CN103788447A - Preparation method of long-chain branch high density polyethylene - Google Patents
Preparation method of long-chain branch high density polyethylene Download PDFInfo
- Publication number
- CN103788447A CN103788447A CN201210429875.4A CN201210429875A CN103788447A CN 103788447 A CN103788447 A CN 103788447A CN 201210429875 A CN201210429875 A CN 201210429875A CN 103788447 A CN103788447 A CN 103788447A
- Authority
- CN
- China
- Prior art keywords
- hdpe
- long
- oxidation inhibitor
- preparation
- 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.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a preparation method of long-chain branch high density polyethylene. The method comprises the following steps: (1) premixing HDPE powder and an anti-oxidant in a mixing device to obtain a premix; (2) adding the premix into a plastication processing device, performing fusion processing at a fusion processing temperature of 200-260 DEG C for 1-6 min; (3) adding the anti-oxidant again, and continuing to perform uniform fusion mixing. The HDPE is chromium catalyst-based vinyl-terminated anti-oxidant-free HDPE powder; the anti-oxidant is one or a combination of a hindered phenol anti-oxidant, a phosphite anti-oxidant, and a sulfur-containing anti-oxidant; the adding amount during premixing is 0-1000 ppm. The preparation method of the present invention has the advantages of simplicity, practicality, and low cost.
Description
Technical field
The present invention relates to polyethylene field, furtherly, relate to a kind of preparation method of long-branched high density polyethylene(HDPE).
Background technology
Polyvinyl resin excellent combination property, applies very extensively, is the resin of worldwide production consumption maximum.Polyethylene can be divided into Low Density Polyethylene (LDPE), linear low density polyethylene (LLDPE), medium-density polyethylene (MDPE) and high density polyethylene(HDPE) (HDPE) according to the difference of density.Being characterized as in molecular chain of LDPE contains long-chain branch, and LLDPE only contains short-chain branch conventionally, and in HDPE molecular chain, contains the short-chain branch than LLDPE less amount, causes it to have higher density.The molecular chain structure feature of HDPE is given it and is had higher use temperature, barrier property, and hardness, mechanical strength and chemical proofing are better, make it to be widely used at aspects such as blow-molded article, injected articles, film and sheet material, tubing.Wherein at high-performance blow molded product, pipe material product and film, application in the tube material of especially high (interior) pressure pipeline (PE80, PE100) or higher voltage withstand class and excellent Large Hollow Container, requiring increases its melt strength, to reduce the susceptibility of its melt to temperature and flow rate.
The method of preparing high melt-strength polyethylene comprises the poly relative molecular mass of raising and increases the methods such as relative molecular weight distribution, long-branched.Compared with other method that improves polyvinyl resin melt strength, long chain branching method can, in improving melt strength, effectively suppress the growth of shear viscosity, makes polymkeric substance keep good processing characteristics.This is because long-chain can promote melt shear shinning behavior, in other words the viscosity ratio general linear polyethylene of melt under high shear rate is low, and viscosity ratio general linear polyethylene under low shear rate is high, this is equivalent to the poly molecular weight distribution of broadening, therefore can improve Drawing abillity.Can not be attached to completely in backbone fold layer structure compared with long-chain branch in addition, disturb the folding of main chain, but can participate in another chain folded crystal through the excessive layer of sheet intergranular, form " frenulum " molecule of sheet intergranular, therefore improve the mechanical property of goods.
The method that makes polyethylene produce long chain branching comprises the directly synthetic polyethylene with long chain branched of original position, and change poly linear structure by post-treatment modification, make it to produce long chain branching, improve the method for melt strength with the entanglement between enhanced polyethylene macromolecular chain.The mechanism of original position direct synthesis method is polystep reaction, and the shortcoming processing condition of this method are complicated (two-step approach) too, needs to increase extra equipment, needs the careful technological process of controlling.Then processing modified method relatively simply, easily realizes industrialization.
