CN1218066A - Resin composition for extrusion blow moulding - Google Patents
Resin composition for extrusion blow moulding Download PDFInfo
- Publication number
- CN1218066A CN1218066A CN 97119782 CN97119782A CN1218066A CN 1218066 A CN1218066 A CN 1218066A CN 97119782 CN97119782 CN 97119782 CN 97119782 A CN97119782 A CN 97119782A CN 1218066 A CN1218066 A CN 1218066A
- Authority
- CN
- China
- Prior art keywords
- resin composition
- blow moulding
- extrusion blow
- film
- peroxide
- 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.)
- Granted
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 9
- 238000010101 extrusion blow moulding Methods 0.000 title claims description 7
- 229920000092 linear low density polyethylene Polymers 0.000 claims abstract description 12
- 239000004707 linear low-density polyethylene Substances 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 6
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-M hydroperoxide group Chemical group [O-]O MHAJPDPJQMAIIY-UHFFFAOYSA-M 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims 1
- 239000011347 resin Substances 0.000 abstract description 7
- 229920005989 resin Polymers 0.000 abstract description 7
- 238000007664 blowing Methods 0.000 abstract description 5
- 238000001125 extrusion Methods 0.000 abstract description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract 2
- -1 polyethylene Polymers 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000000071 blow moulding Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002362 mulch Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- SPTHWAJJMLCAQF-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene;hydrogen peroxide Chemical compound OO.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- AKFOUVKOUGMNAW-UHFFFAOYSA-N cumene;2-hydroperoxy-2-methylpropane Chemical compound CC(C)(C)OO.CC(C)C1=CC=CC=C1 AKFOUVKOUGMNAW-UHFFFAOYSA-N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- XKAIANOCQAMYCA-UHFFFAOYSA-N hydrogen peroxide;1,2,3-tri(propan-2-yl)benzene Chemical compound OO.CC(C)C1=CC=CC(C(C)C)=C1C(C)C XKAIANOCQAMYCA-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 210000001161 mammalian embryo Anatomy 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
A resin composition for extruding out and blowing the agricultural ground film is prepared from LLDPE resin with 0.88-0.95 g/cu.cm of density and 0.5-3 g/10min of flow rate for molten one and hydrogen peroxide (500-10000 ppm) through a dual-screw extrusion. With the resin composition, the film of 10 microns in thickness can be blown with stable physical nature.
Description
The present invention relates to the resin combination that a kind of extrusion-blown modling is used, relate in particular to based on LLDPE, is the resin combination of properties-correcting agent with the organo-peroxide.
As everyone knows, the film tensile strength of LLDPE blowing, shock strength, tear strength and rigidity are all than LDPE height, thereby the thickness of film can attenuate 20～25% under the identical situation of intensity, but LLDPE, especially be that the LLDPE melt strength of comonomer preparation is lower with ethene and butene-1 or hexene-1, only be under the same melt flow rate LDPE 1/3～1/2, the vertical property of shape embryo is big during blow molding, film draws film bubble instability when approaching, thickness fluctuation is big, forming operation should not be controlled, at the LLDPE ultrathin film that is difficult on the common blown film equipment to obtain below the 10 μ m.
In order to improve poly melt strength, improve its processibility, people have done many research work.Adopt the method for the initiator (organo-peroxide) that in polyvinyl resin, adds 0.001～0.10% (weight ratio) to make a kind of coating polyvinyl resin of extruding as clear 59-6241, when having solved the polyethylene coating moulding extrudate break, the phenomenon of the thick intermediate thin in coating both sides, poly melt flow rate (MFR) must be greater than 6g/10min before this invention required modification, and density is at 0.90～0.94g/cm
3Between.US4578481 discloses a kind of method that improves polyethylene melt intensity, promptly adds the organo-peroxide of 100～2000ppm in polyethylene.When cumyl superoxide addition is 100ppm, LLDPE (density 0.920g/cm
3, melt flow rate (MFR) 2g/10min) and under the prerequisite that keeps bubble stability, can be blow molded into the thick film in 1 Mill (equaling 25 μ m).When addition during greater than 500ppm, then the thickness of film falls less than 1 Mill.This mainly is that polyethylene has formed tangible crosslinking structure because of the chemical modification through organo-peroxide, and bigger variation has taken place poly performance.
