CN115521525B - 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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- CN115521525B CN115521525B CN202211225860.6A CN202211225860A CN115521525B CN 115521525 B CN115521525 B CN 115521525B CN 202211225860 A CN202211225860 A CN 202211225860A CN 115521525 B CN115521525 B CN 115521525B
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- 239000002131 composite material Substances 0.000 title claims abstract description 65
- -1 Polyethylene Polymers 0.000 title claims abstract description 42
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 40
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 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
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 24
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 24
- 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 15
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 21
- 229920002554 vinyl polymer Polymers 0.000 claims description 15
- 238000001125 extrusion Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000003963 antioxidant agent Substances 0.000 claims description 10
- 230000003078 antioxidant effect Effects 0.000 claims description 9
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000000314 lubricant Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 238000012360 testing method Methods 0.000 claims description 4
- 238000005336 cracking Methods 0.000 abstract description 36
- 230000006353 environmental stress Effects 0.000 abstract description 35
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 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
- 230000000052 comparative effect Effects 0.000 description 18
- 239000000243 solution Substances 0.000 description 11
- 239000000523 sample Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 230000003247 decreasing effect Effects 0.000 description 5
- 239000004611 light stabiliser Substances 0.000 description 4
- 239000007788 liquid Substances 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
- 239000000178 monomer Substances 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 239000004743 Polypropylene Substances 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
- 239000003973 paint Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000001105 regulatory effect Effects 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
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 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
- 150000001412 amines Chemical class 0.000 description 1
- 238000013459 approach Methods 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
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 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
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000010102 injection blow moulding Methods 0.000 description 1
- 238000007909 melt granulation 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
- 238000005507 spraying Methods 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 239000000126 substance Substances 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, 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 vinyl-terminated hyperbranched polyester comprises 5-70% of vinyl-terminated groups in the total number of the end groups of the hyperbranched polyester. According to the invention, by adding the vinyl-terminated hyperbranched polyester and the ethylene-vinyl acetate copolymer, the three components are compounded, so that the composite material can simultaneously achieve high environmental stress cracking resistance and high surface tension, and the unification of the two components can effectively apply the composite material to the preparation of wire and cable jackets; meanwhile, the cable also has excellent mechanical properties, and meets the application requirements of the sheath; in addition, in the preparation method provided by the invention, 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 wide use temperature, is suitable for extrusion molding, injection molding, blow molding and other technological conditions, can be molded into various shapes, and is widely applied to the fields of automobile manufacture, pipelines, electronic appliances, cable jackets, military and the like.
Although the energy production 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 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 is greatly limited. The research on environmental stress cracking resistance of the high-density polyethylene shows that the HDPE material is sensitive to polar solvents due to the special linear molecular chain structure, and when the polar solvents are immersed, even if the polar solvents are subjected to small external stress, the material can quickly crack from the surface, so that the use value of the HDPE material is greatly lost. On the other hand, the high-density polyethylene belongs to a nonpolar molecular structure because of symmetrical molecular structure, has very low surface polarity and small surface tension, and easily has the problems of infirm adhesion or paint dropping 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, and a preparation method and application thereof.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: the 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 end-capped hyperbranched polyester accounts for 5-70% of the total number of the end-capping groups of the hyperbranched polyester.
The polyethylene composite material provided by the invention is prepared from the high-density polyethylene resin with proper mass parts and the melt fingers within a certain range, and the vinyl-terminated hyperbranched polyester and the ethylene-vinyl acetate copolymer with the vinyl-terminated end capping group number accounting for the total group number of the hyperbranched polyester end groups within a certain range, wherein the vinyl-terminated hyperbranched polyester can be used for modifying 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 cracking resistance of the composite material is improved, and on the other hand, the surface of the hyperbranched polyester contains more polar groups, so that the polarity of the surface of the high-density polyethylene can be effectively improved, and the surface tension 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 act with high-density polyethylene; when proper mass parts are added, the three materials can ensure that the environmental stress cracking resistance and the surface tension of the composite material can reach better effects at the same time, and the polyethylene composite material with excellent comprehensive performance can be 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 addition amount of the component of the invention is within the above range, the environmental stress cracking resistance and the surface tension resistance can be more ensured while achieving the excellent effect, wherein the environmental stress cracking resistance F 50 The surface tension is above 35mN/m at more than 440 h.
As a preferable embodiment of the polyethylene composite material of the invention, the melt index of the high-density polyethylene resin is 0.5-0.9g/10min.
As a preferred embodiment of the polyethylene composite material according to the invention, the melt index of the high-density polyethylene resin is measured according to ISO1133-2011 (190 ℃/2.16 kg).
