CN118271654A - Anti-aging toughened reinforced polyolefin plastic and preparation method thereof - Google Patents
Anti-aging toughened reinforced polyolefin plastic and preparation method thereof Download PDFInfo
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- CN118271654A CN118271654A CN202410491193.9A CN202410491193A CN118271654A CN 118271654 A CN118271654 A CN 118271654A CN 202410491193 A CN202410491193 A CN 202410491193A CN 118271654 A CN118271654 A CN 118271654A
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- 229920000098 polyolefin Polymers 0.000 title claims abstract description 68
- 230000003712 anti-aging effect Effects 0.000 title claims abstract description 51
- 229920003023 plastic Polymers 0.000 title claims abstract description 46
- 239000004033 plastic Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- -1 polysiloxane Polymers 0.000 claims abstract description 72
- 230000003014 reinforcing effect Effects 0.000 claims abstract description 39
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 38
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 28
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 27
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 229920005989 resin Polymers 0.000 claims abstract description 16
- 239000011347 resin Substances 0.000 claims abstract description 16
- 150000001336 alkenes Chemical class 0.000 claims abstract description 14
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003999 initiator Substances 0.000 claims abstract description 12
- 238000001125 extrusion Methods 0.000 claims abstract description 10
- 238000005469 granulation Methods 0.000 claims abstract description 10
- 230000003179 granulation Effects 0.000 claims abstract description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 9
- 239000010703 silicon Substances 0.000 claims abstract description 9
- 229920002545 silicone oil Polymers 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 239000004698 Polyethylene Substances 0.000 claims description 42
- 229920000573 polyethylene Polymers 0.000 claims description 42
- 239000004743 Polypropylene Substances 0.000 claims description 20
- 229920001155 polypropylene Polymers 0.000 claims description 19
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 15
- 229920002050 silicone resin Polymers 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000000155 melt Substances 0.000 claims description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000003377 acid catalyst Substances 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 5
- 229920006124 polyolefin elastomer Polymers 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000032683 aging Effects 0.000 abstract description 36
- 239000000203 mixture Substances 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 239000002861 polymer material Substances 0.000 abstract description 3
- 206010051246 Photodermatosis Diseases 0.000 abstract description 2
- 229920001002 functional polymer Polymers 0.000 abstract description 2
- 230000008845 photoaging Effects 0.000 abstract description 2
- 230000014759 maintenance of location Effects 0.000 description 44
- 229920001684 low density polyethylene Polymers 0.000 description 16
- 239000004702 low-density polyethylene Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 230000000694 effects Effects 0.000 description 12
- 229920001903 high density polyethylene Polymers 0.000 description 12
- 239000004700 high-density polyethylene Substances 0.000 description 12
- 238000012986 modification Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical compound C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 239000000806 elastomer Substances 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- NLDGJRWPPOSWLC-UHFFFAOYSA-N deca-1,9-diene Chemical compound C=CCCCCCCC=C NLDGJRWPPOSWLC-UHFFFAOYSA-N 0.000 description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 2
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 2
- 229960001545 hydrotalcite Drugs 0.000 description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- VJHGSLHHMIELQD-UHFFFAOYSA-N nona-1,8-diene Chemical compound C=CCCCCCC=C VJHGSLHHMIELQD-UHFFFAOYSA-N 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 239000012745 toughening agent Substances 0.000 description 2
- 230000003679 aging effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- GEAWFZNTIFJMHR-UHFFFAOYSA-N hepta-1,6-diene Chemical compound C=CCCCC=C GEAWFZNTIFJMHR-UHFFFAOYSA-N 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/10—Block- or graft-copolymers containing polysiloxane sequences
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- 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 belongs to the technical field of functional polymer materials, and discloses an anti-aging toughening reinforced polyolefin plastic and a preparation method thereof. The preparation method comprises the following steps: adding hydrogen terminated silicone oil and alpha, omega-diene into an organic solvent according to the mol ratio of 1:2-2.2, heating and catalyzing the mixture to react to obtain olefin terminated modified polysiloxane; then carrying out melt blending reaction on polyolefin, olefin end-capped modified polysiloxane, vinyl MQ silicon resin and an initiator, and extruding and granulating to obtain anti-aging toughening reinforcing master batch; and then the obtained anti-aging toughening reinforcing master batch and the polyolefin base material are subjected to melt blending extrusion granulation to obtain the anti-aging toughening reinforcing polyolefin plastic. The invention can obviously improve the strength, toughness, high-temperature aging resistance and photo-aging resistance of polyolefin plastics by introducing chemical grafted long-chain polysiloxane and vinyl MQ silicon resin into the polyolefin base material.
