CN115558194B - Flexible low-temperature-resistant waterproof material and preparation method thereof - Google Patents
Flexible low-temperature-resistant waterproof material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of building materials, and provides a flexible low-temperature-resistant waterproof material and a preparation method thereof. The short branched chain in the ethylene-octene copolymer ensures that the ethylene monomer crystals in the ultrahigh molecular weight polyethylene, the ethylene-vinyl acetate copolymer and the block copolymerization polypropylene can not be in one flaky crystal but penetrate mutually to form the connection among crystals, thereby keeping the good flexibility, strength and low temperature performance of the ultrahigh molecular weight polyethylene, the ethylene-vinyl acetate copolymer and the block copolymerization polypropylene. The flexible low-temperature-resistant waterproof material provided by the invention has the advantages that the mechanical property can meet the requirements of construction standards while the flexibility is increased; in addition, the elongation rate of the material in a severe cold tunnel environment at low temperature can also reach the standard requirement index of the existing product at normal temperature, and meanwhile, the material has excellent wear resistance and corrosion resistance, so that the service life of the material is prolonged.
Description
Technical Field
The invention relates to the technical field of building materials, in particular to a flexible low-temperature-resistant waterproof material and a preparation method thereof.
Background
China northeast belongs to a high-latitude cold area, the freezing phenomenon lasts for a long time, and a series of freezing injury influences are generated on tunnel engineering. Improper tunnel treatment in severe cold areas can bring potential safety hazards to later-stage operation, and great economic loss is caused. The extremely lowest temperature of tunnels in some severe cold areas can reach below-40 ℃, the average temperature of the coldest month is about-30 ℃, most of the existing tunnel waterproof coiled materials are polyethylene waterproof coiled materials, the hardness of the body of the existing tunnel waterproof coiled materials is high, the waterproof coiled materials with high hardness become harder at low temperature, the brittleness is increased, the waterproof coiled materials are more easily damaged when external force (such as frost heaving force) is applied, tunnel lining and supporting structures are corroded, engineering accidents such as tunnel deformation, water burst and collapse are caused, and the maintenance of a tunnel engineering drainage system and the tunnel operation safety are seriously influenced. Meanwhile, the elongation of the composite material is greatly reduced under a low-temperature environment, and the composite material is not easy to be closely attached to a base surface during construction of a severe cold tunnel and is easy to cause a back cavity. Therefore, in severe cold regions, research on a flexible low-temperature-resistant waterproof material is necessary.
Disclosure of Invention
In view of the above, the present invention aims to provide a flexible low temperature resistant waterproof material and a preparation method thereof. The flexible low-temperature-resistant waterproof material provided by the invention has excellent toughness at low temperature.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a flexible low-temperature-resistant waterproof material which comprises the following components in parts by weight:
15-25 parts of a granulated composite material, 45-65 parts of an ethylene-octene copolymer, 5-20 parts of an ethylene-vinyl acetate copolymer, 15-25 parts of metallocene polyethylene and 2-4 parts of an antioxidant;
the granulation composite material comprises the following components in parts by weight:
5 to 15 parts of ultrahigh molecular weight polyethylene, 45 to 65 parts of solvent, 45 to 65 parts of block copolymer polypropylene and 55 to 70 parts of linear low density polyethylene; the mass ratio of the solvent to the ultrahigh molecular weight polyethylene is (1.2 to 1.5): 1.
preferably, the melt flow rate of the ethylene-octene copolymer is 0.8 to 1.2g/10min, the brittle temperature is less than or equal to-60 ℃, and the Shore D hardness is less than or equal to 25 ℃.
Preferably, the melt flow rate of the ethylene-vinyl acetate copolymer is 2.7 to 3.5g/10min, the brittle temperature is less than or equal to-50 ℃, and the Shore D hardness is less than or equal to 40 ℃; the mass content of vinyl acetate in the ethylene-vinyl acetate copolymer is 16-30%.
Preferably, the melt flow rate of the metallocene polyethylene is 5 to 10g/10min.
Preferably, the antioxidant comprises pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
Preferably, the molecular weight of the ultra-high molecular weight polyethylene is (100 to 2000). Times.10 4 。
Preferably, the solvent comprises white oil and/or polyethylene wax.
Preferably, the melt flow rate of the block copolymerization polypropylene is 18 to 26g/10min, the brittle temperature is less than or equal to-35 ℃, and the cantilever beam impact strength at-2 ℃ is more than or equal to 4kJ/m 2 。
The invention also provides a preparation method of the flexible low-temperature-resistant waterproof material, which comprises the following steps:
mixing the ultrahigh molecular weight polyethylene with a solvent, and swelling to obtain an ultrahigh molecular weight polyethylene swelling body;
mixing the ultrahigh molecular weight polyethylene swelling body, the block copolymerization polypropylene and the linear low density polyethylene, and performing first melt extrusion to obtain a granulation composite material;
and mixing the granulated composite material, the ethylene-octene copolymer, the ethylene-vinyl acetate copolymer, the metallocene polyethylene and the antioxidant, and performing second melt extrusion to obtain the flexible low-temperature-resistant waterproof material.
Preferably, the parameters of the first melt extrusion comprise: the temperature of a host screw is 170 to 210 ℃, the frequency of the host screw is 10 to 12Hz, the pre-pump pressure of the host screw is 7.0 to 8.5MPa, the temperature of a machine head is 180 to 220 ℃, and the traction frequency is 15 to 18Hz;
the parameters of the second melt extrusion include: the temperature of a screw of a main machine is 180 to 220 ℃, the temperature of a machine head is 190 to 230 ℃, the length-diameter ratio of the screw of a single-screw extruder is 28 to 33, and the traction frequency is 14 to 169z.
