CN105086095A - Polyethylene composition and preparation method thereof, and gas permeable film prepared from polyethylene composition - Google Patents
Polyethylene composition and preparation method thereof, and gas permeable film prepared from polyethylene composition Download PDFInfo
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Abstract
The present invention discloses a polyethylene composition and a preparation method thereof, and a gas permeable film prepared from the polyethylene composition. The polyethylene composition comprises a polymer component, an inorganic filler, a coupling agent, a dispersing agent and full-vulcanization powder rubber. The preparation method comprises: mixing the inorganic filler, the polymer component and at least one optionally selected from the coupling agent, the dispersing agent and the full-vulcanization powder rubber, extruding, and pelletizing to obtain the polyethylene composition, wherein the gas permeable film is prepared from the polyethylene composition. According to the present invention, the olefin polymer having the wide molecular weight distribution is introduced, such that the gas permeable film prepared from the polyethylene composition has characteristics of high stiffness, excellent appearance and good tensile property, and the production line speed of the gas permeable film product can be improved.
Description
Technical field
The present invention relates to processing modified plastics field, particularly, relate to a kind of polyethylene composition, the preparation method of this polyethylene composition, and the air-permeable envelope prepared by this polyethylene composition.
Background technology
Air-permeable envelope is a kind of is matrix with thermoplastics, fill the matrix material of the inorganic particulate of high-content, film is made through calendering or the method such as curtain coating, blowing, then further by single shaft or biaxial stretch-formedly obtain the tiny and mutually through microporous film material in aperture, the water vapour molecule that this film only can allow molecular structure less through, and cannot allow the water droplet penetration in state of aggregation is passed through, therefore there is the feature of permeable watertight, thus reach the effect of Waterproof Breathable.
In theory, thermoplastics all can be used as the matrix resin of air-permeable envelope material, because polyethylene has hand feel and drape softness, good toughness, widely use as air-permeable envelope base resin material at present, be used for especially producing the related products such as disposable sanitary articles, water proof and moisture permeable material.
In prior art, patent application CN1668689A discloses a kind of air-permeable envelope, adopts bimodal polyethylene composition to prepare air-permeable envelope, the melt flow rate (MFR) MFR of this bimodal polyethylene composition
2for 0.1-4g/10min, density is 918-935kg/m
3, the density of pe prepared by the method is still lower, can not meet the stiffness requirement of final air-permeable envelope, be difficult to improve production rate in follow-up printing, recombining process, and easily occur fold, affect quality product, the requirement of the method to instrument and supplies is higher, and technical difficulty is larger.
Patent application CN1281870A discloses a kind of for high working property and infiltrative air-permeable envelope composition, polyethylene is not only contained, also containing polypropylene, ethylene-propylene copolymer and other polyolefin resin in its composition, although the physicals of air-permeable envelope can be improved to a certain extent, but its constituent species is many, poor compatibility between component, be unfavorable for the improvement effect of performance, and the stability of product is not easy to control.
Patent application CN101591458A discloses a kind of production method of air-permeable envelope, its body material is based on linear low density polyethylene, and be aided with Low Density Polyethylene to improve high processing characteristics of filling air-permeable envelope product, the particularly linear low density polyethylene product of metallocene catalysis, because its molecular weight distribution is narrower, processing characteristics is poor, more need add Low Density Polyethylene to improve processing characteristics, but Low Density Polyethylene add the raising that also can cause the cost of air-permeable envelope product to a certain extent.
Summary of the invention
The object of the invention is to adopt that the air-permeable envelope stiffness prepared of existing polyethylene composition is not high, tensile property is poor, outward appearance is bad and the not high defect of line speed in the course of processing, the air-permeable envelope a kind of new polyethylene composition and preparation method thereof being provided and being prepared by this polyethylene composition to overcome.
To achieve these goals, the invention provides a kind of polyethylene composition, described polyethylene composition contains polymeric constituent and mineral filler, described polymeric constituent is the blend of the first olefin polymer or the first olefin polymer and the second olefin polymer, described first olefin polymer is molecular weight distributing index is 6-12, is preferably the ethene polymers of 8-10; Wherein, with the gross weight of described polyethylene composition for benchmark, the content of described polymeric constituent is 40-60 % by weight, and the content of described mineral filler is 60-40 % by weight.
