CN106366222A - Polyethylene resin, preparation method and applications thereof - Google Patents
Polyethylene resin, preparation method and applications thereof Download PDFInfo
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- CN106366222A CN106366222A CN201510439502.9A CN201510439502A CN106366222A CN 106366222 A CN106366222 A CN 106366222A CN 201510439502 A CN201510439502 A CN 201510439502A CN 106366222 A CN106366222 A CN 106366222A
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Abstract
The present invention provides a polyethylene resin having a low wax content, wherein the density is 0.935-0.960 g/cm<3>, the melt flow rate is 25-120 g/10 min, the average particle size is 100-200 [mu]m, the bulk density is not less than 0.39 g/cm<3>, the weight average molecular weight Mw is 3.2-5.2*10<4> g/mol, the molecular weight distribution index Mw/Mn is 2.3-2.8, and the polyethylene wax content is not higher than 3.5%. The present invention further provides a preparation method of the high-density polyethylene resin, wherein polymerization is performed through a slurry polymerization reaction in the presence of a co-catalyst by adopting a supported metallocene catalyst as a main catalyst. According to the present invention, the prepared polyethylene resin has good chlorination performance, the solubility of the chlorination product is superior to the existing traditional HCPE chloride, and the polyethylene resin can be used for preparing chlorinated polyethylene adopted as the coating material.
Description
Technical field
The present invention relates to a kind of ethylene polymer resins and, its preparation method and its be used for preparation as coating high chlorinated polyethylene
The purposes of alkene.
Background technology
Chlorinated polyethylene (cpe) is the chlorizate of polyethylene (pe), and wherein pe obtains chlorinty through depth chlorination and is more than
60% cpe is commonly known as highly-chlorinated polyethylene (hcpe).Due to the saturability of strand, spatial distribution and high containing
Chlorine dose, imparts the excellent resistance to mineral oil of hcpe, corrosion-resistant, weather-proof, water resistance.Additionally, chlorine atom is highly polar base
Group, is in random distribution in strand, so enhancing the polarity of coating, be favorably improved the adhesive force of coating, intensity,
Thermostability and solvent resistant performance.Hcpe also has the advantages that excellent anti-flammability, soluble, mechanical property are good, is a kind of
Film forming matter well, can be used as pipeline, bridge, chemical industry equipment anticorrosive paint, anti-flaming dope and airport, road mark applies
Material and water-repellent paint.Its thermostability up to 100 DEG C, in terms of dechlorination stability, better than chlorinated rubber.Almost in all fields
Close and all can replace chlorinated rubber, CSM.
Hcpe can be produced using solid phase law technology or solution law technology.So-called solid phase law technology, is that chlorine is passed directly into solid
In polyethylene powders, directly carry out gas-solid phase reaction in ebullated bed and obtain hcpe.This method is due to removing heat difficulty, and reacts
Difficult quality controls and is phased out.Solution law technology refers to pe is dissolved in carbon tetrachloride solution, carries out after being passed through chlorine
The method that liquid phase reactor obtains hcpe.This method chlorination uniformly, reacts easily controllable, properties of product stable homogeneous.But produce
Used in the process of carbon tetrachloride easily enter air, cause depletion of the ozone layer, and also can remain carbon tetrachloride in finished product, thus
Equally gradually eliminate.Recent year develops aqueous phase law technology and produces hcpe, i.e. suspension pe in an aqueous medium, and plus
Enter emulsifying agent, dispersant and initiator, carry out suspension chlorination to prepare hcpe.Water phase suspension due to simple production process,
Post processing cost is low, and on welcoming, impact is little, rapidly becomes the main flow production technology of domestic hcpe.
Although Aqueous phase suspension chlorination produces hcpe technology has obtained successful Application, the selection of polyethylene raw material is met
Arrive larger difficulty.Hcpe is mainly used for coating it is desirable to the viscosity of hcpe is very low, thus pe raw material used
Molecular weight is more much lower than common pe molecular weight.Also there is no the chlorizated raw material dedicated for hcpe in the market.hcpe
Manufacturer generally using higher injection molding material of melt flow rate (MFR) such as ldpe etc. after milling for producing hcpe.This
The cost that aspect causes raw material increases, and on the other hand, traditional low molecular weight polyethylene contains more Tissuemat Es,
Easily melt in advance in chlorination process and lead to glutinous viscous between granule, cause the inequality of the even chlorination of product particle skewness
Even, thus adversely affecting to the solubility property of hcpe, serious in the case of, in chlorination process, reactant is in kettle
Overall bonding, causes the accident.