The invention provides a flexible low-temperature-resistant waterproof material which comprises the following components in parts by weight: 15-25 parts of a granulated composite material, 45-65 parts of an ethylene-octene copolymer, 5-20 parts of an ethylene-vinyl acetate copolymer, 15-25 parts of metallocene polyethylene and 2-4 parts of an antioxidant; the granulation composite material comprises the following components in parts by weight: 5 to 15 parts of ultrahigh molecular weight polyethylene, 45 to 65 parts of solvent, 45 to 65 parts of block copolymer polypropylene and 55 to 70 parts of linear low density polyethylene; the mass ratio of the solvent to the ultrahigh molecular weight polyethylene is (1.2 to 1.5): 1. the short branched chain in the ethylene-octene copolymer ensures that the ethylene monomer crystals in the ultrahigh molecular weight polyethylene, the ethylene-vinyl acetate copolymer and the block copolymerization polypropylene can not be in one flaky crystal but penetrate mutually to form the connection among crystals, thereby keeping the good flexibility, strength and low temperature performance of the ultrahigh molecular weight polyethylene, the ethylene-vinyl acetate copolymer and the block copolymerization polypropylene. The flexible low-temperature-resistant waterproof material provided by the invention has the advantages that the mechanical property can meet the requirements of construction standards while the flexibility is increased, meanwhile, the elongation rate at low temperature in a severe cold tunnel environment can also reach the standard requirement index of the existing product at normal temperature, and meanwhile, the flexible low-temperature-resistant waterproof material has excellent wear resistance and corrosion resistance, and the service life is prolonged.
The invention also provides a preparation method of the flexible low-temperature-resistant waterproof material, which comprises the following steps: mixing the ultrahigh molecular weight polyethylene with a solvent, and swelling to obtain an ultrahigh molecular weight polyethylene swelling body; mixing the ultrahigh molecular weight polyethylene swelling body, the block copolymerization polypropylene and the linear low density polyethylene, and performing first melting extrusion to obtain a granulated composite material; and mixing the granulated composite material, the ethylene-octene copolymer, the ethylene-vinyl acetate copolymer, the metallocene polyethylene and the antioxidant, and performing second melt extrusion to obtain the flexible low-temperature-resistant waterproof material. The preparation method provided by the invention can fully dissolve and mix the preparation raw materials to obtain the waterproof material with excellent performance. Meanwhile, the preparation method provided by the invention is simple to operate and easy to industrialize.
Detailed Description
The invention provides a flexible low-temperature-resistant waterproof material which comprises the following components in parts by weight:
15-25 parts of a granulated composite material, 45-65 parts of an ethylene-octene copolymer, 5-20 parts of an ethylene-vinyl acetate copolymer, 15-25 parts of metallocene polyethylene and 2-4 parts of an antioxidant;
the granulation composite material comprises the following components in parts by weight:
5 to 15 parts of ultrahigh molecular weight polyethylene, 45 to 65 parts of solvent, 45 to 65 parts of block copolymer polypropylene and 55 to 70 parts of linear low density polyethylene; the mass ratio of the solvent to the ultrahigh molecular weight polyethylene is (1.2 to 1.5): 1.
in the present invention, the starting materials used in the present invention are preferably commercially available products unless otherwise specified.
The flexible low-temperature-resistant waterproof material provided by the invention comprises 45 to 65 parts by weight, preferably 50 to 60 parts by weight, and more preferably 55 parts by weight of an ethylene-octene copolymer. In the invention, the melt flow rate of the ethylene-octene copolymer is preferably 0.8 to 1.2g/10min, the brittle temperature is preferably less than or equal to-60 ℃, and the Shore hardness D is preferably less than or equal to 25 ℃. In a particular embodiment of the invention, the ethylene-octene copolymer is particularly preferably dow 8003 or dow 8400.
The flexible low-temperature-resistant waterproof material provided by the invention comprises 5 to 20 parts by weight of ethylene-vinyl acetate copolymer, preferably 10 to 15 parts by weight. In the invention, the melt flow rate of the ethylene-vinyl acetate copolymer is preferably 2.7 to 3.5g/10min, the brittle temperature is preferably less than or equal to-50 ℃, and the Shore hardness D is preferably less than or equal to 40 ℃; the mass content of vinyl acetate in the ethylene-vinyl acetate copolymer is preferably 16-30%. In a specific embodiment of the present invention, the ethylene-vinyl acetate copolymer is specifically preferably Yanshan petrochemical 18-3 or Yanshan petrochemical V5110J.
The flexible low-temperature-resistant waterproof material provided by the invention comprises 15-25 parts by weight of metallocene polyethylene, and preferably 20 parts by weight. In the present invention, the melt flow rate of the metallocene polyethylene is preferably 5 to 10g/10min. In a specific embodiment of the present invention, the metallocene polyethylene is preferably dupont Fusabond E528.
The flexible low-temperature-resistant waterproof material provided by the invention comprises 2-4 parts by weight of antioxidant, preferably 3 parts by weight. In the present invention, the antioxidant preferably includes pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], and more preferably the antioxidant 1010.
