CN115521525A - Polyethylene composite material and preparation method and application thereof - Google Patents
Polyethylene composite material and preparation method and application thereof Download PDFInfo
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- CN115521525A CN115521525A CN202211225860.6A CN202211225860A CN115521525A CN 115521525 A CN115521525 A CN 115521525A CN 202211225860 A CN202211225860 A CN 202211225860A CN 115521525 A CN115521525 A CN 115521525A
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- hyperbranched polyester
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- 239000002131 composite material Substances 0.000 title claims abstract description 63
- -1 Polyethylene Polymers 0.000 title claims abstract description 41
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 38
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229920006150 hyperbranched polyester Polymers 0.000 claims abstract description 63
- 229920001903 high density polyethylene Polymers 0.000 claims abstract description 51
- 239000004700 high-density polyethylene Substances 0.000 claims abstract description 51
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 28
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 26
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 25
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 25
- 229920005989 resin Polymers 0.000 claims abstract description 22
- 239000011347 resin Substances 0.000 claims abstract description 22
- 239000000155 melt Substances 0.000 claims abstract description 14
- 238000001125 extrusion Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000003963 antioxidant agent Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 239000000314 lubricant Substances 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 230000006353 environmental stress Effects 0.000 abstract description 33
- 239000000463 material Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 229920003023 plastic Polymers 0.000 abstract description 2
- 239000004033 plastic Substances 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 1
- 238000005336 cracking Methods 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 17
- 239000000243 solution Substances 0.000 description 10
- 230000003078 antioxidant effect Effects 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000003247 decreasing effect Effects 0.000 description 5
- 239000004611 light stabiliser Substances 0.000 description 4
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 4
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229940037312 stearamide Drugs 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical class OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 1
- 229920003345 Elvax® Polymers 0.000 description 1
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006355 external stress Effects 0.000 description 1
- 238000010102 injection blow moulding Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003873 salicylate salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/18—Protection against damage caused by wear, mechanical force or pressure; Sheaths; Armouring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a polyethylene composite material and a preparation method and application thereof, belonging to the technical field of modified plastics; the composite material provided by the invention comprises the following components in parts by weight: 100 parts of high-density polyethylene resin, 0.5-25 parts of vinyl-terminated hyperbranched polyester and 0.5-8 parts of ethylene-vinyl acetate copolymer; the melt index of the high-density polyethylene resin is 0.1-5g/10min; the end capping groups containing vinyl in the vinyl-terminated hyperbranched polyester account for 5 to 70 percent of the total number of the end groups of the hyperbranched polyester. According to the invention, the vinyl-terminated hyperbranched polyester and the ethylene-vinyl acetate copolymer are added, and the compounding of the vinyl-terminated hyperbranched polyester and the ethylene-vinyl acetate copolymer can enable the composite material to simultaneously achieve high environmental stress crack resistance and high surface tension, and the unification of the two can enable the composite material to be effectively applied to the preparation of the wire and cable sheath; meanwhile, the material also has excellent mechanical properties and meets the application requirements of the sheath; in addition, in the preparation method provided by the invention, the raw materials are easy to obtain, the production process is simple, and the preparation method is suitable for large-scale production.
Description
Technical Field
The invention belongs to the technical field of modified plastics, and particularly relates to a polyethylene composite material and a preparation method and application thereof.
Background
The high-density polyethylene (HDPE) has a wide use temperature, is suitable for the process conditions of extrusion molding, injection molding, blow molding and the like, can be molded into products with various shapes, and is widely applied to the fields of automobile manufacturing, pipelines, electronic and electric appliances, cable sheaths, military affairs and the like.
