CN104817752B - Polyethylene thin film and preparation method thereof - Google Patents
Polyethylene thin film and preparation method thereof Download PDFInfo
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- CN104817752B CN104817752B CN201510226718.7A CN201510226718A CN104817752B CN 104817752 B CN104817752 B CN 104817752B CN 201510226718 A CN201510226718 A CN 201510226718A CN 104817752 B CN104817752 B CN 104817752B
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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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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
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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
- C08K5/49—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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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Abstract
The invention discloses a polyethylene thin film, of which the technical parameters are described as follows: the thickness is not more than 40 [mu]m; the longitudinal tensile strength is not less than 70; the transversal tensile strength is not less than 120; the longitudinal elongation at break is not less than 310; the transversal elongation at break is not less than 70; the longitudinal heat shrinkage is not more than 4; the transversal heat shrinkage is not more than 4; and the haze is not more than 4.8. The polyethylene thin film is prepared through a bidirectional stretching method, so that the polyethylene thin film is less in required raw materials and is environment-friendly, which are the characteristics of the bidirectional stretching method. In addition, the performance parameters of the polyethylene thin film can reach even exceed those of a common polyethylene thin film even the thickness is reduced.
Description
Technical field
The present invention relates to polyethylene film and preparation method thereof, and in particular to polyethylene prepared by a kind of biaxial tension method is thin
Film and preparation method thereof.
Background technology
Polyethylene (abbreviation PE) is a kind of aggregated obtained crystalline thermoplastic resin of ethene, industrially, also including second
The copolymer of alkene and a small amount of alpha-olefin.Polyethylene odorless, nontoxic, feel ceraceous, fusing point is 100-130 DEG C.Its resistance to low temperature
It is excellent, good mechanical property can be still kept at -60 DEG C, but using temperature at 80~110 DEG C;Chemical stability is good, is resistant to
The erosion (intolerant to the acid with oxidizing property) of most of soda acids.Common solvent is not dissolved under normal temperature, water imbibition is little, electrical insulating property
It is excellent.
The chemical constitution of polyethylene, molecular weight, the degree of polymerization and other performances largely all rely on the polymerization for using
Method.Polymerization determines the type of side chain and side chain degree.Degree of crystallinity depends on that the alignment degree of part strand is experienced with it
Thermal history.Polyethylene according to polymerization, molecular weight height, chain structure difference, point high density polyethylene (HDPE), low density polyethylene (LDPE)
And LLDPE.Low density polyethylene (LDPE) (LDPE) is commonly called as polyethylene from high pressure process, its be at high pressure (100-300MPa),
High temperature (190-210C), radical polymerization under the conditions of peroxide catalyzed and produce, it is side chain chemical combination structure.Because close
Degree is relatively low, and material is most soft, is used primarily in plastic bag, film for agricultural use etc..High density polyethylene (HDPE) (HDPE) is commonly called as low-pressure polyethylene, its
Ziegler-Natta is carried out under lower pressure (15-30 atmospheric pressure) organic compound catalytic condition to be polymerized;It is this
Under the conditions of the polyethylene molecule that is polymerized be linear, and strand is very long, and molecular weight is up to hundreds of thousands.HDPE and LDPE and
LLDPE is compared, and has higher heatproof, oil resistivity, resistance to vapour permeability and environmental stress crack resistance, in addition electrical insulating property and anti-
Impact and cold tolerance very well, are mainly used in the fields such as blowing, injection.Linear low density polyethylene (LLDPE) (LLDPE), then be second
The copolymer that alkene is polymerized in the presence of a catalyst with a small amount of senior Α-alkene.LLDPE outward appearances are similar to LDPE, the transparency
More poor, only lustrous surface is good, with low-temperature flexibility, high-modulus, counter-bending and stress cracking resistance, impact strength under low temperature
Preferably the advantages of.Linear low density polyethylene (LLDPE) performance is similar to low density polyethylene (LDPE), and has some of high density polyethylene (HDPE) concurrently
Characteristic, energy ezpenditure is low produce in addition in, therefore development is extremely rapid, becomes one of most compelling new synthetic resin.
