CN117734210A - Preparation method of ultra-high molecular weight polyethylene film composite material - Google Patents
Preparation method of ultra-high molecular weight polyethylene film composite material Download PDFInfo
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- CN117734210A CN117734210A CN202311762221.8A CN202311762221A CN117734210A CN 117734210 A CN117734210 A CN 117734210A CN 202311762221 A CN202311762221 A CN 202311762221A CN 117734210 A CN117734210 A CN 117734210A
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- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 title claims abstract description 170
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 title claims abstract description 170
- 239000002131 composite material Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229920000642 polymer Polymers 0.000 claims abstract description 82
- 239000002344 surface layer Substances 0.000 claims abstract description 56
- 239000010410 layer Substances 0.000 claims abstract description 55
- 239000012792 core layer Substances 0.000 claims abstract description 54
- 238000007493 shaping process Methods 0.000 claims abstract description 41
- 238000001816 cooling Methods 0.000 claims abstract description 40
- 238000001125 extrusion Methods 0.000 claims abstract description 27
- 239000002086 nanomaterial Substances 0.000 claims abstract description 21
- 238000000748 compression moulding Methods 0.000 claims abstract description 3
- 239000002114 nanocomposite Substances 0.000 claims description 63
- 238000000034 method Methods 0.000 claims description 38
- 239000002904 solvent Substances 0.000 claims description 24
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 22
- 238000000605 extraction Methods 0.000 claims description 17
- 239000003960 organic solvent Substances 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 239000005662 Paraffin oil Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 239000004698 Polyethylene Substances 0.000 claims description 12
- -1 polyethylene Polymers 0.000 claims description 12
- 229920000573 polyethylene Polymers 0.000 claims description 12
- 229910021389 graphene Inorganic materials 0.000 claims description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- 239000001993 wax Substances 0.000 claims description 6
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 5
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 4
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 4
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 4
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004414 compression moulding compound Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002861 polymer material Substances 0.000 abstract description 3
- 229920000098 polyolefin Polymers 0.000 abstract description 3
- 230000008961 swelling Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 38
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- 239000011347 resin Substances 0.000 description 16
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- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 3
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Landscapes
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Laminated Bodies (AREA)
Abstract
The invention relates to a preparation method of an ultra-high molecular weight polyethylene film composite material, which comprises the following steps: (1) Preparing a core layer film and two surface layer films by extrusion molding, wherein the core layer film is an ultra-high molecular weight polyethylene layer, and the surface layer films are composite material layers compounded by UHMWPE, low molecular weight polymer and nano materials; (2) And (3) sequentially forming and extracting the two layers of surface films, then carrying out high-temperature stretching and compression molding composite forming on the two layers of surface films and the core film, and finally cooling and shaping to obtain the functionalized ultra-high molecular weight polyethylene composite film, namely the target product. The composite modified film prepared by the invention has a three-layer structure, the inner ultra-high molecular weight polyethylene layer ensures the mechanical property of the composite film, the surface polyolefin film layer has a certain orientation after swelling and stretching, and the low molecular weight polymer and nano material composite ensures the multifunction, thereby realizing very low friction coefficient, hydrophilicity, antistatic property and the like.
Description
Technical Field
The invention belongs to the technical field of composite material preparation, and relates to a preparation method of an ultra-high molecular weight polyethylene film composite material.
Background
The UHMWPE has a highly symmetrical methylene structure, and the highly symmetrical methylene structure ensures the excellent performance of the UHMWPE, but the simple methylene forms an inert chemical surface, the surface chemical reaction activity is extremely low, the chemical bond bonding with the resin is difficult to form, the hydrophilicity is poor, the wide application of the UHMWPE film is greatly limited, and therefore, the improvement of the interface performance of the UHMWPE film is one of the important subjects. The existing ultra-high molecular weight polyethylene film has more surface modification methods, has the defects and advantages, has higher corona treatment and low-temperature plasma treatment cost, has easily attenuated modification effect and is not easy to store for a long time; chemical etching method and high-energy radiation grafting have great damage to the performance of the substrate; the chemical grafting method is easy to cause waste liquid pollution; other methods such as calendaring and coating processes are under development. Among the modification methods, the ultraviolet grafting modification has better prospect due to the environmental protection, low cost, mild reaction condition and obvious modification effect, and compared with other chemical grafting modification methods, the ultraviolet grafting modification has the following outstanding characteristics: (1) The grafting chain is connected with the matrix molecular chain by chemical bond, so that the surface performance obtained by surface grafting modification can be stably and continuously maintained; (2) The ultraviolet light penetrability is poor, the grafting reaction is strictly limited on the surface or subsurface of the material, the amount of the required modifying reagent is small, and the surface performance is improved without influencing the performance of the body; (3) The cost of the light source and the equipment is low, the reaction speed is high, and the continuous and large-scale operation is easy. Therefore, the ultraviolet grafting modification technology is widely applied in the fields of printing, packaging, biological medicine and the like, but the traditional liquid phase grafting reaction time is longer, the homopolymers are more, and many defects still need to be improved. At present, the grafting modification application is severely limited, while the hydrophilic modification effect is good, other properties such as self-lubricity, electric conduction property and the like are relatively poor, and the surface abrasion resistance of the product is poor due to surface grafting, so that a functionalization method of the UHMWPE film needs to be further developed.