Content of the invention
The purpose of the present invention is on existing technical foundation, provides a kind of polyvinyl resin, and it not only has thin and uniform
Particle diameter, melt flow rate (MFR) is high, weight average molecular weight is low, and molecular weight distributing index is narrow, and content of polyethylene wax low so as to
Good chlorination performance is represented, after chlorination, the solubility property of product is better than existing tradition hcpe's in the chlorination process in later stage
Chloride, can be applicable to prepare the chlorinated polyethylene as coating.
The technical solution used in the present invention is as follows: polyvinyl resin is 0.935～0.960g/cm for density3, melt flow rate (MFR)
For 25～120g/10min, mean diameter is 100～200 microns, and bulk density is not less than 0.39g/cm3, weight average molecular weight mw
For 3.2～5.2 × 104G/mol, molecular weight distributing index mw/mn are 2.3～2.8, and Tissuemat E mass content is not higher than 3.5%.
Wherein, described polyvinyl resin is Alathon or ethylene and alpha olefin copolymer.
Described alpha-olefin is propylene, butene-1, hexene -1 and octene-1, preferably propylene, butene-1 and hexene -1, most preferably
Butene-1.
The present invention also provides a kind of preparation method of above-mentioned polyvinyl resin, with carried metallocene catalyst as major catalyst,
In the presence of promoter, so that ethylene homo or ethylene is closed with alpha-olefin copolymer by slurry polymerization and obtain institute
The polyvinyl resin stated.
Concrete preparation process is as follows:
1) first in reactor, add alkane solvent, add major catalyst carried metallocene catalyst and promoter alkyl
Aluminum, and it is warming up to 70～85 DEG C with continuous stirring；
2) add molecular weight regulator h in reactor2And alpha-olefin as comonomer, and continuously it is passed through ethylene, adjust ethylene
It is passed through pressure 0.5～0.8mpa in maintenance reactor and carry out slurry polymerization 2 hours；
3), after reaction terminates, stop being passed through ethylene, by outer circulation water, material in reactor temperature is reduced to 25 ± 1 DEG C, emptying
Reacting kettle inner pressure, releases polymer slurries, obtains described polyvinyl resin through solid-liquid separation with after being dried.
Above-mentioned preparation process can carry out in circle shaped tube type reactor or batch type kettle reactor in carry out；Comonomer
Alpha-olefin can select to be dividedly in some parts or disposably add；
In order to preferably major catalyst and promoter are dispersed in alkane solvent, described alkane solvent be selected from iso-butane,
Pentane, hexane or heptane, preferably iso-butane, pentane or hexane, further preferred iso-butane or hexane.
In order to synthesize the density of the required polyvinyl resin of invention, the addition of alpha-olefin is preferred with the mol ratio of ethylene addition
0～1.2.
In step 2) in, being added to of hydrogen adjusts melt flow rate, and because catalyst is different, hydrogen
Sensitivity differences are also very big, and therefore, the addition of hydrogen and addition scope can be according to polymerizate melt flow rate (MFR) Lai really
Fixed.
Described promoter alkyl aluminum is triethyl aluminum；
The present invention also provides described polyvinyl resin to be used as in the chlorinated polyethylene of coating to apply in preparation.
Carried metallocene catalyst used in the present invention is disclosed in patent us4701432a；
The present invention adopts carried metallocene catalyst, with continuous and batch slurry process polymerisation method, polymerization with existing
The suitable high density polyethylene (HDPE) powder of ziegler-natta catalyst molecule amount, make use of metallocene PE relative molecular mass to divide
Cloth is narrow, and normal heptane can the low feature of extract content.Compared with conventional polyethylene, can be effectively by the polyethylene in polyethylene
Wax content reduces by more than 50%.Additionally, the insertion of comonomer uniformly, forms more general in metallocene PE macromolecular chain
Chemical constitution that polyethylene is more uniformly distributed, can it is ensured that being not in long methylene sequences unit in a large number in polyethylene macromolecular chain
Avoid the formation of blocked up lamellar structure, be conducive to diffusion and the insertion reaction of initiator and chlorine, that improves polymer can chlorination
Property.