Present invention also offers the preparation method of above-mentioned polyethylene composition, the method comprises: mineral filler mixed with at least one in polymeric constituent and optional coupling agent, dispersion agent and fully vulcanized powder rubber, then carries out extruding and granulation.
Present invention also offers a kind of air-permeable envelope, described air-permeable envelope is made up of polyethylene composition described above.
In polyethylene composition provided by the invention, by introducing the olefin polymer had compared with wide molecular weight distribution, make the air-permeable envelope product adopting this polyethylene composition to prepare have higher stiffness, excellent outward appearance and good tensile property, and the line speed of air-permeable envelope product can be improved.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of polyethylene composition, described polyethylene composition contains polymeric constituent and mineral filler, described polymeric constituent is the blend of the first olefin polymer or the first olefin polymer and the second olefin polymer, described first olefin polymer is molecular weight distributing index is 6-12, is preferably the ethene polymers of 8-10; Wherein, with the gross weight of described polyethylene composition for benchmark, the content of described polymeric constituent is 30-70 % by weight, and the content of described mineral filler is 30-70 % by weight.
Under preferable case, in described polyethylene composition, with the gross weight of described polyethylene composition for benchmark, the content of described polymeric constituent is 35-65 % by weight, is more preferably 40-60 % by weight; The content of described mineral filler is 35-65 % by weight, is more preferably 40-60 % by weight.
In the present invention, the molecular weight distributing index of olefin polymer records according to gel permeation chromatography method.
In the present invention, described polymeric constituent is preferably the first olefin polymer.
According to the present invention, the melting index of described first olefin polymer can be 2-10g/10min, is preferably 4.5-8g/10min; Density can be 0.937-0.955g/cm
3, be preferably 0.94-0.95g/cm
3.In the present invention, the melting index of olefin polymer, according to ISO1133-2005, adopts meltflow ability tester to record, probe temperature 190 DEG C, load 2.16Kg.
In the preferred case, described first olefin polymer is the multipolymer of at least one in ethene and butylene, hexene and octene.And in described multipolymer, the content derived to the structural unit of ethene for 1.5-6 % by mole, can be preferably 2-5 % by mole.
Further preferably, described first olefin polymer comprises the low molecular weight part of 40-45 % by weight and the high molecular weight moieties of 55-60 % by weight.Described low molecular weight part and described high molecular weight moieties are the multipolymer of at least one in ethene and butylene, hexene and octene, and the number-average molecular weight of described low molecular weight part can be 4000-6000, the number-average molecular weight of described high molecular weight moieties can be 8000-16000.More preferably, the melting index of described low molecular weight part is 500-750g/10min, is preferably 550-650g/10min; Density is 0.95-0.975g/cm
3, be preferably 0.96-0.97g/cm
3.
According to the present invention, in the blend, with the gross weight of described blend for benchmark, the content of described first olefin polymer can be 50-99 % by weight, is preferably 60-90 % by weight, is more preferably 70-80 % by weight; The content of described second olefin polymer can be 1-50 % by weight, is preferably 10-40 % by weight, is more preferably 20-30 % by weight.
According to the present invention, described second olefin polymer is different from described first olefin polymer.Described second olefin polymer can be one or more in linear low density polyethylene, high density polyethylene(HDPE), Low Density Polyethylene, polypropylene and ethylene-vinyl acetate copolymer, be preferably linear low density polyethylene, particularly metallocene catalysis linear low density polyethylene.
According to the present invention, the particle diameter of described mineral filler can be 0.05-20 μm, is preferably 0.1-10 μm, is more preferably 0.2-5 μm.
According to the present invention, there is no particular limitation in described mineral filler, and the various mineral fillers that this area routine uses all are applicable to the present invention.Under preferable case, described mineral filler is one or more in calcium carbonate, talcum powder, titanium dioxide, silicon-dioxide, barium sulfate, calcium sulfate and wollastonite, most preferably is calcium carbonate.