For example, chinese patent CN202111542365.3 discloses a low friction coefficient ultra-high molecular weight polyethylene fiber composite material and a preparation method thereof, the preparation method comprises the following steps: 1) Preparing a polyethylene multilayer fiber with an outer layer of polyethylene fiber and a core layer of low molecular weight polyolefin nanocomposite by utilizing a coextrusion molding technology; 2) Extracting and stretching polyethylene multi-layer fibers, and then compounding the polyethylene multi-layer fibers with low-molecular-weight polyethylene and ultra-high-molecular-weight polyethylene fibers to prepare composite fiber cloth; 3) And (3) melting and compounding the composite fiber cloth and the ultra-high molecular weight polyethylene resin. The patent mainly prepares a composite fiber layer on the surface layer of the ultra-high molecular weight polyethylene resin, the functional composite material is mainly realized by the composite fiber of the surface layer, the forming process is more complicated, and the balance between the mechanical property and the multifunctional property is still to be improved.
Disclosure of Invention
The invention aims to provide a preparation method of an ultra-high molecular weight polyethylene film composite material, which is used for realizing low friction coefficient and the like on the premise of keeping the excellent mechanical property of ultra-high molecular weight polyethylene resin.
The aim of the invention can be achieved by the following technical scheme:
the preparation method of the ultra-high molecular weight polyethylene film composite material comprises the following steps:
(1) Preparing a three-layer film by extrusion molding, wherein the three-layer film is a core layer film and two surface layer films respectively, the core layer film is an ultra-high molecular weight polyethylene layer, and the surface layer film is a composite material layer compounded by UHMWPE, a low molecular weight polymer and a nano material;
(2) And (3) extracting the two layers of surface films, carrying out high-temperature stretching and compression molding composite forming on the two layers of surface films and the core film in a surface-core-surface mode, and finally cooling and shaping to obtain the functionalized ultra-high molecular weight polyethylene composite film which is a target product.
Further, the ultra-high molecular weight polyethylene used for the core layer has a viscosity average molecular weight of 100×10 4 g/mol～900×10 4 g/mol。
Further, in the composite material used for the surface layer, the weight ratio of the UHMWPE, the low molecular weight polymer and the nano material is 30-60%wt, 39-70%wt and 0.1-1%wt respectively.
Further, the low molecular weight polymer is one or a mixture of more than one of polyethylene wax, oleamide, erucamide and polyethylene glycol. Preferably, the low molecular weight polymer has a molecular weight <8000g/mol.
Further, the nano material is one or a mixture of more of graphene, graphite and molybdenum disulfide.
Further, the UHMWPE in the composite material used for the skin layer has a molecular weight of 100 x 10 4 g/mol-900×10 4 g/mol。
Further, the UHMWPE/low molecular weight polymer/nanocomposite is first mixed with an organic solvent to prepare a mixed heterogeneous solution, wherein the mass fraction of the mixed heterogeneous solution is 6-30% by weight, and the organic solvent is paraffin oil, decalin and the like.
Further, the surface layer film and the core layer film are extruded and molded at 200-230 ℃ through a double screw extruder.
Further, the film composite forming process specifically comprises the following steps: stretching at 200-230 deg.c to 300-2000% and compounding the three layers of film at 180-230 deg.c and molding at 0.1-1.0 MPa.