Thin and uniform particle diameter is not only had using the polyvinyl resin of present invention preparation, melt flow rate (MFR) is high, Weight-average molecular
Amount low, molecular weight distributing index is narrow, and content of polyethylene wax low so as to represent good chlorination in the chlorination process in later stage
Performance, after chlorination, the solubility property of product is better than existing tradition HCPE, is particularly suited for preparation as painting
The chlorinated polyethylene of material.
Specific embodiment
Below by specific embodiment, technical solutions according to the invention are further described in detail, but it is necessary to note that
Following examples are served only for the description to content of the invention, do not constitute limiting the scope of the invention.
For preferably describing hcpe provided by the present invention pe resin and its manufacture method, following examples are suitable narration
May be different with the statement in description content of the invention in sequence, but do not interfere with those skilled in the art to content of the invention
Understand.
Melt flow rate (mfi) measures reference standard gb/t 3682-2008 to be carried out, and measures respectively at 190 DEG C
Mfi under 2.16 kilograms of loads；
The density measurement of polymer is carried out with reference to gb 1033.1-2008；
The apparent density of polymer measures and carries out with reference to gb/t 1636-2008；
Polymer particle size distributional analysiss are carried out on beckman coulter ls230 type laser particle size analyzer, granulometry model
Enclose 0.04～2000 micron.
The relative molecular mass and its distribution of polymer adopts the gpcv-2000 type gel permeation chromatography that pl company of Britain produces
Instrument measures, and trichloro-benzenes are solvent, 150 DEG C of temperature, and polystyrene standards correct.
The test of Tissuemat E mass content is carried out in such a way:
Weigh some grams of (typically taking 10 grams) polyethylene powders samples, be put in the extraction paper web of known weight, by paper web and
Sample is together put into equipped with the extractor of normal heptane, then extractor is put in constant temperature oil bath, and at 80 ± 2 DEG C, extraction 6 is little
When.After extraction finishes, the extraction paper web containing residual polymer is placed in vacuum drying oven, is dried to constant weight at 90 DEG C,
Then move in silica dehydrator case, cooling was weighed (being accurate to 0.1mg) after 30 minutes, and wax content calculates according to the following formula:
In formula: x normal heptane can extract content, %；m1Sample mass before extraction, g；m2Sample after extraction is dry
Quality, g.Result takes the meansigma methodss measuring twice, and its deviation is not more than 5%.
In embodiment, the preparation of hcpe adopts water phase suspension to prepare.Specifically, by weight ratio, in 100 parts of water
Sequentially add 0.2 part of dispersant (polyvinyl alcohol), 0.005 part of suspension stabilizer (SYNPERONIC PE/F68),
0.03 part of emulsifying agent (Polyethylene Octylphenol Ether), adds described hcpe pe toner (5～5.5 under agitation
Part), after being sufficiently stirred for, add initiator peroxidating two by chuck hot water heating to 35-45 DEG C, then the water to after heat up
0.02～0.03 part of benzoyl (bpo), 0.015～0.025 part of initiator cumyl peroxide (dcp), in air-proof condition
Under continue to be heated to 60 DEG C after, be passed through chlorine in the water after secondary temperature elevation, chlorine total amount be 22 weight portions.Chlorination process divides
Three sections are carried out, one section of be passed through chlorine total amount 55%, and in 75～88 DEG C of temperature, pressure, <under the conditions of 0.2mpa, reaction 2.5～3 is little
When, two-stage nitration is passed through the 25% of chlorine total amount, 95～103 DEG C, pressure <under the conditions of 0.3mpa react 1.2～1.8 hours, three sections
It is passed through remaining chlorine, < react 1.5～1.8 hours under the conditions of 0.4mpa in 130～135 DEG C of temperature, pressure.Logical chlorine reaction completes
Afterwards, cool to 60 DEG C, obtain hcpe mother solution, be separated by filtration, wash, neutralizing, being centrifuged, being dried, prepared chlorinty
In 65～68% hcpe product.
The sample preparation of hcpe is carried out according to hg/t 2704-2002 standard；
The chloride content determination of hcpe is carried out by the b method in gb/t 7139-2002；
- 4 glasss of flow cups of the painting of hcpe are measured by gb/t1723-93.
