CN103788447B - A kind of preparation method of long-branched high density polyethylene (HDPE) - Google Patents

A kind of preparation method of long-branched high density polyethylene (HDPE) Download PDF

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CN103788447B
CN103788447B CN201210429875.4A CN201210429875A CN103788447B CN 103788447 B CN103788447 B CN 103788447B CN 201210429875 A CN201210429875 A CN 201210429875A CN 103788447 B CN103788447 B CN 103788447B
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antioxidant
hdpe
long
melt
preparation
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CN103788447A (en
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潘国元
刘轶群
郭敏
张杨
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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    • 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

Abstract

The invention discloses the preparation method of a kind of long-branched high density polyethylene (HDPE).Described method includes: HDPE powder and antioxidant are premixed on mixing apparatus by (1), obtain premix material；(2) premix material is added process equipment of plasticating, carry out melt-processed；Melt processing temperature is 200 ~ 260 DEG C；The melt-processed time is: 1 ~ 6min；(3) again add antioxidant, continue melting mixing uniform.Described HDPE is based on chromium-based catalysts not add antioxidant HDPE powder containing end-vinyl；Described antioxidant is the one in Hinered phenols antioxidant, phosphite ester kind antioxidant, sulfur-bearing antioxidant or combination；Wherein during premix, addition is: 0 1000ppm, the preparation method of the present invention has the advantages such as simple and easy to do, with low cost.