Further, the extraction process of the surface film is carried out at normal temperature, and the extraction solvent is n-hexane or n-heptane.
Further, the temperature of cooling and shaping is 30-60 ℃.
Compared with the prior art, the nano composite modified film prepared by the invention has a three-layer structure, the inner ultra-high molecular weight polyethylene layer ensures the mechanical property of the composite film, the surface polyolefin composite film layer has a certain orientation after swelling and stretching, and the low molecular weight polymer and nano material composite ensures the multifunction, so that the very low friction coefficient, the hydrophilicity and the antistatic property are realized, and after the surface UHMWPE nano composite film and the core UHMWPE film are extracted and stretched and compounded, the surface layer forms a micro-nano structure, so that the composite film still has excellent wear resistance and better industrial application prospect.
Drawings
FIG. 1 is a flow chart of the preparation process of the invention.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples. The present embodiment is implemented on the premise of the technical scheme of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following examples.
In the examples which follow, the remainder, unless specifically indicated, is indicated as conventional commercially available materials or conventional processing techniques in the art.
Example 1
Referring to the process flow shown in FIG. 1, the UHMWPE base material of this example has a molecular weight of 100×10 4 g/mol, respectively preparing three layers of films, namely two layers of surface layers and one layer of core layer by extrusion molding, wherein the core layer adopts ultra-high molecular weight polyethylene with the molecular weight of 100 multiplied by 10 4 g/mol, wherein the surface layer adopts UHMWPE/low molecular weight polymer/nano composite film; UHMWPE/low molecular weight polymer/nanocomposite for extrusion molding is mixed with an organic solventThe mixed heterogeneous solution is prepared by mixing, the solvent is paraffin oil, the mass fraction of UHMWPE/low molecular weight polymer/nano composite material in the heterogeneous solution is 6% wt, and the mixture ratio of the surface layer co-extruded UHMWPE/low molecular weight polymer/nano composite material is 30%:69.7%:0.3 percent of low molecular weight polymer is polyethylene wax, and the nano material is graphene; firstly, the process conditions of forming the outer layer and the core layer film are that UHMWPE/low molecular weight polymer/nano composite material mixed solution and UHMWPE resin are extruded and formed by double screws at 200 ℃; secondly, extracting the surface film, wherein the extraction solvent is n-hexane (at normal temperature); finally, the extracted surface layer film is stretched and compounded with the core layer film (stretching multiplying power is 300 percent and compression strength is 0.1 MPa) at 230 ℃, and after stretching and compounding, cooling and shaping are carried out at a cooling and shaping section at 30 ℃, and after cooling and shaping, the functional ultra-high molecular weight polyethylene composite film is prepared.
The thickness of the composite film obtained in this example was about 0.2mm, wherein the mass ratio of the ultra-high molecular weight polyethylene used for preparing the core film was about 85%, and the mass ratio of the UHMWPE/low molecular weight polymer/nanocomposite used for preparing the skin film was about 15%. The friction coefficient and mechanical properties of the product are shown in the attached table 1.
Example 2
The basic process flow is identical to that of example 1, except that the UHMWPE binder of this example has a molecular weight of 300X 10 4 g/mol, preparing a three-layer film by extrusion molding, namely two surface layers and one core layer, wherein the core layer adopts ultra-high molecular weight polyethylene with the molecular weight of 300 multiplied by 10 4 g/mol, wherein the surface layer adopts an UHMWPE/low molecular weight polymer/nano composite film; the UHMWPE/low molecular weight polymer/nano composite material used for extrusion molding is mixed with an organic solvent to prepare a mixed heterogeneous solution, the solvent is paraffin oil, the mass fraction of the UHMWPE/low molecular weight polymer/nano composite material in the heterogeneous solution is 8% wt, and the mixture ratio of the UHMWPE/low molecular weight polymer/nano composite material co-extruded on the surface layer is 60%:39.6%:0.4 percent, the low molecular weight polymer is erucamide, and the nano material is molybdenum disulfide; first, the forming process conditions of the outer layer and the core layer film are as followsExtruding the polymer/nano composite material mixed solution and UHMWPE resin through a double screw at 230 ℃; secondly, extracting the surface film at normal temperature to prepare an extracted surface film, wherein the extraction solvent is n-hexane; finally, the extracted surface layer film is stretched and compounded with the core layer film (stretching multiplying power is 600 percent and compression strength is 0.6 MPa) at 230 ℃, and then the stretched and compounded film is subjected to cooling shaping at a cooling shaping section at 60 ℃, and the functional ultra-high molecular weight polyethylene composite film is prepared after cooling shaping.
