CN1063198C - Resin composition for extrusion blow moulding - Google Patents
Resin composition for extrusion blow moulding Download PDFInfo
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- CN1063198C CN1063198C CN 97119782 CN97119782A CN1063198C CN 1063198 C CN1063198 C CN 1063198C CN 97119782 CN97119782 CN 97119782 CN 97119782 A CN97119782 A CN 97119782A CN 1063198 C CN1063198 C CN 1063198C
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- resin composition
- extrusion blow
- resin
- blow moulding
- peroxide
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Abstract
The present invention provides a resin composition for extrusion blow molding, which is mainly prepared from LLDPE resin (the density of 0.88 g/cm<3> to 0.95 g/cm<3> and the melt flow rate of 0.5 min to 3g/10 min) and hydroperoxides extruded in a reactivity mode by a double screw extruder with a simple preparation method. The addition amount of the hydroperoxides is from 500 ppm to 10000 ppm (each gram of polyethylene resin is used as a reference). The thickness of films blown by the composition is reduced lower than 10 mu m, and the blowing technology is stable so that physical properties are kept. When the resin composition for extrusion blow molding is used for blowing agricultural mulching films, the economic benefit is obvious.
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
3Melt flow rate (MFR) 2g/10min) 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 because the chemical modification of process organo-peroxide, polyethylene has formed tangible crosslinking structure, 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, the hydrogen peroxide tri-isopropyl benzene, the t-butyl hydroperoxide isopropyl benzene, right _ alkyl peroxide, both can use separately, also can compositely use, decomposition temperature when its transformation period is 1 minute is all greater than 160 ℃, be preferably in 190～230 ℃, add-on is 500～10000ppm, be preferably 1000～5000ppm, (is benchmark with every gram polyvinyl resin) is 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, the reaction times is defined as 3-10 times of properties-correcting agent transformation period, in this scope, 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 0.925g/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
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
The ultra-thin mulch film physical data of table 3 table
| Numbering | Resin | TBHP(ppm) | Melt flow rate (MFR) (g/10min) | 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 |
| 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 |
| 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 is made up of 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 atom, and 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 CN1218066A (en) | 1999-06-02 |
| CN1063198C true 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) |
Families Citing this family (5)
| 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 |
| CN102408616B (en) * | 2010-09-21 | 2013-04-24 | 中国石油天然气股份有限公司 | Over-wide polyethylene greenhouse 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 | Polyethylene greenhouse film resin composition with high intensity and ultra-broad width, and its preparation method |
| 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
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| Publication number | Publication date |
|---|---|
| CN1218066A (en) | 1999-06-02 |
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Granted publication date: 20010314 |