Description

A kind of preparation method of long-branched high density polyethylene (HDPE)
Technical field
The present invention relates to polyethylene field, furtherly, relate to a kind of long-branched high density polyethylene (HDPE) Preparation method.
Background technology
Polyvinyl resin excellent combination property, application widely, is the resin of worldwide production consumption figure maximum. Polyethylene can be divided into Low Density Polyethylene (LDPE), linear low density polyethylene according to the difference of density (LLDPE), medium density polyethylene (MDPE) and high density polyethylene (HDPE) (HDPE).The feature of LDPE For in strand containing long-chain branch, LLDPE generally comprises only short-chain branch, and in HDPE strand containing than The lesser amount of short-chain branch of LLDPE, causes it to have higher density.The molecular chain structure feature of HDPE is composed Giving it and have higher use temperature, barrier property, hardness, mechanical strength and chemical proofing are preferable, It is allowed to be widely used at blow-molded article, injected articles, thin film and the aspect such as sheet material, tubing.Wherein At high-performance blow molded product, pipe material product and thin film, the highest (interior) pressure pipeline (PE80, PE100) Or the application in the tube material of the highest pressure grade and excellent Large Hollow Container, it is desirable to increase its melt strong Degree, to reduce its melt to temperature and the sensitivity of flow rate.
The method preparing high melt-strength polyethylene includes improving the relative molecular mass of polyethylene and increases relatively The method such as molecular weight distribution, long-branched.Compared with other method improving polyvinyl resin melt strength, Long chain branching method while improving melt strength, can effectively suppress the growth of shear viscosity, Make the processing characteristics that polymer holding is good.This is owing to long-chain can promote the thinning behavior of melt shear, it is simply that Say that melt ratio of viscosities general linear polyethylene at high shear rates is low, and viscosity at low shear rates Higher than general linear polyethylene, this is equivalent to the molecular weight distribution of broadening polyethylene, therefore can improve material Processing characteristics.The most relatively long-chain branch can not be completely coupled in backbone fold Rotating fields, disturbs main chain Fold, but another chain folded crystal can be participated in through the excessive layer of sheet intergranular, define sheet intergranular " frenulum " molecule, therefore improves the mechanical property of goods.
The method making polyethylene produce long chain branching includes being directly synthesized the poly-second with long chain branched in situ Alkene, and the linear structure of polyethylene is changed by post-treatment modification, it is allowed to produce long chain branching, to strengthen The method improving melt strength of tangling between polyethylene macromolecular chain.The mechanism of direct synthesis method is in situ Multistep reaction, the shortcoming process conditions of this method are excessively complicated (two-step method), need to increase extra equipment, Need carefully to control technical process.The most processing modified method is relatively easy, easily realize industrialization.
Generally, the branched modification technology of the length of polyethylene includes organic peroxide, cross-linking agent and polyvinyl resin Mixed by extruder or pass through the electron ray irradiation polyethylene etc. added with cross-linking agent.Irradiation method is general Select high density polyethylene (HDPE) or linear low density polyethylene (LLDPE), produce under electronics or gamma-radiation irradiation Raw free radical, and then generate long-chain branch, the advantage of this method is that comparison is easy, easily realizes industrialized production, Shortcoming is that the long-chain branched polyethylene structure prepared is indefinite, and the by-product that degrade and crosslinking etc. produces cannot be kept away Exempting from, the highest to equipment requirements, energy consumption is huge.As Chinese patent literature CN 102030910A discloses one Plant the preparation method of long-chain branched polyethylene, comprise the following steps: (1) utilizes high-power electron beam or gamma-radiation pair Matrix polyethylene carries out radiation treatment, obtains pre-irradiation polyethylene；(2) the poly-second of pre-irradiation that step (1) is obtained Alkene and matrix polyethylene mix, and are uniformly mixing to obtain premix；(3) premix that step (2) is obtained Compound prepares long-chain branched polyethylene by reactive extrursion.
Reactive extrursion is easier to realize, and equipment is simple, and technique is simple.Chinese patent literature CN 101016361 Disclose a kind of enhancing polyolefin polar and the fusion preparation method of the degree of branching simultaneously, it is characterised in that: by matter Amount is than the polyolefin being 100: 0～100: 0～50: 0.01～10: 0～10 mixing: long-chained monomer: polarity Monomer: initiator: cross-linking agent joins in 100～300 DEG C of reactors, under continuous stirring copolyreaction 0.1～ Polarity is obtained and polyolefin that the degree of branching is modified simultaneously after 12 hours.
Summary of the invention
For solving problems of the prior art, the invention provides a kind of long-branched high density polyethylene (HDPE) Preparation method.Can be when granulation for powders, or when post-treatment, or through processing especially, by freedom Base reacts and generates long-chain branch.The preparation method of the present invention has the advantages such as simple and easy to do, with low cost.
It is an object of the invention to provide the preparation method of a kind of long-branched high density polyethylene (HDPE).
Including:
(1) HDPE powder and antioxidant are premixed on mixing apparatus, obtain premix material；