According to the present invention, described polyethylene composition can also contain coupling agent.Described coupling agent can be included in described polyethylene composition with the content range of this area routine, and under preferable case, the content of described coupling agent is 0.1-0.5 % by weight.There is no particular limitation in the present invention for the kind of described coupling agent, and the various coupling agents that this area routine uses all are applicable to the present invention.Under preferable case, described coupling agent is one or more in stearic acid, stearate, titanate coupling agent, aluminate coupling agent and silane coupling agent, most preferably is titanate coupling agent.
According to the present invention, described polyethylene composition can also contain dispersion agent.Described dispersion agent can be included in described polyethylene composition with the content range of this area routine, and under preferable case, the content of described dispersion agent is 0.1-0.5 % by weight.There is no particular limitation in the present invention for the kind of described dispersion agent, and the various dispersion agents that this area routine uses all are applicable to the present invention.Under preferable case, described dispersion agent is one or more in polyethylene wax, Poly Propylene Wax, amine hydroxybenzene, stearylamide, erucicamide, palmitic amide, stearyl erucamide, ethylenebisstearamide and ethylenebisoleoamide, most preferably is polyethylene wax.
According to the present invention, described polyethylene composition can also contain fully vulcanized powder rubber.Described coupling agent can be included in described polyethylene composition with the content range of this area routine, and under preferable case, the content of described fully vulcanized powder rubber is 1-10 % by weight.There is no particular limitation in the present invention for described fully vulcanized powder rubber, and the various fully vulcanized powder rubbers that this area routine uses all are applicable to the present invention.Under preferable case, described fully vulcanized powder rubber is one or more in full sulfuration styrene-butadiene rubber(SBR), full sulfuration carboxylic styrene-butadiene rubber, full vulcanized acrylate rubber, full-sulfurized nitrile rubber, full sulfuration carboxy nitrile rubber, full sulphurated siliastic and full sulfuration vinylpyridiene-styrene-butadiene rubber, most preferably is full sulfuration styrene-butadiene rubber(SBR) and/or full sulfuration carboxylic styrene-butadiene rubber.
Present invention also offers the preparation method of above-mentioned polyethylene composition, the method comprises: mineral filler mixed with at least one in polymeric constituent and optional coupling agent, dispersion agent and fully vulcanized powder rubber, then carries out extruding and granulation.
When needing in described method to add at least one in coupling agent, dispersion agent and fully vulcanized powder rubber, above-mentioned mixing process can be: mineral filler mixed with at least one in coupling agent, dispersion agent and fully vulcanized powder rubber, and then is mixed with polymeric constituent by the mixture obtained; Also can be: at least one added in process that surface-treated mineral filler mixes with polymeric constituent in dispersion agent, fully vulcanized powder rubber will be carried out by coupling agent.Under preferable case, by the process that mineral filler mixes with at least one in polymeric constituent and coupling agent, dispersion agent and fully vulcanized powder rubber be: first mineral filler is mixed with coupling agent and carry out surface treatment, and then at least one mixing added in dispersion agent and fully vulcanized powder rubber, finally again the mixture obtained is mixed with polymeric constituent.
In described method provided by the invention, described in extrude and mode well-known to those skilled in the art can be adopted to implement with the process of granulation, do not repeat them here.
Present invention also offers a kind of air-permeable envelope, described air-permeable envelope is made up of polyethylene composition of the present invention.This air-permeable envelope has higher stiffness, excellent outward appearance and good tensile property.
Below will be described the present invention by embodiment.
In following examples and comparative example, melting index, according to ISO1133-2005, adopts meltflow ability tester to record, probe temperature 190 DEG C, load 2.16Kg, density records according to GB/T1033-2010, and number-average molecular weight and molecular weight distributing index are recorded by gel permeation chromatography.