Description
Technical Field
The invention belongs to the technical field of functional polymer materials, and particularly relates to an anti-aging toughening reinforced polyolefin plastic and a preparation method thereof.
Background
The Polyolefin (PO) material is a material based on a polymer obtained by polymerizing or copolymerizing one or more olefins, and mainly includes Polyethylene (PE), polypropylene (PP), polyolefin elastomer (POE), ethylene-vinyl acetate copolymer (EVA), and the like. Is a polymer material with the largest yield and the largest application; among them, PE and PP are the most important. The method has the characteristics of abundant raw materials, low price, easy processing and forming, excellent comprehensive performance and the like, and is most widely applied in real life.
However, the conventional polyolefin material has the defects of poor high temperature resistance and poor weather resistance, is easy to age and deform after long-term use, and can reduce the defects through modification. Patent CN 112341689B discloses a polyethylene composite material with thermal aging resistance, comprising the following components: polyethylene, a cross-linking agent, an antioxidant, polyethylene wax, light calcium carbonate and hydrotalcite. The polyethylene composite material is based on polyethylene, and a certain amount of polyethylene wax, light calcium carbonate, hydrotalcite, cross-linking agent and antioxidant are added into the polyethylene composite material, so that the thermal stability of the polyethylene composite material is improved by utilizing the interaction of the components, and the polyethylene composite material can work in an environment higher than 100 ℃ for a long time. However, the addition of too high an amount of inorganic material reduces the strength and toughness of the polyethylene material. Patent CN 114933756B discloses an aging-resistant polyethylene material, which comprises the following raw materials in parts by weight: 90-110 parts of polyethylene, 10-20 parts of maleic anhydride grafted polyethylene and 5-10 parts of organic-inorganic complexing agent, wherein the organic-inorganic complexing agent is ultraviolet-resistant metal oxide modified by titanate-organosilicon composition. The ultraviolet-resistant metal oxide modified by the titanate-organic silicon composition has better shielding effect and absorbing effect on ultraviolet rays, so that the ultraviolet aging resistance of the polyethylene is effectively improved. The improvement effect on the mechanical property and the thermo-oxidative aging property of the polyethylene material is limited.
In addition, the polyolefin material has the defect of slightly poor toughness, the toughness of the polyolefin material can be improved by adding a corresponding toughening agent, the common toughening agent is maleic anhydride grafted polyethylene/polypropylene (PE/PP-g-MAH), but the polyolefin material cannot form an elastomer part due to the lack of active groups reacting with maleic anhydride, so that the toughening effect is slightly poor, and in addition, the PE/PP-g-MAH has very limited effect of improving the ageing resistance of the polyolefin material.
Therefore, the polyolefin material which can simultaneously improve the mechanical property, the high-temperature aging resistance and the photo-aging resistance so as to widen the application scene and the durability has obvious research value and commercial value.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the primary purpose of the invention is to provide a preparation method of anti-aging toughening reinforced polyolefin plastic.
The invention also aims to provide the anti-aging toughening reinforced polyolefin plastic prepared by the method.
The invention aims at realizing the following technical scheme:
a preparation method of anti-aging toughened and reinforced polyolefin plastic comprises the following preparation steps:
(1) The mol ratio of the hydrogen-terminated silicone oil to the alpha, omega-diene is 1: 2-2.2 are added into an organic solvent to be stirred and dissolved uniformly, a chloroplatinic acid catalyst is added after deoxidization by nitrogen, then the temperature is raised to 70-90 ℃ to be stirred and reacted, and the solvent is removed by reduced pressure distillation after the reaction is completed, so that olefin end-capped modified polysiloxane (VPDMS) is obtained;
(2) Adding Polyolefin (PO), olefin end-capped modified polysiloxane (VPDMS), vinyl MQ silicon resin (VMQ) and an initiator into an extruder, carrying out melt blending reaction, and then extruding and granulating to obtain anti-aging toughening reinforcing master batch;
(3) And (3) adding the anti-aging toughening and reinforcing master batch obtained in the step (2) and the polyolefin base material into an extruder, and carrying out melt blending, extrusion and granulation to obtain the anti-aging toughening and reinforcing polyolefin plastic.
Preferably, the hydrogen terminated silicone oil in step (1) is hydrogen terminated silicone oil with weight average molecular weight of 1000-20000 and viscosity of 10-600 mpa.s at 25 ℃.