Conventionally, poly drawing money on credit modification technology comprises and organo-peroxide, linking agent is mixed by forcing machine with polyvinyl resin or be added with polyethylene of linking agent etc. by electron rays irradiation.Irradiation method is generally selected high density polyethylene(HDPE) or linear low density polyethylene (LLDPE), under electronics or gamma-radiation irradiation, produce free radical, and then generation long-chain branch, the advantage of this method is easier, easily realize suitability for industrialized production, shortcoming is that the long-chain branched polyethylene structure of preparation is indefinite, and the by product of degraded and the generation such as crosslinked cannot be avoided, also higher to equipment requirements, energy consumption is huge.As Chinese patent literature CN 102030910A discloses a kind of preparation method of long-chain branched polyethylene, comprise the following steps: (1) utilizes high-power electron beam or gamma-radiation to carry out radiation treatment to matrix polyethylene, obtains pre-irradiation polyethylene; (2) the pre-irradiation polyethylene and the matrix polyethylene that step (1) are obtained mix, and stir and obtain premixture; (3) premixture step (2) being obtained is extruded and is made long-chain branched polyethylene by reaction.
Reaction extrusion ratio is easier to realize, and equipment is simple, and technique is simple.Chinese patent literature CN 101016361 discloses a kind of fusion preparation method that simultaneously strengthens polyolefine polarity and the degree of branching, it is characterized in that: be 100: 0～100: 0～50: 0.01～10: 0～10 polyolefine that mix by mass ratio: long-chain monomer: polar monomer: initiator: linking agent joins in 100～300 ℃ of reactors, under continuing to stir, copolyreaction obtains the polyolefine that polarity and the degree of branching are modified simultaneously after 0.1～12 hour.
Summary of the invention
For solving problems of the prior art, the invention provides a kind of preparation method of long-branched high density polyethylene(HDPE).Can be in the time of granulation for powders, or in the time of post-treatment, or process through special, long-chain branch generated by free radical reaction.Preparation method of the present invention has the advantages such as simple and easy to do, with low cost.
The object of this invention is to provide a kind of preparation method of long-branched high density polyethylene(HDPE).
Comprise:
(1) premix on mixing equipment by HDPE powder and oxidation inhibitor, obtains Preblend;
(2) Preblend is added to the processing units of plasticating, carry out melt-processed; Melt processing temperature is 200 ~ 260 ℃; The melt-processed time is: 1 ~ 6min;
(3) again add oxidation inhibitor, continue melting mixing even.
Described HDPE is the HDPE powder that does not add oxidation inhibitor that contains end-vinyl based on chromium-based catalysts;
In step (1), the add-on of oxidation inhibitor is: 0 ~ 1000ppm.Mixing equipment can adopt common mixing equipment in prior art, as homogenizer etc.
The described processing units of plasticating of step (2) comprises Banbury mixer, single screw extrusion machine, twin screw extruder etc.The processing units rotating speed of plasticating described in the present invention can regulate according to actual needs.
In step (3), adding oxidation inhibitor is in order to play oxidation resistant effect, increase the service life, the oxidation inhibitor addition in this step is the conventional amount used of this area, plays antioxygenation, the melting mixing time also mixes in HDPE with oxidation inhibitor, generally preferred 30-90s.
Described oxidation inhibitor is a kind of or combination in Hinered phenols antioxidant, phosphite ester kind antioxidant, sulfur-bearing oxidation inhibitor;
Wherein, hindered phenol antioxygen is preferably antioxidant 264 [2,6-ditertbutylparacresol], antioxidant 1010 [2,6-di-tert-butyl-4-methy phenol], 1076[β-(3,5-di-t-butyl-4-hydroxybenzene) propionic acid octadecanol ester], 3114[1,3,5-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) tricarbimide];
Phosphite antioxidant is preferably irgasfos 168 [three (Isosorbide-5-Nitrae-di-tert-butyl-phenyl) phosphorous acid ester], two (2, the 4 one di-tert-butyl-phenyl) pentaerythritol diphosphate of oxidation inhibitor 626[] and antioxidant 618 [two (octadecyl) pentaerythritol diphosphites];
Sulfur-bearing oxidation inhibitor is preferably the two lauryl alcohol esters of DLTDP[thio-2 acid or two cinnamoyl thiobis propionic acid fat], DSTDP[stearic bicine diester base thiobis propionic acid fat], two 14 esters of DMTDP[thio-2 acid], two 13 esters of DTDTP[thio-2 acid], TDPA[thio-2 acid].