Although the yield and demand of the high-density polyethylene continuously rise every year, on one hand, the simple linear molecular chain structure of the high-density polyethylene determines that the high-density polyethylene product has poor environmental stress cracking resistance, and the environmental stress cracking phenomenon is particularly easy to occur in the application process, so that the service time of the high-density polyethylene product is greatly shortened, and the application range of the high-density polyethylene product is greatly limited. Research on environmental stress cracking resistance of high-density polyethylene shows that due to the special linear molecular chain structure of HDPE, the material is sensitive to polar solvents, and when the HDPE is soaked in the polar solvents, even if the HDPE is subjected to small external stress, the material can be cracked from the surface quickly, so that the use value of the HDPE is greatly lost. On the other hand, the high density polyethylene belongs to a nonpolar molecular structure because of the symmetry of the molecular structure, the surface polarity is very low, the surface tension is small, and the problems of poor adhesion or paint removal by paint spraying easily occur during adhesion or paint spraying.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a polyethylene composite material with high environmental stress cracking resistance and high surface tension, a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the technical scheme that: a polyethylene composite material comprises the following components in parts by weight: 100 parts of high-density polyethylene resin, 5-25 parts of vinyl-terminated hyperbranched polyester and 0.5-8 parts of ethylene-vinyl acetate copolymer (EVA); the melt index of the high-density polyethylene resin is 0.1-5g/10min; the number of the end capping groups containing vinyl in the vinyl-terminated hyperbranched polyester accounts for 5-70% of the total number of the end groups of the hyperbranched polyester.
The polyethylene composite material provided by the invention selects the high-density polyethylene resin with proper mass parts and fused meaning in a certain range, the vinyl-terminated hyperbranched polyester with the number of vinyl terminated groups accounting for the total number of hyperbranched polyester terminal groups in a certain range, and the ethylene-vinyl acetate copolymer, wherein the vinyl-terminated hyperbranched polyester can modify the high-density polyethylene resin with a linear structure to a certain extent due to the hyperbranched structure, so that the overall entanglement effect of the composite material is improved, and the environmental stress crack resistance of the composite material is improved; the ethylene-vinyl acetate copolymer can be further matched with vinyl-terminated hyperbranched polyester, so that the ethylene-vinyl acetate copolymer can fully react with high-density polyethylene; when the three components are added in proper mass parts, the environmental stress cracking resistance and the surface tension of the composite material can simultaneously achieve better effects, and the polyethylene composite material with excellent comprehensive performance is obtained.
As a preferred embodiment of the polyethylene composite material, the polyethylene composite material comprises the following components in parts by weight: 100 parts of high-density polyethylene resin, 10-20 parts of vinyl-terminated hyperbranched polyester and 1-3 parts of ethylene-vinyl acetate copolymer.
When the component addition amount of the present invention is within the above range, the environmental stress cracking resistance and surface tension resistance, wherein F is environmental stress cracking resistance, can be more ensured while achieving superior effects 50 The surface tension is more than 35mN/m when the time is more than 440 h.
As a preferred embodiment of the polyethylene composite material of the present invention, the melt index of the high density polyethylene resin is 0.5 to 0.9g/10min.
As a preferred embodiment of the polyethylene composite material of the invention, the melt index of the high density polyethylene resin is measured according to ISO1133-2011 (190 ℃/2.16 kg).
The melt index of the high-density polyethylene resin is preferably 0.5-0.9g/10min, because if the melt index is too high, the entanglement of the vinyl-terminated hyperbranched polyester and the high-density polyethylene is reduced in a certain range, so that the environmental stress cracking resistance of the composite material is reduced; in the preferred range of the melt index, the composite material prepared by the method has better comprehensive performance, wherein the F with environmental stress cracking resistance 50 The surface tension is more than 37mN/m when the time is more than 490 h.
In a preferred embodiment of the polyethylene composite material of the present invention, the vinyl-terminated hyperbranched polyester is a hyperbranched polyester in which trimellitic anhydride is used as a core, and an AB2 type monomer synthesized from trimellitic anhydride and ethylene glycol is used as a branch and is terminated with a vinyl-containing capping reagent.
As a preferred embodiment of the polyethylene composite material, the vinyl-terminated hyperbranched polyester is self-made, and the preparation method comprises the following steps:
(1) Synthesizing AB2 type monomer through esterification polycondensation reaction between trimellitic anhydride and ethylene glycol, and reacting with the AB2 type monomer by taking trimellitic anhydride as a core to obtain non-terminated hyperbranched polyester;
(2) Using an ethylene end capping agent to end cap the non-end capped hyperbranched polyester to obtain vinyl end capped hyperbranched polyester;
and (3) adjusting the vinyl end-capping rate in the vinyl end-capped hyperbranched polyester by controlling the raw material amount of the ethylene end-capping agent in the step (2), namely adjusting the percentage of the number of the end-capping groups containing vinyl in the vinyl end-capped hyperbranched polyester to the total number of the end-groups of the hyperbranched polyester.