The flexible low-temperature-resistant waterproof material provided by the invention comprises 15-25 parts by weight of a granulated composite material, and preferably 20 parts by weight. In the invention, the granulation composite material comprises the following components in parts by weight:
5 to 15 parts of ultrahigh molecular weight polyethylene, 45 to 65 parts of solvent, 45 to 65 parts of block copolymer polypropylene and 55 to 70 parts of linear low density polyethylene; the mass ratio of the solvent to the ultrahigh molecular weight polyethylene is (1.2 to 1.5): 1.
in the invention, the granulated composite material comprises 5 to 15 parts by weight of ultrahigh molecular weight polyethylene, and preferably 10 parts by weight. In the present invention, the molecular weight of the ultrahigh molecular weight polyethylene is preferably (100 to 2000). Times.10 4 . In a specific embodiment of the present invention, the ultra-high molecular weight polyethylene is specifically preferably mitsui chemical L3000. In the invention, the ultra-high molecular weight polyethylene has excellent low temperature resistance, wear resistance, impact resistance and corrosion resistance; the brittle temperature is as low as-140 ℃, and the ductility is good at low temperature.
In the present invention, the pelletized composite comprises a solvent. In the present invention, the solvent preferably includes white oil and/or polyethylene wax, and more preferably white oil. In the invention, the mass ratio of the solvent to the ultrahigh molecular weight polyethylene is (1.2 to 1.5): 1. in the invention, the solvent can swell the ultra-high molecular weight polyethylene, so that the compatibility of the ultra-high molecular weight polyethylene is improved; meanwhile, in the preparation process, the lubricating effect can be achieved.
In the invention, the granulated composite material comprises 45 to 65 parts by weight of block copolymer polypropylene, preferably 50 to 60 parts by weight, and more preferably 55 parts by weight. In the invention, the melt flow rate of the block copolymerization polypropylene is preferably 18 to 26g/10min, the brittle temperature is preferably less than or equal to-35 ℃, and the cantilever beam impact strength at-2 ℃ is excellentSelecting not less than 4kJ/m 2 . In a specific embodiment of the present invention, the block copolymer polypropylene is specifically preferably Yanshan petrochemical K7726H or Korea Letian JM-360.
In the invention, the granulated composite material comprises 55 to 70 parts by weight of linear low density polyethylene, and preferably 60 to 65 parts by weight. In the present invention, the linear low density polyethylene preferably has a melt flow rate of 1.5 to 2.5g/10min and a density of 0.917 to 0.935g/cm 3 . In a particular embodiment of the invention, the linear low density polyethylene is particularly preferably daqing petrochemical LLDPE9047 polyethylene or daqing petrochemical LLDPE7042 polyethylene.
The invention also provides a preparation method of the flexible low-temperature-resistant waterproof material, which comprises the following steps:
mixing the ultra-high molecular weight polyethylene and a solvent, and swelling to obtain an ultra-high molecular weight polyethylene swelling body;
mixing the ultrahigh molecular weight polyethylene swelling body, the block copolymerization polypropylene and the linear low density polyethylene, and performing first melt extrusion to obtain a granulation composite material;
and mixing the granulated composite material, the ethylene-octene copolymer, the ethylene-vinyl acetate copolymer, the metallocene polyethylene and the antioxidant, and performing second melt extrusion to obtain the flexible low-temperature-resistant waterproof material.
The invention mixes the ultra-high molecular weight polyethylene and solvent to swell, and obtains the ultra-high molecular weight polyethylene swelling body.
In the present invention, the temperature for swelling is preferably 125 to 140 ℃, and more preferably 130 to 135 ℃; the time is preferably 15 to 30min, and more preferably 20 to 25min. In the present invention, the swelling is preferably performed under stirring. In the present invention, the swelling is preferably carried out in a stirred tank.
After said swelling, the present invention preferably further comprises standing and filtering in sequence. In the invention, the standing time is preferably 30 to 60min; the aperture of the filtering sieve for filtering is preferably 30 to 70 meshes, and more preferably 40 meshes.
In the invention, the burning point of the ultra-high molecular weight polyethylene swelling body is more than or equal to 300 ℃.
In the swelling process, the solvent diffuses and permeates into the ultra-high molecular weight polyethylene polymer to promote the full disentanglement of macromolecular chains, reduce the apparent viscosity of the polymer and achieve the entanglement-disentanglement balance state, so that a fluffy swelling body is obtained, the entanglement degree of the macromolecular chains is reduced, and the compatibility of the swelling body is improved.
After the ultrahigh molecular weight polyethylene swelling body is obtained, the ultrahigh molecular weight polyethylene swelling body, the block copolymerization polypropylene and the linear low density polyethylene are mixed, and first melting extrusion is carried out to obtain the granulation composite material.
In the invention, the temperature for mixing the ultrahigh molecular weight polyethylene swelling body, the block copolymerization polypropylene and the linear low density polyethylene is preferably 50 to 70 ℃, more preferably 55 to 65 ℃, and even more preferably 60 ℃; the mixing of the ultra-high molecular weight polyethylene swell, the block co-polypropylene and the linear low density polyethylene is preferably carried out in a mixing bowl.
In the present invention, the parameters of the first melt extrusion include: the temperature of the main machine screw is preferably 170 to 210 ℃, more preferably 180 to 200 ℃, and even more preferably 190 ℃; the frequency of the main machine screw is preferably 10 to 12Hz, and more preferably 10.5 to 11.5Hz; the pre-pump pressure of the main screw is preferably 7.0 to 8.5MPa, and more preferably 7.3 to 8.0MPa; the temperature of the machine head is preferably 180 to 220 ℃, more preferably 190 to 210 ℃, and even more preferably 200 ℃; the traction frequency is preferably 15 to 18Hz, and more preferably 15.5 to 17.5Hz.
In the invention, the ultrahigh molecular weight polyethylene swelling body looses physical entanglement among molecular chains of the ultrahigh molecular weight polyethylene, enhances the fluidity of the ultrahigh molecular weight polyethylene swelling body and improves the processing performance of the ultrahigh molecular weight polyethylene swelling body. And the ethylene monomer, linear low density polyethylene and a small amount of alpha-olefin are copolymerized in the block copolymer polypropylene to form a main chain of linear ethylene, molecular chains of the blend have good compatibility, the entanglement degree is increased after blending, the constraint is strong, the crystal structure is relatively stable under the action of external force, and the structure is not easy to be damaged due to dislocation, so that the performances of stretching, puncture resistance, wear resistance and the like of the blend are remarkably improved after the combination.