In step (2), melt processing temperature is higher, and the melt-processed time is longer, and in step (1), the add-on of oxidation inhibitor is more.
In the time not adding oxidation inhibitor in step (1), the melt processing temperature of step (2) is 200 ~ 230 ℃, and the melt-processed time is 2 ~ 3min.
In step (2), melt processing temperature is higher, and the melt-processed time is shorter.
In the present invention, the principle of HDPE generation long chain branching is: the HDPE powder with terminal double bond can generate free radical in the time of melt-processed, and processing temperature is higher, process period is longer, the free radical producing is more, the free radical generating makes HDPE generate long-chain branch on the one hand, there is on the other hand molecule chain break and degrade, because chromium is the molecular structure feature that HDPE powder has end ethylene double bond, in the course of processing, generate trans vinylidene with end-vinyl, make HDPE to produce long-chain branch as main, but the generation of crossing polyradical will make the HDPE after branching further crosslinked, HDPE product properties is had a negative impact, must be controlled.Control method is: in the Preblend of HDPE, add appropriate free radical scavenger-oxidation inhibitor, to control the concentration of free radical in the HDPE course of processing.In experiment, find, HDPE is under certain processing temperature, process period is longer, more easily produce gel, must process appropriate oxidation inhibitor is controlled, the addition of oxidation inhibitor does not generate gel as lower limit in HDPE melt-processed process, can not generate long-chain branch as the upper limit, is directly proportional to processing temperature and process period.If the antioxygen dosage adding in Preblend is more, suppress the generation of free radical completely, HDPE just can not produce long chain branching; If the antioxygen dosage adding is very few, HDPE is in the course of processing, improper if processing temperature and time are controlled, and just there will be gel; Adding appropriate oxidation inhibitor can, by hindering the generation of free radical, can suppress the degraded of HDPE and the generation of gel, obtains long-chain branch simultaneously.
The present invention can be in the time of granulation for powders, or in the time of post-treatment, or process through special, in processing temperature, time and the Preblend thereof of the HDPE powder that contains end-vinyl by control, the addition of oxidation inhibitor regulates the concentration of free radical in the HDPE course of processing, make HDPE generate long-chain branch, improve the melt strength of HDPE, reduce the susceptibility of its melt to temperature and flow rate, can be used for preparing the tube material of high (interior) pressure pipeline or higher voltage withstand class and the Large Hollow Container of excellent performance.This preparation method has the advantages such as simple and easy to do, with low cost.
Accompanying drawing explanation
Fig. 1 embodiment 3, embodiment 4, the Log[η of embodiment 5 and comparative example 1]-LogM figure
Embodiment
Below in conjunction with embodiment, further illustrate the present invention, scope of the present invention is not subject to the restriction of these embodiment.
Testing method:
1, the sign of the HDPE degree of branching
Adopt gel permeation chromatography (GPC) method, by viscosity detector and refractive index detector coupling, at Log[η] on-LogM figure, by relatively can whether thering is long-chain branch by judgement sample to slope.In the time of identical molecular weight, the limiting viscosity of long-chain branch sample is less, by Log[η] that LogM is done to the slope that figure obtains is little compared with the sample of line style non-branching, and therefore just can to whether there being long-chain branch to characterize in sample.
2, the test of gel content
Testing method: size of (1) clip can wrap up clean, the dry copper mesh of sample and weigh, and is accurate to 1mg, as m
1; (2) about 0.2gHDPE sample is put into screen cloth and be rolled into bag shape and weigh, be accurate to 1mg, as m
2; (3) 300mL dimethylbenzene is poured in the round-bottomed flask of 500ml, then in dimethylbenzene, added 3g antioxidant 1010; (4) will be surrounded by the suspention of screen cloth bag and the round-bottomed flask of HDPE sample with copper wire, should make that sample is whole to be immersed in dimethylbenzene; (5) prolong is installed; (6) open heating unit heated solvent to boiling point, control condensing reflux speed at (20-40) drip/min, extraction time 8h; (7) carefully take out wire and screen cloth bag, and with washing with acetone; (8) screen cloth bag and wire are put into vacuum drying oven inner drying, temperature is 140 ℃, time 3h; (9) take out screen cloth band and wire cools (putting into if desired moisture eliminator) to envrionment temperature, take off wire and weigh screen cloth bag, be accurate to 1mg, as m
3.(10) the degree of crosslinking G of calculating individual sample
i: G
i=(m
3-m
1)/(m
2-m
1) × 100, wherein G
i-degree of crosslinking (%), m
1the quality (mg) of-screen cloth, m
2the quality (mg) of sample and screen cloth before-extraction, m
3the quality (mg) of residue sample and screen cloth after-extraction; (11) each sample is got three samples and is asked arithmetic mean value to be degree of crosslinking.