As a preferred embodiment of the polyethylene composite material, the number of the end capping groups containing vinyl in the vinyl-terminated hyperbranched polyester accounts for 20-40% of the total number of the end groups of the hyperbranched polyester.
Preferably, the amount of the end capping groups containing vinyl in the vinyl-terminated hyperbranched polyester accounts for 20-40% of the total amount of the end groups of the hyperbranched polyester, and the purpose is to enable the entanglement degree and the increase degree of the polar group content to reach a relative balance state, so that the stress crack resistance of the material is improved, the surface tension of the material can be ensured, and a state with better comprehensive performance is achieved, wherein when the amount of the end capping groups containing vinyl in the vinyl-terminated hyperbranched polyester is further preferably 20-40%, the environmental stress crack resistance F 50 Can reach 520h, and the surface tension can reach 37mN/m.
As a preferable embodiment of the polyethylene composite material, the polyethylene composite material further comprises 0.3-8 parts of an auxiliary agent.
As a preferred embodiment of the polyethylene composite material, the auxiliary agents comprise a weather-resistant agent, a lubricant and an antioxidant.
As a preferred embodiment of the polyethylene composite material of the present invention, the polyethylene composite material comprises the following additives in parts by mass: 0.2-2 parts of weather resisting agent, 0.1-3 parts of lubricant and 0.1-3 parts of antioxidant.
As a preferable embodiment of the polyethylene composite material, the weather-resistant agent is at least one of LIGHT STABILIZERs UV-3808PP5, T-81, LA-402AF, M535 LIGHT STABILIZER, o-hydroxybenzophenones, benzotriazoles, salicylates, triazines, substituted acrylonitriles and Hindered Amine LIGHT STABILIZERs (HALS).
As a preferred embodiment of the polyethylene composite material of the present invention, the lubricant is at least one of ethyl bis stearamide and erucamide.
As a preferred embodiment of the polyethylene composite material of the present invention, the antioxidant is at least one of antioxidant SONOX 1010, antioxidant SONOX 168, antioxidant SONOX 1076, and antioxidant DLTDP.
In addition, the invention also provides a preparation method of the polyethylene composite material, which comprises the following steps: the high-density polyethylene resin, the vinyl-terminated hyperbranched polyester, the ethylene-vinyl acetate copolymer and the auxiliary agent are uniformly mixed and then melted and extruded to obtain the polypropylene composite material.
As a preferred embodiment of the preparation method of the present invention, the process conditions of the extrusion are as follows: the length-diameter ratio of the extrusion screw is (36-48): 1, the extrusion temperature is 80-120 ℃ in the 1 region, 180-200 ℃ in the 2-5 region and 200-230 ℃ in the other regions.
In addition, the invention also provides an application of the polyethylene composite material on a wire and cable sheath.
The polyethylene composite material provided by the invention has excellent environmental stress crack resistance and high surface tension on the basis of ensuring the mechanical property of the foundation, so that the characteristics that the inside of the sheath of the electric wire and cable needs to be well bonded with other products and the outside needs to resist water and solution when the sheath is applied can be met.
Compared with the prior art, the invention has the following beneficial effects:
according to the polyethylene composite material provided by the invention, the vinyl-terminated hyperbranched polyester and the ethylene-vinyl acetate copolymer are added and compounded to enable the composite material to simultaneously achieve high environmental stress crack resistance and high surface tension, wherein F of the stress crack resistance 50 The surface tension is more than 34mN/m at more than 280h, and the combination of high environmental stress crack resistance and high surface tension can ensure that the composite material can be effectively applied to the preparation of the wire and cable sheath; meanwhile, the polyethylene composite material provided by the invention also has excellent mechanical properties and meets the application requirements of the sheath; in addition, in the preparation method provided by the invention, the raw materials are convenient and easy to obtain, the production process is simple, and the preparation method is suitable for large-scale production。
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
The reagents, methods and equipment used in the invention are conventional in the art unless otherwise specified.
