CN102382344B - Composition for preparing polyethylene pipe with superhigh molecular weight and preparation method thereof - Google Patents
Composition for preparing polyethylene pipe with superhigh molecular weight and preparation method thereof Download PDFInfo
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Abstract
A composition for preparing polyethylene pipe with superhigh molecular weight and a preparation method thereof are disclosed. The composition is prepared by the following raw materials by weight percentage: polyethylene with superhigh molecular weight: fluoropolymer processing agent: polyethylene wax: calcium stearate/zinc stearate compound: complex antioxidant: carbon black is equal to 100 parts: 0.01-0.1: 1-8:0.1-1.0:0.1-0.5:0.5-3. The preparation method comprises the steps of: putting the polyethylene resin with superhigh molecular weight, starting a mixer, putting the calcium stearate/zinc stearate compound into the mixer to mix for 1-2 hours, then adding the complex antioxidant, polyethylene wax, fluoropolymer processing agent and carbon black to mix for 2-3 hours; and detecting the bulk density according to GB/T1636 and sealing and packaging. The polyethylene pipe composition with superhigh molecular weight prepared by the method has excellent heat-resisting and anti-aging performance with oxidation induction time at 200 DEGC longer than 30 minutes. The polyethylene pipe composition with superhigh molecular weight further has excellent mechanical, wear-resisting, corrosion resisting, heat-resisting and anti-aging properties and extrusion process performance.
Description
Technical field
The invention belongs to technical field of plastic, be specifically related to a kind of composition for the preparation of ultrahigh molecular weight polyethylene tubing and method for making thereof.
Background technology
Ultrahigh molecular weight polyethylene(UHMWPE) (Ultra-high molecular weight Polyethylene, abbreviation UHMWPE) refers generally to relative molecular mass and surpass 1,500,000 polyethylene (PE), and the relative molecular mass of common PE generally only is 20,000～300,000, the relative molecular mass of domestic UHMWPE can reach 4,000,000～5,000,000, and the relative molecular mass of the UHMWPE that Germany produces is up to 10,000,000.
The high relative molecular mass of UHMWPE is given its extremely excellent performance:
1. fabulous environmental stress crack resistance is 200 times of common high density polyethylene(HDPE) (HDPE), 5～10 times of common plastics;
2. extremely strong wear resistance occupies the plastics first place, be common plastics 5-7 doubly, the 7-10 of steel pipe doubly;
3. high shock-resistance, shock strength is the highest in existing plastics, even still keep quite high shock strength under-70 ℃ of conditions;
4. excellent self lubricity is suitable with tetrafluoroethylene (PTFE);
5. good chemical stability, electrical insulating property, resistance to fatigue and weathering resistance;
6. nontoxic, do not absorb water, density is little, do not adhere to, antistatic, inhale noise, and be easy to mechanical workout, pigmentable.
UHMWPE is existing high-quality engineering plastics, compares with metal pipe material with other plastic pipe with its tubing of making, all has in many aspects obvious advantage.
Although UHMWPE has the performance of above-mentioned excellence, but caused just because of the relative molecular mass of its superelevation that its melt viscosity is high (to reach 1 * 108Pas), mobile extreme difference, critical shear rate is extremely low, add and very easily produce melt fracture man-hour, very difficult plastic molding equipment and processes with routine.Want to extrude UHMWPE tubing with common extrusion equipment, must carry out modification to it, namely improve the flowability of UHMWPE by various means, perhaps molding device is improved, perhaps adopt new forming processing technology.
Chinese patent CN101134827 and CN1807062 adopt the liquid crystalline polymers modified UHMWPE, liquid crystalline polymers has excellent mechanical property, wear resistance and flowability, carry out liquid crystalline polymers and UHMWPE compound, the processing characteristics of UHMWPE is significantly improved, and its mechanical property and wear resisting property are improved, weak point is that processing temperature is up to 250-300 ℃, energy consumption is higher, and do not mention heatproof air aging performance in the patent, for UHMWPE tubing, heatproof air aging performance also is a very important index, has influence on the work-ing life of tubing.
Chinese patent CN1428370 mixes 85-95% ultrahigh molecular weight polyethylene(UHMWPE), 3-15% polysiloxane, 0.2-2% oxidation inhibitor, stir, in vacuum drying oven, dried 5-7 hour for 40-60 ℃, the raw material of drying is carried out extruding pelletization, this blend composition is owing to add organosilicon as properties-correcting agent, flowability is greatly improved, prepared UHMWPE tubing has fabulous wear resistance, erosion resistance and lower temperature resistance, but this patent has been carried out granulation to PP Pipe Compound, cost is higher, does not also mention heatproof air aging performance in the patent.