Preferably, the high-density polyethylene resin has a melt index of 0.5 to 0.9g/10min, which is composed ofIf the melt index is too high, entanglement of the vinyl-terminated hyperbranched polyester with the high-density polyethylene can be reduced within a certain range, so that the environmental stress cracking resistance of the composite material is reduced; in the preferred melt finger range of the invention, the composite material prepared by the method has better comprehensive performance, wherein F of environmental stress cracking resistance 50 The surface tension is above 37mN/m at 490 h.
As a preferred embodiment of the polyethylene composite material, the vinyl-terminated hyperbranched polyester is a hyperbranched polyester in which trimellitic anhydride is used as a core, AB2 type monomers synthesized by trimellitic anhydride and ethylene glycol are used as branches, and the vinyl-terminated hyperbranched polyester is terminated by a vinyl-containing end-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) The esterification polycondensation reaction between trimellitic anhydride and glycol is used for synthesizing AB2 type monomer, and then trimellitic anhydride is used as a core to react with the AB2 monomer to obtain un-blocked hyperbranched polyester;
(2) Capping the uncapped hyperbranched polyester with an ethylene capping agent to obtain a hyperbranched polyester containing vinyl capping;
and (3) regulating the vinyl end-capping rate of the hyperbranched polyester containing vinyl end capping by controlling the raw material dosage of the vinyl end-capping agent in the step (2), namely regulating the percentage of the number of end-capping groups containing vinyl in the hyperbranched polyester containing vinyl end capping to the total number of groups of the hyperbranched polyester end group.
As a preferred embodiment of the polyethylene composite material, the vinyl-terminated hyperbranched polyester comprises 20-40% of the total number of terminal groups of the hyperbranched polyester.
Preferably, the vinyl-terminated hyperbranched polyester has a vinyl-containing end-capping group amount of 20-40% of the total end-capping group amount of the hyperbranched polyester, and is also used for achieving a relatively balanced state between entanglement and increased polar group content, thereby improving the stress cracking resistance of the materialThe surface tension of the material can be ensured to reach a state with better comprehensive performance, wherein when the total performance is more preferably 20-40%, F with environmental stress cracking resistance is more preferable 50 Up to 520h, 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 auxiliary agent.
As a preferable embodiment of the polyethylene composite material, the auxiliary agent comprises a weather-proof 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 auxiliary agents in parts by mass: 0.2-2 parts of weather-proof agent, 0.1-3 parts of lubricant and 0.1-3 parts of antioxidant.
As a preferred 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 preferable embodiment of the polyethylene composite material of the invention, the lubricant is at least one of ethyl distearamide and erucamide.
As a preferable implementation mode of the polyethylene composite material, 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: and uniformly mixing the high-density polyethylene resin, the vinyl-terminated hyperbranched polyester, the ethylene-vinyl acetate copolymer and the auxiliary agent, and then carrying out melt extrusion to obtain the polypropylene composite material.
As a preferred embodiment of the preparation method of the present invention, the extrusion process conditions are as follows: extrusion screw aspect ratio (36-48): 1, the extrusion temperature is 1 zone 80-120 ℃,2-5 zone 180-200 ℃ and other zone 200-230 ℃.
In addition, the invention also provides application of the polyethylene composite material to a wire and cable sheath.
The polyethylene composite material provided by the invention has excellent environmental stress cracking resistance and high surface tension on the basis of ensuring the mechanical properties of the foundation, so that the characteristics that the inside of the sheath needs to be well adhered with other products and the outside needs to be water-resistant and solution-resistant when the wire and cable sheath is applied can be satisfied.
Compared with the prior art, the invention has the beneficial effects that:
according to the polyethylene composite material provided by the invention, the vinyl-terminated hyperbranched polyester and the ethylene-vinyl acetate copolymer are added, and the three components are compounded, so that the composite material can achieve high environmental stress cracking resistance and high surface tension at the same time, wherein the stress cracking resistance F is realized 50 The surface tension is above 34mN/m over 280 hours, and the unification of high environmental stress cracking resistance and high surface tension can effectively apply the composite material 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, raw materials are convenient and easy to obtain, and the production process is simple and is suitable for large-scale production.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples.
The reagents, methods and apparatus employed in the present invention are those conventional in the art unless otherwise indicated.