After the granulated composite material is obtained, the granulated composite material, the ethylene-octene copolymer, the ethylene-vinyl acetate copolymer, the metallocene polyethylene and the antioxidant are mixed and subjected to second melt extrusion to obtain the flexible low-temperature-resistant waterproof material.
In the invention, the mixing temperature of the granulated composite material, the ethylene-octene copolymer, the ethylene-vinyl acetate copolymer, the metallocene polyethylene and the antioxidant is preferably 50 to 70 ℃, and more preferably 60 ℃; the mixing of the granulated composite material, the ethylene-octene copolymer, the ethylene-vinyl acetate copolymer, the metallocene polyethylene and the antioxidant is preferably carried out in a mixing tank.
In the present invention, the parameters of the second melt extrusion include: the temperature of the main machine screw is preferably 180 to 220 ℃, more preferably 190 to 210 ℃, and more preferably 200 ℃; the temperature of the machine head is preferably 190 to 230 ℃, more preferably 200 to 220 ℃, and still more preferably 210 ℃; the length-diameter ratio of the screw of the single-screw extruder is preferably 28 to 33, and more preferably 29 to 32; the traction frequency is preferably 14 to 169z Hz, and more preferably 14.5 to 15.5Hz.
The flexible low temperature resistant waterproof material and the preparation method thereof provided by the present invention will be described in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention.
Example 1
(1) Preparing an ultra-high molecular weight polyethylene swelling body: 5 parts by weight of ultra-high molecular weight polyethylene (Japan three-well chemical L3000) and industrial white oil according to the mass ratio of 1:1.2, stirring for 15min at the temperature of 125 ℃, standing and precipitating for 30min, and filtering by using a 40-mesh screen to obtain the ultra-high molecular weight polyethylene swelling body.
(2) Mixing 65 parts by weight of prepared ultrahigh molecular weight polyethylene swelling body and block copolymerization polypropylene (Yanshan petrochemical K7726H) with 55 parts by weight of linear low density polyethylene (Daqing petrochemical LLDPE 9047), putting into a double-screw extruder for melt extrusion, wherein the temperature of a material mixing tank is 50 ℃, the temperature of a main machine screw is 170 ℃, the frequency of the main machine screw is 10Hz, the pre-pump pressure of the main machine screw is 7.0MPa, the temperature of a machine head is 180 ℃, and the traction frequency is 15Hz, so as to obtain the granulated composite material.
(3) 15 parts of a granulated composite material, 65 parts of an ethylene-octene copolymer (Dow 8003), 20 parts of an ethylene-vinyl acetate copolymer (Yanshan petrochemical 18-3), 15 parts of metallocene polyethylene (DuPont Fusabond E528) and 4 parts of an antioxidant (1010), putting the mixture into a single-screw extruder for second melt extrusion, wherein the temperature of a material mixing tank is 50 ℃, the temperature of a main machine screw is 180 ℃, the temperature of a machine head is 230 ℃, the length-diameter ratio of the screw of the single-screw extruder is 28, the traction frequency is 14Hz, and extruding and molding the waterproof coiled material with the thickness of 1.5 mm.
And (2) detecting the mechanical property of the obtained waterproof coiled material, wherein the tensile property is detected according to GB/T528, the tearing property is detected according to GB/T529, the low-temperature bending property is detected according to GB/T18173.1, the shore hardness is detected according to GB531.1, and the result is as follows: tensile strength at break at 23 ℃: 21.6MPa in the longitudinal direction and 21.3MPa in the transverse direction. Elongation at break at 23 ℃: the machine direction was 1163% and the cross direction was 1098%. Tear strength at 23 ℃: the machine direction was 112kN/m and the transverse direction was 106kN/m. Shore hardness (D): 22 degrees. Bending at low temperature of-35 ℃: has no crack. No crack when bending at-45 deg.C. -35 ℃ tensile strength at break: 18.6MPa in the longitudinal direction and 18.1MPa in the transverse direction. Elongation at break at-35 ℃: the machine direction was 641% and the cross direction was 659%. Tear strength at 35 ℃: the machine direction was 113kN/m and the transverse direction was 106kN/m.
Example 2
(1) Preparing an ultra-high molecular weight polyethylene swelling body: 7 parts by weight of ultra-high molecular weight polyethylene (Japan three-well chemical L3000) and industrial white oil according to the mass ratio of 1:1.2, stirring at the temperature of 128 ℃ for 20min, standing for precipitation for 35min, and filtering by using a 40-mesh screen to obtain the ultra-high molecular weight polyethylene swelling body.
(2) Mixing 60 parts by weight of the prepared ultrahigh molecular weight polyethylene swelling body and 60 parts by weight of block copolymerization polypropylene (Yanshan petrochemical K7726H) with 60 parts by weight of linear low density polyethylene (Daqing petrochemical LLDPE 9047), putting the mixture into a double-screw extruder for melt extrusion, wherein the temperature of a material mixing tank is 55 ℃, the temperature of a main machine screw is 180 ℃, the frequency of the main machine screw is 10.5Hz, the pre-pump pressure of the main machine screw is 7.3MPa, the temperature of a machine head is 190 ℃ and the traction frequency is 15.5Hz, and obtaining the granulation composite material.
