CN109723090A - A kind of polyethylene composite geo-membrane and preparation method thereof - Google Patents
A kind of polyethylene composite geo-membrane and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of polyethylene composite geo-membrane, the polyethylene composite geo-membrane includes high-density polyethylene geomembrane, non-woven geotextile and the modified bisphenol A type epoxy adhesive between the high-density polyethylene geomembrane and non-woven geotextile；Wherein, the epoxide number of the modified bisphenol A type epoxy adhesive is 0.02-0.56eq/100g.Invention also provides the preparation methods of the polyethylene composite geo-membrane, including high-density polyethylene geomembrane and the modified bisphenol type epoxy adhesive of non-woven geotextile are hot bonding compound obtain.High-density polyethylene geomembrane of the invention has anti-aging layer and conductive layer, and there is preferable uvioresistant to be exposed to the sun ability, can resist prolonged exposure in sunshine for anti-aging layer；The conductivity and intensity of polyethylene composite geo-membrane can be substantially improved in conductive layer；Polyethylene composite geo-membrane of the invention has important economic value and realistic meaning.
Description
Technical field
The present invention relates to the preparation methods of a kind of polyethylene composite geo-membrane and the polyethylene composite geo-membrane.
Background technique
High-density polyethylene geomembrane and polyethylene composite geo-membrane are all the waterproof material with extremely low infiltration coefficient, mesh
Before be widely used in the fields such as water conservancy, the tailings glass in mine, Petrochemical, urban construction.But it is answered in actual production and engineering
In, both products still have some problems.
Firstly, high-density polyethylene geomembrane needs to spread below when in use in order to protect it from being exposed by sharp object
If one layer of non-woven geotextile is as protective layer, the two is individually laid with, and increases construction cost.
Secondly, the polyethylene composite geo-membrane used in the market, generallys use polyethylene film and non-woven geotextile is whole
Compound, although laying can once be constructed, it is pure polyvinyl resin production that polyethylene film used, which is by secondary recovery,
Without anti-aging modification, the polyethylene film anti-uv-ray is poor, and brittle destruction is easy to happen after long-time use.
Again, polyethylene composite geo-membrane is formed with non-woven geotextile by hot pressing roll pressing by polyethylene film, right
The process is not controlled properly easilys lead to polyethylene film and generate invisible small hole for the conditions such as temperature, speed, this
Some holes hole can become breakthrough in composite geo-membrane use process, seriously affect construction quality.
In addition, also due to when manufacture temperature process control unreasonable and polyethylene film for earthwork and both geotextiles
Thermal expansion coefficient is different, and the polyethylene composite geo-membrane of production is caused to be easy to generate warpage；In addition extraneous larger cold and hot change
Change can also make polyethylene composite geo-membrane that fold, crimp occur, and influence normal use.When polyethylene composite geo-membrane is laid with
After, it is also detected at present without breakthrough of the means to its small hole formation.
Therefore, develop it is that that resist warping of cold-resistant thermal change a kind of is combined through adhesive bonding, being capable of one-time laying
The high density polyethylene (HDPE) composite geo-membrane of construction is very necessary.
Summary of the invention
It is an object of the invention to according to technical problem of the existing technology, provide a kind of polyethylene composite geo-membrane and
Preparation method.Polyethylene composite geo-membrane of the invention is by high-density polyethylene geomembrane and the modified bis-phenol of non-woven geotextile
A type epoxy adhesive be hot bonding it is compound obtain, high-density polyethylene geomembrane have anti-aging layer and conductive layer, anti-aging layer
It is exposed to the sun ability with preferable uvioresistant, prolonged exposure in sunshine can be resisted；Conductive layer includes by modification
On the one hand the conductivity of polyethylene composite geo-membrane can be substantially improved in carbon fiber, can quick positioning searching breakthrough, it is another
Aspect can be improved polyethylene composite earthwork film strength；Thus polyethylene composite geo-membrane of the invention has important economy
Value and realistic meaning.
According to an aspect of the present invention, a kind of polyethylene composite geo-membrane, the polyethylene composite geo-membrane packet are provided
Include high-density polyethylene geomembrane, non-woven geotextile and between the high-density polyethylene geomembrane and non-woven geotextile
Modified bisphenol A type epoxy adhesive.
According to some embodiments of the present invention, the epoxide number of the modified bisphenol A type epoxy adhesive is 0.02-
0.56eq/100g, preferably 0.52-0.54eq/100g.
According to the preferred embodiment of the present invention, the modified bisphenol A type epoxy adhesive through bisphenol A type epoxy resin,
Curing agent and toughener blending are prepared.
