CN1944515A - Beta-crystal polypropylene composition and its preparing method - Google Patents
Beta-crystal polypropylene composition and its preparing method Download PDFInfo
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- CN1944515A CN1944515A CN 200610096877 CN200610096877A CN1944515A CN 1944515 A CN1944515 A CN 1944515A CN 200610096877 CN200610096877 CN 200610096877 CN 200610096877 A CN200610096877 A CN 200610096877A CN 1944515 A CN1944515 A CN 1944515A
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Abstract
The beta-crystalline polypropylene composition consists of polypropylene in 90.00-100.00 wt%; and inorganic filler, antioxidant, lubricant, nucleating agent and light stabilizer in 0.00-10.00 wt%. It is prepared through compounding the components; mixing in a mixer at room temperature; smelting, extruding and palletizing in a double screw extruder set; and cooling to room temperature to obtain the beta-crystalline polypropylene composition. The composition of the present invention has very high tensile strength, outstanding heat resistance and excellent impact resistance, and may be used in producing wide bore pipes, valve, etc.
Description
One, technical field
The invention belongs to the applied chemistry field, particularly a kind of beta-crystal polypropylene composition and preparation method thereof.
Two, background technology
Prior art: usually said polypropylene is meant that its degree of isotacticity of isotatic polypropylene (IPP) is about 96%, its crystalline structure mainly is the alpha-crystal form of monocrystalline system, this crystal formation is more stable, but its rigidity and toughness imbalance, shock resistance particularly, has only 5J/m at normal temperatures, for overcoming these shortcomings, improving its toughness and tensile strength does not reduce again, vast domestic and international scientific worker of past concentrates research ethylene-propylene rubber(EPR), thermoplastic elastomer such as SBS or POE wait modified polypropene, improve its resistance to impact shock and resistance to low temperature, though there is certain effect technological process complicated, cost is also higher.The method of beta nucleater has all appearred adding in recent years both at home and abroad, improve the content of beta-crystal in the polypropylene, thereby improve its performance, disclose as CN001173391 that the beta-crystal relative content reaches about 33% in the polypropylene that adds the preparation of different nucleators, shock strength can improve 30%, and other mechanical property is not seen the data report; CN 02134498.1 discloses the goods of polypropylene beta-crystal-type nucleater and gained, and these different goods beta-crystal relative contents can reach 75-89%, and it is about 85% that shock resistance can improve, but do not see concrete data equally.
Three, summary of the invention
The invention provides a kind of tensile strength height, heat-resisting, shock proof beta-crystal polypropylene composition and preparation method thereof.
Technical solution of the present invention is: a kind of beta-crystal polypropylene composition, and it comprises following component:
A.90.00～100.00% (weight) polypropylene;
B.0.00～10.00% (weight) mineral filler;
C.0.10～2.00% (a, b gross weight) oxidation inhibitor;
D.0.10～1.00% (a, b gross weight) lubricant;
E.0.05～3.00% (a, b gross weight) nucleator;
F.0.10～1.00% (a, b gross weight) photostabilizer.
Described homo-polypropylene or Co-polypropylene are under 230 ℃, pressure 2.16Kg condition, and its melt flow rate (MFR) is 0.5-6.0g/10min, and the melt flow rate (MFR) of recommendation is 1.0-3.0g/10min.
Described nucleator can use calcium salt, calcium benzoate or the substituted benzene amides of Succinic Acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid or sebacic acid separately; Can use the mixture of any and calcium stearate in the above-mentioned organic dibasic acid salt, its quality proportioning is not limit, but recommends 1: 0.5-2 yet.
Oxidation inhibitor is any proportioning mixture of any and four [β-(3,5-di-tert-butyl-hydroxy phenyl) propylene] tetramethylolmethane in Tyox B or three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, preferably is 1: 1-2.
Lubricant is stearic acid or molecular weight 1500～5000, and density is 0.9g/cm
3White powder low-molecular polypropylene, low molecular polyethylene.These lubricants can use separately, also can compositely use, and its compound proportion generally is not specifically limited.Recommending consumption is the 0.3-0.8% of polypropylene and mineral filler gross weight.
