CN102276891A - Polyolefin resin composition for tubing - Google Patents
Polyolefin resin composition for tubing Download PDFInfo
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- CN102276891A CN102276891A CN2010102053560A CN201010205356A CN102276891A CN 102276891 A CN102276891 A CN 102276891A CN 2010102053560 A CN2010102053560 A CN 2010102053560A CN 201010205356 A CN201010205356 A CN 201010205356A CN 102276891 A CN102276891 A CN 102276891A
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- density polyethylene
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- peroxide
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Abstract
Based on the weight of high density polyethylene, a polyolefin resin composition for tubing comprises the following components of: by weight, 1) 100% of high density polyethylane with the melt flow rate being 0.1-0.5g/10min and the density being 0.945-0.957g/cm<3>; 2) 10-30% of very low density polyethylene with the melt flow rate being 0.1-20g/10min and the density being 0.860-0.900g/cm<3>; 3) 0.1-0.30% of a peroxide modifier. By the reactive extrusion technology, the composition undergoes a micro-crosslinking reaction so as to improve the environmental stress cracking resistance of high density polyethylane (greater than 2000 hours) and expand the application of high density polyethylane in tubing or other fields. The invention also further discloses a preparation method of the resin composition.
Description
Affiliated technical field
The present invention relates to a kind of tubing polyolefine resin composition, be specifically related to little cross-linking modified polyvinyl piping materials resin combination.
Background technology
In recent years, development along with plastics industry, polyvinyl piping materials is so that it is in light weight, corrosion-resistant, thermal conductivity is low, good insulation preformance, construction and installation and characteristics such as easy to maintenance more and more are subject to people's attention, and become after PVC, the plastic conduit kind of world consumption amount maximum, Application Areas spread all over engineering and fields such as oil field, chemical industry and post and telecommunications such as feedwater, agricultural irrigation, combustion gas conveying, blowdown, mine mortar conveying.
In polyvinyl piping materials, high density polyethylene(HDPE) (HDPE) pipe has characteristics such as light weight, mechanical property excellence, crimp tendency and flexibility are good, is the tubing kind that competitive capacity is arranged most.But because structure, the form of HDPE resin itself, easily cause tubing under certain hour, certain load effect, fracture phenomena can occur, be that environmental stress cracking resistance (ESCR) is relatively poor, thereby influenced of the application of HDPE tubing in fields such as outdoor water supply pipe, gas line, irrigation usefulness pipes.Therefore, ESCR is an important indicator estimating and influence the HDPE tubing life-span.
" supply water and use the polyvinyl piping materials standard " (ISO 4427:1996) is divided into PE different gradess such as PE 32, PE40, PE 63, PE 80, PE 100 according to the tubing longterm strength.In China, on the market modal tubing resin dedicated be the PE63 level, as trades mark such as 6100M, HD4810EX.The ESCR of PE63 grade resins is all less than 1000 hours, therefore limited use range, price and class all can't with PE80, resin dedicated the contending with of other tubing of PE100 level.And the polyvinyl piping materials of PE80, PE100 or higher category is resin dedicated, and ESCR is all above 1000 hours, but resin is directly to obtain from polyreaction, and technical sophistication and cost are higher.
There are some researches show, the ESCR of HDPE resin is subjected to the influence of extraneous factors such as temperature, external force, but it is bigger with molecular weight, molecular weight distribution, the degree of branching of resin itself and the internal cause relations such as chain length, crystallization situation of propping up, therefore, in the prior art, have from the polymeric angle, by reactors in series, add long-chain branch monomer, control reaction conditions, change the polyvinyl resin that modes such as catalyst system can be produced high ESCR, as reports such as CN1903896, CN1513002.But more be angle from the modification of resin post-treatment, improve the ESCR of material by the modulation resinous molecular structure, main path has two kinds: the one, and sneak into second components such as polyolefine, elastomerics in the resin and carry out modification, second component plays the refinement spherocrystal, reduces degree of crystallinity and stop crackle to stretch in polyethylene effect.This method is present the most frequently used method, relevant report is more, as CN1556835, CN1247204, CN1262972, US2007282071 (A1), US2006276593 (A1), US2003088021 (A1), US7153909, WO0105852 (A1), JP57031945 (A) etc.The 2nd, by chemical crosslinking modified, form crosslinked structure, increase the molecule interchain and connect, improve the environmental stress cracking resistance of polythene material.Adopt the organosilane crosslinked polyethylene layer as CN2492729; US4390666 mixes the polyvinyl resin of two kinds of different molecular weights, and the polyethylene composition that utilizes organo-peroxide to carry out crosslinked preparation again has good rerum natura, as has high rigidity, high ESCR, high impact resistance etc.
