CN1566192A - Agricultural polyethylene resin composition - Google Patents
Agricultural polyethylene resin composition Download PDFInfo
- Publication number
- CN1566192A CN1566192A CN 03137608 CN03137608A CN1566192A CN 1566192 A CN1566192 A CN 1566192A CN 03137608 CN03137608 CN 03137608 CN 03137608 A CN03137608 A CN 03137608A CN 1566192 A CN1566192 A CN 1566192A
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- Prior art keywords
- film
- resin
- resin composition
- linear low
- density polyethylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000011342 resin composition Substances 0.000 title claims abstract description 7
- 229920013716 polyethylene resin Polymers 0.000 title claims abstract description 5
- 229920000092 linear low density polyethylene Polymers 0.000 claims abstract description 26
- 239000004707 linear low-density polyethylene Substances 0.000 claims abstract description 26
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011347 resin Substances 0.000 claims description 24
- 229920005989 resin Polymers 0.000 claims description 24
- 239000003112 inhibitor Substances 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 239000000314 lubricant Substances 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 7
- 229920001684 low density polyethylene Polymers 0.000 abstract description 7
- 239000004702 low-density polyethylene Substances 0.000 abstract description 7
- 238000012545 processing Methods 0.000 abstract description 7
- 238000007664 blowing Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 230000000704 physical effect Effects 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 3
- 239000008116 calcium stearate Substances 0.000 description 3
- 235000013539 calcium stearate Nutrition 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000013074 reference sample Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000013022 venting Methods 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000006446 extruder reaction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
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Abstract
The agricultural polyethylene resin composition mainly comprises linear low-density polyethylene and di-tert-butyl peroxide, wherein the dosage of the di-tert-butyl peroxide is 0.3-0.6 (weight percent based on the linear low-density polyethylene). The resin composition is used for blowing agricultural greenhouse films with 8000 multiplied by 0.08mm, has stable processing technology, completely meets the national standard and use requirements of film physical properties, replaces the LDPE greenhouse films widely used at present in China, and has good economical efficiency.
Description
Technical field
The present invention relates to a kind of polyethylene resin composition, being specifically related to the linear low density of polyethylene is the agricultural canopy film resin combination of base-material.
Background technology
China is a large agricultural country, along with agrotechnical continuous development, has promoted the application in agricultural greenhouse and greenhouse.At present, domestic most employing LDPE film is as the booth covering material, and seldom adopt the LLDPE film, reason is that the melt strength of LLDPE self is little, drawdown is big, bubble stability is poor in blowfilm shaping processing, therefore the control of parison has problems, but LLDPE compares with LDPE and has more excellent rerum natura simultaneously, and production cost also has more competitiveness, it is more excellent to make performance, the film that price is lower, the producer that has adopts the technology of LDPE/LLDPE blending system canopy film for reducing cost and improving the canopy film quality, but this blending method makes cost decline limited, also increased because the labour cost that the blending process is brought increases, in addition LDPE, the trade mark of LLDPE, the difference of mixing proportion produces greatly influence to quality product.
Utilize processibility or the product performance of organo-peroxide and LLDPE generation crosslinking reaction improvement LLDPE open in many patents.Typically as having proposed to improve the method for LLDPE melt strength among the US4578431, be that the cumyl superoxide that adds 100～200ppm in LLDPE (MFR2g/10min) carries out extrusion reaction, the gained material is under the processing stability good premise, can be blow molded into the thick LLDPE film of 25 μ m, also point out in the invention, amount of peroxide can not guarantee processing stability when being lower than selected scope, gel appears on the resin molding and can make when being higher than selected scope, produce rupture of membranes, influence quality product.CN1218066A also discloses the technology of hydroperoxide prepared in reaction blowing usefulness resin in twin screw extruder of LLDPE and 500～10000ppm in addition.Can be reduced to below the 10 μ m by the film thickness of this resin blowing, and technological process for blowing is stable, it is good that rerum natura keeps.But blow the canopy film of the above thickness of 80 μ m by this resin, it is big the resin drawdown still can to occur, easily is deposited on the vane, and film steeps not problem such as easy-formation.