The raw materials used in the following examples and comparative examples are as follows:
high density polyethylene resin a (HDPE a): HDPE HD5502W, melt means 0.5g/10min (190 ℃/2.16 kg), china Korean petrochemical;
high density polyethylene resin B (HDPE B): HDPE 5000S, melt index 0.9g/10min (190 ℃/2.16 kg), medium petroleum;
high density polyethylene resin C (HDPE C): HDPE HMCRP100N, melt index 0.1g/10min (190 ℃/2.16 kg), sichuan petrochemical;
high density polyethylene resin D (HDPE D): HDPE a and HDPE E as per HDPE a: the weight ratio of HDPE D = 2;
high density polyethylene resin E (HDPE E): HDPE DMDA8008, melt means 8g/10min (190 ℃/2.16 kg), blue;
vinyl-terminated hyperbranched polyester a: the end capping groups containing vinyl account for 20 percent of the total number of the terminal groups of the hyperbranched polyester;
vinyl terminated hyperbranched polyester B: the end capping groups containing vinyl account for 40 percent of the total number of the terminal groups of the hyperbranched polyester;
vinyl terminated hyperbranched polyester C: the end capping groups containing vinyl account for 5 percent of the total number of the terminal groups of the hyperbranched polyester;
vinyl terminated hyperbranched polyester D: the end capping groups containing vinyl account for 70 percent of the total number of the terminal groups of the hyperbranched polyester;
vinyl terminated hyperbranched polyester E: the end capping groups containing vinyl account for 1 percent of the total number of the terminal groups of the hyperbranched polyester;
vinyl terminated hyperbranched polyester F: the end capping groups containing vinyl account for 80 percent of the total number of the terminal groups of the hyperbranched polyester; siloxane-terminated hyperbranched polyester: the siloxane-containing end capping groups account for 20 percent of the total number of the terminal groups of the hyperbranched polyester;
ethylene-vinyl acetate copolymer (EVA): EVA 40L-03, duPont Elvax brand;
POE elastomer: POE ENGAGE 7467, dow chemistry;
lubricant: ethyl bis stearamide, commercially available;
weather-resistant agent: light stabilizer UV-3808PP5, commercially available;
antioxidant: antioxidant 1010, antioxidant 168, commercially available.
The preparation methods of the examples and comparative examples are as follows:
uniformly mixing high-density polyethylene resin, hyperbranched polyester, ethylene-vinyl acetate copolymer and an auxiliary agent, and then carrying out melt extrusion to obtain a polypropylene composite material; the extrusion process conditions are as follows: the length-diameter ratio of the extrusion screw is 42:1, the extrusion temperature is 100 ℃ in a 1 zone, 190 ℃ in a 2-5 zone and 215 ℃ in other zones.
Wherein, the lubricants, weather-resistant agents and antioxidants in the examples and the comparative examples are all kept consistent.