Summary of the invention
The object of the present invention is to provide a kind of ultrahigh molecular weight polyethylene tubing composition, it is compared with existing such composition, adopt the fluoroelastomer modification, and sneak into specific antioxidant system, make composition have good mechanical property, wear resisting property, erosion resistance, heatproof air aging performance and extrude processing characteristics.
The present invention also aims to provide a kind of method for preparing the present composition, the method can guarantee that each component mixes, and the composition bulk density of preparing is high, can improve and extrude working (machining) efficiency.
The present invention implements by following technical solution:
Develop a kind of composition for the preparation of ultrahigh molecular weight polyethylene tubing, made by the Raw material processing of following mass ratio:
Ultrahigh molecular weight polyethylene(UHMWPE): fluoropolymer additive: polyethylene wax: calcium stearate/Zinic stearas mixture: composite antioxidant: carbon black=100 part: 0.01～0.1: 1～8: 0.1～1.0: 0.1～0.5: 0.5～3
Wherein,
The viscosity-average molecular weight scope of described ultrahigh molecular weight polyethylene(UHMWPE) is set to 150 * 10
4～400 * 10
4
Described fluoropolymer additive is set to the fluorinated copolymers of vinylidene fluoride;
The mass ratio of described calcium stearate/Zinic stearas mixture is set to 1～3: 1;
Described composite antioxidant is set to the mixture of A Hinered phenols antioxidant and B phosphite ester kind antioxidant, and mass ratio is set to A: B=1: 1～3;
The proterties of described ultra-high molecular weight polyvinyl composite is: black pulverulent mixture material, the high (〉=0.48g/cm of bulk density
3), can improve extrude working (machining) efficiency (extruded velocity can reach 〉=3m/h);
Tensile break stress, MPa, 26～29; The tension fracture strain, %, 260～340; Simple beam impact strength, kJ/m
2, do not rupture; Tensile yield strength, MPa, 23～26; Oxidation induction period, min, 35～68; Wear rate, %, 0.05～0.50; Extrusion performance Φ 159mm, m/h, 3.
Above-mentioned composition is characterized in that the viscosity-average molecular weight scope of described ultrahigh molecular weight polyethylene(UHMWPE) is set to 200 * 10
4～300 * 10
4
Above-mentioned composition, made by the Raw material processing of following mass ratio:
Ultrahigh molecular weight polyethylene(UHMWPE): fluoropolymer additive: polyethylene wax: calcium stearate/Zinic stearas mixture: composite antioxidant: carbon black=100 part: 0.03～0.08: 3～5: 0.1～1.0: 0.1～0.5: 0.5～3.
The preparation method of above-mentioned composition, it is characterized in that in the conical mixer of appropriate volume, polyvinyl resin with super-high molecular weight is put into, start mixing machine, with after mixing 1～2 hour in calcium stearate and the Zinic stearas mixture input mixing machine, add successively composite antioxidant, polyethylene wax, fluoropolymer additive and carbon black first, mixed 2～3 hours, press GB/T1636 and detect bulk density, generally greater than 0.45g/cm
3, pack.
The effect of invention
Ultrahigh molecular weight polyethylene tubing composition by above method preparation has good heatproof air aging performance, 200 ℃ of oxidation induction periods had simultaneously good mechanical property, wear resisting property, erosion resistance, heatproof air aging performance and extruded processing characteristics greater than 30 minutes.
Embodiment
Embodiment 1 (the dosage ratio is mass fraction, and is as follows)
Ultrahigh molecular weight polyethylene(UHMWPE) (viscosity-average molecular weight 120 * 10
4) 100
Polyethylene wax 2
Calcium stearate 0.2
Zinic stearas 0.5
Composite antioxidant 0.1
* (fluoropolymer additive FX-5920 0.1
Carbon black 2
Desired raw material, be the commercial goods, wherein, * (fluoropolymer additive FX-5920 be the fluoropolymer additive PPA of Minnesota Mining and Manufacturing Company series product (for example, FX-5911,5920,5924) a kind of model in also claims " rheological agent ", " brightening agent ", " slipping agent " etc. in some fields.Be that a class of being developed by Minnesota Mining and Manufacturing Company is the additive of foundation structure by the fluoro containing polymers polymkeric substance, it can help you to improve the processing characteristics of polymkeric substance.
Below each embodiment herewith.