Summary of the invention
The LLDPE canopy film resin composition that the purpose of this invention is to provide a kind of easy-formation.
Resin combination of the present invention mainly (form, and the consumption of ditertiary butyl peroxide is 0.3wt%～0.6wt% (is benchmark with LLDPE) by LLDPE by MFR:0.5～2.5g/10min) and ditertiary butyl peroxide (TA).
LLDPE can be powdery or granular resin among the present invention, but with powdered resin the best.The contriver also found through experiments, and when the add-on of TA was lower than 0.3wt%, film was steeped oneself-meeting and run into vane during blowing canopy film, and can't film forming; When the TA add-on was higher than 0.6wt%, film bubble was highly stable, but " flake " showed increased on the film influences the visual appearance of processing stability and canopy film.
The process of LLDPE among the present invention and TA reaction can be carried out in Banbury mixer, kneader, forcing machine, and wherein the twin screw extruder reaction effect is best, possesses commercial production conditions most.The reaction conditions that the present invention recommends is: 170 ℃～210 ℃ were reacted 1～4 minute down.
For helping processing, resin combination of the present invention can also add oxidation inhibitor or lubricant in preparation process, do not influence effect of the present invention.
Resin combination of the present invention has higher melt strength, can blow the agriculture greenhouse film of 8000 * 0.08mm on common three layers of compound blown film unit without any transformation, and film bubble is stable does not pile film, do not swing, the volume type is tight and neat.Every performance all reaches relative national standards, and cost far below LDPE canopy film and stretch, tear, aspect such as puncture property is far above LDPE canopy film.
Description of drawings
The Φ 67 twin screw extruder apparatus sketch of Fig. 1 suitability for industrialized production resin combination of the present invention
The 1-charging opening; 2-side direction charging opening; 3-liquid drips mouth;
The 4-venting port; The 5-head
Embodiment
Embodiment
Starting material: LLDPE DFDA7042 powder Jilin Petrochemical company produces
LLDPE 103AA powder Lanzhou Petrochemical Company is produced
Auxiliary reagent factory, TA Lanzhou produces
The organic factory of oxidation inhibitor B561 orchidization produces
Produce in calcium stearate Yangtse River in Chongqing chemical plant
The preparation of resin combination:
Φ 67 twin screw extruders of producing with German Lestreiz company are reactor, and the LLDPE resin is added by charging opening 1, and B561 and calcium stearate enter forcing machine by side direction charging opening 2, and TA drips mouthfuls 3 by liquid and adds.The reaction devolatilization can realize at venting port 4 places of forcing machine.Reaction mass finally by head 5 extrude, granulation obtains the LLDPE resin combination, concrete composition of raw materials and preparation process condition see Table 1 and table 2.