Polyethylene film is generally made using blow moulding or the tape casting, and Biaxial tension polyethylene film is a kind of newly developed
PE films, be the film produced using the method for flat embrane method biaxial orientation step drawing processing technology.At present, twin shaft takes
It is mainly used in the production of the films such as PP films, PA films and PET film to step drawing technique;But PE is due to the structure of itself
The technique productions cannot be used with crystallization situation.Biaxially oriented film has advantages below relative to general thin:50% film is light
Quantify, can make the thickness of packaging base material reduces by 50%, therefore can save ample resources, and significantly reduces cost;
The friendly of environment:Save resources, reduce the discharge of CO2, renewable recycling, do not use adhesive;User friendly:Tool
Standby line easy-tear performance, tearing notch is neat;Above the ordinary resistance to low temperature, there is excellent impact resistance and anti-pin hole under low-temperature condition
Energy.
In view of film prepared by biaxial tension method can be realized under the conditions of same performance compared with film prepared by conventional method
Reduce polyethylene a small amount of and therefore its relevant parameter can't reduce, thus the film prepared using the method is compared with conventional method
The film of preparation has lower cost and can also reduce environmental pollution.
The content of the invention
It is an object of the invention to solve the above problems, there is provided a kind of poly- second of the excellent performance prepared by biaxial tension method
Alkene film.
In order to achieve the above object, scheme of the present invention is:
A kind of polyethylene film, it is characterised in that the polyethylene film thickness is less than or equal to 40um, longitudinal tensile strength
More than or equal to 70, transverse tensile strength is more than or equal to 120, and longitudinal elongation at break rate is more than or equal to 310, and transverse breakage elongation is big
In equal to 70, longitudinal thermal contraction is less than or equal to 4, and horizontal thermal contraction is less than or equal to 4, and mist degree is less than or equal to 4.8.
Preferably, the polyethylene film is prepared by biaxial tension method;Prepare the poly- second that polyethylene film is used
Alkene product is prepared by polyvinyl resin and nucleator and additive;The MFR of the polyvinyl resin:80-120g/10min,
Cr contents are less than 3PPMW, and Ti contents are less than 3PPMW, nucleation agent content 0.05-0.3%.
Preferably, the polyvinyl resin is that the chromium-based catalysts are by titanium dioxide by chromium-based catalysts catalytic polymerization
Silicon, chromium oxide, titanium oxide, silicon fluoride and Organic Chromium composition, SiO2Content is more than or equal to 8%, Cr more than or equal to 85%, Ti contents
Content is more than or equal to 1%, and activity is more than or equal to 5000 times.
The preparation method of above-mentioned polyethylene film, the preparation method is comprised the following steps:
(1) granulate after polyvinyl resin and additive, nucleator being mixed by proportioning high-speed stirred;Additive is
Irganox 1010 and Irgafos 168, both account for total weight percent and are 0.05-0.10%, and nucleator is sorbierite, nothing
Machine salt, organic salt, nucleator accounts for total weight percent for 0.05-0.3%.
(2) above-mentioned particle is put in biaxial tension film-making machine, thickness is less than or equal to 40um after setting, then makes poly- second
Alkene film.
Preferably, the nucleator is organic calcium salt.
The polyethylene film of the present invention is prepared via biaxial tension method, and it possesses the materials that biaxial tension method has
The characteristics of few and environmental friendliness;Also, in the case where thickness is reduced, it can still reach or even surmount Plain PE film
The various performance parameters for being possessed.
Specific embodiment
Below, the present invention is described in detail in conjunction with specific embodiments, so that those skilled in the art can be preferably
The present invention is understood, so as to make clear restriction to protection scope of the present invention.