Embodiment 1
According to the hcpe of present invention pe resin, it is prepared as follows: in 300 liters of reactor, 1) add 200
Rise hexane solvent；Rinsed by 1l hexane, disposable addition carried metallocene catalyst and promoter triethyl aluminum are (own
Alkane solvents, concentration is 0.88mol/l), open stirring, speed of agitator is 250rpm, pass through outer circulation water by reactor simultaneously
Interior material is heated to 70～85 DEG C；
2) disposable 5 grams of the hydrogen of addition in reactor, is continuously passed through ethylene, is dividedly in some parts comonomer 1-butylene 200g simultaneously；
Regulation ethylene is passed through pressure 0.5～0.8mpa in maintenance reactor and carries out slurry polymerization 2 hours, and during this, ethylene is total
Addition is 22kg.
3), after reaction terminates, stop being passed through ethylene, by outer circulation water, material in reactor temperature is reduced to 25 DEG C, emptying is anti-
Answer pressure in kettle, release polymer slurries, obtain polyethylene powder resin through solid-liquid separation with after being dried.
The test result of this polyvinyl resin is shown in Table 1；The performance of polyvinyl resin chlorization product is shown in Table 2.
Embodiment 2
Difference from Example 1 is:
Solvent is changed to iso-butane, and added hydrogen is 4 grams, and comonomer butene -1 is changed to hexene -1, and addition is changed to 75 grams；
The test result of this polyvinyl resin is shown in Table 1；The performance of polyvinyl resin chlorization product is shown in Table 2.
Embodiment 3
Difference from Example 1 is:
Added hydrogen is changed to 3 grams, and comonomer addition is changed to 100 grams；
The test result of this polyvinyl resin is shown in Table 1；The performance of polyvinyl resin chlorization product is shown in Table 2.
Embodiment 4
Difference from Example 1 is:
Added hydrogen is changed to 2 grams, and comonomer is changed to propylene, and addition is 5 grams；
The test result of this polyvinyl resin is shown in Table 1；The performance of polyvinyl resin chlorization product is shown in Table 2.
Comparative example 1
200 liters of hexane solvents are added in 300 liters of reactors；Rinsed by 1l hexane, disposably add ziegler-natta
Catalyst (bch catalyst) and promoter triethyl aluminum (hexane solvent, concentration is 0.88mol/l), open stirring,
Speed of agitator is 250rpm, by outer circulation water, material in reactor is heated to 70～85 DEG C simultaneously；Disposable addition hydrogen
500 grams, continuously it is passed through ethylene, be dividedly in some parts 100g comonomer butene -1 simultaneously；Adjust ethylene to be passed through in maintenance reactor
Pressure 0.5～0.8mpa carries out slurry polymerization 2～3 hours.Stop being passed through ethylene, by outer circulation water by thing in reactor
Material temperature degree is reduced to 25 DEG C, is vented reacting kettle inner pressure, releases polymer slurries, obtains powdery second through solid-liquid separation with after being dried
Alkene polymer.
The test result of comparative example high density polyethylene (HDPE) is shown in Table 1.
The performance of high density polyethylene (HDPE) chlorization product is shown in Table 2.
Comparative example 2
Essentially identical with comparative example 1, only alpha-olefin is changed to propylene, and addition is changed to 110 grams, and added hydrogen is changed to 200
Gram.
The test result of comparative example high density polyethylene (HDPE) is shown in Table 1.
The performance of high density polyethylene (HDPE) chlorization product is shown in Table 2.
The performance of table 1 polyvinyl resin
| Performance | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 |
| Density (g/cm3) | 0.935 | 0.942 | 0.950 | 0.960 | 0.949 | 0.953 |
| mfi(g/10min) | 120 | 78 | 51 | 25 | 50 | 26 |
| Mean diameter (μm) | 101.2 | 122.5 | 156.4 | 198.6 | 142.7 | 153.1 |
| mn(104g/mol) | 1.3 | 1.3 | 1.8 | 2.1 | 0.96 | 1.2 |
| mw(104g/mol) | 3.2 | 3.7 | 4.2 | 5.2 | 4.6 | 5.3 |
| mw/mn | 2.4 | 2.8 | 2.3 | 2.5 | 4.8 | 4.5 |
| Bulk density (g/cm3) | 0.46 | 0.45 | 0.45 | 2.3 | 0.42 | 0.43 |
| Wax content (wt%) | 3.5 | 3.3 | 2.3 | 1.1 | 5.7 | 4.4 |
The performance of table 2 chlorinated polyethylene resin
As seen from the results in Table 1, can effectively obtain described polyethylene, resin density using the slurry polymerization processes of the present invention is
0.935～0.960g/cm3, melt flow rate (MFR) is 25～120g/10min, and mean diameter is 100～200 microns, piles up close
Degree is not less than 0.39g/cm3, weight average molecular weight mw is 3.2～5.2 × 104G/mol, molecular weight distributing index mw/mn are
2.3～2.8, Tissuemat E mass content is not higher than 3.5%.