3, MFR test
The melt flow rate (MFR) (MFR) of sample is measured the GB/T3682-2000 standard of press, and use Zwick/Roell4106 type melt fusion index instrument (German Zwick/Roell company), at 190 ℃, is tested under 5.0kg and 21.6kg load.
Raw materials used in embodiment:
(melt flow rate is MFR to high density polyethylene(HDPE) DGDA 6098 powders for Qilu Petrochemical, butene-1 copolymerization
2.16=0.09g/10min, MFR
21.6=11.5g/10min(190 ℃, GB/T 3682-2000)
Antioxidant 1010 (technical grade, vapour Ba-Jia Ji company of Switzerland)
Irgasfos 168 (technical grade, Beijing addition auxiliary agent institute)
The preparation of HDPE Preblend
High density polyethylene(HDPE) powder and composite antioxidant (antioxidant 1010: 168=1:4) are added to high-speed mixer (model GH-10DY, English special plastics machinery head factory in Beijing is produced) in mix, then stop stirring, discharging obtains Preblend, specifically fill a prescription in table 1, wherein the amount of oxidation inhibitor is take the weight of DGDA 6098 powders as radix.
Get the Preblend of 45g high density polyethylene(HDPE) powder, adopt Haake torque rheometer Poly OS system (Thremo fisher company, model Poly OS, Germany manufactures) Banbury mixer annex with the rotating speed of 60rpm to high density polyethylene(HDPE) powder Preblend carry out banburying processing, temperature setting is set to 230 ° of C, 230 ° of C, 230 ° of C or 200 ° of C, 200 ° of C, 200 ° of C, after mixing certain hour (specifically in table 1), add again appropriate composite antioxidant (formula is in table 1), the sample of collecting preparation after continuation processing 1min characterizes, result is as shown in table 1, in addition, embodiment 3, 4, the GPC characterization result of 5 correspondences as shown in Figure 1.
Comparative example 1
According to the preparation method of Preblend and get final product, specifically to fill a prescription in table 1, sample characterizes, and result is as shown in table 1 and Fig. 1.
Comparative example 2
Get 45g high density polyethylene(HDPE) powder Preblend (formula is in table 1), adopt Haake torque rheometer Poly OS system (Thremo fisher company, model Poly OS, Germany manufactures) Banbury mixer annex with the rotating speed of 60rpm to high density polyethylene(HDPE) powder Preblend carry out banburying processing, temperature setting is set to 230 ° of C, 230 ° of C, 230 ° of C, mix after 2min, the sample of collecting preparation after continuation processing 1min characterizes, and result is as shown in table 1.
Comparative example 3
Except banburying 6min, all the other are identical with comparative example 2, and sample characterization result is as shown in table 1.Table 1 oxidation inhibitor addition, process period and the impact of temperature on HDPE melting index and gel content
Note: oxidation inhibitor is the mixture of antioxidant 1010 and irgasfos 168, wherein 1010:168=1:4
Data by table 1 can be found out, all there is not gel in the sample of embodiment 1 ~ 5 and comparative example 2 and comparative example 3, the MFR value of embodiment 1 ~ 5 sample is all than sample (comparative example 1) little through the processing of plasticating not, and all large than comparative example 1 of the MFR value of comparative example 2 and comparative example 3 samples, this sample that shows embodiment 1 ~ 5 has all produced long chain branching.Contrast by Fig. 1 can be found out: the Log[η of the sample of embodiment 3 ~ 5]-LogM slope all than not through plasticate processing sample (comparative example 1) little, further show that the sample of embodiment 3 ~ 5 has all produced long chain branching.