According to certain embodiments of the present invention, the curing agent is fatty amine curing agent, preferably polyethers amine hardener.
Preferred embodiment in accordance with the present invention, the toughener are amino terminated liquid nitrile rubber.
It is the dosage of the curing agent in terms of 100 parts by bisphenol A type epoxy resin dosage in some specific embodiments
It is 45-55 parts, preferably 45-50 parts, more preferably 50 parts, the dosage of the toughener are 25-75 parts, preferably 30-60
Part.
High-density polyethylene geomembrane and non-woven geotextile are due to thermal expansion coefficient difference, when temperature varies widely
It will lead to composite geo-membrane and generate serious warpage, influence product quality.The bisphenol-A type epoxy adhesive crossed by toughening modifying,
Still there is biggish elongation, certain thickness this adhesive can be in high-density polyethylene geomembrane and nonwoven under room temperature
Buffer function is played between geotextiles, is guaranteed when temperature varies widely, high density polyethylene (HDPE) composite geo-membrane can be protected
Maintain an equal level whole.
According to some embodiments of the present invention, the high-density polyethylene geomembrane successively includes anti-aging layer from top to bottom
And conductive layer.Each thickness degree is according to the decision of the actual operation requirements of the polyethylene film for earthwork, the thickness of the preferably described anti-aging layer
Degree be 0.5~1.5mm, conductive layer with a thickness of 0.05~0.1mm.
It in some embodiments of the invention, is in terms of 100% by the weight of anti-aging layer, the anti-aging layer includes:
High-density polyethylene resin 80wt%~98wt%, preferably 88wt%~96wt%；
Carbon black color masterbatch 1wt%~15wt%, preferably 2wt%~10wt%；
Antioxidant 1wt%~5wt%, preferably 1wt%~2wt%；
In some specific embodiments, density >=0.930g/cm of the high-density polyethylene resin3, preferably
0.935~0.950g/cm3。
Preferred embodiment in accordance with the present invention, the carbonarius main bag includes polyethylene and carbon black, wherein the conductive black
Content of carbon black in color masterbatch is 30%~50%.
For the polyethylene, there is no particular limitation, selects polyvinyl resin commonly used in the art.
According to the preferred embodiment of the present invention, the antioxidant can be common using polyethylene field in the prior art
Antioxidant, dosage also use conventional amount used.The preferably mixture or commercially available of Hinered phenols antioxidant and phosphoric acid ester antioxidant
Hinered phenols antioxidant and phosphoric acid ester antioxidant compound antioxidant, such as the antioxidant B225 of BASF joint-stock company.
When antioxidant is selected from the mixture of Hinered phenols antioxidant and phosphoric acid ester antioxidant, Hinered phenols antioxidant and
The weight ratio of phosphoric acid ester antioxidant is preferably 1:1~1:3, more preferably 1:1.5~1:2.5.
The Hinered phenols antioxidant is more preferably from four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythrites
Ester, β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester, N, N'- is bis--(3- (3,5- di-t-butyl -4- hydroxyl
Base phenyl) propiono) hexamethylene diamine, at least one of 1,3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid；Institute
Phosphoric acid ester antioxidant is stated more preferably from three (2,4- di-tert-butyl-phenyl) phosphite esters, bis- (2,4-DTBP) seasons
At least one of penta tetrol diphosphites.
There is anti-aging layer preferable uvioresistant to be exposed to the sun ability, can resist prolonged exposure in sunshine；And it can
The heat-resistant air aging property for improving high-density polyethylene geomembrane, prolongs the service life.
It according to some embodiments of the present invention, is in terms of 100% by the weight of conductive layer, the conductive layer includes:
High-density polyethylene resin 80wt%~98wt%, preferably 90wt%~96wt%；
Carbon fiber 2wt%~20wt%, preferably 4wt%~10wt%；
Density >=0.930g/cm of the high-density polyethylene resin3, preferably 0.935~0.950g/cm3。
According to a particular embodiment of the invention, the carbon fiber be selected from polyacrylonitrile-based carbon fibre T300, T700 and
T800, fiber count 3k, 6k, 12k, 24k or 48k, preferably polyacrylonitrile-based carbon fibre T700,12k；The carbon fiber exists
Need to be surface-treated it using silane coupling agent before use, the silane coupling agent be preferably silane coupling A -151,
KH540 and KH551.