A kind of polyethylene film, it is characterised in that the polyethylene film thickness is less than or equal to 40um, longitudinal tensile strength
More than or equal to 70, transverse tensile strength is more than or equal to 120, and longitudinal elongation at break rate is more than or equal to 310, and transverse breakage elongation is big
In equal to 70, longitudinal thermal contraction is less than or equal to 4, and horizontal thermal contraction is less than or equal to 4, and mist degree is less than or equal to 4.8.The polyethylene film
Prepared by biaxial tension method;Prepare the polyethylene product that polyethylene film used be by polyvinyl resin and nucleator and
Prepared by additive;The MFR of the polyvinyl resin:80-120g/10min, Cr content is less than 3PPMW, and Ti contents are less than
3PPMW, nucleation agent content 0.05-0.3%.The chromium-based catalysts are by silica, chromium dioxide, titanium dioxide, silicon fluoride
With Organic Chromium composition, catalyst grain size is D50:20-50um, SiO2Content is more than or equal to 8% more than or equal to 85%, Ti contents,
Cr contents are more than or equal to 1%, and activity is more than or equal to 5000 times.
Catalyst is prepared using following steps:(1) silica-gel carrier (Davsion957) containing Cr is done below 200 DEG C
It is dry;(2) add it in reactor after silica-gel carrier cooling, add solvent hexane and titanium salt, stir, be then dried
Into the powder of flowing;(3) fluorine compounds are added in dried product, to move to be heated in high temperature furnace makes it less than 860 DEG C
Fully activation;(4) add it in reactor after cooling down, and add solvent and two luxuriant chromium, stir, be then dried to stream
Dynamic powder, obtains final product chromium-based catalysts.
Titanium salt is titanium tetrachloride, tetra isopropyl titanium etc.;Fluorine compounds are amido hexa-fluoride, and Davsion957 is commercial
Silica-gel carrier.
9 experiments are designed by method made above, the condition of each experiment is as shown in table 1.
The catalyst preparation of table 1
In order to carry out polymerization evaluation to the catalyst prepared by above-mentioned each experiment, by the catalyst of sample 1 to sample 9 by following
Condition carries out gas phase catalytic reaction, and polyethylene performance obtained in each laboratory sample catalysis is as shown in table 2.
Polymerizing condition:Reaction temperature:85℃;Reaction pressure:2.1MPa;C4/C2:0.1;H2/C2:0.07.
The polymerization evaluation of table 2
Sequence number | Project | Sample 1 | Sample 2 | Sample 3 | Sample 4 | Sample 5 | Sample 6 | Sample 7 | Sample 8 | Sample 9 |
1 | MI | 2.7 | 3.6 | 2.8 | 3.4 | 2.5 | 1.2 | 3.2 | 3.5 | 3.0 |
2 | MFR | 120 | 109 | 111 | 106 | 119 | 85 | 110 | 97 | 130 |
3 | D | 925 | 923 | 924 | 921 | 917 | 921 | 925 | 927 | 935 |
4 | Activity | 4500 | 5000 | 4700 | 4200 | 4050 | 3200 | 5000 | 5500 | 5600 |
In addition, in order to contrast the catalyst of preparation for the validity that polyethylene polymerization reacts, we are common from the market
Catalyst in randomly selected four as control sample, comparative example 1,2,3 is three kinds of common Chromium-polyethylencatalyst catalysts,
Can easily buy, comparative example 4 is a kind of commercial Titanium series catalyst.By four comparative examples in same gas-phase polymerization bar
Catalyzed polyethylene polymerisation under part, the performance of the polyethylene obtained by each catalyst is as shown in table 3.
The comparative catalyst's polymerization evaluation of table 3
Sequence number | Project | To 1 | To 2 | To 3 | To 4* |
1 | MI | 1.0 | 30 | 0.4 | 2.0 |
2 | MFR | 70 | 30 | 78 | 45 |
3 | D | 920 | 955 | 945 | 918 |
4 | Activity | 3000 | 5500 | 2500 | 6000 |
In table 2, table 3:MI refers to that the MI of polyethylene is melt index, and unit is g/10min;MFR refers to melt quality stream
Dynamic speed, unit is g/10min;D refers to the density of polyethylene, and unit is kg/m3;Activity refers to that catalyst polyethylene gathers
The fold activity for closing reaction, typically there is two kinds of computational methods, and a kind of is divided by the catalysis for adding by the yield of the polyethylene of gained
The amount of agent, another kind is the inverse for taking catalyst residue amount in product, and what is remained when can be burned by product during measurement is inorganic
The amount of thing calculates the residual volume of catalyst in product, and industrially latter is often used using former computational methods more than laboratory
Computational methods, the present invention adopts former computational methods.