Preferably, the alpha, omega= -diene in the step (1) is an alpha, omega-diene with carbon number more than or equal to 6. Such as 1, 5-hexadiene, 1, 6-heptadiene, 1, 7-octadiene, 1, 8-nonadiene, 1, 9-decadiene, and the like. According to the invention, the olefin with the carbon number of more than or equal to 6 is adopted to carry out end capping modification on polysiloxane so as to achieve the effects of compatibilization and plasticization, the compatibility of long-chain polysiloxane and polyolefin can be obviously improved, and the thermoplasticity of a solid product is improved, so that the grafting efficiency of the mixing reaction of the long-chain polysiloxane and polyolefin material is improved, and meanwhile, the olefin end capping modified polysiloxane can form an elastomer structure with polyolefin, and finally, the effects of obviously improving ageing resistance and toughness are achieved.
Preferably, the organic solvent in the step (1) is toluene, xylene, petroleum ether, isopropanol, butanol, etc.
Preferably, the polyolefin in step (2) is Polyethylene (PE) or polypropylene (PP).
Preferably, the vinyl MQ silicone resin in the step (2) is a vinyl MQ silicone resin with a molecular weight of 3000-8000 g/mol and a vinyl content of 0.5-3.0 wt%. It is commercially available and can be solvent type liquid vinyl MQ silicone resin or powder vinyl MQ silicone resin, such as 5202P vinyl VMQ resin, 5202S vinyl VMQ resin, 5202N vinyl VMQ resin, etc. of Hubei New four-sea chemical industry Co., ltd. The invention adopts vinyl MQ silicon resin as a reinforcing agent, and can obviously improve the strength of the obtained polyolefin plastic. And the reinforcing effect is more obvious under the compatibilization effect of the olefin end-capped modified polysiloxane.
Preferably, the mass ratio of polyolefin, olefin end-capped modified polysiloxane, vinyl MQ silicone resin added in the step (2) is 100: 2-10: 2 to 10.
Preferably, the initiator in step (2) is dicumyl peroxide (DCP), benzoyl Peroxide (BPO) or Azobisisobutyronitrile (AIBN); the addition amount of the initiator is 0.1 to 0.5 percent of the mass of the polyolefin.
Preferably, the temperature of the melt blending reaction in the step (2) is 180-220 ℃ and the time is 15-90 min.
Preferably, the polyolefin substrate in step (3) is Polyethylene (PE), polypropylene (PP), polyolefin elastomer (POE) or ethylene vinyl acetate copolymer (EVA).
Preferably, the addition amount of the anti-aging toughening reinforcing master batch in the step (3) is 5-15% of the mass of the polyolefin base material.
The anti-aging toughened and reinforced polyolefin plastic is prepared by the method.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the invention, the anti-aging toughening reinforcing master batch is prepared by carrying out graft copolymerization on the olefin end-capped modified polysiloxane and the polyolefin, and the chemically grafted long-chain polysiloxane can be introduced into the polyolefin base material, so that an elastomer structure can be formed, and the anti-aging performance and toughness of the polyolefin plastic are obviously improved.
(2) According to the invention, by introducing the vinyl MQ silicon resin and by the compatibilization of the olefin end-capped modified polysiloxane, a cross-linked network can be formed in the polyolefin base material, so that the reinforcing effect is achieved, and the strength of the obtained polyolefin plastic is obviously improved.
Detailed Description
The present invention will be described in further detail with reference to examples, but embodiments of the present invention are not limited thereto.
Example 1
A preparation method of anti-aging toughened and reinforced polyolefin plastic comprises the following preparation steps:
(1) Hydrogen terminated silicone oil (commercially available, average molecular weight 6000, h content 0.032, viscosity 100mpa.s at 25 ℃) was mixed with 1, 7-octadiene in a molar ratio of 1:2.1 adding the mixture into toluene solvent, stirring and dissolving uniformly, adding chloroplatinic acid catalyst solution after deoxidizing by nitrogen, heating to 80 ℃ and stirring and reacting for 5 hours, detecting the H content, and removing the solvent and unreacted raw materials by reduced pressure distillation to obtain pale yellow viscous liquid octene end-capped modified polysiloxane (VPDMS), wherein the alkenyl content (calculated by CH 2 =CH < - >) of the product is measured to be 0.92wt.%.