By the carbon fiber of surface modification treatment, the conductivity of polyethylene composite geo-membrane on the one hand can be substantially improved,
Can quick positioning searching breakthrough, on the other hand can be improved polyethylene composite earthwork film strength；Enable conductive layer
Simple shifting brush detecting devices is cooperated quickly to position breakthrough.
In some embodiments of the invention, the non-woven geotextile be selected from long filament or short silk polypropylene non-woven geotextiles and
Long filament or short silk PET non-woven geotextile, specification 100g/m2~300g/m2。
Preferred embodiment in accordance with the present invention, the non-woven geotextile of stating are selected from long filament polypropylene non-woven geotextiles and long filament
PET non-woven geotextile, specification 100g/m2~200g/m2。
According to another aspect of the present invention, a kind of preparation method of above-mentioned polyethylene composite geo-membrane is provided, including will
High-density polyethylene geomembrane is hot bonding compound obtain with the modified bisphenol type epoxy adhesive of non-woven geotextile.
According to certain embodiments of the present invention, the preparation method of polyethylene composite geo-membrane includes the following steps:
(1) high-density polyethylene resin, carbon black color masterbatch, antioxidant and carbon fiber according to anti-aging layer and are led respectively
The composition of each layer is made in the content melt blending of electric layer, then the high density polyethylene (HDPE) geotechnique is made in composition coextrusion
Film；
(2) bisphenol A type epoxy resin, toughener and curing agent are blended according to respective dosage, are made described and change
Property bisphenol type epoxy adhesive；
(3) the modified bisphenol A type epoxy adhesive obtained using step (2) is by high density polyethylene (HDPE) made from step (1)
Geomembrane, through be bonded, obtains the polyethylene composite geo-membrane through hot pressing is compound with non-woven geotextile.
According to some embodiments of the present invention, the step (1) includes:
1A) high-density polyethylene resin, carbon black color masterbatch and antioxidant are melted altogether according to the anti-aging layer content
It is mixed, double screw extruder extruding pelletization is then used, the anti-aging layer composition is obtained；
1B) by the high-density polyethylene resin and the carbon fiber being surface-treated through silane coupling agent according to the conductive layer
Then content melt blending uses double screw extruder extruding pelletization, obtains the conductive layer combination object；
The obtained composition of step 1A) and step 1B) is coextruded by double-layer coextrusion equipment 1C), is made containing anti-aging
The high-density polyethylene geomembrane of layer and conductive layer.
In addition, material can be blended according to the needs specifically processed in the process of high-density polyethylene geomembrane
Common processing aid in middle addition polyvinyl resin processing film, such as: lubricant, antistatic agent, dispersing agent, pigment etc.,
Its dosage is conventional amount used, or requirement according to the actual situation is adjusted.
In the process of polyethylene film for earthwork of the present invention, material melts blending temperature is usual polyethylene
Blending temperature used in processing, it should it will not be made to select in the range of decomposition not only guaranteeing that matrix resin melts completely,
Generally 180~200 DEG C.
In above-mentioned steps (1), various mixing equipments used in the prior art are can be used in the mixing apparatus of material, are such as stirred
Mix machine, kneading machine etc..Melt blending equipment used in the above method of the invention is the general blending in rubber and plastic processing industry
Equipment can be double screw extruder, BUSS is kneaded unit etc..It is preferred that double screw extruder, revolving speed is generally 200~
450rpm。
In above-mentioned steps (1), it is thin that coextrusion casting in the prior art can be used in the double-layer coextrusion equipment of each layer composition
Film device and coextrusion blow membrane equipment, the preferred single screw extrusion machine of extruder.
According to some embodiments of the present invention, for the step (2), there is no particular limitation, according to the routine of this field
Method carries out.Such as the bisphenol A type epoxy resin, toughener and curing agent can be glued according to modified bisphenol A type ring oxygen
The mixing of mixture content with the revolving speed degassing mixing 1min of 3000r/min in high mixer, obtains described change after mixing evenly
Property bisphenol type epoxy adhesive.
According to some embodiments of the present invention, for the step (2), there is no particular limitation, according to the routine of this field
Method carries out.
In a preferred embodiment of the invention, the modified bisphenol A type epoxy adhesive that step (2) obtains is evenly coated with
The conduction of the high-density polyethylene geomembrane made from step (1) is laminated, the non-woven geotextile is covered on, with pressure
Roller hot pressing it is compound to get arrive the polyethylene composite geo-membrane.
Wherein, the coating thickness of the modified bisphenol A type epoxy adhesive is 0.1-0.5mm；The compound pressure of the hot pressing
Roll temperature is 30-80 DEG C, preferably 50-70 DEG C.