The thickness of the composite film obtained in this example was about 0.2mm, wherein the mass ratio of the ultra-high molecular weight polyethylene used for preparing the core film was about 85%, and the mass ratio of the UHMWPE/low molecular weight polymer/nanocomposite used for preparing the skin film was about 15%. The friction coefficient and mechanical properties of the prepared product are shown in the attached table 1.
Example 3
The basic process flow is identical to that of example 1, except that the UHMWPE binder of this example has a molecular weight of 600X 10 4 g/mol, preparing a three-layer film by extrusion molding, namely two surface layers and one core layer, wherein the core layer adopts ultra-high molecular weight polyethylene with the molecular weight of 600 multiplied by 10 4 g/mol, wherein the surface layer adopts an UHMWPE/low molecular weight polymer/nano composite film; the UHMWPE/low molecular weight polymer/nano composite material used for extrusion molding is mixed with an organic solvent to prepare a mixed heterogeneous solution, the solvent is paraffin oil, the mass fraction of the UHMWPE/low molecular weight polymer/nano composite material in the heterogeneous solution is 18% wt, and the mixture ratio of the UHMWPE/low molecular weight polymer/nano composite material co-extruded on the surface layer is 50%:49.5%:0.5 percent of low molecular weight polymer is oleamide, and the nano material is graphene; firstly, the process conditions of forming the outer layer and the core layer film are that UHMWPE/low molecular weight polymer/nano composite material mixed solution and UHMWPE resin are extruded and formed by double screws at 200 ℃; secondly, extracting the surface film at normal temperature to prepare an extracted surface film, wherein the extraction solvent is n-hexane; finally, the extracted surface layer film is compounded with the core layer film after being stretched at 200 ℃ (stretching multiplying power is 900 percent, compression strength is 0.8 MPa), and cooling is carried out at 30 ℃ after stretching compoundingCooling and shaping in the shaping section, and preparing the functional ultra-high molecular weight polyethylene composite film after cooling and shaping.
The thickness of the composite film obtained in this example was about 0.2mm, wherein the mass ratio of the ultra-high molecular weight polyethylene used for preparing the core film was about 85%, and the mass ratio of the UHMWPE/low molecular weight polymer/nanocomposite used for preparing the skin film was about 15%. The friction coefficient and mechanical properties of the product are shown in the attached table 1.
Example 4
The basic process flow is identical to that of example 1, except that the UHMWPE binder of this example has a molecular weight of 900X 10 4 g/mol, preparing a three-layer film by extrusion molding, namely two surface layers and one core layer, wherein the core layer adopts ultra-high molecular weight polyethylene with the molecular weight of 900 multiplied by 10 4 g/mol, wherein the surface layer adopts an UHMWPE/low molecular weight polymer/nano composite film; the UHMWPE/low molecular weight polymer/nano composite material used for extrusion molding is mixed with an organic solvent to prepare a mixed heterogeneous solution, the solvent is paraffin oil, the mass fraction of the UHMWPE/low molecular weight polymer/nano composite material in the heterogeneous solution is 30% wt, and the mixture ratio of the UHMWPE/low molecular weight polymer/nano composite material co-extruded on the surface layer is 60%:39%:1%, the low molecular weight polymer is polyethylene wax, and the nano material is graphite; firstly, the process conditions of forming the outer layer and the core layer film are that UHMWPE/low molecular weight polymer/nano composite material mixed solution and UHMWPE resin are extruded and formed at 230 ℃ through a double screw; secondly, extracting the surface film at normal temperature to prepare an extracted surface film, wherein the extraction solvent is n-heptane; finally, the extracted multilayer film is compounded with the core layer film after being stretched at 230 ℃ (stretching multiplying power is 900 percent and compression strength is 1 MPa), and after being stretched and compounded, the multilayer film is subjected to cooling and shaping at a cooling shaping section at 30 ℃, and the functional ultra-high molecular weight polyethylene composite film is prepared after cooling and shaping.