Examples 1 to 9 and comparative examples 1 to 5
The component contents (parts by weight) of examples 1 to 9 and comparative examples 1 to 5 are shown in Table 1;
TABLE 1
Examples 10 to 15 and comparative examples 6 to 10
The component contents (parts by weight) of examples 10 to 15 and comparative examples 6 to 10 are shown in Table 2;
TABLE 2
Effects of the invention
The polyethylene composites prepared in examples 1 to 15 and comparative examples 1 to 10 were tested,
1. environmental stress cracking resistance: preparing ISO mechanical sample bars from the polyethylene composite materials prepared in examples 1-15 and comparative examples 1-10 by injection molding, preparing light plates with the size of 100 x 2mm by a melt hot pressing method, cutting the middle position for testing the environmental stress cracking resistance, and testing by referring to GB/T1842; the operation method comprises the following steps: 1) Preparing a sample plate with the thickness of 2mm by hot pressing the sample material, and notching by a standard nicking tool in a central sampling test; 2) Bending and placing the sample into a medium (nonylphenol polyoxyethylene ether TX-10) of a surfactant according to the requirement, keeping the constant temperature of the water bath at 50 +/-0.5 ℃, and counting the time of 50 percent of the damage ratio of the sample in the medium, namely F 50 The larger the value is, the better the environmental stress cracking resistance is, otherwise, the worse is;
2. surface tension: various grades of surface tension solutions were prepared according to the Ford BO 116-03 standard and tested as follows: the solution was applied to the sample plate with a cotton swab at a concentration and when a film of liquid was formed on the surface of the sample plate, if the time for the film to spread from a continuous state to a small droplet exceeded 2s, the experiment was repeated with a solution of greater surface tension on a new sample plate. Until the liquid film duration approaches 2s; if the liquid film duration is less than 2s, then testing with a lower surface tension solution allows it to approach 2s; the prepared solution is stored in a volumetric flask until the time before the test is not more than 24 hours; the solution ratios and corresponding surface tension values are given in table 3 below;
TABLE 3
The results obtained from the tests are shown in table 4;
TABLE 4
As can be seen from examples 1-4, when the number of vinyl terminated hyperbranched polyester added is changed, the surface tension of the obtained composite material is increased with the increase of the number of vinyl terminated hyperbranched polyester added in a certain range, and F, the environmental stress cracking resistance of the reaction is improved 50 The value is increased and then decreased, when the adding part of the vinyl-terminated hyperbranched polyester is 10 to 20 parts, the obtained F resisting the environmental stress cracking 50 The value is more than 490h, and the surface tension is more than 36 mN/m; as can be seen from examples 1 to 4 and comparative examples 3 to 4, when the number of added parts of the vinyl-terminated hyperbranched polyester is too small, for example, only 1 part of the vinyl-terminated hyperbranched polyester in comparative example 3, the surface tension of the resulting composite is too low, and only 32mN/m, and when the number of added parts of the vinyl-terminated hyperbranched polyester is too large, the environmental stress cracking resistance of the resulting composite is lowered, and F is a factor F 50 The value is reduced to be below 200 h;
as can be seen from examples 1, 13 to 15 and 7 to 8, when the percentage of the terminal group containing vinyl group in the vinyl-terminated hyperbranched polyester to the total number of terminal groups of the hyperbranched polyester is changed, the overall properties of the composite material are also affected, and when the percentage is too low, the composite material obtained has insufficient environmental stress cracking resistance and F 50 The value is only 220h, and when the percentage content is increased on the basis of 70%, the environmental stress cracking resistance and the surface tension of the obtained composite material show a descending trend; as can be seen from example 1 and comparative example 9, when not a vinyl-terminated hyperbranched polyester but a siloxane-terminated hyperbranched polyester is used, the composite obtained has a poor environmental stress crack resistance, corresponding to F 50 The value is only 150h;
as can be seen from example 1, examples 5 to 7 and comparative example 5, when the number of added parts of EVA was changed, as the number of added parts of EVA increased,the influence on the surface tension was insignificant and a slight upward tendency was exhibited as compared with the environmental stress cracking resistance, but the environmental stress cracking resistance exhibited a tendency of being significantly increased and then significantly decreased, particularly when the number of EVA added was increased from 8 parts in example 7 to 10 parts in comparative example 5, F, which reflects the environmental stress cracking resistance 50 The value is reduced from 400h to 250h, and the reduction amplitude reaches 37.5%; it was found from example 1 and examples 5 to 7 that the environmental stress crack resistance started to exhibit a decreasing tendency as the number of parts of EVA added continued to increase from 3 parts in example 1 to 8 parts in example 7, and therefore, it is further preferable that the number of parts of EVA added is 1 to 3 parts;
as can be seen from examples 1, 10-12 and comparative example 6, the melt index of the high density polyethylene also has an effect on the environmental stress crack resistance of the composite material, but has no significant effect on the surface tension; the environmental stress cracking resistance of the obtained composite material shows a tendency of increasing and then decreasing along with the increase of the melt index, and when the melt index is 0.1-5g/10min, the obtained F 50 The value is above 300 h; in particular, when the melt index is between 0.5 and 0.9g/10min, F is obtained 50 The value is above 490 h; the obtained composite material has better comprehensive performance;
as can be seen from example 1 and comparative examples 1-2, when no vinyl-terminated hyperbranched polyester or EVA was added, the environmental stress crack resistance of the resulting composite was significantly deteriorated, and F thereof 50 Value compared to F of example 1 50 The value is reduced by 76.92-80.77%, and the surface tension also shows a descending trend; as can be seen from example 1 and comparative example 10, when not EVA but POE was used, the surface tension and environmental stress crack resistance of the resulting composite were significantly deteriorated, wherein F, which reflects the environmental stress crack resistance, was significantly deteriorated 50 Value compared to F of example 1 50 The value decreased by 71.15%.