Table 1 composition of raw materials
| Numbering | Base resin | ????TA(wt％) | ????B561(wt％) | Calcium stearate (wt%) |
| Embodiment 1 | ??LL103AA | ????0.35 | ????0.1 | 0.1 |
| Embodiment 2 | ??LL103AA | ????0.40 | ????0.1 | 0.1 |
| Embodiment 3 | ??LL103AA | ????0.55 | ????0.1 | 0.1 |
| Embodiment 4 | ??DFDA7042 | ????0.35 | ????0.1 | 0.1 |
| Embodiment 5 | ??DFDA7042 | ????0.40 | ????0.1 | 0.1 |
| Embodiment 6 | ??DFDA7042 | ????0.55 | ????0.1 | 0.1 |
| Comparative Examples 1 | ??LL103AA | ????- | ????0.1 | 0.1 |
| Comparative Examples 2 | ??DFDA7042 | ????- | ????0.1 | 0.1 |
Table 2 preparation process condition
| Numbering | Twin screw extruder | Volume pump | ||||||||||||
| Barrel temperature (℃) | Engine speed (rpm) | Main frame electric current (A) | Melt pressure (bar) | Rate of addition (ml/min) | ????TA(wt％) | |||||||||
| 1 section | 2 sections | 3 sections | 4 |
5 sections | 6 sections | 7 sections | 8 sections | 9 sections | ||||||
| Embodiment 1 | ?170 | ?170 | ?190 | ?200 | ?200 | ?200 | ?200 | ?190 | ?190 | ??100 | ??16.4 | ??2500 | ????6.0 | ????0.35 |
| Embodiment 2 | ?170 | ?170 | ?190 | ?200 | ?200 | ?200 | ?200 | ?190 | ?190 | ??100 | ??13.2 | ??2280 | ????7.0 | ????0.40 |
| Embodiment 3 | ?170 | ?170 | ?190 | ?200 | ?200 | ?200 | ?200 | ?190 | ?190 | ??100 | ??14.5 | ??2310 | ????8.5 | ????0.55 |
| Embodiment 4 | ?170 | ?170 | ?190 | ?200 | ?200 | ?200 | ?200 | ?190 | ?190 | ??100 | ??15.5 | ??2400 | ????6.0 | ????0.35 |
| |
?170 | ?170 | ?190 | ?200 | ?200 | ?200 | ?200 | ?190 | ?190 | ??100 | ??16.0 | ??2460 | ????7.0 | ????0.40 |
| Embodiment 6 | ?170 | ?170 | ?190 | ?200 | ?200 | ?200 | ?200 | ?190 | ?190 | ??100 | ??16.5 | ??2510 | ????8.5 | ????0.55 |
| Comparative Examples 1 | ?170 | ?170 | ?190 | ?200 | ?200 | ?200 | ?200 | ?190 | ?190 | ??100 | ??17.2 | ??2700 | ????- | ????- |
| Comparative Examples 2 | ?170 | ?170 | ?190 | ?200 | ?200 | ?200 | ?200 | ?190 | ?190 | ??100 | ??14.8 | ??2480 | ????- | ????- |
Above-mentioned resin combination carries out the test of physicals and application performance, the results are shown in table 3 to table 5.
The physicals of table 3 resin
| Numbering | ??MFR(g/10min) | Melt flow ratio * | Melt strength (cN) * |
| Embodiment 1 | ??0.47 | ????60.3 | ?3.89 |
| Embodiment 2 | ??0.42 | ????62.5 | ?3.96 |
| Embodiment 3 | ??0.29 | ????79.5 | ?4.15 |
| Embodiment 4 | ??0.61 | ????61.2 | ?3.86 |
| Embodiment 5 | ??0.56 | ????66.3 | ?3.91 |
| Embodiment 6 | ??0.43 | ????85.5 | ?4.08 |
| Comparative Examples 1 | ??0.98 | ????25.3 | ?2.53 |
| Comparative Examples 2 | ??1.20 | ????27.5 | ?2.43 |
*. melt flow ratio: the ratio that is the melt flow rate (MFR) (MFR) of (2.16kg and 21.6kg) under two different loads.
*Melt strength: the fusion sample maximum stretching force when brittle rupture taking place or becoming unstable drawing-off vibration that stretched.