The thickness of the composite film obtained in this example was about 0.2mm, wherein the mass ratio of the ultra-high molecular weight polyethylene used for preparing the core film was about 85%, and the mass ratio of the UHMWPE/low molecular weight polymer/nanocomposite used for preparing the skin film was about 15%. The friction coefficient and mechanical properties of the product are shown in the attached table 1.
Example 5
The basic process flow is identical to that of example 1, except that the UHMWPE binder of this example has a molecular weight of 800X 10 4 g/mol, preparing a three-layer film by extrusion molding, namely two surface layers and one core layer, wherein the core layer adopts ultra-high molecular weight polyethylene with molecular weight of 800 multiplied by 10 4 g/mol, wherein the surface layer adopts an UHMWPE/low molecular weight polymer/nano composite film; the UHMWPE/low molecular weight polymer/nano composite material used for extrusion molding is mixed with an organic solvent to prepare a mixed heterogeneous solution, the solvent is paraffin oil, the mass fraction of the UHMWPE/low molecular weight polymer/nano composite material in the heterogeneous solution is 30% wt, and the mixture ratio of the UHMWPE/low molecular weight polymer/nano composite material co-extruded on the surface layer is 30%:69%:1%, the low molecular weight polymer is polyethylene wax, and the nano material is graphene; firstly, the process conditions of forming the outer layer and the core layer film are that UHMWPE/low molecular weight polymer/nano composite material mixed solution and UHMWPE resin are extruded and formed at 230 ℃ through a double screw; secondly, extracting the surface film at normal temperature to prepare an extracted surface film, wherein the extraction solvent is n-hexane; finally, the extracted surface layer film is stretched and compounded with the core layer film (stretching multiplying power is 1500 percent and compression strength is 0.6 MPa) at 230 ℃, and then the stretched and compounded film is subjected to cooling shaping at a cooling shaping section at 60 ℃, and the functional ultra-high molecular weight polyethylene composite film is prepared after cooling shaping.
The thickness of the composite film obtained in this example was about 0.2mm, wherein the mass ratio of the ultra-high molecular weight polyethylene used for preparing the core film was about 85%, and the mass ratio of the UHMWPE/low molecular weight polymer/nanocomposite used for preparing the skin film was about 15%. The friction coefficient and mechanical properties of the product are shown in the attached table 1.
Example 6
The basic process flow is identical to that of example 1, except that the UHMWPE binder of this example has a molecular weight of 200X 10 4 g/mol, preparing a three-layer film by extrusion molding, namely two surface layers and one core layer, wherein the core layer isThe molecular weight of the polyethylene is 200 multiplied by 10, and the ultra-high molecular weight polyethylene is adopted 4 g/mol, wherein the surface layer adopts an UHMWPE/low molecular weight polymer/nano composite film; the UHMWPE/low molecular weight polymer/nano composite material used for extrusion molding is mixed with an organic solvent to prepare a mixed heterogeneous solution, the solvent is paraffin oil, the mass fraction of the UHMWPE/low molecular weight polymer/nano composite material in the heterogeneous solution is 30% wt, and the mixture ratio of the UHMWPE/low molecular weight polymer/nano composite material co-extruded on the surface layer is 30%:69%:1, the low molecular weight polymer is erucamide, and the nano material is molybdenum disulfide; firstly, the process conditions of forming the outer layer and the core layer film are that UHMWPE/low molecular weight polymer/nano composite material mixed solution and UHMWPE resin are extruded and formed at 230 ℃ through a double screw; secondly, extracting the surface film at normal temperature to prepare an extracted surface film, wherein the extraction solvent is n-hexane; finally, the extracted surface layer film is stretched and compounded with the core layer film (stretching multiplying power is 2000 percent and compression strength is 0.6 MPa) at 230 ℃, and then is subjected to cooling shaping at a cooling shaping section of 60 ℃ after stretching compounding, and the functional ultra-high molecular weight polyethylene composite film is prepared after cooling shaping.
The thickness of the composite film obtained in this example was about 0.2mm, wherein the mass ratio of the ultra-high molecular weight polyethylene used for preparing the core film was about 85%, and the mass ratio of the UHMWPE/low molecular weight polymer/nanocomposite used for preparing the skin film was about 15%. The friction coefficient and mechanical properties of the product are shown in the attached table 1.