Conductive layer of the present invention will connect metal plate with the one of DC power supply anode first when detecting breakthrough,
Metal plate is placed or cathode is connected on anti-aging layer, then with the removable brush detection of connection another electrode of DC power supply
Each panel region of anti-aging layer geomembrane.The voltage of the DC power supply is usually
Ten thousand volts of 3000V-1 or more.Since undermost conductive layer is electrically conductive, and the anti-aging color layers of top layer cannot
Conduction, metal plate and removable brush form a capacitor, are moved to Mobyneb polyethylene film for earthwork when working as removable brush
On the hole of polyethylene composite geo-membrane or when breakthrough, capacitor electric discharge will occur between conductive layer for removable brush, produce
Raw electric spark, so that it is determined that the position of hole breakthrough.
Polyethylene composite geo-membrane of the invention is by high-density polyethylene geomembrane and the modified bisphenol A-type of non-woven geotextile
Epoxy adhesive be hot bonding it is compound obtain, high-density polyethylene geomembrane have anti-aging layer and conductive layer, anti-aging layer tool
There is preferable uvioresistant to be exposed to the sun ability, prolonged exposure in sunshine can be resisted；Conductive layer includes the carbon by modification
On the one hand the conductivity of polyethylene composite geo-membrane can be substantially improved in fiber, can quick positioning searching breakthrough, another party
Face can be improved polyethylene composite earthwork film strength；Thus polyethylene composite geo-membrane of the invention has important economic valence
Value and realistic meaning.
Specific embodiment
Combined with specific embodiments below, the present invention is described in further details:
Raw material used in embodiment:
High-density polyethylene resin: density 0.939g/cm3, model TR400N, Sinopec Group
The production of Maoming branch company；
Antioxidant: the antioxidant B225 of BASF joint-stock company is four [β-(3,5- di-tert-butyl-hydroxy phenyl) third
Acid] pentaerythritol ester and three (2,4- di-tert-butyl-phenyl) phosphite esters compound；
Black masterbatch: pigment carbon black, concentration 46%, three friendly plastics technology Co., Ltd of Beijing benefit；
Conductive black color masterbatch: conductive black, concentration 46%, three friendly plastics technology Co., Ltd of Beijing benefit；
Carbon fiber: polyacrylonitrile-based carbon fibre T700,12K, toray company；KH540 silane coupling agent is used using preceding
It is surface-treated；
Bisphenol A type epoxy resin: epoxide equivalent 190g/eq, epoxide number 0.526eq/100g, the new occasion chemical industry in Nantong have
Limit company；
Fatty amine curing agent: modified polyether amine hardener, active hydrogen equivalent weight=95g/eq, self-control；
Toughener: amino terminated liquid nitrile rubber ATBN, X21 type, acrylonitrile content 10%, amido equivalent (AEW)=
1200；
Polyurethane adhesive: dual-component polyurethane adhesive, host agent are hydroxy component, are the polyadipate second two of terminal hydroxy group
The prepolymer of alcohol ester and toluene di-isocyanate(TDI)；Curing agent is the component rolled into a ball containing free isocyanate groups, the new photochemical factory in Shanghai.
Performance test standard and instrument:
Tensile break strength: for high-density polyethylene geomembrane according to GB/T 1040.3-2006 standard testing, polyethylene is multiple
It closes geomembrane and presses GB/T 176425788-20058 standard testing, test equipment is Taiwan GOTECH company AL-7000L-A5 drawing
Force tester；
Peel strength: pressing GB/T 17642-2008 standard testing, and test equipment is Taiwan GOTECH company AL-7000L-
A5 tensile testing machine；
Surface resistivity: according to GB/T 1410-2006 standard testing, Anjelen Sci. & Tech. Inc, the test equipment U.S.
4339B high resistance tester.