By the analysis of above experimental data, sample 7 is a preferable sample in each laboratory sample.Below, by sample 7
Catalyst test different gas phase polymerisation conditions respectively, experimental condition and result are as shown in table 4:
The vapor phase method pilot scale polymerizing condition of table 4:
Sequence number | Project | Unit | 1# | 2# | 3# | 4# | 5#* | 6# | 7# | 8# |
1 | Temperature | ℃ | 85 | 80 | 90 | 95 | 85 | 105 | 95 | 85 |
2 | H2/C2 | %v | 0.07 | 0.05 | 0.09 | 0.07 | 0.07 | 0.07 | 0.07 | 0.07 |
3 | C4/C2 | %v | 0.1 | 0.1 | 0.05 | 0.1 | 0.1 | 0.05 | 0.1 | 0.1 |
4 | O2 | PPb | 10 | 100 | 300 | 100 | 200 | 0 | 0 | 0 |
5 | MI | g/10min | 3.2 | 2.5 | 5.0 | Caking | 1.0 | 30 | 0.4 | 2.0 |
6 | MFR | 110 | 115 | 105 | 70 | 30 | 78 | 45 | ||
7 | D | Kg/m3 | 925 | 926 | 930 | 920 | 955 | 945 | 918 | |
8 | Activity | 103 | 5.0 | 4.2 | 3.2 | 3.0 | 5.5 | 2.5 | 6.0 |
Gas-phase polymerization preferably polymerizing condition is:Polymerization temperature:80-90℃;H2/C2:0.05-0.09%v;C4/C2:
0.05-0.1%v;C4/C6:0.05-0.1%v;O2:0-300ppb.
Catalyst sample 7 is prepared into respectively 7 polyethylene by above-mentioned polymerizing condition, the polyethylene product specification for obtaining such as table 5
Shown in.
The polyethylene product specification of table 5
Sequence number | Project | Unit | F1 | F2 | F3 | F4 | F5 | F6 | F7 |
1 | MI | g/10min | 1.5 | 1.0 | 3.0 | 5.0 | 3.0 | 3.0 | 3.0 |
2 | MFR | 70 | 85 | 110 | 105 | 85 | 75 | 150 | |
3 | D | Kg/m3 | 920 | 920 | 925 | 930 | 930 | 920 | 925 |
4 | ASH | %w | < 0.03 | < 0.03 | < 0.03 | < 0.03 | < 0.03 | < 0.03 | < 0.03 |
5 | Activity | Times | 3000 | 3000 | 5000 | 3200 | 4000 | 3000 | Blending |
6 | Cr | PPM | < 3 | < 3 | < 3 | < 3 | < 3 | < 0.3 | 0 |
After the sample of following parameter and additive, nucleator will be met in above-mentioned each polyethylene product by proportioning high-speed stirred
Granulation, the sample parameters for obtaining are shown in Table 6.
Polyethylene product:MI:1-5g/10min;
MFR:80-120g/10min;
D:0.920-0.930g/cm3;
ASH:Less than 0.03%;
Cr contents:Less than 3PPMW;
Additive:Irganox 1010:0.05-0.10%;
Irgafos 168:0.05-0.10%;
Nucleator:0.05-0.30%.
Irganox 1010 and Irgafos 168 are two kinds of common additives, can easily be buied;Nucleator is
Sorbierite, inorganic salts, organic salt, organic calcium salt is better;Wherein, organic salt is a kind of preferably nucleator;ASH is ash
Point, i.e. the inorganic matter that PE left behind Jing after high temperature sintering.