Example 7
The basic process flow is identical to that of example 1, except that the UHMWPE binder of this example has a molecular weight of 200X 10 4 g/mol, preparing a three-layer film by extrusion molding, namely two surface layers and one core layer, wherein the core layer adopts ultra-high molecular weight polyethylene with the molecular weight of 200 multiplied by 10 4 g/mol, wherein the surface layer adopts an UHMWPE/low molecular weight polymer/nano composite film; the UHMWPE/low molecular weight polymer/nano composite material used for extrusion molding is mixed with an organic solvent to prepare a mixed heterogeneous solution, the solvent is paraffin oil, and the mass fraction of the UHMWPE/low molecular weight polymer/nano composite material in the heterogeneous solution is 30%wt, the surface layer co-extruded UHMWPE/low molecular weight polymer ratio is 30%:69.7%:0.3% of a low molecular weight polymer which is erucamide; firstly, the process conditions of forming the outer layer and the core layer film are that UHMWPE/low molecular weight polymer/nano composite material mixed solution and UHMWPE resin are extruded and formed at 230 ℃ through a double screw; secondly, extracting the surface film at normal temperature to prepare an extracted surface film, wherein the extraction solvent is n-hexane; finally, the extracted surface layer film is stretched and compounded with the core layer film (stretching multiplying power is 600 percent and compression strength is 0.6 MPa) at 230 ℃, and then the stretched and compounded film is subjected to cooling shaping at a cooling shaping section at 60 ℃, and the functional ultra-high molecular weight polyethylene composite film is prepared after cooling shaping.
The thickness of the composite film obtained in this example was about 0.2mm, wherein the mass ratio of the ultra-high molecular weight polyethylene used for preparing the core film was about 85%, and the mass ratio of the UHMWPE/low molecular weight polymer/nanocomposite used for preparing the skin film was about 15%. The friction coefficient and mechanical properties of the product are shown in the attached table 1.
Example 8
The basic process flow is identical to that of example 1, except that the UHMWPE binder of this example has a molecular weight of 200X 10 4 g/mol, preparing a three-layer film by extrusion molding, namely two surface layers and one core layer, wherein the core layer adopts ultra-high molecular weight polyethylene with the molecular weight of 200 multiplied by 10 4 g/mol, wherein the surface layer adopts an UHMWPE/low molecular weight polymer/nano composite film; the UHMWPE/low molecular weight polymer/nano composite material used for extrusion molding is mixed with an organic solvent to prepare a mixed heterogeneous solution, the solvent is paraffin oil, the mass fraction of the UHMWPE/low molecular weight polymer/nano composite material in the heterogeneous solution is 30% wt, and the mixture ratio of the UHMWPE/low molecular weight polymer/nano composite material co-extruded on the surface layer is 30%:69%:1%, wherein the low molecular weight polymer is polyethylene glycol, and the nano material is graphene; firstly, the process conditions of forming the outer layer and the core layer film are that UHMWPE/low molecular weight polymer/nano composite material mixed solution and UHMWPE resin are extruded and formed at 230 ℃ through a double screw; secondly, extracting the surface film at normal temperature to prepare the extracted surface filmA membrane, wherein the extraction solvent is n-hexane; finally, the extracted surface layer film and the core layer film are stretched and compounded (stretching multiplying power is 600 percent and compression strength is 0.6 MPa) at 230 ℃, and then are subjected to cooling shaping at a cooling shaping section of 60 ℃ after being stretched, and the functional ultra-high molecular weight polyethylene composite film is prepared after cooling shaping.
The thickness of the composite film obtained in this example was about 0.2mm, wherein the mass ratio of the ultra-high molecular weight polyethylene used for preparing the core film was about 85%, and the mass ratio of the UHMWPE/low molecular weight polymer/nanocomposite used for preparing the skin film was about 15%. The friction coefficient and mechanical properties of the product are shown in the attached table 1.
Blank example 9
The UHMWPE base stock of this example has a molecular weight of 600X 10 4 And g/mol, firstly preparing an ultra-high molecular weight polyethylene single-layer film by extrusion molding, stretching the single-layer film at 230 ℃ (stretching multiplying power is 600%), cooling and shaping at a cooling and shaping section at 60 ℃ after stretching, and preparing the ultra-high molecular weight polyethylene film after cooling and shaping.
In addition, the thickness of the prepared film is 0.2mm, and the friction coefficient and mechanical properties of the product are shown in the attached table 1.
