtains the pre-dispersed masterbatch HCT-2 of mineral filler.
(2) with 80 parts of atactic copolymerized polypropenes (MFR=0.6g/10min), 5 parts of environmental protection fire retarding agents (50 parts of TDE, 40 parts of PBDE and 20 parts of Sb
2O
3), the 5 parts of above-mentioned weight part meter of anti-impact modifier SBS proportion ingredients, in high speed mixer, mixed 4 minutes with 800r/min speed.
(3) with the pre-dispersed masterbatch HCT-2 of 10 parts of mineral fillers and step (2) the gained mixing of materials of step (1), add 1 part of 4 parts of composite antibiosis masterbatch EMB-3 (20 parts of pyridinium chloride hexadecyldimethyl benzyl ammonium antiseptic-germicide+20 parts of nano zine oxide load silver ion antiseptic-germicide+60 parts of acrylic resins) of above-mentioned weight part meter proportioning, 0.3 part of antioxidant 1010 and polyester type ultra-dispersant agent again, in high speed mixer, mixed 3 minutes with 200r/min speed.
(4) be that 40: 1, screw diameter are that the twin screw extruder of 75mm melt extrudes granulation, drying and vacuum-packed with the material that mixes through length-to-diameter ratio, obtain multifunctional modified random Co-polypropylene tubing PP Pipe Compound PPM-4.The performance index of PPM-4 are as shown in table 2.
Embodiment 5
50 parts of atactic copolymerized polypropenes (MFR=0.3g/10min)
Environmental protection fire retarding agent
(50 parts of TDE, 30 parts of PBDE and 20 parts of Sb
2O
3) 15 parts
25 parts of the pre-dispersed masterbatch of mineral filler (HCT-3)
10 parts of anti-impact modifiers (PP-g-MA)
0.3 part in oxidation inhibitor (0.15 part of 1010+0.15 part 168)
3 parts of composite antibiosis masterbatch EMB-3
0.1 part of Poly Propylene Wax
(1) in the high-speed mixer of 200L, press table 1 formulation ratio, with 60 parts of 10 parts of 10 parts of nano-calcium carbonates (particle diameter is 30～65 nanometers), talcum powder (east, Liaoning occasion 1250 orders) and water-ground limestones (particle diameter is 6～10 microns), stir with 400r/min speed, be docile and obedient 15 parts of 3 parts of preface adding titante coupling agents and 3 parts of macromole compatilizer EVA-g-MA and homo-polypropylene (melt flow rate (MFR) is 10g/10min) then, after finishing, stir with 800r/min speed again and obtained mixture in 2 minutes.Said mixture is joined in the feeding hopper of twin screw extruder, with length-to-diameter ratio be 40: 1, screw diameter be extrude in the twin screw extruder of 75mm, pelletizing, the engine speed of twin screw extruder is 250 rev/mins, 30 rev/mins of rate of feeding, the temperature of each section of forcing machine is followed successively by 150 ℃, 195 ℃, 195 ℃, 195 ℃, 195 ℃, 190 ℃, 190 ℃, 185 ℃, 180 ℃, 180 ℃, and final drying promptly obtains the pre-dispersed masterbatch HCT-3 of mineral filler.
(2) with 50 parts of atactic copolymerized polypropenes (MFR=0.3g/10min), 15 parts of environmental protection fire retarding agents (50 parts of TDE, 30 parts of PBDE and 20 parts of Sb
2O
3), the 10 parts of above-mentioned weight part meter of anti-impact modifier PP-g-MA proportion ingredients, in high speed mixer, mixed 2 minutes with 1000r/min speed.
(3) with the pre-dispersed masterbatch HCT-3 of 25 parts of mineral fillers and step (2) the gained mixing of materials of step (1), add 0.1 part of 3 parts of composite antibiosis masterbatch EMB-3 (20 parts of pyridinium chloride hexadecyldimethyl benzyl ammonium antiseptic-germicide+20 parts of nano zine oxide load silver ion antiseptic-germicide+60 parts of acrylic resins), 0.3 part of oxidation inhibitor (0.15 part of 1010+0.15 part 168) of above-mentioned weight part meter proportioning and Poly Propylene Wax again, in high speed mixer, mixed 1 minute with 500r/min speed.