(3) 18 parts of a granulated composite material, 60 parts of an ethylene-octene copolymer (Dow 8400), 17 parts of an ethylene-vinyl acetate copolymer (Yanshan petrochemical 18-3), 18 parts of metallocene polyethylene (Dupont Fusabond E528) and 4 parts of an antioxidant (1010), and the components are put into a single-screw extruder for melt extrusion, wherein the temperature of a mixing tank is 55 ℃, the temperature of a main machine screw is 190 ℃, the temperature of a machine head is 200 ℃, the length-diameter ratio of the single-screw extruder screw is 29, the traction frequency is 14.3Hz, and a waterproof coiled material with the thickness of 1.5mm is formed by extrusion.
And (2) detecting the mechanical property of the obtained waterproof roll, wherein the tensile property is detected according to GB/T528, the tearing property is detected according to GB/T529, the low-temperature bending property is detected according to GB/T18173.1, the Shore hardness is detected according to GB531.1, and the result is that: tensile strength at break at 23 ℃: the machine direction was 23.7MPa, and the transverse direction was 21.4MPa. Elongation at break at 23 ℃: the machine direction was 1087% and the cross direction was 1014%. Tear strength at 23 ℃: the machine direction was 117kN/m and the transverse direction was 109kN/m. Shore hardness (D): 25 degrees. Bending at low temperature of-35 ℃: has no crack. No crack when bending at-45 deg.C. -35 ℃ tensile strength at break: 21.9MPa in the longitudinal direction and 19.8MPa in the transverse direction. Elongation at break at-35 ℃: the machine direction was 749% and the cross direction was 773%. Tear strength at 35 ℃: the machine direction was 117kN/m and the transverse direction was 109kN/m.
Example 3
(1) Preparing an ultra-high molecular weight polyethylene swelling body: 8 parts by weight of ultra-high molecular weight polyethylene (Nippon Mitsui chemical L3000) and industrial white oil according to a mass ratio of 1:1.2, stirring at 130 ℃ for 22min, standing for 40min, and filtering with a 40-mesh screen to obtain the ultra-high molecular weight polyethylene swelling body.
(2) Mixing 55 parts by weight of the prepared ultrahigh molecular weight polyethylene swelling body and 55 parts by weight of block copolymerization polypropylene (Korea Letian JM-360) with 63 parts by weight of linear low density polyethylene (Daqing petrochemical LLDPE 7042), putting the mixture into a double-screw extruder for melt extrusion, wherein the temperature of a material mixing tank is 60 ℃, the temperature of a host screw is 190 ℃, the frequency of the host screw is 10.7Hz, the pressure in front of a pump of the host screw is 7.5MPa, the temperature of a machine head is 200 ℃, and the traction frequency is 16Hz, and obtaining the granulation composite material.
(3) 20 parts of granulated composite material, 55 parts of ethylene-octene copolymer (Dow 8400), 15 parts of ethylene-vinyl acetate copolymer (Yanshan petrochemical 18-3), 20 parts of metallocene polyethylene (Dupont Fusobond E528) and 3 parts of antioxidant (1010) by weight are put into a single-screw extruder for melt extrusion, the temperature of a mixing tank is 60 ℃, the temperature of a main machine screw is 200 ℃, the temperature of a machine head is 210 ℃, the length-diameter ratio of the screw of the single-screw extruder is 30, the traction frequency is 14.7Hz, and a waterproof coiled material with the thickness of 1.5mm is formed by extrusion.
And (2) detecting the mechanical property of the obtained waterproof roll, wherein the tensile property is detected according to GB/T528, the tearing property is detected according to GB/T529, the low-temperature bending property is detected according to GB/T18173.1, the Shore hardness is detected according to GB531.1, and the result is that: tensile strength at break at 23 ℃: the machine direction was 26.9MPa and the transverse direction was 24.7MPa. Elongation at break at 23 ℃: the machine direction was 1124% and the cross direction was 1039%. Tear strength at 23 ℃: the machine direction was 124kN/m and the transverse direction was 119kN/m. Shore hardness (D): 34 degrees. Bending at low temperature of-35 ℃: has no crack. No crack is generated when the steel is bent at the low temperature of minus 45 ℃. -35 ℃ tensile strength at break: the machine direction was 23.6MPa, and the transverse direction was 22.1MPa. Elongation at break at-35 ℃: the machine direction was 716% and the cross direction was 686%. Tear strength at-35 ℃: the machine direction was 119kN/m and the transverse direction was 109kN/m.
Example 4
(1) Preparing an ultra-high molecular weight polyethylene swelling body: 9 parts by weight of ultra-high molecular weight polyethylene (Japan three-well chemical L3000) and industrial white oil according to the mass ratio of 1:1.2, stirring for 25min at the temperature of 135 ℃, standing and precipitating for 45min, and filtering by using a 40-mesh screen to obtain the ultra-high molecular weight polyethylene swelling body.
(2) Mixing 52 parts by weight of the prepared ultrahigh molecular weight polyethylene swelling body and block copolymerization polypropylene (Korea Letian JM-360) with 65 parts by weight of linear low density polyethylene (Daqing petrochemical LLDPE 9047), putting into a double-screw extruder for melt extrusion, wherein the temperature of a material mixing tank is 65 ℃, the temperature of a main machine screw is 190 ℃, the frequency of the main machine screw is 11Hz, the pre-pump pressure of the main machine screw is 7.8MPa, the temperature of a machine head is 200 ℃, and the traction frequency is 16.5Hz, and obtaining the granulation composite material.