Comparative example 1:
referring to the process flow shown in FIG. 1, the UHMWPE base material of this example has a molecular weight of 100×10 4 g/mol, respectively preparing three layers of films, namely two layers of surface layers and one layer of core layer by extrusion molding, wherein the core layer adopts ultra-high molecular weight polyethylene with the molecular weight of 100 multiplied by 10 4 g/mol, wherein the surface layer adopts UHMWPE/low molecular weight polymer/nano composite film; the UHMWPE/low molecular weight polymer/nano composite material used for extrusion molding is mixed with an organic solvent to prepare a mixed heterogeneous solution, the solvent is paraffin oil, the mass fraction of the UHMWPE/low molecular weight polymer/nano composite material in the heterogeneous solution is 6% wt, and the mixture ratio of the UHMWPE/low molecular weight polymer/nano composite material co-extruded on the surface layer is 30%:69.7%:0.3 percent of low molecular weight polymer is polyethylene wax, and the nano material is graphene; firstly, the forming process condition of the outer layer and the core layer film is that UHMWPE/low molecular weight polymer/nano composite material is mixedExtruding the mixed solution and UHMWPE resin through a double screw at 200 ℃; the surface layer film and the core layer film are stretched and compounded (stretching multiplying power is 300 percent and compression strength is 0.1 MPa) at 230 ℃, cooling and shaping is carried out at a cooling and shaping section at 30 ℃ after stretching and compounding, and the functional ultra-high molecular weight polyethylene composite film is prepared after cooling and shaping.
The thickness of the composite film obtained in this example was about 0.2mm, wherein the mass ratio of the ultra-high molecular weight polyethylene used to prepare the core film to the UHMWPE/low molecular weight polymer/nanocomposite used to prepare the skin film was about 85%:15%. The friction coefficient and mechanical properties of the product are shown in the attached table 1.
Comparative example 3:
the basic process flow is identical to that of example 1, except that the UHMWPE binder of this example has a molecular weight of 600X 10 4 g/mol, preparing a three-layer film by extrusion molding, namely two surface layers and one core layer, wherein the core layer adopts ultra-high molecular weight polyethylene with the molecular weight of 600 multiplied by 10 4 g/mol, wherein the surface layer adopts an UHMWPE nano composite film; the UHMWPE/nanocomposite used for extrusion molding is mixed with an organic solvent to prepare a mixed heterogeneous solution, the solvent is paraffin oil, the mass fraction of the UHMWPE nanocomposite in the heterogeneous solution is 18% wt, and the mixture ratio of the UHMWPE/nanocomposite co-extruded on the surface layer is 99.5%:0.5% of nano material which is graphene; firstly, the process conditions of forming the outer layer and the core layer film are that UHMWPE/nanocomposite mixed solution and UHMWPE resin are extruded and formed at 200 ℃ through double screws; secondly, extracting the surface film at normal temperature to prepare an extracted surface film, wherein the extraction solvent is n-hexane; finally, the extracted surface layer film and the core layer film are stretched and compounded (stretching multiplying power is 900 percent and compression strength is 0.8 MPa) at 200 ℃, and then are subjected to cooling shaping at 30 ℃ for cooling shaping, and the functional ultra-high molecular weight polyethylene composite film is prepared after cooling shaping.
In addition, the thickness of the composite film was about 0.2mm, wherein the mass ratio of the ultra-high molecular weight polyethylene used for preparing the core film was about 85%, and the mass ratio of the composite material used for preparing the skin film was about 15%. The friction coefficient and the mechanical properties of the product are shown in the attached table 1
Comparative example 8:
the basic process flow is identical to that of example 1, except that the UHMWPE binder of this example has a molecular weight of 200X 10 4 g/mol, preparing a three-layer film by extrusion molding, namely two surface layers and one core layer, wherein the core layer adopts ultra-high molecular weight polyethylene with the molecular weight of 200 multiplied by 10 4 g/mol, the surface layer adopts UHMWPE/low molecular weight polymer; the UHMWPE/low molecular weight polymer composite material used for extrusion molding is mixed with an organic solvent to prepare a mixed heterogeneous solution, the solvent is paraffin oil, the mass fraction of the UHMWPE/low molecular weight polymer composite material in the heterogeneous solution is 30% wt, and the surface layer co-extruded UHMWPE/low molecular weight polymer ratio is 30%:70 percent of low molecular weight polymer is polyethylene glycol, and the process conditions for forming the outer layer and the core layer film are that UHMWPE/low molecular weight polymer mixed solution and UHMWPE resin are extruded and formed by twin screws at 230 ℃; secondly, extracting the surface film at normal temperature to prepare an extracted surface film, wherein the extraction solvent is n-hexane; finally, the extracted surface layer film and the core layer film are stretched and compounded (stretching multiplying power is 600 percent and compression strength is 0.6 MPa) at 230 ℃, and then are subjected to cooling shaping at a cooling shaping section of 60 ℃ after being stretched, and the functional ultra-high molecular weight polyethylene composite film is prepared after cooling shaping.