Preparation example 1
Obtain a kind of polyethylene compared with wide molecular weight distribution (BMWD-PE) by polymerization process, selected comonomer is butylene, and wherein, low molecular weight part is high density polyethylene(HDPE), and its melting index is 560g/10min, and density is 0.963g/cm
3, its proportion in polyethylene is 41 % by weight; High molecular weight moieties is linear low density polyethylene, and its proportion in polyethylene is 59 % by weight.The melting index of the BMWD-PE obtained is 4.5g/10min, and density is 0.942g/cm
3, molecular weight distributing index is 9.3.
Embodiment 1
The calcium carbonate being 2 microns by 50 weight part particle diameters adds in high-speed mixer, design temperature is 110 DEG C, stir under the rotating speed of 1500r/min after 10 minutes, add 0.5 weight part titanate coupling agent (fly chemistry institute purchased from Nanjing Xiang, the trade mark is NXT-102) and continue stirring 10 minutes; Then, add 0.5 parts per weight dispersing agent polyethylene wax (purchased from DOWPOL company, the trade mark is DP0060P) and continue stirring 10 minutes; Finally, add the BMWD-PE50 weight part of preparation in the preparation example 1 of powdery, after being uniformly mixed under the rotating speed of 750r/min, join in twin screw extruder, extrude after melt blending, granulation obtains polyethylene composition, in preparation process, the consumption of each component is as shown in table 1.This polyethylene composition obtains air-permeable envelope through curtain coating, stretching.The performance test results and the line speed of air-permeable envelope are as shown in table 2.
Embodiment 2
The calcium carbonate being 6 microns by 45 weight part particle diameters adds in high-speed mixer, and design temperature is 115 DEG C, stirs after 10 minutes, add 0.5 weight part titanate coupling agent and continue stirring 10 minutes under the rotating speed of 1500r/min; Then, adding particle diameter is 80 nanometers, and gel content is full sulfuration styrene-butadiene rubber(SBR) (Sinopec Beijing Chemical Research Institute produces, and the trade mark is VP101) 5 weight parts of 80%, polyethylene of dispersing agent wax 0.5 weight part, and continues stirring 10 minutes; Finally, add BMWD-PE45 weight part in the preparation example 1 of powdery, metallocene catalysis linear low density polyethylene (m-LLDPE) is (purchased from Sinopec asphalt in Shenli Refinery, the trade mark is QHM23F) 5 weight parts, after being uniformly mixed under the rotating speed of 750r/min, join in twin screw extruder, extrude after melt blending, granulation obtains polyethylene composition, in preparation process, the consumption of each component is as shown in table 1.This polyethylene composition obtains air-permeable envelope through curtain coating, stretching, and the performance test results and the line speed of air-permeable envelope are as shown in table 2.
Embodiment 3
The calcium carbonate being 8 microns by 50 weight part particle diameters adds in high-speed mixer, and design temperature is 120 DEG C, stirs after 10 minutes, add 0.5 weight part titanate coupling agent and continue stirring 10 minutes under the rotating speed of 1500r/min; Then, add polyethylene of dispersing agent wax 0.5 weight part, and continue stirring 10 minutes; Finally, add BMWD-PE37.5 weight part in the preparation example 1 of powdery, m-LLDPE12.5 weight part, after being uniformly mixed under the rotating speed of 750r/min, join in twin screw extruder, extrude after melt blending, granulation obtains polyethylene composition, in preparation process, the consumption of each component is as shown in table 1.This polyethylene composition obtains air-permeable envelope through curtain coating, stretching, and the performance test results and the line speed of air-permeable envelope are as shown in table 2.
Embodiment 4
Prepare polyethylene composition according to the method for embodiment 1, replace with talcum powder unlike by calcium carbonate.In this polyethylene composition preparation process, the consumption of each component is as shown in table 1.This polyethylene composition obtains air-permeable envelope through curtain coating, stretching, and the performance test results and the line speed of air-permeable envelope are as shown in table 2.
Embodiment 5
Polyethylene composition is prepared, unlike titanate coupling agent being replaced with silane coupling agent (purchased from Nanjing Pin Ning coupling agent company limited, the trade mark is KH-550) according to the method for embodiment 1.In this polyethylene composition preparation process, the consumption of each component is as shown in table 1.This polyethylene composition obtains air-permeable envelope through curtain coating, stretching, and the performance test results and the line speed of air-permeable envelope are as shown in table 2.