Summary of the invention
The object of the invention provides a kind of tubing polyolefine resin composition, is base-material with HDPE, ULDPE resin, by little crosslinking reaction technology, and its molecular structure of modulation, thus make resin have good ESCR (＞2000 hours).The present invention further proposes the preparation method of resin combination.
Particularly, be a hundred per cent in the weight of high density polyethylene(HDPE), resin combination of the present invention comprises:
1) 100% high density polyethylene(HDPE), melt flow rate (MFR) 0.1～0.5g/10min;
2) 10%～30% ultra-low density polyethylene, melt flow rate (MFR) 0.1～20g/10min, density 0.860～0.900g/cm
3
3) 0.10%～0.30% peroxide modified agent,
Described peroxide modified agent is a tertbutyl peroxide (TBHP) and 2,5-dimethyl-2, and the compound of 5-di-t-butyl hexane peroxide (BPDH), both weight ratios are 0.2～0.6.
HDPE can be an Alathon, also can be the multipolymer of ethene and 1%～2% butene-1, general Mw:10～20 * 10
4Mw/Mn:10～20, density 0.945～0.957g/cm
3Can be powdery or granular resin, with powdered resin the best.
ULDPE is the multipolymer of ethene and propylene, butylene, octene or hexene, the multipolymer of optimal ethylene and butylene.
Tertbutyl peroxide (TBHP) and 2,5-dimethyl-2,5-di-t-butyl hexane peroxide (BPDH) can be the commercially available prod, the half life temperature of superoxide is because of manufacturer's difference difference slightly, transformation period T=260～278 of general TBHP ℃/1min; Transformation period T=175～189 of BPDH ℃/1min.
The strict control of both used in amounts, when consumption surpasses 0.30%, can occur excessively crosslinked, the mechanics mechanical property variation such as elongation at break of processibility and product; Add-on is lower than 0.1%, and little cross-linking effect is not obvious, and the ESCR increase rate of resin is little.
According to the resin treatment needs, can add processing aids such as stearate stabilizers, oxidation inhibitor in the preparation process among the present invention.
Described stearate is selected from Zinic stearas or calcium stearate, is a hundred per cent in the HDPE consumption, stearate consumption 0.1%～0.15%.
Described oxidation inhibitor is phenols, hindered amines or phosphite ester kind antioxidant, commonly used as antioxidant 1010, oxidation inhibitor 168, antioxidant 1076 and antioxidant 2246 etc., in the HDPE consumption is a hundred per cent, oxidation inhibitor consumption 0.1%～0.2%, preferred 0.1%～0.15%.
For satisfying the needs of product application, also can add various auxiliary agents such as UV light absorber or filler in the composition of the present invention.
The preparation of resin combination can select various mixing rolls, mixing machine, forcing machine as conversion unit, and wherein, preparation is more feasible in suitability for industrialized production in forcing machine.Select forcing machine as conversion unit, can adopt raw material to be pre-mixed, to carry out again reacting in the forcing machine; Also can adopt the technology of raw material online reaction in forcing machine.A kind of in the past method is an example, and concrete preparation process comprises the steps:
1) with HDPE, ULDPE, tertbutyl peroxide, 2,5-dimethyl-2,5-di-t-butyl hexane peroxide, oxidation inhibitor, stearate mixed in super mixer 2～10 minutes;
2) mixed raw material adds twin screw extruder, 140～220 ℃ of temperature of reaction, and reaction times 3～6min extrudes, granulation.
Composition of the present invention, select the bigger superoxide of two kinds of half-life difference as base resin properties-correcting agent, by control reaction temperature and two kinds of amount of peroxide, free radical trigger rate difference in conjunction with two kinds of superoxide, make resin control crosslinking degree comparatively ideally, reach the appropriate modulation of the little crosslinked and molecular structure of molecule, under the prerequisite that guarantees processibility, improve rerum natura, the especially environmental stress cracking resistance of resin; Also avoided to greatest extent simultaneously being used alone the crosslinked excessive or crosslinked not enough problem that superoxide occurs, amount of peroxide is reasonable, has reduced the safety problem in the course of processing.This resin combination has good processibility, can on common pipe extruder group, stably process the tubing of various internal diameters without any transformation, and tubing have good environmental stress cracking resistance (＞2000hr), solved the insufficient problem of common HDPE resin environmental stress crack resistance.