(2) Adding low-density polyethylene (LDPE), octene end-capped modified polysiloxane (VPDMS), powder vinyl MQ silicone resin (5202P vinyl VMQ resin, molecular weight 5150g/mol, vinyl content 1.07 wt%) and initiator dicumyl peroxide (DCP) into a double-screw extruder, carrying out melt blending reaction, extruding and granulating to obtain the anti-aging toughening reinforcing master batch. Wherein LDPE, VPDMS, VMQ is added in the mass ratio of 100:5:5, DCP is added in an amount of 0.4% by mass of LDPE. The temperature of each section from the feeding port to the outlet in the double-screw extruder is controlled to be 180 ℃, 190 ℃, 210 ℃, 200 ℃ and 180 ℃ respectively, and the feeding rotation speed is controlled to control the melt blending reaction to be 60 minutes.
(3) Adding the anti-aging toughening and reinforcing master batch obtained in the step (2) and high-density polyethylene (HDPE) into a double-screw extruder, carrying out melt blending, extrusion and granulation, wherein the addition amount of the anti-aging toughening and reinforcing master batch is 10% of the mass of the HDPE, and the temperatures of all sections from a feeding port to an outlet in the double-screw extruder are respectively controlled to 170 ℃, 185 ℃,200 ℃, 180 ℃ and 175 ℃ to obtain the anti-aging toughening and reinforcing polyethylene plastic.
The polyethylene plastic obtained in this example was subjected to tensile strength (GB/T1040-2018), impact strength (GB/T1843-2008), heat aging resistance (GB/T7141-2008, heat aging conditions were 135℃for 168 hours, then tested for tensile strength retention (tensile strength after aging/tensile strength before aging X100%) and impact strength retention (impact strength after aging/impact strength before aging X100%), ultraviolet aging resistance (GB/T16422.3-2022, UVA-340 (type 1A) fluorescent ultraviolet lamp, 5 exposure cycles were conducted according to the artificially accelerated weathering conditions of method A, and then tested for tensile strength retention and impact strength retention). And the polyethylene prepared by using equivalent maleic anhydride grafted polyethylene (PE-g-MAH) to replace VPDMS is used as a control group.
The test result shows that the tensile strength of the polyethylene plastic obtained in the embodiment is 65.2MPa, and the impact strength is 77.9KJ/m 2; the retention rate of the heat aging tensile strength is 93.2 percent, and the retention rate of the impact strength is 95.1 percent; the retention of tensile strength by ultraviolet aging was 94.5%, and the retention of impact strength was 92.8%. The tensile strength of the polyethylene plastic prepared by PE-g-MAH is 62.6MPa, and the impact strength is 68.4KJ/m 2; the retention of heat aged tensile strength is 82.6% and the retention of impact strength is 79.8%; the retention of tensile strength by ultraviolet aging is 81.2%, and the retention of impact strength is 85.0%.
Example 2
A preparation method of anti-aging toughened and reinforced polyolefin plastic comprises the following preparation steps:
(1) Hydrogen terminated silicone oil (commercially available, average molecular weight 18000, h content 0.011, viscosity 500mpa.s at 25 ℃) was combined with 1, 9-decadiene in a molar ratio of 1:2.0 is added into toluene solvent, stirred and dissolved uniformly, the chloroplatinic acid catalyst solution is added after deoxidization by nitrogen, then the temperature is raised to 90 ℃ and stirred and reacted for 4 hours, the solvent and unreacted raw materials are removed by reduced pressure distillation after the reaction of detecting the H content is completed, and the white solid decene end-capped modified polysiloxane (VPDMS) is obtained, and the alkenyl content of the product is measured to be 0.30 wt%.
(2) Polypropylene (PP), decene end-capped modified polysiloxane (VPDMS), powder vinyl MQ silicon resin (5202P vinyl VMQ resin, molecular weight 5150g/mol, vinyl content 1.07 wt%) and initiator Benzoyl Peroxide (BPO) are added into a double-screw extruder for melt blending reaction, and then extrusion granulation is carried out, so that the anti-aging toughening reinforcing master batch is obtained. Wherein PP, VPDMS, VMQ is added in the mass ratio of 100:2: the addition amount of the BPO is 0.4 percent of the mass of the PP. The temperature of each section from the feeding port to the outlet in the double-screw extruder is controlled to be 180 ℃, 190 ℃, 210 ℃, 200 ℃ and 180 ℃ respectively, and the feeding rotation speed is controlled to control the melt blending reaction to be 60 minutes.