Embodiment 6
Polyethylene composition is prepared, unlike polyethylene wax being replaced with stearylamide (create Science and Technology Ltd. purchased from city far away, Wuhan, the trade mark is Stearamide) according to the method for embodiment 1.In this polyethylene composition preparation process, the consumption of each component is as shown in table 1.This polyethylene composition obtains air-permeable envelope through curtain coating, stretching, and the performance test results and the line speed of air-permeable envelope are as shown in table 2.
Comparative example 1
Polyethylene composition is prepared according to the method for embodiment 1, unlike BMWD-PE being replaced with normal linear Low Density Polyethylene (LLDPE) (purchased from Sinopec Maoming branch office, the trade mark is MLPE-8060), melting index is 5g/10min, molecular weight distributing index is 3.7, density 0.936g/cm
3.This polyethylene composition obtains air-permeable envelope through curtain coating, stretching, and the performance test results and the line speed of air-permeable envelope are as shown in table 2.
Comparative example 2
Prepare polyethylene composition according to the method for embodiment 1, replace with m-LLDPE unlike by BMWD-PE, wherein, m-LLDPE is pilot product, and melting index is 2g/10min, and molecular weight distributing index is 2.5.This polyethylene composition obtains air-permeable envelope through curtain coating, stretching, and the performance test results and the line speed of air-permeable envelope are as shown in table 2.
Comparative example 3
Polyethylene composition is prepared according to the method for embodiment 1, unlike BMWD-PE50 weight part being replaced with m-LLDPE45 weight part and Low Density Polyethylene (LDPE) (purchased from Sinopec Yanshan Mountain branch office, the trade mark is 1C7A) 5 weight parts, wherein, m-LLDPE is pilot product, melting index is 2g/10min, and molecular weight distributing index is the melting index of 2.5, LDPE is 7g/10min.This polyethylene composition obtains air-permeable envelope through curtain coating, stretching, and the performance test results and the line speed of air-permeable envelope are as shown in table 2.
Table 1
Table 2
As can be seen from the data of table 2, the air-permeable envelope adopting described polyethylene composition of the present invention to prepare has higher toughness and physical strength.Concrete, by embodiment 1 and comparative example 1 and 2 are compared and can find out, embodiment 1 adopts BMWD-PE can reduce processing temperature significantly as matrix resin, and enhance productivity, this is owing to playing interior lubricant effect compared with low molecular weight part in the BMWD-PE of wide molecular weight distribution, reduce the friction between molecular chain, be conducive to the raising of processing characteristics, reduce processing temperature, and high molecular weight moieties wherein gives the good melt strength of air-permeable envelope and the final mechanical property (as pull-off force and elongation at break) improving air-permeable envelope, improve line speed, improve the outward appearance of air-permeable envelope.Meanwhile, BMWD-PE density is higher, and prepared air-permeable envelope deflection significantly promotes, and is conducive to follow-up printing and recombining process, also provides possibility for the thinning further of air-permeable envelope.
By embodiment 1 and comparative example 3 are compared and can find out, in comparative example 3, a small amount of Low Density Polyethylene (LDPE) is added in metallocene catalysis linear low density polyethylene (m-LLDPE) is for matrix resin, processing characteristics can be improved to a certain extent, improve production efficiency and product quality, but it is very limited to improve effect; Meanwhile, the mechanical property of air-permeable envelope (as pull-off force and elongation at break) is made to have obvious reduction adding of Low Density Polyethylene.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (14)
1. a polyethylene composition, it is characterized in that, described polyethylene composition contains polymeric constituent and mineral filler, described polymeric constituent is the blend of the first olefin polymer or the first olefin polymer and the second olefin polymer, described first olefin polymer is molecular weight distributing index is 6-12, is preferably the ethene polymers of 8-10; Wherein, with the gross weight of described polyethylene composition for benchmark, the content of described polymeric constituent is 40-60 % by weight, and the content of described mineral filler is 60-40 % by weight.