Embodiment
1 raw material
| Resin | HDPE | ULDPE |
| MFR，g/10min | 0.17 | 1.5 |
| ρ，g/cm 3 | 0.945 | 0.880 |
| ESCR/hr | 338 | 1460 |
| The manufacturer | Jilin Petrochemical company of CNPC | Exxon Mobil company |
Tertbutyl peroxide transformation period T=264 ℃/1min, the auxiliary reagent factory, Lanzhou
2,5-dimethyl-2,5-di-t-butyl hexane peroxide transformation period T=186 ℃/1min, auxiliary reagent factory, Lanzhou
Oxidation inhibitor B561 (antioxidant 1010 and oxidation inhibitor 168 with 1: 4 composite mixture) Switzerland vapour Bagong department
Zinic stearas Yangtse River in Chongqing chemical plant
2 performance test standards
Melt flow rate (MFR) MFR (g/10min) GB/T3682-2000
Density (g/cm
3) GB/T1033-1986
Resisting environmental stress and cracking (h) GB/T 1842-2008
Tensile strength (MPa) GB/T 2567-2008
Cantilever beam impact strength (J/m) GB/T 1843-2008
3 equipment and instrument
Φ 67 twin screw extruders are long/directly=34/1 German Lestreiz company
The fast mixing machine of 10 risings Fuxin plastics machinery factory
Embodiment and Comparative Examples
With base resin HDPE is 100 parts, and each components contents sees Table 1 in the composition.
Table 1 composition of raw materials
Above-mentioned each component mixed 5 minutes in high-speed mixer after, drop into twin screw extruder and react, reaction conditions sees Table 2, and the performance of reaction product sees Table 3.
Table 2 preparation process condition
Table 3 test result
Claims (8)
1. a tubing polyolefine resin composition is characterized in that the weight in high density polyethylene(HDPE) is a hundred per cent, and described resin combination comprises:
1) 100% high density polyethylene(HDPE), melt flow rate (MFR) 0.1～0.5g/10min;
2) 10%～30% ultra-low density polyethylene, melt flow rate (MFR) 0.1～20g/10min, density 0.860～0.900g/cm
3
3) 0.1%～0.30% peroxide modified agent,
Wherein, the peroxide modified agent is tertbutyl peroxide and 2,5-dimethyl-2, and the compound of 5-di-t-butyl hexane peroxide, both weight ratios are 0.2～0.6.
2. resin combination according to claim 1 is characterized in that high density polyethylene(HDPE) is an Alathon, or the multipolymer of ethene and 1%～2% butene-1, weight-average molecular weight 10～20 * 10
4, molecular weight distribution 10～20, density 0.945～0.957g/cm
3
3. resin combination according to claim 1 and 2, ultra-low molecular weight northylen are the multipolymer of ethene and butylene.
4. resin combination according to claim 1 and 2 is characterized in that the transformation period T=260～278 ℃/1min of tertbutyl peroxide; 2,5-dimethyl-2, transformation period T=175～189 of 5-di-t-butyl hexane peroxide ℃/1min.
5. one kind prepares the described method for compositions of claim 1, it is characterized in that the preparation of resin combination is carried out in mixing roll, mixing machine or forcing machine.
6. according to the preparation method of the described resin combination of claim 5, it is characterized in that concrete preparation process comprises:
1) with high density polyethylene(HDPE), ultra-low density polyethylene, tertbutyl peroxide, 2,5-dimethyl-2,5-di-t-butyl hexane peroxide, oxidation inhibitor, stearate mixed in super mixer 2～10 minutes;
2) mixed raw material adds twin screw extruder, 140～215 ℃ of temperature of reaction, and reaction times 3～6min extrudes, granulation.
7. according to the preparation method of the described resin combination of claim 6, it is characterized in that stearate is Zinic stearas or calcium stearate, is a hundred per cent in high density polyethylene(HDPE) weight, stearate consumption 0.1%～0.15%.