Embodiment 1
1) high-density polyethylene resin, carbon black color masterbatch and antioxidant are weighed according to the weight ratio of 95:4:1, is put into high mixed
It is mixed in machine 3 minutes, then uses double screw extruder melt blending extruding pelletization, screw speed is 200 revs/min, extrusion temperature
Between 180~200 DEG C, anti-aging layer composition is obtained；
2) high-density polyethylene resin and the carbon fiber being surface-treated through silane coupling agent are claimed according to the weight ratio of 95:5
Weight, is put into high-speed mixer and mixing 3 minutes, then uses double screw extruder extruding pelletization, and screw speed is 200 revs/min, squeezes out
Temperature obtains conductive layer combination object between 180~200 DEG C；
3) by anti-aging layer composition and conductive layer combination object on double-layer coextrusion blow moulding equipment apparatus for blow moulding co-extrusion
Out, the high-density polyethylene geomembrane containing anti-aging layer and conductive layer is made；Wherein, upper layer is anti-aging layer, with a thickness of
1.4mm, lower layer is conductive layer, with a thickness of 0.1mm；
4) bisphenol A type epoxy resin, toughener and curing agent are weighed according to the weight ratio of 100:45:50, stirring
After uniformly, it is put into the revolving speed degassing mixing 1min in high mixer with 3000r/min, modified bisphenol A type epoxy adhesive is made；
5) the modified bisphenol A type epoxy adhesive that step 4) obtains is uniformly coated on step 3) with the thickness of 0.2mm
Laminated, the 200g/m in covering of conduction of high-density polyethylene geomembrane obtained2Non-woven geotextile, then use pressure roller hot pressing
Compound, roller temperature is 60 DEG C, obtains polyethylene composite geo-membrane.
By polyethylene composite geo-membrane made from high-density polyethylene geomembrane made from step 3) and step 5) through overshooting
It is tailored into standard batten, carries out properties test according to above-mentioned test condition.
Embodiment 2
1) high-density polyethylene resin, carbon black color masterbatch and antioxidant are weighed according to the weight ratio of 94:4:2, is put into high mixed
It is mixed in machine 3 minutes, then uses double screw extruder melt blending extruding pelletization, screw speed is 200 revs/min, extrusion temperature
Between 180~200 DEG C, anti-aging layer composition is obtained；
2) high-density polyethylene resin and the carbon fiber being surface-treated through silane coupling agent are claimed according to the weight ratio of 96:4
Weight, is put into high-speed mixer and mixing 3 minutes, then uses double screw extruder extruding pelletization, and screw speed is 200 revs/min, squeezes out
Temperature obtains conductive layer combination object between 180~200 DEG C；
3) by anti-aging layer composition and conductive layer combination object on double-layer coextrusion blow moulding equipment apparatus for blow moulding co-extrusion
Out, the high-density polyethylene geomembrane containing anti-aging layer and conductive layer is made；Wherein, upper layer is anti-aging layer, with a thickness of
1.4mm, lower layer is conductive layer, with a thickness of 0.1mm；
4) bisphenol A type epoxy resin, toughener and curing agent are weighed according to the weight ratio of 100:50:45, stirring
After uniformly, it is put into the revolving speed degassing mixing 1min in high mixer with 3000r/min, modified bisphenol A type epoxy adhesive is made；
5) the modified bisphenol A type epoxy adhesive that step 4) obtains is uniformly coated on step 3) with the thickness of 0.5mm
Laminated, the 200g/m in covering of conduction of high-density polyethylene geomembrane obtained2Non-woven geotextile, then use pressure roller hot pressing
Compound, roller temperature is 50 DEG C, obtains polyethylene composite geo-membrane.
By polyethylene composite geo-membrane made from high-density polyethylene geomembrane made from step 3) and step 5) through overshooting
It is tailored into standard batten, carries out properties test according to above-mentioned test condition.
Embodiment 3
Except step 2) medium high density polyethylene resin and the weight ratio of the carbon fiber through silane coupling agent surface treatment is 98:
Outside 2, remaining is the same as embodiment 2.
Embodiment 4
Except step 2) medium high density polyethylene resin and the weight ratio of the carbon fiber through silane coupling agent surface treatment is 90:
Outside 10, remaining is the same as embodiment 2.
Embodiment 5
Except step 2) medium high density polyethylene resin and the weight ratio of the carbon fiber through silane coupling agent surface treatment is 80:
Outside 20, remaining is the same as embodiment 2.
Embodiment 6
In addition to the weight ratio of bisphenol A type epoxy resin, toughener and curing agent described in the step 4) is 100:30:50,
Remaining same embodiment 2.
Embodiment 7
In addition to the weight ratio of bisphenol A type epoxy resin, toughener and curing agent described in the step 4) is 100:60:50,
Remaining same embodiment 2.
Embodiment 8
In addition to the weight ratio of bisphenol A type epoxy resin, toughener and curing agent described in the step 4) is 100:75:45,
Remaining same embodiment 2.
Embodiment 9
In addition to the weight ratio of bisphenol A type epoxy resin, toughener and curing agent described in the step 4) is 100:25:55,
Remaining same embodiment 2.