The object of the present invention is to provide a kind of resin combination that is suitable for blowing ultrathin membrane (thickness≤10 μ m).
Resin composition for extrusion blow moulding of the present invention mainly is made up of LLDPE and a certain amount of properties-correcting agent.LLDPE is ethene and the multipolymer that contains the alkene of 4～8 carbon atoms, and density is 0.88～0.95g/cm
3, be preferably 0.90～0.93g/cm
3, melt flow rate (MFR) is 0.5～3g/10min, is preferably 1～2g/10min; Properties-correcting agent is hydroperoxide, comprise hydrogen phosphide cumene, di-isopropylbenzene hydroperoxide, hydrogen peroxide tri-isopropyl benzene, t-butyl hydroperoxide isopropyl benzene, to the alkyl peroxide, both can use separately, also can compositely use, decomposition temperature when its transformation period is 1 minute is preferably in 190～230 ℃ all greater than 160 ℃, and add-on is 500～10000ppm, be preferably 1000～5000ppm, (is benchmark with every gram polyvinyl resin).When add-on during greater than 10000ppm, can produce gel, film performance obviously descends, and when add-on during less than 500ppm, processing stability is poor.
According to customer requirements, the present composition can also add oxidation inhibitor, photostabilizer, slipping agent, lubricant etc.
Resin composition for extrusion blow moulding preparation method of the present invention is very simple, can on common double screw extrusion press or Banbury mixer, realize modified-reaction, with properties-correcting agent and suitable dispersant, be added dropwise in the polyethylene and mix, directly enter forcing machine reaction granulation.Reaction times is defined as 3～10 times of properties-correcting agent transformation period.In this scope, the time, long more reaction was abundant more, thorough more, but surpass this range materials the tendency that thermal destruction takes place was arranged.
Resin composition for extrusion blow moulding of the present invention is owing to used high temperature poor efficiency organo-peroxide and selected suitable processing conditions, crosslinking degree is low, in xylene solution, do not cause swelling polymer, promptly do not produce gel, just molecular chain has the chain of trace to increase, side chain increases, thereby makes the film of blowing thinner (≤10 μ m) under the prerequisite that keeps the original performance of polymkeric substance, has saved starting material.With resin composition for extrusion blow moulding blowing mulch film of the present invention, economic benefit is very remarkable.
Embodiment
(LL103AA, Lan Hua company petroleum chemical plant provides the tertbutyl peroxide (TBHP) of selection different amounts, the multipolymer of ethene and butene-1, density 0.9259/cm with LLDPE
3, melt flow rate (MFR) 0.66g/10min, melt strength 3.03cN, fusing speed 197.92m/min), under 210 ℃, to extrude through parallel dual-screw extruding machine, in 2 minutes reaction times, the resin modified results of property is listed in table 1.
Table 1 modified resin performance
| Numbering | Resin | ?TBHP(ppm) | Melt flow rate (MFR) (g/10mm) | Melt strength (cN) | Fusing speed (m/min) |
| ?1 | ?LL103AA | ????1000 | ????0.31 | ????3.55 | ????129.59 |
| ?2 | ?LL103AA | ????1500 | ????0?29 | ????3.60 | ????119.78 |
| ?3 | ?LL103AA | ????2000 | ????0.28 | ????3.66 | ????110.60 |
| ?4 | ?LL103AA | ????2500 | ????0.27 | ????3?86 | ????104.44 |
| ?5 | ?LL103AA | ????5000 | ????0.23 | ????4.01 | ????84.86 |
At 180 ℃ of following blown films, its processing and product performance see Table 2, table 3 with above-mentioned modifying material.