(4) be that 40: 1, screw diameter are that the twin screw extruder of 75mm melt extrudes granulation, drying and vacuum-packed with the material that mixes through length-to-diameter ratio, obtain multifunctional modified random Co-polypropylene tubing PP Pipe Compound PPM-5.The performance index of PPM-5 are as shown in table 3.
Embodiment 6
60 parts of atactic copolymerized polypropenes (MFR=0.4g/10min)
Environmental protection fire retarding agent
(50 parts of TDE, 30 parts of PBDE and 20 parts of Sb
2O
3) 15 parts
25 parts of the pre-dispersed masterbatch of mineral filler (HCT-3)
4 parts of anti-impact modifiers (PP-g-MA)
(1098) 0.3 parts in oxidation inhibitor
3 parts of composite antibiosis masterbatch EMB-1
1 part of stearic acid
(1) in the high-speed mixer of 200L, press table 1 formulation ratio, with 60 parts of 10 parts of 10 parts of nano-calcium carbonates (particle diameter is 30～65 nanometers), talcum powder (east, Liaoning occasion 1250 orders) and water-ground limestones (particle diameter is 6～10 microns), stir with 400r/min speed, be docile and obedient 15 parts of 3 parts of preface adding titante coupling agents and 3 parts of macromole compatilizer EVA-g-MA and homo-polypropylene (melt flow rate (MFR) is 5g/10min) then, after finishing, stir with 800r/min speed again and obtained mixture in 2 minutes.Said mixture is joined in the feeding hopper of twin screw extruder, with length-to-diameter ratio be 40: 1, screw diameter be extrude in the twin screw extruder of 75mm, pelletizing, the engine speed of twin screw extruder is 250 rev/mins, 30 rev/mins of rate of feeding, the temperature of each section of forcing machine is followed successively by 150 ℃, 195 ℃, 195 ℃, 195 ℃, 195 ℃, 190 ℃, 190 ℃, 185 ℃, 180 ℃, 180 ℃, and final drying promptly obtains the pre-dispersed masterbatch HCT-3 of mineral filler.
(2) with 60 parts of atactic copolymerized polypropenes (MFR=0.4g/10min), 15 parts of environmental protection fire retarding agents (50 parts of TDE, 30 parts of PBDE and 20 parts of Sb
2O
3), the 4 parts of above-mentioned weight part meter of anti-impact modifier PP-g-MA proportion ingredients, in high speed mixer, mixed 3 minutes with 900r/min speed.
(3) with the pre-dispersed masterbatch HCT-3 of 25 parts of mineral fillers and step (2) the gained mixing of materials of step (1), add 1 part of 3 parts of composite antibiosis masterbatch EMB-1 (20 parts of poly-(4-vinylpridine quaternary ammonium salt-acrylamide) antiseptic-germicide+20 part nano silicon load silver ion antiseptic-germicide+60 parts of acrylic resins) of above-mentioned weight part meter proportioning and 0.3 part of oxidation inhibitor (1098), stearic acid again, in high speed mixer, mixed 1 minute with 500r/min speed.
(4) be that 40: 1, screw diameter are that the twin screw extruder of 75mm melt extrudes granulation, drying and vacuum-packed with the material that mixes through length-to-diameter ratio, obtain multifunctional modified random Co-polypropylene tubing PP Pipe Compound PPM-6.The performance index of PPM-6 are as shown in table 3.