Described mineral filler is light calcium carbonate, water-ground limestone, talcum powder or layered silicate master batch.These fillers can use separately also can mix use, and its ratio is not specifically limited, and recommending consumption is the 2-8% of total amount, and the granularity of mineral filler is generally 0.1-3 μ m.
Described photostabilizer is that Whitfield's ointment is to octyl phenyl ester (UV light absorber OPS); Right, to '-isopropylidene bis-phenol salicylate (UV Absorber BAD); 2-hydroxyl 4-n-octyloxy-benzophenone (ultraviolet absorbent UV-531); Three (1,2,2 ', 6,6 ' pentamethyl-piperidyl)-phosphorous acid esters (photostabilizer GW-540).These photostabilizers both can use separately also and can compositely use, and its compound proportion does not have concrete restriction, and recommending consumption is the 0.1-0.4% of polypropylene and mineral filler gross weight.
A kind of preparation method of beta-crystal polypropylene composition, it is characterized in that each component being weighed up by above-mentioned prescription, join in the super mixer, speed setting is 1000 rev/mins, at room temperature mix and emitted in 1-3 minute, this mixture is added in the barrel of twin screw extruder, processing condition in accordance with regulations melt extrude granulation in twin screw extruder again.
The processing parameter span of control of setting is that each section of twin screw extruder temperature is 170-230 ℃ from feeding section to getting to know; Screw speed is 190-240 rev/min; Vacuum tightness is located at 0.04-0.08Mpa; The temperature of water coolant is controlled between 20-45 ℃; The rotating speed of dicing machine is controlled at 700-900 rev/min.
Compared with prior art, the present composition not only have superelevation tensile strength (〉=42Mpa), outstanding thermotolerance and good shock resistance, and cost is low, preparation technology is simple, easily operation.Can be used for making bigbore pipe for building and industrial pipe, valve, pipe fitting, also can be used for the fly-ash separator of steel mill, power plant, the electrolyzer and the dividing plate of Electroplate Factory.
Four, description of drawings
Fig. 1 is preparation technology's block diagram
Five, embodiment
The usefulness that detailed description of the present invention explains it should be appreciated by those skilled in the art that these details only are used for this purpose, not departing under the spirit and scope of the invention condition that claims define, can change the present invention.
Embodiment 1:
The composition of beta-crystal polypropylene composition is 3Kg homo-polypropylene (melt flow rate (MFR) 0.5g/10min), nucleator pentanedioic acid calcium 30g, antioxidant 1010 12g, oxidation inhibitor 168 24g, lubricant low-molecular-weight wax 15g, light calcium carbonate 120g, photostabilizer GW 5406g.Preparation flow according to Fig. 1, above-mentioned component is weighed up, be added in the 10 liter super mixers, 1000 rev/mins of rotating speeds, at room temperature mix after 1 minute and take out, the material that mixes is added in the hopper of φ 30 twin screw extruders, through fusion, extrude, cooling, pelletizing can make beta-crystal polypropylene composition.Twin screw extruder is controlled at 170-180 ℃, 180-195 ℃, 195-220 ℃, 200-220 ℃, the temperature of getting to know respectively at 200-230 ℃ from first section to the 5th section temperature; Screw speed is at 200-230r/min; Vacuum tightness is 0.05-0.07Mpa; Temperature of cooling water is 20-30 ℃.
The beta-crystal polypropylene composition that this embodiment makes is injection molded into the test specimen of regulation shape and size, the mechanical property of test material with the regulation of injection moulding machine by GB GB/T17037.3-2003 under 200-255 ℃; Again with vulcanizing press in 210 ℃ of thin slices that are molded into less than 1mm, depress naturally cooling adding, the relative content that thin slice is measured the polypropylene beta-crystal by wide-angle x-ray diffraction (WAXD) method is 42%, and tensile strength is that 46.5Mpa, IZOD notched Izod impact strength are 53KJ/m
2
Embodiment 2:
Except nucleator used mixture 45g, the homo-polypropylene 3Kg (melt flow rate (MFR) 5.5g/10min) of pentanedioic acid calcium and calcium stearate, other component was identical with embodiment 1 with preparation condition.The performance measurement result is tensile strength 45.6Mpa, IZOD notched Izod impact strength 48.8KJ/m
2, beta-crystal polypropylene relative content be 35.8%.