(3) 21 parts of a granulated composite material, 53 parts of ethylene-octene copolymer (Dow 8003), 11 parts of ethylene-vinyl acetate copolymer (Yangzhi petrochemical V5110J), 23 parts of metallocene polyethylene (Dupont Fusabond E528) and 3 parts of antioxidant (1010), and the granulated composite material is put into a single-screw extruder for melt extrusion, wherein the temperature of a mixing tank is 65 ℃, the temperature of a main machine screw is 200 ℃, the temperature of a machine head is 210 ℃, the length-diameter ratio of the single-screw extruder screw is 31, the traction frequency is 15Hz, and a waterproof coiled material with the thickness of 1.5mm is formed by extrusion.
And (2) detecting the mechanical property of the obtained waterproof roll, wherein the tensile property is detected according to GB/T528, the tearing property is detected according to GB/T529, the low-temperature bending property is detected according to GB/T18173.1, the Shore hardness is detected according to GB531.1, and the result is that: tensile strength at break at 23 ℃: the machine direction was 28.4MPa and the transverse direction was 27.5MPa. Elongation at break at 23 ℃: the machine direction was 1043% and the transverse direction was 967%. Tear strength at 23 ℃: the machine direction was 136kN/m and the transverse direction was 129kN/m. Shore hardness (D): and 36 degrees. Bending at low temperature of-35 ℃: has no crack. No crack when bending at-45 deg.C. -35 ℃ tensile strength at break: the machine direction was 26.9MPa and the transverse direction was 25.7MPa. Elongation at break at-35 ℃: the machine direction is 769% and the cross direction is 741%. Tear strength at 35 ℃: the machine direction was 121kN/m and the transverse direction was 119kN/m.
Example 5
(1) Preparing an ultra-high molecular weight polyethylene swelling body: 11 parts by weight of ultra-high molecular weight polyethylene (Japan three-well chemical L3000) and industrial white oil according to the mass ratio of 1:1.2, stirring for 25min at the temperature of 135 ℃, standing and precipitating for 50min, and filtering by using a 40-mesh screen to obtain the ultra-high molecular weight polyethylene swelling body.
(2) Mixing 50 parts by weight of prepared ultra-high molecular weight polyethylene swelling body and 50 parts by weight of block co-polypropylene (Yanshan petrochemical K7726H) with 68 parts by weight of linear low density polyethylene (Daqing petrochemical LLDPE 7042), putting the mixture into a double-screw extruder for melt extrusion, wherein the temperature of a material mixing tank is 65 ℃, the temperature of a main machine screw is 200 ℃, the frequency of the main machine screw is 11.5Hz, the pressure in front of a pump of the main machine screw is 8.0MPa, the temperature of a machine head is 210 ℃, and the traction frequency is 17.3Hz, and obtaining the granulated composite material.
(3) 23 parts of a granulated composite material, 48 parts of an ethylene-octene copolymer (Dow 8400), 9 parts of an ethylene-vinyl acetate copolymer (Yangzhi petrochemical V5110J), 23 parts of metallocene polyethylene (Dupont Fusabond E528) and 2 parts of an antioxidant (1010), which are put into a single-screw extruder for melt extrusion, wherein the temperature of a mixing tank is 65 ℃, the temperature of a main machine screw is 210 ℃, the temperature of a machine head is 220 ℃, the length-diameter ratio of the single-screw extruder screw is 32, the traction frequency is 15.4Hz, and a waterproof coiled material with the thickness of 1.5mm is extruded and molded.
And (2) detecting the mechanical property of the obtained waterproof coiled material, wherein the tensile property is detected according to GB/T528, the tearing property is detected according to GB/T529, the low-temperature bending property is detected according to GB/T18173.1, the shore hardness is detected according to GB531.1, and the result is as follows: tensile strength at break at 23 ℃: the machine direction was 26.7MPa and the transverse direction was 25.0MPa. Elongation at break at 23 ℃: the machine direction was 843% and the cross direction was 799%. Tear strength at 23 ℃: the machine direction was 131kN/m and the transverse direction was 123kN/m. Shore hardness (D): 34 degrees. Bending at low temperature of-35 ℃: has no crack. No crack when bending at-45 deg.C. -35 ℃ tensile strength at break: the machine direction was 23.5MPa, and the transverse direction was 22.4MPa. Elongation at break at-35 ℃: 678% in the machine direction and 690% in the transverse direction. Tear strength at-35 ℃: the machine direction was 115kN/m and the transverse direction was 106kN/m.
Example 6
(1) Preparing an ultra-high molecular weight polyethylene swelling body: 15 parts by weight of ultra-high molecular weight polyethylene (Japan three-well chemical L3000) and industrial white oil according to the mass ratio of 1:1.2, stirring for 30min at the temperature of 140 ℃, standing and precipitating for 60min, and filtering by using a 40-mesh screen to obtain the ultra-high molecular weight polyethylene swelling body.
(2) Mixing 45 parts by weight of the prepared ultrahigh molecular weight polyethylene swelling body and block copolymerization polypropylene (Korea Letian JM-360) with 70 parts by weight of linear low density polyethylene (Daqing petrochemical LLDPE 9047), putting into a double-screw extruder for melt extrusion, wherein the temperature of a material mixing tank is 70 ℃, the temperature of a main machine screw is 210 ℃, the frequency of the main machine screw is 12Hz, the pre-pump pressure of the main machine screw is 8.5MPa, the temperature of a machine head is 220 ℃, and the traction frequency is 18Hz, and obtaining the granulation composite material.