8. the preparation method of resin combination according to claim 6 is characterized in that oxidation inhibitor is phenols, hindered amines or phosphite ester kind antioxidant, is a hundred per cent in high density polyethylene(HDPE) weight, oxidation inhibitor consumption 0.1%～0.2%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102053560A CN102276891A (en) | 2010-06-11 | 2010-06-11 | Polyolefin resin composition for tubing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102053560A CN102276891A (en) | 2010-06-11 | 2010-06-11 | Polyolefin resin composition for tubing |
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|---|---|
| CN102276891A true CN102276891A (en) | 2011-12-14 |
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| CN2010102053560A Pending CN102276891A (en) | 2010-06-11 | 2010-06-11 | Polyolefin resin composition for tubing |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103160006A (en) * | 2011-12-15 | 2013-06-19 | 中国石油天然气股份有限公司 | Special polyethylene resin composition for tubing |
| CN103160022A (en) * | 2011-12-15 | 2013-06-19 | 中国石油天然气股份有限公司 | Polyolefin resin composition special for tubing |
| CN103183859A (en) * | 2011-12-31 | 2013-07-03 | 北京低碳清洁能源研究所 | Polyethylene compounding composition containing mico-crosslinking component and pipe products prepared from polyethylene compounding composition |
| CN103289157A (en) * | 2012-02-24 | 2013-09-11 | 上海宝利纳材料科技有限公司 | Method for preparing recovered high-density polyethylene (HDPE) modified pipeline material with excellent weather resistance |
| CN103756084A (en) * | 2013-12-10 | 2014-04-30 | 芜湖佳诚电子科技有限公司 | Polyethylene communication cable insulating material and preparation method thereof |
| CN104508453A (en) * | 2012-05-31 | 2015-04-08 | 切弗朗菲利浦化学公司 | Controlling melt fracture in bimodal resin pipe |
| CN106117701A (en) * | 2016-06-23 | 2016-11-16 | 郁世超 | A kind of high-density polyethylene material being prone to welding |
| CN106188739A (en) * | 2016-07-08 | 2016-12-07 | 广安奥海通讯电子科技有限公司 | A kind of corrosion-resistant buried communication tubing and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4390666A (en) * | 1981-08-14 | 1983-06-28 | Asahi Kasei Kogyo Kabushiki Kaisha | Polyethylene blend composition |
| JPH10101854A (en) * | 1996-09-30 | 1998-04-21 | Asahi Chem Ind Co Ltd | Improved polyethylene composition |
| US20070282071A1 (en) * | 2002-10-01 | 2007-12-06 | Donna Jean Crowther | Enhanced ESCR of HDPE resins |
-
2010
- 2010-06-11 CN CN2010102053560A patent/CN102276891A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4390666A (en) * | 1981-08-14 | 1983-06-28 | Asahi Kasei Kogyo Kabushiki Kaisha | Polyethylene blend composition |
| JPH10101854A (en) * | 1996-09-30 | 1998-04-21 | Asahi Chem Ind Co Ltd | Improved polyethylene composition |
| US20070282071A1 (en) * | 2002-10-01 | 2007-12-06 | Donna Jean Crowther | Enhanced ESCR of HDPE resins |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103160006A (en) * | 2011-12-15 | 2013-06-19 | 中国石油天然气股份有限公司 | Special polyethylene resin composition for tubing |
| CN103160022A (en) * | 2011-12-15 | 2013-06-19 | 中国石油天然气股份有限公司 | Polyolefin resin composition special for tubing |
| CN103160022B (en) * | 2011-12-15 | 2015-02-25 | 中国石油天然气股份有限公司 | Polyolefin resin composition special for tubing |
| CN103160006B (en) * | 2011-12-15 | 2015-05-13 | 中国石油天然气股份有限公司 | Special polyethylene resin composition for tubing |
| CN103183859A (en) * | 2011-12-31 | 2013-07-03 | 北京低碳清洁能源研究所 | Polyethylene compounding composition containing mico-crosslinking component and pipe products prepared from polyethylene compounding composition |
| CN103183859B (en) * | 2011-12-31 | 2015-01-07 | 北京低碳清洁能源研究所 | Polyethylene compounding composition containing mico-crosslinking component and pipe products prepared from polyethylene compounding composition |
| CN103289157A (en) * | 2012-02-24 | 2013-09-11 | 上海宝利纳材料科技有限公司 | Method for preparing recovered high-density polyethylene (HDPE) modified pipeline material with excellent weather resistance |
| CN104508453A (en) * | 2012-05-31 | 2015-04-08 | 切弗朗菲利浦化学公司 | Controlling melt fracture in bimodal resin pipe |
| CN103756084A (en) * | 2013-12-10 | 2014-04-30 | 芜湖佳诚电子科技有限公司 | Polyethylene communication cable insulating material and preparation method thereof |
| CN106117701A (en) * | 2016-06-23 | 2016-11-16 | 郁世超 | A kind of high-density polyethylene material being prone to welding |
| CN106188739A (en) * | 2016-07-08 | 2016-12-07 | 广安奥海通讯电子科技有限公司 | A kind of corrosion-resistant buried communication tubing and preparation method thereof |
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Application publication date: 20111214 |