Embodiment 3:
Except that 240g, homo-polypropylene 3Kg (melt flow rate (MFR) 3.5g/10min) were used in mineral filler, other component and condition were with embodiment 1, and the performance measurement result is tensile strength 45Mpa, IZOD notched Izod impact strength 26KJ/m
2, beta-crystal polypropylene relative content be 28.6%.
Embodiment 4:
Except that nucleator uses mixture 60 grams, homo-polypropylene 3Kg (melt flow rate (MFR) 2.0g/10min) of pentanedioic acid calcium and calcium stearate, other component and condition are with embodiment 1, and the performance measurement result is tensile strength 46.7Mpa, IZOD notched Izod impact strength 43.3KJ/m
2, beta-crystal polypropylene relative content be 45.2%.
Embodiment 5:
| Experiment 1 | Experiment 2 | Experiment 3 | |
| Polypropylene (kg) | 3.0 | 3.0 | 3.0 |
| Mineral filler (g) | 300 | 150 | 0 |
| Oxidation inhibitor (g) | 10 | 30 | 60 |
| Lubricant (g) | 7 | 14 | 28 |
| Nucleator (g) | 15 | 45 | 90 |
| Photostabilizer (g) | 6 | 12 | 24 |
(optional reagent in each component is selected arbitrarily in the requsst listed below)
Wherein: polypropylene is homo-polypropylene or Co-polypropylene, is under the 2.16Kg condition at 230 ℃, pressure, and its melt flow rate (MFR) is 0.5-60g/10min.
Nucleator is C
4～C
10Organic dibasic acid, as the mixture of calcium salt, benzoate, substituted benzene amides or the above-mentioned organic dibasic acid salt and the calcium stearate of Succinic Acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid or sebacic acid.
Oxidation inhibitor is any proportioning mixture of any and four [β-(3,5-di-tert-butyl-hydroxy phenyl) propylene] tetramethylolmethane in Tyox B or three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester.
Lubricant is stearic acid or molecular weight 1500-5000, and density is 0.9g/cm
3White powder low-molecular polypropylene, low molecular polyethylene.
Mineral filler is light calcium carbonate, water-ground limestone, talcum powder or layered silicate master batch, and particle fineness is 0.1～3 μ m.
Photostabilizer is that Whitfield's ointment is to the octyl phenyl ester; Right, to '-isopropylidene bis-phenol salicylate; 2-hydroxyl 4-n-octyloxy-benzophenone; Three (1,2,2 ', 6,6 ' pentamethyl-piperidyl)-phosphorous acid esters.
Experiment 1, experiment 2, experiment 3 performance measurement results are respectively tensile strength and are respectively 47.8Mpa, 45.2Mpa, 42.8Mpa, and the IZOD notched Izod impact strength is respectively 25.1KJ/m
2, 28.5KJ/m
2, 49.3KJ/m
2, the relative content of beta-crystal polypropylene is respectively 25.3%, 28.6%, 43.1%.
Embodiment 6:
By operating process shown in Figure 1, with any one joins in the mixing tank in three kinds of mixtures of gained among the embodiment 5, at room temperature thorough mixing makes B after evenly; B is joined in the barrel of twin screw extruder group, melt extrude granulation, make C; After C was cooled to room temperature, pelletizing was prepared into beta-crystal polypropylene composition.Wherein, each section of twin screw extruder temperature is 170-230 ℃ from feeding section to getting to know; Screw speed is 190-240 rev/min; Vacuum tightness is located at 0.04-0.08Mpa; The temperature of water coolant is controlled between 20-45 ℃; The rotating speed of dicing machine is controlled at 700-900 rev/min.
Claims (9)
1. beta-crystal polypropylene composition, it comprises following component:
A.90.00～100.00% (weight) polypropylene;
B.0.00～10.00% (weight) mineral filler;
C.0.10～2.00% (a, b gross weight) oxidation inhibitor;
D.0.10～1.00% (a, b gross weight) lubricant;
E.0.05～3.00% (a, b gross weight) nucleator;
F.0.10～1.00% (a, b gross weight) photostabilizer.