The thickness of the resulting composite film was about 0.2mm, wherein the mass ratio of the ultra-high molecular weight polyethylene used for preparing the core film was about 85%, and the mass ratio of the composite material used for preparing the skin film was about 15%. The friction coefficient and mechanical properties of the product are shown in the attached table 1.
Table 1 mechanical properties of UHMWPE articles of examples
As can be seen from comparative examples 1, 3 and 8, comparative example 1 did not undergo an extraction step, and the solvent therein was not recovered by extraction, which affected the antistatic effect of the nanomaterial graphene; comparative example 3 the surface film UHMWPE resin lacks complexing with the low molecular weight polymer oleamide, so the friction coefficient of the article has a certain gap from example 3; comparative example 8 the top film lacks nanomaterial graphene and thus its article is an insulating material relative to example 8.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (10)
1. The preparation method of the ultra-high molecular weight polyethylene film composite material is characterized by comprising the following steps of:
(1) Preparing a three-layer film by extrusion molding, wherein the three-layer film is a core layer film and two surface layer films respectively, the core layer film is an ultra-high molecular weight polyethylene layer, and the surface layer film is a composite material layer compounded by UHMWPE, a low molecular weight polymer and a nano material;
(2) And (3) extracting the two layers of surface films, carrying out high-temperature stretching and compression molding composite forming on the two layers of surface films and the core film in a surface-core-surface mode, and finally cooling and shaping to obtain the functionalized ultra-high molecular weight polyethylene composite film which is a target product.
2. The method for producing an ultra-high molecular weight polyethylene film composite according to claim 1, wherein the ultra-high molecular weight polyethylene used in said core film has a viscosity average molecular weight of 100X 10 4 g/mol～900×10 4 g/mol。
3. The method for preparing the ultra-high molecular weight polyethylene film composite material according to claim 1, wherein the weight ratio of the UHMWPE, the low molecular weight polymer and the nano material in the composite material used for the surface layer is 30-60%wt, 39-70%wt and 0.1-1%wt respectively.
4. The method for preparing an ultra-high molecular weight polyethylene film composite material according to claim 1 or 3, wherein the low molecular weight polymer is one or a mixture of several of polyethylene wax, oleamide, erucamide and polyethylene glycol;
the nano material is one or a mixture of more of graphene, graphite and molybdenum disulfide.
5. The method for preparing an ultra-high molecular weight polyethylene film composite according to claim 1, wherein the UHMWPE/low molecular weight polymer/nanocomposite is first mixed with an organic solvent to prepare a mixed heterogeneous solution, and the mass fraction of the mixed heterogeneous solution is 6-30% wt.
6. The method for preparing an ultra-high molecular weight polyethylene film composite material according to claim 5, wherein the organic solvent is paraffin oil or decalin.
7. The method for preparing the ultra-high molecular weight polyethylene film composite material according to claim 1, wherein the core film and the surface film are prepared in a twin-screw extruder, and the extrusion molding temperature of the twin-screw extruder is 200-230 ℃.
8. The method for preparing the ultra-high molecular weight polyethylene film composite material according to claim 1, wherein the core layer film and the surface layer film are stretched at 200-230 ℃, the stretching multiplying power is 300-2000%, and finally the three layers of films are compounded at 180-230 ℃, and the compression molding compound forming pressure is 0.1-1.0 MPa.
9. The method for preparing an ultra-high molecular weight polyethylene film composite material according to claim 1, wherein the temperature for cooling and shaping is 30-60 ℃.
10. The method for preparing an ultra-high molecular weight polyethylene film composite material according to claim 1, wherein the extraction process of the surface film is carried out at normal temperature, and the extraction solvent used in the extraction process is n-hexane or n-heptane.
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