The test-results of table 1 also shows: in Preblend, add relatively many oxidation inhibitor (comparative example 2, comparative example 3), though there is not gel in the HDPE course of processing, cannot form long-chain branch.In Preblend, do not add oxidation inhibitor, process period is (embodiment 1, embodiment 2) more in short-term, does not produce gel, and produced long-chain branch in the HDPE course of processing, and processing temperature is higher, and the MFR value of HDPE is less, shows that the long-chain branch generating is more.In Preblend, add appropriate oxidation inhibitor (embodiment 3, embodiment 4, embodiment 5), the formation of gel-free in the HDPE course of processing, HDPE has produced long-chain branch simultaneously, and process period is longer, needs the antioxygen dosage of interpolation just more.Therefore, in the present invention, all can avoid the high density polyethylene(HDPE) course of processing to produce gel by the addition of controlled working temperature, process period or oxidation inhibitor, obtain the long-chain branch that can increase HDPE melt strength simultaneously.
Claims (7)
1. a preparation method for long-branched high density polyethylene(HDPE), is characterized in that described method comprises:
(1) premix on mixing equipment by HDPE powder and oxidation inhibitor, obtains Preblend;
(2) Preblend is added to the processing units of plasticating, carry out melt-processed; Melt processing temperature is 200 ~ 260 ℃; The melt-processed time is: 1 ~ 6min;
(3) again add oxidation inhibitor, continue melting mixing even;
Described HDPE is the HDPE powder that does not add oxidation inhibitor that contains end-vinyl based on chromium-based catalysts;
In step (1), the add-on of oxidation inhibitor is: 0 ~ 1000ppm.
2. the preparation method of long-branched high density polyethylene(HDPE) as claimed in claim 1, is characterized in that:
Described oxidation inhibitor is a kind of or its combination in Hinered phenols antioxidant, phosphite ester kind antioxidant, sulfur-bearing oxidation inhibitor.
3. the preparation method of long-branched high density polyethylene(HDPE) as claimed in claim 2, is characterized in that:
Described hindered phenol antioxygen is 2,6 ditertiary butyl p cresol, 2,6 di tert butyl 4 methyl phenol, β-(3,5-di-t-butyl-4-hydroxybenzene) propionic acid octadecanol ester, 1,3,5-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) tricarbimide;
Described phosphite antioxidant is three (Isosorbide-5-Nitrae-di-tert-butyl-phenyl) phosphorous acid ester, two (2,4 one di-tert-butyl-phenyl) pentaerythritol diphosphate, two (octadecyl) pentaerythritol diphosphites;
Described sulfur-bearing oxidation inhibitor is the two lauryl alcohol esters of thio-2 acid or two cinnamoyl thiobis propionic acid fat, stearic bicine diester base thiobis propionic acid fat, two 14 esters of thio-2 acid, two 13 esters of thio-2 acid, thio-2 acid.
4. the preparation method of the long-branched high density polyethylene(HDPE) as described in one of claim 1 ~ 3, is characterized in that:
In step (2), melt processing temperature is higher, and the melt-processed time is longer, and in step (1), the add-on of oxidation inhibitor is more.
5. the preparation method of long-branched high density polyethylene(HDPE) as claimed in claim 4, is characterized in that:
In the time not adding oxidation inhibitor in step (1), the melt processing temperature of step (2) is 200 ~ 230 ℃, and the melt-processed time is 2 ~ 3min.
6. the preparation method of the long-branched high density polyethylene(HDPE) as described in one of claim 1 ~ 3, is characterized in that:
In step (2), melt processing temperature is higher, and the melt-processed time is shorter.