(2) premix material is added process equipment of plasticating, carry out melt-processed；Melt processing temperature is 200～260 DEG C；The melt-processed time is: 1～6min；
(3) again add antioxidant, continue melting mixing uniform.
Described HDPE is the HDPE powder not adding antioxidant containing end-vinyl based on chromium-based catalysts Material；
In step (1), the addition of antioxidant is: 0～1000ppm.Mixing apparatus can use in prior art Common mixing apparatus, such as homogenizer etc..
Process equipment of plasticating described in step (2) includes banbury, single screw extrusion machine, double screw extruder Deng.Heretofore described process equipment rotating speed of plasticating can be adjusted according to actual needs.
Adding antioxidant in step (3) is to play antioxidative effect, increasing the service life, this step In antioxidant addition be the conventional amount used of this area, play antioxidation, melting mixing time Also with antioxidant mix homogeneously in HDPE, general preferable 30-90s.
Described antioxidant is the one in Hinered phenols antioxidant, phosphite ester kind antioxidant, sulfur-bearing antioxidant Or combination；
Wherein, hindered phenol antioxygen is preferably antioxidant 264 [2,6 ditertiary butyl p cresol], antioxidant 1010 [2,6-di-tert-butyl-4-methy phenol], 1076[β-(3,5-di-t-butyl-4-hydroxy benzenes) propanoic acid 18 carbon Alcohol ester], 3114[1,3,5-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid]；
Phosphite antioxidant is preferably irgasfos 168 [three (2,4-di-tert-butyl-phenyl) phosphite ester], anti- Double (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites of oxygen agent 626[] and antioxidant 618 [double (ten Eight alkyl) pentaerythritol diphosphites]；
Sulfur-bearing antioxidant is preferably the double lauryl alcohol ester of DLTDP[thio-2 acid], DSTDP[stearic bicine diester Base thiobis propanoic acid fat], the double tetradecane ester of DMTDP[3,3'-thio-2 acid], DTDTP[3,3'-sulfur generation The double tridecanol ester of dipropionic acid], TDPA[thio-2 acid].
In step (2), melt processing temperature is the highest, and the melt-processed time is the longest, then antioxygen in step (1) The addition of agent is the most.
When being added without antioxidant in step (1), the melt processing temperature of step (2) is 200～230 DEG C, The melt-processed time is 2～3min.
In step (2), melt processing temperature is the highest, then the melt-processed time is the shortest.
In the present invention, the principle of HDPE generation long chain branching is: have the HDPE powder of terminal double bond melted Adding and can generate free radical man-hour, and processing temperature is the highest, process time is the longest, and the free radical of generation is the most, On the one hand the free radical generated makes HDPE generate long-chain branch, on the other hand occurs molecule chain break to degrade, Because chromium system HDPE powder has the molecular structure feature of end ethylene double bond, raw with end-vinyl in the course of processing Become trans-vinylene, make HDPE to produce long-chain branch, but cross polyradical generation will make prop up HDPE after change cross-links further, has a negative impact HDPE product properties, it is necessary to be controlled by. Control method is: add appropriate free radical scavenger antioxidant in the premix material of HDPE, to control The concentration of free radical in the HDPE course of processing.It was found that, HDPE is under certain processing temperature, add Between man-hour the longest, the most easily produce gel, it is necessary to process appropriate antioxidant and be controlled by, adding of antioxidant Dosage is not to generate gel during HDPE melt-processed as lower limit, so that long-chain branch can not be generated as the upper limit, It is directly proportional to processing temperature and process time.If the antioxygen dosage added in premix material is more, then completely inhibit The generation of free radical, HDPE would not produce long chain branching；If the antioxygen dosage added is very few, then HDPE In the course of processing, if processing temperature and time control are improper, arise that gel；Add appropriate antioxygen Agent can suppress the degraded of HDPE and the generation of gel by hindering the generation of free radical, obtain length simultaneously Side chain.
The present invention can be when granulation for powders, or when post-treatment, or through processing especially, is contained by control The addition of antioxidant in the processing temperature of HDPE powder, time and the premix material thereof of end-vinyl is had to adjust The concentration of free radical in the joint HDPE course of processing so that HDPE generates long-chain branch, improves HDPE's Melt strength, reduces its melt to temperature and the sensitivity of flow rate, can be used for preparation high (interior) pressure Pipeline or the tube material of the highest pressure grade and the Large Hollow Container of excellent performance.This preparation method has letter Easy row, the advantage such as with low cost.
Accompanying drawing explanation
Fig. 1 embodiment 3, embodiment 4, Log [the η]-LogM figure of embodiment 5 and comparative example 1
Detailed description of the invention
Below in conjunction with embodiment, further illustrating the present invention, the scope of the present invention is not limited by these embodiments System.
Method of testing:
1, the sign of the HDPE degree of branching
Use gel permeation chromatography (GPC) method, be combined by viscosity detector and refractive index detector, On Log [η]-LogM figure, by slope relatively be may determine that whether sample has long-chain branch.Identical Molecular weight time, the intrinsic viscosity of long-chain branch sample is less, will Log [η] LogM is done that figure obtains oblique Rate is little compared with the sample of line style non-branching, the most just to whether there being long-chain branch in sample can characterize.
2, the test of gel content