As seen from Table 2 so as to represent good chlorination performance in the chlorination process in later stage, compared with control sample, through chlorine
The chlorinated polyethylene obtaining after change has lower volatile content, and after chlorination, the solubility property of product is better than existing
The chloride of the hdpe of ziegler-natta catalyst preparation, is particularly suited for preparing the chlorinated polyethylene as coating.
Claims (8)
1. a kind of polyvinyl resin is it is characterised in that described polyvinyl resin is 0.935～0.960g/cm for density3, melt
Body flow rate is 25～120g/10min, and mean diameter is 100～200 microns, and bulk density is not less than 0.39g/cm3, weight
Average molecular weight mw is 3.2～5.2 × 104G/mol, molecular weight distributing index mw/mn are 2.3～2.8, and Tissuemat E quality contains
Amount not higher than 3.5%.
2. polyvinyl resin according to claim 1 is it is characterised in that described polyvinyl resin is Alathon
Or ethylene and alpha olefin copolymer.
3. polyvinyl resin according to claim 1 and 2 is it is characterised in that described alpha-olefin is propylene, butylene
- 1, hexene -1 and octene-1.
4. the preparation method of the polyvinyl resin described in claim 1-3 any one claim is it is characterised in that with negative
Load type metallocene catalyst is major catalyst, in the presence of promoter, makes ethylene homo by slurry polymerization
Or ethylene is closed with alpha-olefin copolymer and obtains described polyvinyl resin.
5. polyvinyl resin according to claim 4 is it is characterised in that the addition of alpha-olefin and ethylene addition
Mol ratio is 0～1.2.
6. the polyvinyl resin described in claim 4 preparation method it is characterised in that
1) first in reactor, add alkane solvent, add major catalyst carried metallocene catalyst and promoter alkyl
Aluminum, and it is warming up to 70～85 DEG C with continuous stirring；
2) add molecular weight regulator h in reactor2And alpha-olefin as comonomer, and continuously it is passed through ethylene, adjust ethylene
It is passed through pressure 0.5～0.8mpa in maintenance reactor and carry out slurry polymerization 2 hours；
3), after reaction terminates, stop being passed through ethylene, by outer circulation water, material in reactor temperature is reduced to 25 ± 1 DEG C, emptying
Reacting kettle inner pressure, releases polymer slurries, obtains described polyvinyl resin through solid-liquid separation with after being dried.
7. polyvinyl resin according to claim 6 it is characterised in that described alkane solvent be selected from iso-butane, penta
Alkane, hexane or heptane.
8. the polyvinyl resin described in claims 1 to 3 any one claim is used as in the chlorinated polyethylene of coating in preparation
Application.
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| CN201510439502.9A CN106366222A (en) | 2015-07-23 | 2015-07-23 | Polyethylene resin, preparation method and applications thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112521539A (en) * | 2020-11-02 | 2021-03-19 | 中煤陕西榆林能源化工有限公司 | Method for improving granule yield by adjusting powder particle size distribution and granule production system |
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| CN101173011A (en) * | 2006-10-31 | 2008-05-07 | 中国石油化工股份有限公司 | Magnesium chloride load non-metallocene schiff base catalyst component, its manufacturing method and application |
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| CN101516931A (en) * | 2006-06-27 | 2009-08-26 | 尤尼威蒂恩技术有限责任公司 | Polymers made with metallocene catalysts, for use in rotomolding and injection molding products |
| CN101173011A (en) * | 2006-10-31 | 2008-05-07 | 中国石油化工股份有限公司 | Magnesium chloride load non-metallocene schiff base catalyst component, its manufacturing method and application |
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| CN112521539A (en) * | 2020-11-02 | 2021-03-19 | 中煤陕西榆林能源化工有限公司 | Method for improving granule yield by adjusting powder particle size distribution and granule production system |
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Application publication date: 20170201 |