2. beta-crystal polypropylene composition as claimed in claim 1 is characterized in that described polypropylene is homo-polypropylene or Co-polypropylene, is under the 2.16Kg condition at 230 ℃, pressure, and its melt flow rate (MFR) is 0.5～6.0g/10min.
3. beta-crystal polypropylene composition as claimed in claim 1 is characterized in that described nucleator is C
4～C
10Organic dibasic acid, as the mixture of calcium salt, benzoate, substituted benzene amides or the above-mentioned organic dibasic acid salt and the calcium stearate of Succinic Acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid or sebacic acid.
4. beta-crystal polypropylene composition as claimed in claim 1 is characterized in that described oxidation inhibitor is any proportioning mixture of any and four [β-(3,5-di-tert-butyl-hydroxy phenyl) propylene] tetramethylolmethane in Tyox B or three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester.
5. beta-crystal polypropylene composition as claimed in claim 1 is characterized in that described lubricant is stearic acid or molecular weight 1500～5000, and density is 0.9g/cm
3White powder low-molecular polypropylene, low molecular polyethylene.
6. beta-crystal polypropylene composition as claimed in claim 1 is characterized in that described mineral filler is light calcium carbonate, water-ground limestone, talcum powder or layered silicate master batch, and particle fineness is 0.1～3 μ m.
7. beta-crystal polypropylene composition as claimed in claim 1 is characterized in that described photostabilizer is that Whitfield's ointment is to the octyl phenyl ester; Right, to '-isopropylidene bis-phenol salicylate; 2-hydroxyl 4-n-octyloxy-benzophenone; Three (1,2,2 ', 6,6 ' pentamethyl-piperidyl)-phosphorous acid esters.
8. a method for preparing beta-crystal polypropylene composition is characterized in that comprising the following steps:
A. make composition A by above-mentioned beta-crystal polypropylene composition component prescription, A is joined in the mixing tank, at room temperature thorough mixing makes B after evenly;
B. B is joined in the barrel of twin screw extruder group, melt extrude granulation, make C;
C. after C being cooled to room temperature, pelletizing is prepared into beta-crystal polypropylene composition.
9. the method for preparing beta-crystal polypropylene composition as claimed in claim 8 is characterized in that each section of twin screw extruder temperature is 170-230 ℃ from feeding section to getting to know; Screw speed is 190-240 rev/min; Vacuum tightness is located at 0.04-0.08Mpa; The temperature of water coolant is controlled between 20-45 ℃; The rotating speed of dicing machine is controlled at 700-900 rev/min.
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| CNB2006100968770A CN100482733C (en) | 2006-10-24 | 2006-10-24 | Beta-crystal polypropylene composition and its preparing method |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101168609B (en) * | 2007-09-30 | 2010-05-19 | 广州市合诚化学有限公司 | Special-purpose material for beta nucleater modified random copolymerization polypropylene pipe and preparation method thereof |
| CN101955610A (en) * | 2010-10-12 | 2011-01-26 | 中山大学 | Calcium carbonate fillers having high beta-nucleation effect on polypropylene and copolymers of polypropylene and preparation method thereof |
| CN102070826A (en) * | 2010-12-03 | 2011-05-25 | 江南大学 | New method for toughening and reinforcing polypropylene composite |
| CN102086285A (en) * | 2010-12-09 | 2011-06-08 | 中山大学 | Eggshell filler having high beta nucleation on polypropylene and preparation method thereof |
| CN101429309B (en) * | 2008-10-29 | 2012-04-25 | 上海赛科石油化工有限责任公司 | Impact-resistant polypropylene composition and preparation method thereof |
| CN101955608B (en) * | 2009-07-14 | 2012-07-04 | 中国石油化工股份有限公司 | Barrier polypropylene composition and preparation method thereof |