Method of testing: one piece of size of (1) clip can wrap up the cleaning of sample, dry copper mesh and weigh, It is accurate to 1mg, as m1；(2) about 0.2gHDPE sample is put into screen cloth is rolled into pouch-shaped and weighs, It is accurate to 1mg, as m2；(3) 300mL dimethylbenzene is poured in the round-bottomed flask of 500ml, then to Dimethylbenzene adds 3g antioxidant 1010；(4) with copper wire, the screen cloth bag being surrounded by HDPE sample is suspended in midair and circle In end flask, should make that sample is whole to be immersed in dimethylbenzene；(5) condensing tube is installed；(6) unlatching adds hot charging Put heated solvent and drip/min, extraction time 8h to boiling point, control condensing reflux speed at (20-40)；(7) Careful taking-up tinsel and screen cloth bag, and use washing with acetone；(8) screen cloth bag and tinsel are put into vacuum to do Being dried in dry case, temperature is 140 DEG C, time 3h；(9) take out screen belt to cool down (if desired with tinsel Put into exsiccator) to after ambient temperature, take off tinsel and weigh screen cloth bag, be accurate to 1mg, as m3。 (10) degree of cross linking G of individual sample is calculatedi: Gi=(m3-m1)/(m2-m1) × 100, wherein Gi-the degree of cross linking (%), m1The quality (mg) of-screen cloth, m2Sample and the quality (mg) of screen cloth, m before-extraction3Sample is remained after-extraction Quality (mg) with screen cloth；(11) each sample takes three samples and asks arithmetic average to be the degree of cross linking.
3, MFR test
The melt flow rate (MFR) (MFR) of sample measures and presses GB/T3682-2000 standard, uses Zwick/Roell 4106 type melt Index Instruments (Zwick/Roell company of Germany) are at 190 DEG C, 5.0kg and 21.6kg carries Test under lotus.
In embodiment raw materials used:
(melt flow rate is high density polyethylene (HDPE) DGDA 6098 powder for Qilu Petrochemical, butene-1 copolymerization MFR2.16=0.09g/10min, MFR21.6=11.5g/10min (190 DEG C, GB/T 3682-2000)
Antioxidant 1010 (technical grade, Switzerland vapour Ba-Jia Ji company)
Irgasfos 168 (technical grade, Beijing addition auxiliary agent institute)
The preparation of HDPE premix material
High density polyethylene (HDPE) powder and composite antioxidant (antioxidant 1010: 168=1:4) are added high-speed mixer Mix homogeneously in (model GH-10DY, Beijing's English spy's plastics machinery head factory produce), then stop stirring, Discharging obtains premix material, and concrete formula is shown in Table 1, and wherein the amount of antioxidant is with the weight of DGDA 6098 powder For radix meter.
Embodiment 1～5
Take 45g high density polyethylene (HDPE) powder premix material, use Haake torque rheometer Poly OS system (Thremo Fisher company, model Poly OS, Germany manufactures) banbury adnexa with the rotating speed of 60rpm, high density is gathered Ethylene powder premix material carries out banburying processing, temperature be set to 230 DEG C, 230 DEG C, 230 DEG C or 200 DEG C, 200 DEG C, 200 DEG C, after mixing certain time (being specifically shown in Table 1), add appropriate composite antioxidant (formula is shown in Table 1), The sample collecting preparation after continuing processing 1min characterizes, and result is as shown in table 1, it addition, embodiment 3, 4, the GPC characterization result of 5 correspondences is as shown in Figure 1.
Comparative example 1
According to the preparation method of premix material and get final product, concrete formula is shown in Table 1, and sample characterizes, result such as table 1 Shown in Fig. 1.
Comparative example 2
Take 45g high density polyethylene (HDPE) powder premix material (formula is shown in Table 1), use Haake torque rheometer Poly OS Banbury adnexa the turning with 60rpm of system (Germany manufactures for Thremo fisher company, model Poly OS) Speed carries out banburying processing to high density polyethylene (HDPE) powder premix material, and temperature is set to 230 DEG C, 230 DEG C, 230 DEG C, After mixing 2min, the sample collecting preparation after continuing processing 1min characterizes, and result is as shown in table 1.
Comparative example 3
In addition to banburying 6min, remaining is identical with comparative example 2, and sample characterization result is as shown in table 1.
Table 1 antioxidant addition, process time and temperature are on HDPE melt index and the impact of gel content
Note: antioxidant is the complex of antioxidant 1010 and irgasfos 168, wherein 1010:168=1:4
By the data of table 1 it can be seen that embodiment 1～5 and the sample of comparative example 2 and comparative example 3 all do not go out Existing gel, the MFR value of embodiment 1～5 sample all ratios not through sample (comparative example 1) little of processing of plasticating, And the MFR value of comparative example 2 and comparative example 3 sample all big than comparative example 1, this shows embodiment 1～5 Sample all creates long chain branching.By the contrast of Fig. 1 it can be seen that the Log of the sample of embodiment 3～5 [η]-LogM slope is all little through the sample (comparative example 1) of processing of plasticating than not, further demonstrates that embodiment 3～5 Sample all create long chain branching.
The result of the test of table 1 also shows: add relatively large number of antioxidant (comparative example 2, contrast in premix material Example 3), though the HDPE course of processing does not occur gel, but long-chain branch cannot be formed.Premix material does not adds Add antioxidant, when process time is shorter (embodiment 1, embodiment 2), the HDPE course of processing does not produce Gel, and create long-chain branch, processing temperature is the highest, and the MFR value of HDPE is the least, shows the length generated Side chain is the most.Premix material is added appropriate antioxidant (embodiment 3, embodiment 4, embodiment 5), HDPE Without the formation of gel in the course of processing, HDPE creates long-chain branch simultaneously, and process time is the longest, needs to add Antioxygen dosage the most.Therefore, by controlling processing temperature, process time or antioxidant in the present invention Addition be all avoided that the high density polyethylene (HDPE) course of processing produce gel, simultaneously obtain can increase HDPE melt The long-chain branch of body intensity.