The raw materials used in the following examples and comparative examples are as follows:
high density polyethylene resin a (HDPE a): HDPE HD5502W, melt finger 0.5g/10min (190 ℃/2.16 kg), 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): for HDPE a and HDPE E according to HDPE a: modified HDPE material with a melt finger of 5.0g/10min (190 ℃/2.16 kg) prepared by melt granulation of HDPE D=2:8 through a double-screw extruder after blending;
high density polyethylene resin E (HDPE E): HDPE DMDA8008, melt finger 8g/10min (190 ℃/2.16 kg), blue;
vinyl-terminated hyperbranched polyester a: the end capping group containing vinyl groups accounts for 20% of the total number of the end groups of the hyperbranched polyester;
vinyl-terminated hyperbranched polyester B: the end capping group containing vinyl groups accounts for 40% of the total number of the end groups of the hyperbranched polyester;
vinyl-terminated hyperbranched polyester C: the end capping group containing vinyl groups accounts for 5% of the total number of the end groups of the hyperbranched polyester;
vinyl-terminated hyperbranched polyester D: the end capping group containing vinyl groups accounts for 70% of the total number of the end groups of the hyperbranched polyester;
vinyl-terminated hyperbranched polyester E: the end capping group containing vinyl groups accounts for 1% of the total number of the end groups of the hyperbranched polyester;
vinyl-terminated hyperbranched polyester F: the end capping group containing vinyl groups accounts for 80% of the total number of the end groups of the hyperbranched polyester; siloxane-terminated hyperbranched polyesters: the end capping group containing siloxane accounts for 20% of the total number of hyperbranched polyester end groups;
ethylene-vinyl acetate copolymer (EVA): EVA 40L-03, duPont Elvax brand;
POE elastomer: POE ENGAGE 7467, dow chemical;
and (3) a lubricant: ethyl bis-stearamide, commercially available;
weather-resistant agent: light stabilizer UV-3808PP5, commercially available;
an antioxidant: antioxidant 1010, antioxidant 168, commercially available.
The preparation methods of 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: extrusion screw aspect ratio was 42:1, extrusion temperature was 1 zone 100 ℃,2-5 zone 190 ℃, other zones 215 ℃.
Among them, the lubricants, weather-resistant agents and antioxidants in the examples and comparative examples were kept the same.
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
Effect example
The polyethylene composites prepared in examples 1-15 and comparative examples 1-10 were tested,
1. environmental stress cracking resistance: the polyethylene composite materials prepared in examples 1-15 and comparative examples 1-10 are subjected to injection molding to prepare ISO mechanical splines, a 100 x 2 mm-sized light plate is prepared by a melt hot pressing method, and the middle position is intercepted for testing the environmental stress cracking resistance and is tested by referring to GB/T1842; the operation method is as follows: 1) Hot-pressing the sample material to prepare a sample plate with the thickness of 2mm, and scoring the sample plate by a standard nicking tool in a central sampling test; 2) Bending according to requirement, placing into medium of surfactant (nonylphenol polyoxyethylene ether TX-10), keeping constant temperature water bath at 50+ -0.5deg.C, and counting the time when the breakage ratio of sample in medium is 50%, namely F 50 This value isThe larger the resistance to environmental stress cracking is, the better the resistance to environmental stress cracking is, and conversely, the worse the resistance to environmental stress cracking is;
2. surface tension: different grades of surface tension solutions were prepared according to the Ford BO 116-03 standard and tested as follows: when a liquid film is formed on the surface of a sample by applying a solution of a certain concentration to the sample with a cotton swab, if the liquid film is dispersed from a continuous state to a small droplet for more than 2 seconds, the experiment is repeated on a new sample with a solution of a larger surface tension. Until the liquid film duration is approximately 2s; if the liquid film duration is less than 2s, it is tested with a lower surface tension solution to make it possible to approach 2s; the prepared solution is stored in a volumetric flask until the solution is tested for no more than 24 hours; the solution ratios and corresponding surface tension values are shown in table 3 below;
TABLE 3 Table 3
The results obtained from the test are shown in Table 4;
TABLE 4 Table 4
As can be seen from examples 1 to 4, when the added fraction of the vinyl-terminated hyperbranched polyester is changed, the surface tension of the resulting composite increases with the increase of the added fraction of the vinyl-terminated hyperbranched polyester within a certain range, and F which reflects the environmental stress cracking resistance 50 The value is increased and then decreased, when the added part of the vinyl terminated hyperbranched polyester is 10 to 20 parts, the F which is resistant to environmental stress cracking is obtained 50 The value is above 490h, and the surface tension is above 36 mN/m; as can be seen from examples 1-4 and comparative examples 3-4, when the added portion of the vinyl-terminated hyperbranched polyester is excessiveWhen the amount of the vinyl-terminated hyperbranched polyester is too small, for example, only 1 part of the compound of comparative example 3, the surface tension of the obtained composite material is too low, only 32mN/m, and when the amount of the vinyl-terminated hyperbranched polyester is too large, the environmental stress cracking resistance of the obtained composite material is lowered, F 50 The value is reduced to below 200 h;