Comparative example 1
Except step 2) medium high density polyethylene resin and the weight ratio of the carbon fiber through silane coupling agent surface treatment is 99:
Outside 1, remaining is the same as embodiment 2.
Comparative example 2
The carbon fiber used in the step 2) is in addition to being surface-treated without silane coupling agent, remaining is the same as embodiment 2.
Comparative example 3
In addition to the carbon fiber being surface-treated using the replacement of conductive black color masterbatch through silane coupling agent in step 2), remaining is the same as real
Apply example 2.
Comparative example 4
In addition to the weight ratio of bisphenol A type epoxy resin, toughener and curing agent in step 4) is 100:15:50, remaining is same
Embodiment 2.
Comparative example 5
In addition to the weight ratio of bisphenol A type epoxy resin, toughener and curing agent in step 4) is 100:80:50, remaining is same
Embodiment 2.
Comparative example 6
In addition to the weight ratio of bisphenol A type epoxy resin, toughener and curing agent in step 4) is 100:50:30, remaining is same
Embodiment 2.
Comparative example 7
In addition to the weight ratio of bisphenol A type epoxy resin, toughener and curing agent in step 4) is 100:50:60, remaining is same
Embodiment 2.
Comparative example 8
In addition to the weight ratio of bisphenol A type epoxy resin, toughener and curing agent in step 4) is 100:15:30, remaining is same
Embodiment 2.
Comparative example 9
1) high-density polyethylene resin, carbon black color masterbatch and antioxidant are weighed according to the weight ratio of 94:4:2, is put into high mixed
It is mixed in machine 3 minutes, then uses double screw extruder melt blending extruding pelletization, screw speed is 200 revs/min, extrusion temperature
Between 180~200 DEG C, anti-aging layer composition is obtained；
2) high-density polyethylene resin and the carbon fiber being surface-treated through silane coupling agent are claimed according to the weight ratio of 96:4
Weight, is put into high-speed mixer and mixing 3 minutes, then uses double screw extruder extruding pelletization, and screw speed is 200 revs/min, squeezes out
Temperature obtains conductive layer combination object between 180~200 DEG C；
3) by anti-aging layer composition and conductive layer combination object on double-layer coextrusion blow moulding equipment apparatus for blow moulding co-extrusion
Out, the high-density polyethylene geomembrane containing anti-aging layer and conductive layer is made；Wherein, upper layer is anti-aging layer, with a thickness of
1.4mm, lower layer is conductive layer, with a thickness of 0.1mm；
4) polyurethane adhesive is uniformly coated on the geotechnique of high density polyethylene (HDPE) made from step 3) with the thickness of 0.5mm
Laminated, the 200g/m in covering of conduction of film2Non-woven geotextile, then with pressure roller hot pressing it is compound, roller temperature be 50 DEG C, obtain
To polyethylene composite geo-membrane.
By polyethylene composite geo-membrane made from high-density polyethylene geomembrane made from step 3) and step 4) through overshooting
It is tailored into standard batten, carries out properties test according to above-mentioned test condition.
The aging layer and conductive layer of the high-density polyethylene geomembrane prepared in testing example 1~9 and comparative example 1~9
Surface resistivity, the results are shown in Table 2.
The tensile break strength and peel strength data of 1 high-density polyethylene geomembrane of table and polyethylene composite geo-membrane
The surface resistivities of table 2 high-density polyethylene geomembrane and polyethylene composite geo-membrane
| Project | Conductive layer surface resistivity (Ω) | Anti-aging layer surface resistivity (Ω) |
| Embodiment 1 | 9.5×109 | 5.9×1016 |
| Embodiment 2 | 4.5×1010 | 7.6×1016 |
| Embodiment 3 | 6.9×1010 | 5.3×1016 |
| Embodiment 4 | 6.4×108 | 5.3×1016 |
| Embodiment 5 | 5.4×107 | 4.6×1016 |
| Embodiment 6 | 6.5×1010 | 4.5×1016 |
| Embodiment 7 | 5.6×1010 | 6.5×1016 |
| Embodiment 8 | 4.6×1010 | 5.6×1016 |
| Embodiment 9 | 5.9×1010 | 4.8×1016 |
| Comparative example 1 | 6.5×1015 | 6.5×1010 |
| Comparative example 2 | 6.7×1013 | 6.5×1016 |
| Comparative example 3 | 7.5×1013 | 8.8×1016 |
| Comparative example 4 | 6.5×1010 | 5.8×1016 |
| Comparative example 5 | 5.8×1010 | 5.6×1016 |
| Comparative example 6 | 6.5×1010 | 7.2×1016 |
| Comparative example 7 | 7.4×1010 | 7.1×1016 |
| Comparative example 8 | 7.9×1010 | 8.5×1016 |
| Comparative example 9 | 4.8×1010 | 4.9×1016 |
Meanwhile the high density polyethylene (HDPE) composite geo-membrane for preparing above-described embodiment 1~9 and comparative example 1~9 respectively-
Restore again after handling 4h under the conditions of 20 DEG C to 23 DEG C of room temperature, sees whether that warping phenomenon occurs.