| CN102869484A (en) * | 2010-04-28 | 2013-01-09 | Wpc株式会社 | Method for producing composite pellet for extrusion molding, and composite pellet for extrusion molding produced by the method |
| WO2013097647A1 (en) | 2011-12-31 | 2013-07-04 | 广州呈和科技有限公司 | Β-crystal form nucleating agent composition for polypropylene and application thereof |
| CN103483688A (en) * | 2013-10-15 | 2014-01-01 | 重庆顾地塑胶电器有限公司 | Impact-resistant and stretching-resistant beta-crystal form polypropylene composite material, and preparation method and application thereof |
| CN105037928A (en) * | 2015-07-01 | 2015-11-11 | 昆明亘宏源科技有限公司 | Preparation method of electrolysis negative plate high-performance insulation edge clamping strip |
| CN106519511A (en) * | 2016-11-24 | 2017-03-22 | 安徽意力电缆有限公司 | Low-temperature-resistant PVC cable material formula |
| CN110185851A (en) * | 2019-04-02 | 2019-08-30 | 浙江中财管道科技股份有限公司 | A kind of high voltage, composite polypropylene of highly corrosion resistant and preparation method thereof |
| CN114806024A (en) * | 2022-05-05 | 2022-07-29 | 横店集团得邦工程塑料有限公司 | High-impact-resistance low-temperature-resistance polypropylene material and preparation method thereof |
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2006
- 2006-10-24 CN CNB2006100968770A patent/CN100482733C/en not_active Expired - Fee Related
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101168609B (en) * | 2007-09-30 | 2010-05-19 | 广州市合诚化学有限公司 | Special-purpose material for beta nucleater modified random copolymerization polypropylene pipe and preparation method thereof |
| CN101429309B (en) * | 2008-10-29 | 2012-04-25 | 上海赛科石油化工有限责任公司 | Impact-resistant polypropylene composition and preparation method thereof |
| CN101955608B (en) * | 2009-07-14 | 2012-07-04 | 中国石油化工股份有限公司 | Barrier polypropylene composition and preparation method thereof |
| CN102869484A (en) * | 2010-04-28 | 2013-01-09 | Wpc株式会社 | Method for producing composite pellet for extrusion molding, and composite pellet for extrusion molding produced by the method |
| CN101955610A (en) * | 2010-10-12 | 2011-01-26 | 中山大学 | Calcium carbonate fillers having high beta-nucleation effect on polypropylene and copolymers of polypropylene and preparation method thereof |
| CN102070826A (en) * | 2010-12-03 | 2011-05-25 | 江南大学 | New method for toughening and reinforcing polypropylene composite |
| CN102086285A (en) * | 2010-12-09 | 2011-06-08 | 中山大学 | Eggshell filler having high beta nucleation on polypropylene and preparation method thereof |
| WO2013097647A1 (en) | 2011-12-31 | 2013-07-04 | 广州呈和科技有限公司 | Β-crystal form nucleating agent composition for polypropylene and application thereof |
| US9243123B2 (en) | 2011-12-31 | 2016-01-26 | Gch Technology Co., Ltd. | B-crystal form nucleating agent composition for polypropylene and use thereof |
| CN103483688A (en) * | 2013-10-15 | 2014-01-01 | 重庆顾地塑胶电器有限公司 | Impact-resistant and stretching-resistant beta-crystal form polypropylene composite material, and preparation method and application thereof |
| CN103483688B (en) * | 2013-10-15 | 2016-01-06 | 重庆顾地塑胶电器有限公司 | Beta-crystal polypropylene matrix material of shock resistance and stretch-proof and its preparation method and application |
| CN105037928A (en) * | 2015-07-01 | 2015-11-11 | 昆明亘宏源科技有限公司 | Preparation method of electrolysis negative plate high-performance insulation edge clamping strip |
| CN106519511A (en) * | 2016-11-24 | 2017-03-22 | 安徽意力电缆有限公司 | Low-temperature-resistant PVC cable material formula |
| CN110185851A (en) * | 2019-04-02 | 2019-08-30 | 浙江中财管道科技股份有限公司 | A kind of high voltage, composite polypropylene of highly corrosion resistant and preparation method thereof |
| CN114806024A (en) * | 2022-05-05 | 2022-07-29 | 横店集团得邦工程塑料有限公司 | High-impact-resistance low-temperature-resistance polypropylene material and preparation method thereof |
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