Embodiment 7
65 parts of atactic copolymerized polypropenes (MFR=0.6g/10min)
Environmental protection fire retarding agent
(50 parts of TDE, 30 parts of PBDE and 20 parts of Sb
2O
3) 15 parts
25 parts of the pre-dispersed masterbatch of mineral filler (HCT-4)
10 parts of anti-impact modifiers (CPE)
0.3 part in oxidation inhibitor (B-215)
3 parts of composite antibiosis masterbatch EMB-2
1 part of stearic acid
(1) in the high-speed mixer of 200L, press table 1 formulation ratio, with 65 parts of 5 parts of 15 parts of nano-calcium carbonates (particle diameter is 30～65 nanometers), talcum powder (east, Liaoning occasion 1250 orders) and water-ground limestones (particle diameter is 6～10 microns), stir with 400r/min speed, be docile and obedient preface then and add 10 parts of 3 parts of silane coupling agents, 6 parts of macromole compatilizer PP-g-MA and homo-polypropylene (melt flow rate (MFR) is 3g/10min), after finishing, stir with 1000r/min speed again and obtained mixture in 1 minute.Said mixture is joined in the feeding hopper of twin screw extruder, with length-to-diameter ratio be 40: 1, screw diameter be extrude in the twin screw extruder of 75mm, pelletizing, the engine speed of twin screw extruder is 250 rev/mins, 30 rev/mins of rate of feeding, the temperature of each section of forcing machine is followed successively by 150 ℃, 195 ℃, 195 ℃, 195 ℃, 195 ℃, 190 ℃, 190 ℃, 185 ℃, 180 ℃, 180 ℃, and final drying promptly obtains the pre-dispersed masterbatch HCT-4 of mineral filler.
(2) with 65 parts of atactic copolymerized polypropenes (MFR=0.6g/10min), 15 parts of environmental protection fire retarding agents (50 parts of TDE, 30 parts of PBDE, 20 parts of Sb
2O
3), the 10 parts of above-mentioned weight part meter of anti-impact modifier CPE proportion ingredients, in high speed mixer, mixed 4 minutes with 800r/min speed.
(3) with the pre-dispersed masterbatch HCT-4 of 25 parts of mineral fillers and step (2) the gained mixing of materials of step (1), add 1 part of 3 parts of composite antibiosis masterbatch EMB-2 (20 parts of benzoglyoxaline antiseptic-germicide+20 part nano titanium oxide load silver ion antiseptic-germicide+60 parts of acrylic resins) of above-mentioned weight part meter proportioning and 0.3 part of oxidation inhibitor (B-215), stearic acid again, in high speed mixer, mixed 2 minutes with 400r/min speed.
(4) be that 40: 1, screw diameter are that the twin screw extruder of 75mm melt extrudes granulation, drying and vacuum-packed with the material that mixes through length-to-diameter ratio, obtain multifunctional modified random Co-polypropylene tubing PP Pipe Compound PPM-7.The performance index of PPM-7 are as shown in table 3.
Embodiment 8
60 parts of atactic copolymerized polypropenes (MFR=0.6g/10min)
Environmental protection fire retarding agent
(50 parts of TDE, 30 parts of PBDE and 20 parts of Sb
2O
3) 15 parts
25 parts of the pre-dispersed masterbatch of mineral filler (HCT-4)
10 parts of anti-impact modifier POE-g-MA
(1010) 0.3 parts in oxidation inhibitor
3 parts of composite antibiosis masterbatch EMB-1
1 part of Poly Propylene Wax
(1) in the high-speed mixer of 200L, press table 1 formulation ratio, with 65 parts of 5 parts of 15 parts of nano-calcium carbonates (particle diameter is 30～65 nanometers), talcum powder (east, Liaoning occasion 1250 orders) and water-ground limestones (particle diameter is 6～10 microns), stir with 400r/min speed, be docile and obedient preface then and add 10 parts of 3 parts of silane coupling agents, 6 parts of macromole compatilizer PP-g-MA and homo-polypropylene (melt flow rate (MFR) is 10g/10min), after finishing, stir with 1000r/min speed again and obtained mixture in 1 minute.Said mixture is joined in the feeding hopper of twin screw extruder, with length-to-diameter ratio be 40: 1, screw diameter be extrude in the twin screw extruder of 75mm, pelletizing, the engine speed of twin screw extruder is 250 rev/mins, 30 rev/mins of rate of feeding, the temperature of each section of forcing machine is followed successively by 150 ℃, 195 ℃, 195 ℃, 195 ℃, 195 ℃, 190 ℃, 190 ℃, 185 ℃, 180 ℃, 180 ℃, and final drying promptly obtains the pre-dispersed masterbatch HCT-4 of mineral filler.