Properties test result from the embodiments above is it can be seen that passing through and modified carbon fiber composite
Afterwards, embodiment 1 and high-density polyethylene geomembrane and high density polyethylene (HDPE) composite geo-membrane in embodiment 2, intensity difference
Better than the high-density polyethylene geomembrane and high density polyethylene (HDPE) composite geo-membrane for adding non-modified carbon fiber in comparative example 2,
Also superior to the high-density polyethylene geomembrane and high density polyethylene (HDPE) composite geo-membrane for only adding carbon black color masterbatch in comparative example 3.It is real
Applying example 3~5 is respectively the high density polyethylene (HDPE) composite geo-membrane for adding the modified carbon fiber of different proportion and being prepared, highly dense
Polyethylene film for earthwork and high density polyethylene (HDPE) composite earthwork film strength are spent better than high density polyethylene (HDPE) geotechnique prepared by comparative example 1
Film and high density polyethylene (HDPE) composite geo-membrane.Embodiment 6~9 is respectively to add the bisphenol-A of different proportion toughener and curing agent
Type epoxy adhesive, peel strength of the peel strength better than high density polyethylene (HDPE) composite geo-membrane prepared by comparative example 4~8.
Each high density polyethylene (HDPE) composite geo-membrane discovery, the high density prepared by comparative example 4~9 after high/low temperature is handled of comparison simultaneously are poly-
Warping phenomenon has occurred in ethylene composite geo-membrane, illustrates that toughener and hardener dose specified in the present invention can obtain preferably
That resist warping effect.
The surface resistivity test result of the high-density polyethylene geomembrane conductive layer of 1~9 preparation can from the embodiments above
To find out, the surface resistivity of conductive layer is up to 6.5 × 1010Ω, the conductive layer in embodiment can conduct under high voltages
Conductor, and the surface resistivity of the high-density polyethylene geomembrane anti-aging layer of Examples 1 to 9 preparation is 1016The Ω order of magnitude, can
To regard insulator as, when hole on the high density polyethylene (HDPE) composite geo-membrane, brush above-mentioned will be in the position of hole
It discharges with conductive layer, so that it is determined that the position of breakthrough.High-density polyethylene geomembrane conductive layer in comparative example 1 does not have
Conductive matter, the high-density polyethylene geomembrane conductive layer electric conductivity in comparative example 2~3 is very poor, cannot utilize detection electrode
Quickly determine hole and breakthrough.
Therefore, polyethylene composite earthwork film stretching and peel strength provided by the invention are high, and that resist warping effect is good, conductive layer
Conduct electricity very well, anti-aging layer is almost become attached to, can quick positioning searching breakthrough, with conventional high-density polyethylene film for earthwork phase
It is more obvious than advantage, there is biggish market competition advantage, be worthy of popularization.
It should be noted that embodiment described above for explaining only the invention, is not constituted to of the invention any
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word used in it is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to particular case disclosed in it, on the contrary, this hair
It is bright that can be extended to other all with the same function.
Claims (12)
1. a kind of polyethylene composite geo-membrane, the polyethylene composite geo-membrane includes high-density polyethylene geomembrane, nonwoven soil
Work cloth and the modified bisphenol A type epoxy adhesive between the high-density polyethylene geomembrane and non-woven geotextile；Its
In, the epoxide number of the modified bisphenol A type epoxy adhesive is 0.02-0.56eq/100g, preferably 0.52-0.54eq/
100g。
2. polyethylene composite geo-membrane according to claim 1, which is characterized in that the modified bisphenol A type epoxy adhesive
Agent is prepared through the blending of bisphenol A type epoxy resin, curing agent and toughener；The curing agent is fatty amine curing agent, preferably
For polyethers amine hardener；And/or the toughener is amino terminated liquid nitrile rubber.
3. polyethylene composite geo-membrane according to claim 1 or 2, which is characterized in that with bisphenol A type epoxy resin dosage
It is counted for 100 parts, the dosage of the curing agent is 45-55 parts, and preferably 45-50 parts, the dosage of the toughener is 25-75 parts,
Preferably 30-60 parts.