Finally, it should be noted that the above embodiments are intended to illustrate the technical solutions of the present invention and not to limit the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (9)
1. The polyethylene composite material is characterized by comprising the following components in parts by weight: 100 parts of high-density polyethylene resin, 5-25 parts of vinyl-terminated hyperbranched polyester and 0.5-8 parts of ethylene-vinyl acetate copolymer;
the melt index of the high-density polyethylene resin is 0.1-5g/10min;
the number of the end capping groups containing vinyl in the vinyl-terminated hyperbranched polyester accounts for 5-70% of the total number of the end groups of the hyperbranched polyester.
2. The polyethylene composite material as claimed in claim 1, characterized by comprising the following components in parts by weight: 100 parts of high-density polyethylene resin, 10-20 parts of vinyl-terminated hyperbranched polyester and 1-3 parts of ethylene-vinyl acetate copolymer.
3. The polyethylene composite material according to claim 1, wherein the high density polyethylene resin has a melt index of 0.5 to 0.9g/10min.
4. The polyethylene composite material according to claim 1, wherein the amount of the terminal groups containing vinyl groups in the vinyl-terminated hyperbranched polyester is 20-40% of the total amount of terminal groups in the hyperbranched polyester.
5. The polyethylene composite according to claim 1, further comprising 0.3-8 parts of an auxiliary.
6. The polyethylene composite according to claim 5, wherein the auxiliary agents comprise weather-resistant agents, lubricants and antioxidants.
7. Process for the preparation of a polyethylene composite according to any one of claims 1 to 6, characterized in that it comprises the following steps: the high-density polyethylene resin, the vinyl-terminated hyperbranched polyester, the ethylene-vinyl acetate copolymer and the auxiliary agent are uniformly mixed and then melted and extruded to obtain the polypropylene composite material.
8. The method of claim 7, wherein the extrusion process conditions are: the length-diameter ratio of the extrusion screw is (36-48): 1, the extrusion temperature is 80-120 ℃ in a zone 1, 180-200 ℃ in a zone 2-5 and 200-230 ℃ in other zones.
9. Use of the polyethylene composite according to any one of claims 1 to 6 in a sheath for electric wires and cables.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20030212173A1 (en) * | 2002-05-13 | 2003-11-13 | The Procter & Gamble Company | Compositions of polyolefins and hyperbranched polymers with improved tensile properties |
| CN110885433A (en) * | 2019-05-24 | 2020-03-17 | 武汉金发科技有限公司 | Hyperbranched polyester and synthesis method thereof, and thermoplastic resin composition and preparation method thereof |
| CN114213736A (en) * | 2021-12-10 | 2022-03-22 | 临海伟星新型建材有限公司 | Modified high-density polyethylene hose and composition thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030212173A1 (en) * | 2002-05-13 | 2003-11-13 | The Procter & Gamble Company | Compositions of polyolefins and hyperbranched polymers with improved tensile properties |
| CN110885433A (en) * | 2019-05-24 | 2020-03-17 | 武汉金发科技有限公司 | Hyperbranched polyester and synthesis method thereof, and thermoplastic resin composition and preparation method thereof |
| CN114213736A (en) * | 2021-12-10 | 2022-03-22 | 临海伟星新型建材有限公司 | Modified high-density polyethylene hose and composition thereof |
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