Table 2 blow molding process
| Numbering | Screw speed (rpm) | Main frame electric current (A) | Thickness (μ m) | Blow-up ratio | Processing stability |
| ????1 | ????20 | ????8 | ????7 | ????2.3 | Good |
| ????2 | ????20 | ????8 | ????6 | ????2.8 | Good |
| ????3 | ????20 | ????7 | ????6 | ????2.8 | Good |
| ????4 | ????20 | ????6.5 | ????5 | ????2?8 | Good |
| ????5 | ????20 | ????6?3 | ????4 | ????2.9 | Good |
The ultra-thin mulch film physical data of table 3 table
| Numbering | Tensile strength (MPa) | Elongation at break (%) | Tear strength (N/mm) | Mist degree % | |||
| Laterally | Vertically | Laterally | Vertically | Laterally | Vertically | ||
| ????1 | ????21.0 | ????46.0 | ????472 | ????220 | ?173.3 | ????180.0 | ?21.7 |
| ????2 | ????21.1 | ????47.8 | ????394 | ????173 | ?171.4 | ????158.0 | ?22.1 |
| ????3 | ????23.9 | ????46.9 | ????370 | ????153 | ?166.4 | ????125.0 | ?23.6 |
| ????4 | ????25.6 | ????56 | ????319 | ????152 | ?195.9 | ????118.0 | ?23.9 |
| ????5 | ????22.5 | ????58 | ????250 | ????142 | ?216.3 | ????86.5 | ?26.2 |
Claims (1)
1, a kind of resin composition for extrusion blow moulding, mainly form by linear low density polyethylene and organo-peroxide properties-correcting agent, it is characterized in that linear low density polyethylene is ethene and the copolymerization product that contains the alkene of 4～8 carbon atoms, density is 0.88～0.95g/cm
3, melt flow rate (MFR) is 0.5～3g/10min, and organo-peroxide is hydroperoxide, and its consumption is 500-10000ppm (is benchmark with every gram polyvinyl resin).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97119782 CN1063198C (en) | 1997-11-13 | 1997-11-13 | Resin composition for extrusion blow moulding |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97119782 CN1063198C (en) | 1997-11-13 | 1997-11-13 | Resin composition for extrusion blow moulding |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1218066A true CN1218066A (en) | 1999-06-02 |
| CN1063198C CN1063198C (en) | 2001-03-14 |
Family
ID=5175570
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 97119782 Expired - Lifetime CN1063198C (en) | 1997-11-13 | 1997-11-13 | Resin composition for extrusion blow moulding |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1063198C (en) |
Cited By (5)
| 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 |
| CN102408616A (en) * | 2010-09-21 | 2012-04-11 | 中国石油天然气股份有限公司 | A kind of ultra-wide polyethylene shed film resin composition and preparation method thereof |
| CN102408614A (en) * | 2010-09-21 | 2012-04-11 | 中国石油天然气股份有限公司 | High-strength, ultra-wide polyethylene greenhouse film resin composition and preparation method thereof |
| CN107189173A (en) * | 2017-07-17 | 2017-09-22 | 宿松县柳溪茶厂 | A kind of waterproof high-density polyethylene plastics mulch film |
-
1997
- 1997-11-13 CN CN 97119782 patent/CN1063198C/en not_active Expired - Lifetime
Cited By (7)
| 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 |
| 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 |
| CN102408616A (en) * | 2010-09-21 | 2012-04-11 | 中国石油天然气股份有限公司 | A kind of ultra-wide polyethylene shed film resin composition and preparation method thereof |
| CN102408614A (en) * | 2010-09-21 | 2012-04-11 | 中国石油天然气股份有限公司 | High-strength, ultra-wide polyethylene greenhouse film resin composition and preparation method thereof |
| CN102408616B (en) * | 2010-09-21 | 2013-04-24 | 中国石油天然气股份有限公司 | A kind of ultra-wide polyethylene shed film resin composition and preparation method thereof |
| CN102408614B (en) * | 2010-09-21 | 2013-04-24 | 中国石油天然气股份有限公司 | High-strength, ultra-wide polyethylene greenhouse film resin composition and preparation method thereof |
| CN107189173A (en) * | 2017-07-17 | 2017-09-22 | 宿松县柳溪茶厂 | A kind of waterproof high-density polyethylene plastics mulch film |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1063198C (en) | 2001-03-14 |
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| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
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Granted publication date: 20010314 |