2. polyethylene composition according to claim 1, wherein, the melting index of described first olefin polymer is 2-10g/10min, is preferably 4.5-8g/10min; Density is 0.937-0.955g/cm
3, be preferably 0.94-0.95g/cm
3.
3. polyethylene composition according to claim 1 and 2, wherein, described first olefin polymer is the multipolymer of at least one in ethene and butylene, hexene and octene, and the content derived to the structural unit of ethene is 1.5-6 % by mole, is preferably 2-5 % by mole.
4. polyethylene composition according to claim 1, wherein, described first olefin polymer comprises the low molecular weight part of 40-45 % by weight and the high molecular weight moieties of 55-60 % by weight; Described low molecular weight part and described high molecular weight moieties are the multipolymer of at least one in ethene and butylene, hexene and octene, and the number-average molecular weight of described low molecular weight part can be 4000-6000, the number-average molecular weight of described high molecular weight moieties can be 8000-16000.
5. the polyethylene composition according to claim 1 or 4, wherein, the melting index of described low molecular weight part is 500-750g/10min, is preferably 550-650g/10min; Density is 0.95-0.975g/cm
3, be preferably 0.96-0.97g/cm
3.
6. polyethylene composition according to claim 1, wherein, in the blend, with the gross weight of described blend for benchmark, the content of described first olefin polymer is 50-99 % by weight, be preferably 60-90 % by weight, the content of described second olefin polymer is 1-50 % by weight, is preferably 10-40 % by weight.
7. the polyethylene composition according to claim 1 or 6, wherein, described second olefin polymer is one or more in high density polyethylene(HDPE), Low Density Polyethylene, polypropylene and ethylene-vinyl acetate copolymer.
8. polyethylene composition according to claim 1, wherein, the particle diameter of described mineral filler is 0.05-20 μm, is preferably 0.1-10 μm, more preferably 0.2-5 μm.
9. the polyethylene composition according to claim 1 or 8, wherein, described mineral filler is one or more in calcium carbonate, talcum powder, titanium dioxide, silicon-dioxide, barium sulfate, calcium sulfate and wollastonite.
10. according to the polyethylene composition in claim 1,2,4,6 and 8 described in any one, wherein, described polyethylene composition is also containing coupling agent, described coupling agent content is preferably 0.1-0.5 % by weight, described coupling agent be preferably in stearic acid, stearate, titanate coupling agent, aluminate coupling agent and silane coupling agent one or more.
11. according to the polyethylene composition in claim 1,2,4,6 and 8 described in any one, wherein, described polyethylene composition is also containing dispersion agent, the content of described dispersion agent is preferably 0.1-0.5 % by weight, described dispersion agent be preferably in polyethylene wax, Poly Propylene Wax, amine hydroxybenzene, stearylamide, erucicamide, palmitic amide, stearyl erucamide, ethylenebisstearamide and ethylenebisoleoamide one or more.
12. according to claim 1, 2, 4, polyethylene composition in 6 and 8 described in any one, wherein, described polyethylene composition is also containing fully vulcanized powder rubber, the content of described fully vulcanized powder rubber is preferably 1-10 % by weight, described fully vulcanized powder rubber is preferably full sulfuration styrene-butadiene rubber(SBR), full sulfuration carboxylic styrene-butadiene rubber, full vulcanized acrylate rubber, full-sulfurized nitrile rubber, full sulfuration carboxy nitrile rubber, one or more in full sulphurated siliastic and full sulfuration vinylpyridiene-styrene-butadiene rubber, be more preferably full sulfuration styrene-butadiene rubber(SBR) and/or full sulfuration carboxylic styrene-butadiene rubber.
The preparation method of the polyethylene composition in 13. claim 1-12 described in any one, the method comprises: mineral filler mixed with at least one in polymeric constituent and optional coupling agent, dispersion agent and fully vulcanized powder rubber, then carries out extruding and granulation.
14. 1 kinds of air-permeable envelopes, is characterized in that, described air-permeable envelope is made up of the polyethylene composition in claim 1-12 described in any one.
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