The formula of special material of table 6
Sequence number | Project | Sample A | Sample B | Sample C | Sample D | Sample E | Sample F |
1 | Resin | F1 | F2 | F3 | F4 | F5 | F6 |
2 | Irganox 1010 | 0.1 | 0.1 | 0.1 | 0.05 | 0.1 | 0.1 |
3 | Irgafos 168 | 0.1 | 0.1 | 0.1 | 0.1 | 0.05 | 0.1 |
4 | Nucleator | 0.1 | 0.1 | 0.2 | 0.05 | 0.3 | 0.1 |
By above-mentioned A~F samples, PE films processed are processed through biaxial tension, thickness is set as that rear thickness is less than or equal to 40um.
Sample A, F are unable to film forming, and tensile property is poor.B, C, D, E filming performance is good, and each sample performance is shown in Table 7.
The performance of table 7PE films
Sequence number | Project | Sample B | Sample C | Sample D | Sample E | Contrast 1 |
1 | Tensile strength (vertical/horizontal) | 70/120 | 80/120 | 75/130 | 73/120 | 70/130 |
2 | Elongation at break (vertical/horizontal) | 380/210 | 350/150 | 310/70 | 320/110 | 300/100 |
3 | Thermal contraction (vertical/horizontal) | 4/3.2 | 3.5/3.3 | 4/3.5 | 3.1/4 | 3.9/3.5 |
4 | Mist degree | 4.2 | 3.9 | 4.8 | 4.5 | 5.3 |
Claims (3)
1. a kind of polyethylene film, it is characterised in that the polyethylene film thickness is less than or equal to 40 μm, and longitudinal tensile strength is big
In equal to 70, transverse tensile strength is more than or equal to 120, and longitudinal elongation at break rate is more than or equal to 310, and transverse breakage elongation is more than
Equal to 70, longitudinal thermal contraction is less than or equal to 4, and horizontal thermal contraction is less than or equal to 4, and mist degree is less than or equal to 4.8;
The polyethylene film is prepared by biaxial tension method;It is by gathering to prepare the polyethylene product that polyethylene film used
Vinyl is prepared with nucleator and additive;
The polyvinyl resin be by chromium-based catalysts catalytic polymerization, the chromium-based catalysts be by silica, chromium oxide,
Titanium oxide, silicon fluoride and Organic Chromium composition, SiO2Content is more than more than or equal to 85%, Ti contents more than or equal to 8%, Cr contents
Equal to 1%.
2. the preparation method of polyethylene film according to claim 1, it is characterised in that the preparation method includes following
Step:
(1) granulate after polyvinyl resin and additive, nucleator being mixed by proportioning high-speed stirred;Additive is Irganox
1010 and Irgafos 168, both account for total weight percent and are 0.05-0.10%, and nucleator is sorbierite, inorganic salts, has
Machine salt, nucleator accounts for total weight percent for 0.05-0.3%;
(2) above-mentioned particle is put in biaxial tension film-making machine, setting thickness is less than or equal to 40 μm, then makes polyethylene thin
Film.
3. preparation method according to claim 2, it is characterised in that the nucleator is organic calcium salt.
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US4011382A (en) * | 1975-03-10 | 1977-03-08 | Union Carbide Corporation | Preparation of low and medium density ethylene polymer in fluid bed reactor |
US4369295A (en) * | 1979-12-21 | 1983-01-18 | Phillips Petroleum Company | Impregnated second valence chromium compound in supported catalyst |
US7288596B2 (en) * | 2003-12-22 | 2007-10-30 | Univation Technologies, Llc | Polyethylene compositions having improved tear properties |
CN100400553C (en) * | 2006-02-25 | 2008-07-09 | 中国石油化工股份有限公司 | Improved catalyst system for ethylene polymerization or ethylene and alpha-olefin copolymerization |
CN102059836A (en) * | 2010-10-11 | 2011-05-18 | 中山火炬职业技术学院 | Thermal shrinkage biaxially oriented film |
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