(2) with 60 parts of atactic copolymerized polypropenes (MFR=0.6g/10min), 15 parts of environmental protection fire retarding agents (50 parts of TDE, 30 parts of PBDE and 20 parts of Sb
2O
3), the 10 parts of above-mentioned weight part meter of anti-impact modifier POE-g-MA proportion ingredients, in high speed mixer, mixed 2 minutes with 1000r/min speed.
(3) with the pre-dispersed masterbatch HCT-4 of 25 parts of mineral fillers and step (2) the gained mixing of materials of step (1), add 1 part of 3 parts of composite antibiosis masterbatch EMB-1 (20 parts of poly-(4-vinylpridine quaternary ammonium salt-acrylamide) antiseptic-germicide+20 part nano silicon load silver ion antiseptic-germicide+60 parts of acrylic resins) of above-mentioned weight part meter proportioning and 0.3 part of antioxidant 1010, Poly Propylene Wax again, in high speed mixer, mixed 1 minute with 500r/min speed.
(4) be that 40: 1, screw diameter are that the twin screw extruder of 75mm melt extrudes granulation, drying and vacuum-packed with the material that mixes through length-to-diameter ratio, obtain multifunctional modified random Co-polypropylene tubing PP Pipe Compound PPM-8.The performance index of PPM-8 are as shown in table 3.
The technical feature contrast of the multifunctional modified random Co-polypropylene tubing PP Pipe Compound of the various embodiments described above and Korea S star R200P dawn special material for tube sees Table 2, table 3.
Table 1
| The pre-dispersed masterbatch of mineral filler | HCT-1 | ?HCT-2 | ?HCT-3 | ?HCT-4 |
| Nano-calcium carbonate (weight part) | ?25 | ?10 | ?10 | ?15 |
| Water-ground limestone (weight part) | ?50 | ?75 | ?60 | ?65 |
| Talcum powder (weight part) | ?10 | ?5 | ?10 | ?5 |
| Silane coupling agent (weight part) | ?0.5 | ?3 | ||
| Aluminium esters of gallic acid coupling agent (weight part) | ?2 | |||
| Titante coupling agent (weight part) | ?3 | |||
| PP-g-AA (weight part) | ?3 | |||
| PP-g-MA (weight part) | ?6 | ?6 | ||
| EVA-g-MA (weight part) | ?3 | |||
| Homo-polypropylene (weight part) | ?10 | ?5 | ?15 | ?10 |
Table 2
Table 3
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. multifunctional modified random Co-polypropylene tubing PP Pipe Compound, it is characterized in that: described PP Pipe Compound is made up of atactic copolymerized polypropene, environmental protection fire retarding agent, the pre-dispersed masterbatch of mineral filler, anti-impact modifier, oxidation inhibitor, composite antibiosis masterbatch and dispersion agent, and the component of described PP Pipe Compound is counted by weight:
50～80 parts of atactic copolymerized polypropenes
5～15 parts of environmental protection fire retarding agents
10～25 parts of the pre-dispersed masterbatch of mineral filler
4～10 parts of anti-impact modifiers
0.1～0.3 part in oxidation inhibitor
2～4 parts of composite antibiosis masterbatch
0.1～3 part of dispersion agent;
Counting organic antibacterial agent in the described composite antibiosis masterbatch by weight and be 1～30 part, inorganic antiseptic and be 1～30 part and polypropylene carrier resin is 40～90 parts; Described organic antibacterial agent is meant quaternary ammonium salts antiseptic-germicide, phenolic antiseptic, organo-metallic class antiseptic-germicide, pyridines antiseptic-germicide, imidazoles antiseptic-germicide or thiophene-based antiseptic-germicide, and described inorganic antiseptic is meant nano silicon load silver ion antiseptic-germicide, nano titanium oxide load silver ion antiseptic-germicide, nano zine oxide load silver ion antiseptic-germicide or nano-stannic oxide load silver ion antiseptic-germicide.
2. a kind of multifunctional modified random Co-polypropylene tubing PP Pipe Compound according to claim 1 is characterized in that: described atactic copolymerized polypropene is that melt flow rate (MFR) is the atactic copolymerized polypropene of 0.3～0.6g/10min.