(3) Adding the anti-aging toughening and reinforcing master batch obtained in the step (2) and polypropylene (PP) into a double-screw extruder, carrying out melt blending extrusion granulation, wherein the addition amount of the anti-aging toughening and reinforcing master batch is 15% of the mass of the PP, and the temperatures of all sections from a feeding port to an outlet in the double-screw extruder are respectively controlled to 170 ℃, 185 ℃, 200 ℃, 180 ℃ and 175 ℃ to obtain the anti-aging toughening and reinforcing polypropylene plastic.
The polypropylene plastic obtained in the example has a tensile strength of 73.8MPa and an impact strength of 60.2KJ/m 2; the retention of heat aged tensile strength is 92.5% and the retention of impact strength is 92.4%; the retention of tensile strength by ultraviolet aging is 92.8%, and the retention of impact strength is 90.3%. The tensile strength of the polypropylene plastic prepared by adopting equivalent PP-g-MAH to replace VPDMS is 69.4MPa, and the impact strength is 48.7KJ/m 2; the retention rate of the heat aging tensile strength is 81.7 percent, and the retention rate of the impact strength is 82.5 percent; the retention of tensile strength by ultraviolet aging was 74.6%, and the retention of impact strength was 69.2%.
Example 3
A preparation method of anti-aging toughened and reinforced polyolefin plastic comprises the following preparation steps:
(1) Hydrogen terminated silicone oil (commercially available with an average molecular weight of 1000, an h content of 0.203% and a viscosity of 10mpa.s at 25 ℃) was combined with 1, 5-hexadiene in a molar ratio of 1:2.2 adding the mixture into toluene solvent, stirring and dissolving uniformly, adding chloroplatinic acid catalyst solution after deoxidizing by nitrogen, heating to 70 ℃, stirring and reacting for 6 hours, detecting the H content, and removing the solvent and unreacted raw materials by reduced pressure distillation to obtain light yellow liquid hexene end-capped modified polysiloxane (VPDMS), wherein the alkenyl content of the product is measured to be 4.76 wt%.
(2) Adding low-density polyethylene (LDPE), hexene end-capped modified polysiloxane (VPDMS), powder vinyl MQ silicone resin (5202P vinyl VMQ resin, molecular weight 3200g/mol, vinyl content 1.12 wt%) and initiator dicumyl peroxide (DCP) into a double-screw extruder, carrying out melt blending reaction, extruding and granulating to obtain the anti-aging toughening reinforcing master batch. Wherein PE, VPDMS, VMQ is added in the mass ratio of 100:10:10, the DCP is added in an amount of 0.5% by mass of LDPE. The temperature of each section from the feeding port to the outlet in the double-screw extruder is controlled to be 180 ℃, 190 ℃, 210 ℃, 200 ℃ and 180 ℃ respectively, and the feeding rotation speed is controlled to control the melt blending reaction to be 60 minutes.
(3) Adding the anti-aging toughening and reinforcing master batch obtained in the step (2) and high-density polyethylene (HDPE) into a double-screw extruder, carrying out melt blending, extrusion and granulation, wherein the addition amount of the anti-aging toughening and reinforcing master batch is 5% of the mass of the HDPE, and the temperatures of all sections from a feeding port to an outlet in the double-screw extruder are respectively controlled to 170 ℃, 185 ℃, 200 ℃, 180 ℃ and 175 ℃ to obtain the anti-aging toughening and reinforcing polyethylene plastic.
The polyethylene plastic obtained in the example has a tensile strength of 57.3MPa, an impact strength of 68.6KJ/m 2, a heat aging tensile strength retention of 96.0% and an impact strength retention of 96.7%; the retention of tensile strength by ultraviolet aging was 95.7%, and the retention of impact strength was 94.2%. The tensile strength of the polyethylene plastic prepared by adopting equivalent PE-g-MAH to replace VPDMS is 53.1MPa, and the impact strength is 55.3KJ/m 2; the retention of heat aging tensile strength is 79.3%, and the retention of impact strength is 80.7%; the retention of tensile strength by ultraviolet aging was 76.9%, and the retention of impact strength was 79.2%.
As can be seen from the results of the examples 1 to 3, according to the invention, VPDMS and VMQ are adopted to carry out chemical grafting and blending modification on polyolefin plastics, compared with PE/PP-g-MAH and VMQ modification, the heat aging resistance and ultraviolet aging resistance of the polyethylene plastics can be obviously improved, and meanwhile, the toughness improvement effect on the materials is more obvious. In addition, under the compatibilization effect of VPDMS, the VMQ has more remarkable reinforcing effect.