Table 4 resin combination blown film test conditions
*
| Numbering | Screw speed (rpm) | Main frame electric current (A) | Thickness (mm) | Fabric width (m) | Processing stability | ||||
| 1 car | 2 cars | 3 cars | 1 car | 2 cars | 3 cars | ||||
| Embodiment 1 | ?120 | ?105 | ?105 | ?76 | ?142 | ?115 | ?0.08 | ?10 | The film bubble is than the low vane that just has been higher than in stabilizing membrane footpath |
| Embodiment 2 | ?120 | ?105 | ?105 | ?77 | ?142 | ?115 | ?0.08 | ?10 | The film bubble is stable, and film directly is " V " type |
| Embodiment 3 | ?120 | ?105 | ?105 | ?77 | ?142 | ?114 | ?0.08 | ?10 | The film bubble is stable, and film directly is " V " type but occurs obvious flake on the film |
| Embodiment 4 | ?120 | ?105 | ?105 | ?74 | ?139 | ?108 | ?0.08 | ?10 | The film bubble is stablized but the low vane that just has been higher than in |
| Embodiment | |||||||||
| 5 | ?120 | ?105 | ?105 | ?75 | ?140 | ?110 | ?0.08 | ?10 | The film bubble is stable, and film directly is " V " type |
| Embodiment 6 | ?120 | ?105 | ?105 | ?75 | ?140 | ?111 | ?0.08 | ?10 | The film bubble is stable, and film directly is " V " type but occurs obvious flake on the film |
*90 3 layers of compound blown film unit of the φ that Dalian rubber and plastics machine factory provides
The physicals of table 5 film
| Numbering | Tensile strength (MPa) | Tear strength (N/mm) | Elongation at break (%) | Mist degree (%) | |||
| Laterally | Vertically | Laterally | Vertically | Laterally | Vertically | ||
| Embodiment 1 | ????23.7 | ????29.0 | ????125.7 | ????124.2 | ????758.3 | ????829.8 | ????25.4 |
| Embodiment 2 | ????24.8 | ????25.5 | ????133.5 | ????121.4 | ????907.2 | ????878.3 | ????27.8 |
| Embodiment 3 | ????22.1 | ????23.4 | ????121.3 | ????120.2 | ????731.2 | ????793.5 | ????29.8 |
| Embodiment 4 | ????27.4 | ????28.3 | ????125.7 | ????119.3 | ????812.2 | ????866.3 | ????25.3 |
| |
????28.3 | ????29.2 | ????126.4 | ????120.3 | ????862.3 | ????879.6 | ????26.1 |
| Embodiment 6 | ????26.9 | ????27.5 | ????123.6 | ????118.2 | ????790.3 | ????812.5 | ????27.5 |
| Reference sample * | ????22.0 | ????23.4 | ????131.2 | ????118.0 | ????902.5 | ????859.6 | ????25.2 |
Reference sample: the canopy film of 8000 * 0.08mm that plastics film factory of company of commercially available orchidization HTC produces.
Claims (4)
1. agricultural polyethylene resin composition is characterized in that mainly being made up of linear low density polyethylene and ditertiary butyl peroxide, and the consumption of ditertiary butyl peroxide is 0.3～0.6 weight percent, is as the criterion with linear low density polyethylene.
2. resin combination according to claim 1, the melt flow rate (MFR) that it is characterized in that linear low density polyethylene are 0.5～2.5 gram/10 minutes.
3. resin combination according to claim 2 is characterized in that linear low density polyethylene is a powdered resin.
4. the resin combination one of described according to claim 1 to 3 is characterized in that adding in the resin oxidation inhibitor, lubricant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03137608 CN1254500C (en) | 2003-06-18 | 2003-06-18 | Agricultural polyethylene resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03137608 CN1254500C (en) | 2003-06-18 | 2003-06-18 | Agricultural polyethylene resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1566192A true CN1566192A (en) | 2005-01-19 |
| CN1254500C CN1254500C (en) | 2006-05-03 |
Family
ID=34470470
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03137608 Expired - Fee Related CN1254500C (en) | 2003-06-18 | 2003-06-18 | Agricultural polyethylene resin composition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1254500C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101824178A (en) * | 2010-04-06 | 2010-09-08 | 湖北众联塑业有限公司 | Method for reducing flow rate of polyethylene melt |
| CN101538386B (en) * | 2008-03-19 | 2011-06-22 | 中国石油天然气股份有限公司 | Agricultural polyethylene resin composition |
| CN101962453B (en) * | 2009-07-22 | 2012-07-18 | 中国石油天然气股份有限公司 | Polyethylene greenhouse film resin composition and preparation method thereof |
-
2003
- 2003-06-18 CN CN 03137608 patent/CN1254500C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101538386B (en) * | 2008-03-19 | 2011-06-22 | 中国石油天然气股份有限公司 | Agricultural polyethylene resin composition |
| CN101962453B (en) * | 2009-07-22 | 2012-07-18 | 中国石油天然气股份有限公司 | Polyethylene greenhouse film resin composition and preparation method thereof |
| CN101824178A (en) * | 2010-04-06 | 2010-09-08 | 湖北众联塑业有限公司 | Method for reducing flow rate of polyethylene melt |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1254500C (en) | 2006-05-03 |
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