as can be seen from examples 1, 13-15 and comparative examples 7-8, when the percentage of vinyl-terminated hyperbranched polyester containing vinyl-terminated end groups to the total number of hyperbranched polyester end groups is changed, the combination properties of the composite material are also affected, and when the percentage is too small, the resulting composite material has insufficient environmental stress cracking resistance, 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 decreasing trend; as can be seen from example 1 and comparative example 9, when not vinyl-terminated hyperbranched polyesters but siloxane-terminated hyperbranched polyesters are used, the resulting composites have poor environmental stress crack resistance, corresponding to F 50 The value is only 150h;
as can be seen from examples 1, examples 5 to 7 and comparative example 5, when the added fraction of EVA was changed, as the added fraction of EVA was increased, the effect on the surface tension was insignificant compared to the environmental stress cracking resistance, and a weak upward trend was exhibited, but the environmental stress cracking resistance exhibited a tendency of significantly increasing before significantly decreasing, especially when the added fraction of EVA was increased from 8 parts in example 7 to 10 parts in comparative example 5, F, which reacted to the environmental stress cracking resistance 50 The value is reduced from 400h to 250h, and the reduction amplitude reaches 37.5%; from examples 1 and 5 to 7, it was found that when the added part of EVA was continuously increased from 3 parts in example 1 to 8 parts in example 7, the environmental stress cracking resistance had begun to exhibit a decreasing tendency, and therefore, it was further preferable that the added part of EVA was 1 to 3 parts;
as can be seen from examples 1, 10-12 and comparative example 6, the melt fingers of the high density polyethylene also have an effect on the environmental stress cracking resistance of the composite without significantly affecting the surface tensionThe method comprises the steps of carrying out a first treatment on the surface of the With the increase of the melt index, the environmental stress cracking resistance of the obtained composite material shows a trend of increasing and then decreasing, and when the melt index is 0.1-5g/10min, F is obtained 50 The value is more than 300 h; in particular, F is obtained when the melt index is 0.5-0.9g/10min 50 The value is above 490 h; the composite material obtained 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 resulting composite had significantly poorer environmental stress cracking resistance, F 50 The value is compared with F of example 1 50 The value is reduced by 76.92-80.77%, and the surface tension also shows a tendency of reduction; as can be seen from example 1 and comparative example 10, when EVA is not used but POE is used, the surface tension and environmental stress cracking resistance of the resulting composite material are significantly deteriorated, wherein F, which reacts environmental stress cracking resistance 50 The value is compared with F of example 1 50 The value drop was 71.15%.
Finally, it should be noted that the above-mentioned embodiments illustrate rather than limit the scope of the invention, and that those skilled in the art will understand that changes can be made to the technical solutions of the invention or equivalents thereof without departing from the spirit and scope of the technical solutions of the 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 obtained by testing under the condition of 190 ℃/2.16kg is 0.1-5g/10min;
the number of the end-capping groups containing vinyl in the vinyl end-capped hyperbranched polyester accounts for 5-70% of the total number of the end-capping groups of the hyperbranched polyester.
2. The polyethylene composite material according to claim 1, 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 vinyl-terminated hyperbranched polyester comprises 20 to 40% of the total number of terminal groups of the hyperbranched polyester.
5. The polyethylene composite material according to claim 1, wherein the polyethylene composite material further comprises 0.3 to 8 parts of an auxiliary agent.
6. The polyethylene composite material according to claim 5, wherein the auxiliary agent comprises a weather resistant agent, a lubricant and an antioxidant.
7. A method of preparing a polyethylene composite material according to any one of claims 1 to 6, wherein the method of preparing comprises the steps of: and uniformly mixing the high-density polyethylene resin, the vinyl-terminated hyperbranched polyester, the ethylene-vinyl acetate copolymer and the auxiliary agent, and then carrying out melt extrusion to obtain the polyethylene composite material.
8. The method of claim 7, wherein the extrusion process conditions are: extrusion screw aspect ratio (36-48): 1, the extrusion temperature is 1 zone 80-120 ℃,2-5 zone 180-200 ℃ and other zone 200-230 ℃.
9. Use of the polyethylene composite material according to any one of claims 1-6 in wire and cable jackets.
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| 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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