3. a kind of multifunctional modified random Co-polypropylene tubing PP Pipe Compound according to claim 1, it is characterized in that: described environmental protection fire retarding agent is the compound of TDE, decabromodiphynly oxide and antimonous oxide, counts by weight:
30～50 parts of TDE
30～50 parts of decabromodiphynly oxides
10～20 parts of antimonous oxides
4. a kind of multifunctional modified random Co-polypropylene tubing PP Pipe Compound according to claim 1, it is characterized in that: described anti-impact modifier is meant one or more in polyolefin elastomer grafted maleic anhydride, polypropylene grafted maleic anhydride, Chlorinated Polypropylene III or the thermoplastic elastomer.
5. a kind of multifunctional modified random Co-polypropylene tubing PP Pipe Compound according to claim 1, it is characterized in that: the component of the pre-dispersed masterbatch of described mineral filler is counted by weight:
70～85 parts in lime carbonate
5～10 parts of talcum powder
0.5～3 part of coupling agent
3～6 parts of macromole compatilizers
5～15 parts of homo-polypropylene
6. a kind of multifunctional modified random Co-polypropylene tubing PP Pipe Compound according to claim 5, it is characterized in that: described lime carbonate is made up of nano-calcium carbonate and water-ground limestone, and described coupling agent is meant one or more in titante coupling agent, aluminium esters of gallic acid coupling agent, Borate Ester as Coupling or the silane coupling agent; Described macromole compatilizer is meant one or more in polypropylene grafted vinylformic acid, polypropylene grafted maleic anhydride or the ethylene-vinyl acetate copolymer grafted maleic anhydride, and described homo-polypropylene is that melt flow rate (MFR) is the homo-polypropylene of 3～10g/10min.
7. a kind of multifunctional modified random Co-polypropylene tubing PP Pipe Compound according to claim 1, it is characterized in that: described composite antibiosis masterbatch is 20 parts of quaternary ammonium salts antiseptic-germicide+20 part nano silicon load silver ion antiseptic-germicide+60 parts of polyolefin resines, 20 parts of imidazoles antiseptic-germicide+20 part nano titanium oxide load silver ion antiseptic-germicide+60 parts of polyolefin resines or 20 parts of pyridines antiseptic-germicide+20 part nano zine oxide load silver ion antiseptic-germicide+60 parts of polyolefin resines, above-mentioned all by weight.
8. a kind of multifunctional modified random Co-polypropylene tubing PP Pipe Compound according to claim 1, it is characterized in that: described dispersion agent is meant one or more in Poly Propylene Wax, organic silicone oil, stearic acid or the polyester type ultra-dispersant agent.
9. the preparation method of the described multifunctional modified random Co-polypropylene of claim 1 tubing PP Pipe Compound is characterized in that comprising the steps:
(1) lime carbonate, talcum powder, macromole compatilizer, coupling agent and homo-polypropylene are prepared burden by said ratio, in high speed mixer, mixed 1～3 minute with 600～1000r/min speed, carry out surface activation process, in twin screw extruder, make the pre-dispersed masterbatch of mineral filler;
(2) atactic copolymerized polypropene, environmental protection fire retarding agent and anti-impact modifier are prepared burden by said ratio, in high speed mixer, mixed 2～4 minutes with 800～1000r/min speed;
(3) with step (1) and step (2) gained mixing of materials, add oxidation inhibitor, composite antibiosis masterbatch and dispersion agent again by said ratio, in high speed mixer, mixed 1～3 minute with 200～500r/min speed;
(4) material that step (3) is mixed melt extrudes granulation, drying and vacuum-packed through twin screw extruder, promptly obtains multifunctional modified random Co-polypropylene tubing PP Pipe Compound.
10. the application of the described special-purpose multifunctional modified random polypropylene material for pipe of claim 1 in the irrigation system in cold and hot water building pipe, tap water and foodstuffs industry tubing system, floor heating and traditional heat supply heating system, farmland.
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|---|---|---|---|
| CNB2007100300735A CN100560645C (en) | 2007-09-04 | 2007-09-04 | Special-purpose multifunctional modified random polypropylene material for pipe and its production and application |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100300735A CN100560645C (en) | 2007-09-04 | 2007-09-04 | Special-purpose multifunctional modified random polypropylene material for pipe and its production and application |
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| CN100560645C CN100560645C (en) | 2009-11-18 |
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