(3) 25 parts of a granulated composite material, 45 parts of an ethylene-octene copolymer (Dow 8400), 5 parts of an ethylene-vinyl acetate copolymer (Yanshan petrochemical 18-3), 25 parts of metallocene polyethylene (Du Pont Fusabond E528) and 2 parts of an antioxidant (1010), and the components are put into a single-screw extruder for melt extrusion, wherein the temperature of a mixing tank is 70 ℃, the temperature of a main machine screw is 210 ℃, the temperature of a machine head is 220 ℃, the length-diameter ratio of the single-screw extruder screw is 33, the traction frequency is 16Hz, and a waterproof coiled material with the thickness of 1.5mm is formed by extrusion.
And (2) detecting the mechanical property of the obtained waterproof coiled material, wherein the tensile property is detected according to GB/T528, the tearing property is detected according to GB/T529, the low-temperature bending property is detected according to GB/T18173.1, the shore hardness is detected according to GB531.1, and the result is as follows: tensile strength at break at 23 ℃: the machine direction was 24.4MPa and the transverse direction was 22.9MPa. Elongation at break at 23 ℃: the machine direction was 741% and the cross direction was 732%. Tear strength at 23 ℃: the machine direction was 126kN/m and the transverse direction was 121kN/m. Shore hardness (D): 43 degrees. Bending at low temperature of-35 ℃: has no crack. No crack is generated when the steel is bent at the low temperature of minus 45 ℃. -35 ℃ tensile strength at break: the machine direction was 21.4MPa and the transverse direction was 20.6MPa. Elongation at break at-35 ℃: 594% in the longitudinal direction and 573% in the transverse direction. Tear strength at 35 ℃: the machine direction was 106kN/m and the transverse direction was 98kN/m.
Comparative example 1
The waterproof coiled material of the comparative example is calculated according to the mass parts. The preparation raw materials comprise the following components: 30 parts of ethylene-vinyl acetate copolymer (Yanshan petrochemical 18-3) and 30 parts of linear low-density polyethylene (Daqing petrochemical LLDPE 9047); 40 parts of high-density polyethylene (Zhonghai shell 5502A); 1 part of 1010 antioxidant.
And (2) detecting the mechanical property of the obtained waterproof coiled material, wherein the tensile property is detected according to GB/T528, the tearing property is detected according to GB/T529, the low-temperature bending property is detected according to GB/T18173.1, the shore hardness is detected according to GB531.1, and the result is as follows: tensile strength at break at 23 ℃: 19.4MPa in the longitudinal direction and 18.6MPa in the transverse direction. Elongation at break at 23 ℃: 641% in the machine direction and 639% in the transverse direction. Tear strength at 23 ℃: the machine direction was 106kN/m and the transverse direction was 103kN/m. Shore hardness (D): and 65 degrees. Bending at low temperature of-35 ℃: has no crack. Cracks are formed when the steel is bent at the low temperature of minus 45 ℃. -35 ℃ tensile strength at break: the machine direction was 14.6MPa and the transverse direction was 12.8MPa. Elongation at break at-35 ℃: 216% in the machine direction and 198% in the transverse direction. Tear strength at-35 ℃: the machine direction was 64kN/m and the transverse direction was 62kN/m.
Comparative example 2
The differences from example 1 are: the same procedure as in example 1 was repeated except that the ethylene-octene copolymer was not added.
And (2) detecting the mechanical property of the obtained waterproof roll, wherein the tensile property is detected according to GB/T528, the tearing property is detected according to GB/T529, the low-temperature bending property is detected according to GB/T18173.1, the Shore hardness is detected according to GB531.1, and the result is that: tensile strength at break at 23 ℃: 20.9MPa in the longitudinal direction and 20.6MPa in the transverse direction. Elongation at break at 23 ℃: the machine direction was 713% and the cross direction was 725%. Tear strength at 23 ℃: the machine direction was 110kN/m and the transverse direction was 101kN/m. Shore hardness (D): and 82 degrees. Bending at low temperature of-35 ℃: has no crack. Cracks are formed when the steel is bent at the low temperature of minus 45 ℃. -35 ℃ tensile strength at break: the longitudinal direction was 15.9MPa and the transverse direction was 15.7MPa. Elongation at break at-35 ℃: the machine direction was 462% and the transverse direction was 397%. Tear strength at-35 ℃: the machine direction was 83kN/m and the transverse direction was 81kN/m.
Comparative example 3
The differences from example 1 are: the same procedure as in example 1 was repeated except that no block copolymer polypropylene was added.
And (2) detecting the mechanical property of the obtained waterproof roll, wherein the tensile property is detected according to GB/T528, the tearing property is detected according to GB/T529, the low-temperature bending property is detected according to GB/T18173.1, the Shore hardness is detected according to GB531.1, and the result is that: tensile strength at break at 23 ℃: the machine direction was 19.3MPa and the transverse direction was 18.7MPa. Elongation at break at 23 ℃: the machine direction is 1047% and the transverse direction is 1041%. Tear strength at 23 ℃: the machine direction was 101kN/m and the transverse direction was 91kN/m. Shore hardness (D): and 39 degrees. Bending at low temperature of-35 ℃: has no crack. No crack when bending at-45 deg.C. -35 ℃ tensile strength at break: the machine direction was 15.4MPa and the transverse direction was 14.8MPa. Elongation at break at-35 ℃: 491% in the machine direction and 462% in the transverse direction. Tear strength at 35 ℃: the machine direction was 61kN/m and the transverse direction was 54kN/m.
Comparative example 4
The differences from example 1 are: the same procedure as in example 1 was repeated except that the ultrahigh-molecular weight polyethylene was not added.