Embodiment 2
Ultrahigh molecular weight polyethylene(UHMWPE) (viscosity-average molecular weight 185 * 10
4) 100
Polyethylene wax 3
Calcium stearate 0.3
Zinic stearas 0.1
Composite antioxidant 0.2
Fluoropolymer additive FX-5920 0.08
Carbon black 1.5
Embodiment 3
Ultrahigh molecular weight polyethylene(UHMWPE) (viscosity-average molecular weight 202 * 10
4) 100
Polyethylene wax 4
Calcium stearate 0.2
Zinic stearas 0.5
Composite antioxidant 0.3
Fluoropolymer additive FX-5920 0.06
Carbon black 1.2
Embodiment 4
Ultrahigh molecular weight polyethylene(UHMWPE) (viscosity-average molecular weight 237 * 10
4) 100
Polyethylene wax 5
Calcium stearate 0.5
Zinic stearas 0.1
Composite antioxidant 0.3
Fluoropolymer additive FX-5920 0.02
Carbon black 1
Embodiment 5
Ultrahigh molecular weight polyethylene(UHMWPE) (viscosity-average molecular weight 256 * 10
4) 100
Polyethylene wax 8
Calcium stearate 0.2
Zinic stearas 0.1
Composite antioxidant 0.3
Fluoropolymer additive FX-5920 0.01
Carbon black 0.8
Embodiment 6
Ultrahigh molecular weight polyethylene(UHMWPE) (viscosity-average molecular weight 278 * 10
4) 100
Polyethylene wax 7
Calcium stearate 0.1
Zinic stearas 0.3
Composite antioxidant 0.4
Fluoropolymer additive FX-5920 0.01
Carbon black 0.5
Embodiment 7
Ultrahigh molecular weight polyethylene(UHMWPE) (viscosity-average molecular weight 295 * 10
4) 100
Polyethylene wax 4
Calcium stearate 0.3
Zinic stearas 0.2
Composite antioxidant 0.25
Fluoropolymer additive FX-5920 0.03
Carbon black 1
Embodiment 8
Ultrahigh molecular weight polyethylene(UHMWPE) (viscosity-average molecular weight 323 * 10
4) 100
Polyethylene wax 7
Calcium stearate 0.2
Zinic stearas 0.1
Composite antioxidant 0.3
Fluoropolymer additive FX-5920 0.01
Carbon black 0.8
Embodiment 9
Ultrahigh molecular weight polyethylene(UHMWPE) (viscosity-average molecular weight 358 * 10
4) 100
Polyethylene wax 5
Calcium stearate 0.3
Zinic stearas 0.4
Composite antioxidant 0.4
Fluoropolymer additive FX-5920 0.03
Carbon black 0.5
Embodiment 10
Ultrahigh molecular weight polyethylene(UHMWPE) (viscosity-average molecular weight 376 * 10
4) 100
Polyethylene wax 1
Calcium stearate 0.4
Zinic stearas 0.4
Composite antioxidant 0.4
Fluoropolymer additive FX-5920 0.1
Carbon black 1
* by the combination formula preparation tube material of above each embodiment, test data sees Table 1
Claims (4)
1. composition for the preparation of ultrahigh molecular weight polyethylene tubing, made by the Raw material processing of following mass ratio:
Ultrahigh molecular weight polyethylene(UHMWPE): fluoropolymer additive: polyethylene wax: calcium stearate/Zinic stearas mixture: composite antioxidant: carbon black=100 part: 0.01～0.1: 1～8: 0.1～1.0: 0.1～0.5: 0.5～3
Wherein,
The viscosity-average molecular weight scope of described ultrahigh molecular weight polyethylene(UHMWPE) is set to 150 * 10
4～400 * 10
4
Described fluoropolymer additive is set to the fluorinated copolymers of vinylidene fluoride;
The mass ratio of described calcium stearate/Zinic stearas mixture is set to 1～3: 1;
Described composite antioxidant is set to the mixture of A Hinered phenols antioxidant and B phosphite ester kind antioxidant, and mass ratio is set to A: B=1: 1～3;
The proterties of described ultrahigh molecular weight polyethylene tubing composition is:
Black pulverulent mixture material, bulk density 〉=0.48g/cm
3, extruded velocity 〉=3m/h;
Tensile break stress, MPa, 26～29; The tension fracture strain, %, 260～340; Simple beam impact strength, kJ/m
2, do not rupture; Tensile yield strength, MPa, 23～26; Oxidation induction period, min, 35～68; Wear rate, %, 0.05～0.50.