Claims (7)

1. the preparation method of a long-branched high density polyethylene (HDPE), it is characterised in that described method includes:
(1) HDPE powder and antioxidant are premixed on mixing apparatus, obtain premix material；
(2) premix material is added process equipment of plasticating, carry out melt-processed；Melt processing temperature is 200～260 DEG C；The melt-processed time is: 1～6min；
(3) again add antioxidant, continue melting mixing uniform；
Described HDPE is the HDPE powder not adding antioxidant containing end-vinyl based on chromium-based catalysts Material；
In step (1), the addition of antioxidant is: 0～1000ppm.
2. the preparation method of long-branched high density polyethylene (HDPE) as claimed in claim 1, it is characterised in that:
Described antioxidant is the one in Hinered phenols antioxidant, phosphite ester kind antioxidant, sulfur-bearing antioxidant Or a combination thereof.
3. the preparation method of long-branched high density polyethylene (HDPE) as claimed in claim 2, it is characterised in that:
Described hindered phenol antioxygen be 2,6 ditertiary butyl p cresol, 2,6-di-tert-butyl-4-methy phenol, β- (3,5-di-t-butyl-4-hydroxy benzenes) propanoic acid octadecanol ester, 1,3,5-tri-(3,5-di-tert-butyl-4-hydroxyl benzyls) Isocyanuric acid；
Described phosphite antioxidant is three (2,4-di-tert-butyl-phenyl) phosphite ester, double (2,4-bis-tertiary fourths Base phenyl) pentaerythritol diphosphites, double (octadecyl) pentaerythritol diphosphites；
Described sulfur-bearing antioxidant is thio-2 acid double lauryl alcohol ester, stearic bicine diester base thiobis propanoic acid fat, 3,3'- The double tetradecane ester of thio-2 acid, 3,3'-thio-2 acid double tridecanol ester, thio-2 acid.
4. the preparation method of the long-branched high density polyethylene (HDPE) as described in one of claims 1 to 3, its feature exists In:
In step (2), melt processing temperature is the highest, and the melt-processed time is the longest, then antioxygen in step (1) The addition of agent is the most.
5. the preparation method of long-branched high density polyethylene (HDPE) as claimed in claim 4, it is characterised in that:
When being added without antioxidant in step (1), the melt processing temperature of step (2) is 200～230 DEG C, The melt-processed time is 2～3min.
6. the preparation method of the long-branched high density polyethylene (HDPE) as described in one of claims 1 to 3, its feature exists In:
In step (2), melt processing temperature is the highest, then the melt-processed time is the shortest.
7. the preparation method of the long-branched high density polyethylene (HDPE) as described in one of claims 1 to 3, its feature exists In:
The melting mixing time in step (3) is 30-90s.
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CN101437878A (en) * 2006-03-10 2009-05-20 陶氏环球技术公司 Polyethylene resins for sheet and thermoforming applications

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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

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多分散性对采用铬催化剂聚合的HDPE的热-机械降解的影响;杨逊嫥;《合成材料老化与应用》;19931001(第4期);49 *

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