And (2) detecting the mechanical property of the obtained waterproof roll, wherein the tensile property is detected according to GB/T528, the tearing property is detected according to GB/T529, the low-temperature bending property is detected according to GB/T18173.1, the Shore hardness is detected according to GB531.1, and the result is that: tensile strength at break at 23 ℃: 20.5MPa in the longitudinal direction and 19.6MPa in the transverse direction. Elongation at break at 23 ℃: the machine direction was 1031% and the cross direction was 974%. Tear strength at 23 ℃: the machine direction was 106kN/m and the transverse direction was 100kN/m. Shore hardness (D): 34 degrees. Bending at low temperature of-35 ℃: has no crack. No crack is generated when the steel is bent at the low temperature of minus 45 ℃. -35 ℃ tensile strength at break: the longitudinal direction was 15.9MPa and the transverse direction was 15.3MPa. Elongation at break at-35 ℃: the longitudinal direction is 494% and the lateral direction is 431%. Tear strength at 35 ℃: the machine direction was 73kN/m and the transverse direction was 62kN/m.
The performance test results of the waterproof coiled materials obtained in the comparative examples 1 to 6 and the comparative examples 1 to 4 show that: under the condition of 23 ℃, the flexible low-temperature-resistant waterproof material provided by the invention has the advantages that the longitudinal breaking tensile strength is more than 21.6MPa, the transverse breaking tensile strength is more than 21.3MPa, the longitudinal elongation at break is more than 843%, the transverse elongation at break is more than 799%, the longitudinal tearing strength is more than 112kN/m, the transverse tearing strength is more than 106kN/m, and the Shore hardness D is less than 39 ℃, and no crack exists when the flexible low-temperature-resistant waterproof material is bent at the low temperature of-35 ℃ and-45 ℃. The flexible low-temperature-resistant waterproof material provided by the invention has the advantages that the longitudinal breaking tensile strength is more than 18.6MPa, the transverse breaking tensile strength is more than 18.1MPa, the longitudinal elongation at break is more than 594%, the transverse elongation at break is more than 573%, the longitudinal tearing strength is more than 106kN/m, and the transverse tearing strength is more than 98kN/m under the condition of minus 35 ℃. Compared with a comparative example, the flexible low-temperature-resistant waterproof material has higher tensile strength and tearing strength at normal temperature and low temperature, and is better in flexibility.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (6)
1. The flexible low-temperature-resistant waterproof material is characterized by comprising the following components in parts by weight:
15-25 parts of a granulating composite material, 45-65 parts of an ethylene-octene copolymer, 5-20 parts of an ethylene-vinyl acetate copolymer, 15-25 parts of metallocene polyethylene and 2-4 parts of an antioxidant;
the granulation composite material comprises the following components in parts by weight:
5 to 15 parts of ultrahigh molecular weight polyethylene, 45 to 65 parts of solvent, 45 to 65 parts of block copolymer polypropylene and 55 to 70 parts of linear low density polyethylene; the mass ratio of the solvent to the ultrahigh molecular weight polyethylene is (1.2 to 1.5): 1;
the solvent comprises white oil and/or polyethylene wax;
mixing the ultrahigh molecular weight polyethylene with a solvent, and swelling to obtain an ultrahigh molecular weight polyethylene swelling body;
the melt flow rate of the ethylene-octene copolymer is 0.8 to 1.2g/10min, the brittle temperature is less than or equal to-60 ℃, and the Shore hardness D is less than or equal to 25 ℃;
the melt flow rate of the ethylene-vinyl acetate copolymer is 2.7 to 3.5g/10min, the brittle temperature is less than or equal to-50 ℃, and the Shore hardness D is less than or equal to 40 ℃; the mass content of vinyl acetate in the ethylene-vinyl acetate copolymer is 16-30%;
the melt flow rate of the block copolymerization polypropylene is 18 to 26g/10min, the brittle temperature is less than or equal to-35 ℃, and the cantilever beam impact strength at-2 ℃ is more than or equal to 4kJ/m 2 。
2. The flexible low temperature resistant waterproof material of claim 1, wherein the melt flow rate of the metallocene polyethylene is 5 to 10g/10min.
3. The flexible, low temperature resistant, water repellent material of claim 1, wherein said antioxidant comprises pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
4. The flexible low-temperature-resistant waterproof material as claimed in claim 1, wherein the molecular weight of the ultra-high-molecular-weight polyethylene is (100 to 2000). Times.10 4 。
5. The preparation method of the flexible low-temperature-resistant waterproof material as claimed in any one of claims 1 to 4, which is characterized by comprising the following steps:
mixing the ultrahigh molecular weight polyethylene with a solvent, and swelling to obtain an ultrahigh molecular weight polyethylene swelling body;
mixing the ultrahigh molecular weight polyethylene swelling body, the block copolymerization polypropylene and the linear low density polyethylene, and performing first melt extrusion to obtain a granulation composite material;
and mixing the granulated composite material, the ethylene-octene copolymer, the ethylene-vinyl acetate copolymer, the metallocene polyethylene and the antioxidant, and performing second melt extrusion to obtain the flexible low-temperature-resistant waterproof material.
6. The method of claim 5, wherein the parameters of the first melt extrusion comprise: the temperature of a host screw is 170 to 210 ℃, the frequency of the host screw is 10 to 12Hz, the pre-pump pressure of the host screw is 7.0 to 8.5MPa, the temperature of a machine head is 180 to 220 ℃, and the traction frequency is 15 to 18Hz;
the parameters of the second melt extrusion include: the temperature of a screw of a main machine is 180 to 220 ℃, the temperature of a machine head is 190 to 230 ℃, the length-diameter ratio of the screw of a single-screw extruder is 28 to 33, and the traction frequency is 14 to 169z.
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| CN106674708A (en) * | 2016-11-30 | 2017-05-17 | 中广核三角洲（苏州）新材料研发有限公司 | Low-smoke halogen-free ceramic polyolefin fire-resistant insulation material and preparation method thereof |
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