2. according to composition claimed in claim 1, it is characterized in that the viscosity-average molecular weight scope of described ultrahigh molecular weight polyethylene(UHMWPE) is set to 200 * 10
4～300 * 10
4
3. according to composition claimed in claim 1, made by the Raw material processing of following mass ratio:
Ultrahigh molecular weight polyethylene(UHMWPE): fluoropolymer additive: polyethylene wax: calcium stearate/Zinic stearas mixture: composite antioxidant: carbon black=100 part: 0.03～0.08: 3～5: 0.1～1.0: 0.1～0.5: 0.5～3.
4. according to the method for making of claim 1,2 or 3 described compositions, it is characterized in that in the conical mixer of appropriate volume, polyvinyl resin with super-high molecular weight is put into, start mixing machine, with after mixing 1～2 hour in calcium stearate and the Zinic stearas mixture input mixing machine, add successively composite antioxidant, polyethylene wax, fluoropolymer additive and carbon black first, mixed 2～3 hours, press GB/T1636 and detect bulk density, pack.
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Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103789860A (en) * | 2012-10-30 | 2014-05-14 | 中国石油化工股份有限公司 | High molecular weight polyethylene fiber, preparation method and application thereof |
| CN103788445B (en) * | 2012-10-30 | 2016-02-24 | 中国石油化工股份有限公司 | A kind of High molecular weight polyethylene composition |
| CN104031305B (en) * | 2014-05-08 | 2017-09-12 | 上海化工研究院有限公司 | The PP Pipe Compound of ultrahigh molecular weight polyethylene tubing and its preparation and application |
| CN104262677A (en) * | 2014-10-18 | 2015-01-07 | 江苏爱特恩东台新材料科技有限公司 | Preparation and application of complex antioxidant |
| CN105801986A (en) * | 2016-05-05 | 2016-07-27 | 日丰科技有限公司 | Processing aid master batch for PE-RT pipe and preparation method for processing aid master batch |
| CN106750724A (en) * | 2016-07-21 | 2017-05-31 | 佛山瑞箭体育器材有限公司 | A kind of composition for preparing ultrahigh molecular weight polyethylene tubing |
| CN108239320A (en) * | 2016-12-27 | 2018-07-03 | 上海邦中高分子材料有限公司 | A kind of abrasion-proof pipe material and preparation method thereof |
| CN107312222A (en) * | 2017-06-14 | 2017-11-03 | 山西华星管业科技有限公司 | Produce the modified additive and tubing of ultrahigh molecular weight polyethylene tubing |
| CN107266832A (en) * | 2017-06-23 | 2017-10-20 | 山西华星管业科技有限公司 | Produce the modified additive and tubing of ultrahigh molecular weight polyethylene tubing |
| CN109181065A (en) * | 2018-08-19 | 2019-01-11 | 福建师范大学泉港石化研究院 | A kind of composition being used to prepare UHMWPE/HDPE tubing |
| CN109608754B (en) * | 2018-12-25 | 2022-05-17 | 山东东宏管业股份有限公司 | Special material for high-wear-resistance polyolefin pipeline and preparation method thereof |
| CN110698747B (en) * | 2019-10-10 | 2021-12-31 | 扬中市长龙管业有限公司 | Creep-resistant impact-resistant PE pipe and production method thereof |
| CN113337026A (en) * | 2021-06-25 | 2021-09-03 | 广西顺通高分子材料科技有限公司 | Preparation process of corrosion-resistant PE drain pipe |
| CN115703904A (en) * | 2021-08-09 | 2023-02-17 | 中国石油化工股份有限公司 | High-heat-resistance polyethylene pipe composition and preparation method thereof |
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|---|---|---|---|---|
| CN101240092A (en) * | 2008-03-14 | 2008-08-13 | 株洲时代新材料科技股份有限公司 | Super-high molecular weight polyethylene low frictional coefficient wearable composite material and its preparation and use |
| CN101585941A (en) * | 2008-05-23 | 2009-11-25 | 乐少兵 | Ultra-high molecular weight polyethylene product |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| BR0207759A (en) * | 2001-03-02 | 2004-04-27 | Exxonmobil Res & Eng Co | Polymeric composition and method for improving the metal flux of thermoplastic polymer suitable for forming rigid shaped articles |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101240092A (en) * | 2008-03-14 | 2008-08-13 | 株洲时代新材料科技股份有限公司 | Super-high molecular weight polyethylene low frictional coefficient wearable composite material and its preparation and use |
| CN101585941A (en) * | 2008-05-23 | 2009-11-25 | 乐少兵 | Ultra-high molecular weight polyethylene product |
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