4. polyethylene composite geo-membrane described in any one of -3 according to claim 1, which is characterized in that the high density is poly-
Ethylene geomembrane successively includes anti-aging layer and conductive layer from top to bottom；It is preferred that the anti-aging layer with a thickness of 0.5~
1.5mm, conductive layer with a thickness of 0.05~0.1mm.
5. polyethylene composite geo-membrane described in any one of -4 according to claim 1, which is characterized in that with anti-aging layer
Weight is 100% meter, and the anti-aging layer includes:
High-density polyethylene resin 80wt%~98wt%, preferably 88wt%~96wt%；
Carbon black color masterbatch 1wt%~15wt%, preferably 2wt%~10wt%；
Antioxidant 1wt%~5wt%, preferably 1wt%~2wt%；
It is preferred that the content of carbon black in the conductive black color masterbatch is 30%~50%；
Density >=0.930g/cm of the high-density polyethylene resin3, preferably 0.935~0.950g/cm3。
6. polyethylene composite geo-membrane described in any one of -5 according to claim 1, which is characterized in that the antioxidant is
The mixture or Hinered phenols antioxidant of Hinered phenols antioxidant and phosphoric acid ester antioxidant and the compounding of phosphoric acid ester antioxidant
Antioxidant, the preferably weight ratio of Hinered phenols antioxidant and phosphoric acid ester antioxidant are 1:1~1:3, more preferably 1:1.5~1:
2.5。
7. polyethylene composite geo-membrane described in any one of -6 according to claim 1, which is characterized in that the Hinered phenols
Antioxidant is selected from four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, β-(3,5- di-t-butyl -4- hydroxyl
Base phenyl) propionic acid n-octadecyl alcohol ester, N, N'- is bis--(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine, 1,
At least one of 3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid；And/or the phosphoric acid ester antioxidant choosing
At least from three (2,4- di-tert-butyl-phenyl) phosphite esters, bis- (2,4-DTBP) pentaerythritol diphosphites
It is a kind of.
8. polyethylene composite geo-membrane according to any one of claims 1-7, which is characterized in that with the weight of conductive layer
Amount is 100% meter, and the conductive layer includes:
High-density polyethylene resin 80wt%~98wt%, preferably 90wt%~96wt%；
Carbon fiber 2wt%~20wt%, preferably 4wt%~10wt%；
Density >=0.930g/cm of the high-density polyethylene resin3, preferably 0.935~0.950g/cm3。
9. polyethylene composite geo-membrane described in any one of -8 according to claim 1, which is characterized in that the carbon fiber choosing
From polyacrylonitrile-based carbon fibre T300, T700 and T800, fiber count 3k, 6k, 12k, 24k or 48k, preferably polyacrylonitrile-based carbon
Fiber T700,12k；The carbon fiber needs to be surface-treated it using silane coupling agent before use, and the silane is even
Joining agent is preferably silane coupling A -151, KH540 and KH551.
10. polyethylene composite geo-membrane according to claim 1 to 9, which is characterized in that the nonwoven geotechnique
Cloth is selected from long filament or short silk polypropylene non-woven geotextiles and long filament or short silk PET non-woven geotextile, specification 100g/m2~
300g/m2；Preferably, the non-woven geotextile of stating is selected from long filament polypropylene non-woven geotextiles and long filament PET non-woven geotextile, rule
Lattice 100g/m2~200g/m2。
11. the preparation method of polyethylene composite geo-membrane described in any one of -10 according to claim 1, including will be highly dense
It spends polyethylene film for earthwork and is hot bonding compound obtain with the modified bisphenol type epoxy adhesive of non-woven geotextile.
12. the preparation method of polyethylene composite geo-membrane according to claim 11, which is characterized in that including walking as follows
It is rapid:
(1) by the high-density polyethylene resin, carbon black color masterbatch, antioxidant and carbon fiber respectively according to anti-aging layer and conductive layer
Content melt blending the composition of each layer is made, then the high-density polyethylene geomembrane is made in composition coextrusion；
(2) bisphenol A type epoxy resin, toughener and curing agent are blended according to respective dosage, it is double that the modification is made
Phenol A type epoxy adhesive；
(3) the modified bisphenol A type epoxy adhesive obtained using step (2) is geotechnological by high density polyethylene (HDPE) made from step (1)
Film, through be bonded, obtains the polyethylene composite geo-membrane through hot pressing is compound with non-woven geotextile.
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