7. the preparation method of the long-branched high density polyethylene(HDPE) as described in one of claim 1 ~ 3, is characterized in that:
The melting mixing time in step (3) is 30-90s.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210429875.4A CN103788447B (en) | 2012-10-31 | 2012-10-31 | A kind of preparation method of long-branched high density polyethylene (HDPE) |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210429875.4A CN103788447B (en) | 2012-10-31 | 2012-10-31 | A kind of preparation method of long-branched high density polyethylene (HDPE) |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103788447A true CN103788447A (en) | 2014-05-14 |
| CN103788447B CN103788447B (en) | 2016-08-10 |
Family
ID=50664530
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210429875.4A Active CN103788447B (en) | 2012-10-31 | 2012-10-31 | A kind of preparation method of long-branched high density polyethylene (HDPE) |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103788447B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105924584A (en) * | 2016-05-15 | 2016-09-07 | 贵州大学 | Long-chain branched high-density polyethylene material resisting environmental stress cracking and preparation method thereof |
| CN108943634A (en) * | 2018-06-05 | 2018-12-07 | 宁波大学 | A kind of injection molding forming method of bimodal polyethylene product |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101437878A (en) * | 2006-03-10 | 2009-05-20 | 陶氏环球技术公司 | Polyethylene resins for sheet and thermoforming applications |
-
2012
- 2012-10-31 CN CN201210429875.4A patent/CN103788447B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101437878A (en) * | 2006-03-10 | 2009-05-20 | 陶氏环球技术公司 | Polyethylene resins for sheet and thermoforming applications |
Non-Patent Citations (1)
| Title |
|---|
| 杨逊嫥: "多分散性对采用铬催化剂聚合的HDPE的热-机械降解的影响", 《合成材料老化与应用》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105924584A (en) * | 2016-05-15 | 2016-09-07 | 贵州大学 | Long-chain branched high-density polyethylene material resisting environmental stress cracking and preparation method thereof |
| CN108943634A (en) * | 2018-06-05 | 2018-12-07 | 宁波大学 | A kind of injection molding forming method of bimodal polyethylene product |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103788447B (en) | 2016-08-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chen et al. | Melting and crystallization behavior of partially miscible high density polyethylene/ethylene vinyl acetate copolymer (HDPE/EVA) blends | |
| ES2949551T3 (en) | Method to increase the melt resistance of a polyethylene resin | |
| Taghizadeh et al. | High molecular weight plasticizers in thermoplastic starch/polyethylene blends | |
| Cano et al. | Morphological and mechanical study of nanostructured epoxy systems modified with amphiphilic poly (ethylene oxide-b-propylene oxide-b-ethylene oxide) triblock copolymer | |
| CN105254999A (en) | Scratch-resistant high-impact polypropylene resin material and preparing method | |
| CN103589059A (en) | Radiation crosslinking polypropylene heat shrinkable belt base material | |
| CN104479273B (en) | thermoplastic resin composition for blow molding and preparation method thereof | |
| Wang et al. | Thermal stability and non-isothermal crystallization kinetics of metallocene poly (ethylene-butene-hexene)/high fluid polypropylene copolymer blends | |
| CN102050981A (en) | Polyethylene composition for woven bag coating material and preparation method thereof | |
| Yesil | Effect of carbon nanotube reinforcement on the properties of the recycled poly (ethylene terephthalate)/poly (ethylene naphthalate)(r-PET/PEN) blends containing functional elastomers | |
| CN103788447A (en) | Preparation method of long-chain branch high density polyethylene | |
| CN108727704A (en) | Acrylic resin composition and injection molded article | |
| CN103102639B (en) | A kind of acrylonitrile butadient styrene composite and preparation method | |
| CN109553842A (en) | Composition for preparing linear low density polyethylene film and preparation method thereof | |
| CN109705446A (en) | A kind of modified polyolefin mother material and its preparation method and application | |
| Shao et al. | Rheological behaviors of polypropylene/poly (1-butene) blends | |
| CN106554542B (en) | A kind of polyethylene composition and its microporous barrier | |
| US3789085A (en) | Polyethylene block-graft copolymers and method for preparing the same | |
| CN108503934A (en) | A kind of drip irrigation pipe/belt polyethylene composition | |
| WO2024121189A1 (en) | Polyolefin composition comprising polyethylene and recycled plastic material | |
| EP3172276A1 (en) | A polyethylene blend composition and film made therefrom | |
| CN106633325B (en) | A kind of polyethylene composition and durable membrane | |
| CN107513262B (en) | Polyketone compositions | |
| CN105623055B (en) | A kind of polyethylene composition and its film | |
| US20200165428A1 (en) | Composition comprising polypropylene for injection stretch blow molding, methods of making and using the same |
Legal Events
| 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 |