Comparative example 1
Compared with the example 1, the comparative example is not added with VMQ, and is replaced by VPDMS (namely, the mass ratio of LDPE and VPDMS added in the anti-aging toughening reinforcing master batch is 100:10), and the rest is the same.
The polyethylene plastic obtained in the example has a tensile strength of 46.5MPa and an impact strength of 70.2KJ/m 2; the retention rate of the heat aging tensile strength is 88.5 percent, and the retention rate of the impact strength is 87.8 percent; the retention of tensile strength by ultraviolet aging is 90.1%, and the retention of impact strength is 89.6%.
As can be seen from the comparison result of the comparative example and the example 1, the mechanical strength of the polyolefin material can be obviously improved by introducing VMQ as the reinforcing agent, and the polyolefin material has a certain synergistic effect on the improvement of the toughness and the ageing resistance of the material.
Comparative example 2
In this comparative example, compared to example 1, octene-terminated modified polysiloxane (VPDMS) was added in step (3), specifically prepared as follows:
step (1) is the same as in example 1.
(2) Low-density polyethylene (LDPE), powder vinyl MQ silicon resin (5202P vinyl VMQ resin, molecular weight 5150g/mol, vinyl content 1.07 wt%) and initiator dicumyl peroxide (DCP) are added into a double-screw extruder to be subjected to melt blending reaction, and then extrusion granulation is carried out, so that the reinforced master batch is obtained. Wherein the mass ratio of LDPE to VMQ is 100:5, DCP is added in an amount of 0.4% by mass of LDPE. The temperature of each section from the feeding port to the outlet in the double-screw extruder is controlled to be 180 ℃, 190 ℃, 210 ℃, 200 ℃ and 180 ℃ respectively, and the feeding rotation speed is controlled to control the melt blending reaction to be 60 minutes.
(3) Adding the reinforced master batch obtained in the step (2), the octene end-capped modified polysiloxane (VPDMS) and the high-density polyethylene (HDPE) obtained in the step (1) into a double-screw extruder, carrying out melt blending extrusion granulation, wherein the addition amount of VPDMS is 5% of the mass of the reinforced master batch, the addition amount of the reinforced master batch is 10% of the mass of the HDPE, and the temperatures of all sections from a feeding port to an outlet in the double-screw extruder are respectively controlled to be 170 ℃, 185 ℃,200 ℃, 180 ℃ and 175 ℃ to obtain the reinforced polyethylene plastic.
The polyethylene plastic obtained in this comparative example had a tensile strength of 61.7MPa and an impact strength of 64.5KJ/m 2; the retention rate of the heat aging tensile strength is 85.1 percent, and the retention rate of the impact strength is 83.8 percent; the retention of tensile strength by ultraviolet aging is 84.3%, and the retention of impact strength is 87.4%.
As can be seen from the comparison of the present comparative example with example 1, by performing chemical grafting reaction of VPDMS with the polyolefin material in advance and further forming a crosslinked elastomer structure, the aging resistance and toughness of the obtained polyolefin material can be remarkably improved. And under the compatibilization effect of VPDMS, the VMQ has more remarkable reinforcing effect.
Comparative example 3
In this comparative example, as compared to example 1, a powdered vinyl MQ silicone resin (VMQ) was added in step (3), specifically prepared as follows:
step (1) is the same as in example 1.
(2) Adding low-density polyethylene (LDPE), octene end-capped modified polysiloxane (VPDMS) and initiator dicumyl peroxide (DCP) into a double-screw extruder, carrying out melt blending reaction, and then extruding and granulating to obtain the anti-aging toughening reinforcing master batch. Wherein the mass ratio of LDPE to VPDMS is 100:5, DCP is added in an amount of 0.4% by mass of LDPE. The temperature of each section from the feeding port to the outlet in the double-screw extruder is controlled to be 180 ℃, 190 ℃, 210 ℃, 200 ℃ and 180 ℃ respectively, and the feeding rotation speed is controlled to control the melt blending reaction to be 60 minutes.
(3) Adding the anti-aging toughening reinforcing master batch obtained in the step (2), powder vinyl MQ silicone resin (5202P vinyl VMQ resin, molecular weight 5150g/mol, vinyl content 1.07 wt%) and high-density polyethylene (HDPE) into a double-screw extruder, carrying out melt blending, extrusion and granulation, wherein the addition amount of the VMQ is 5% of the mass of the anti-aging toughening reinforcing master batch, the addition amount of the anti-aging toughening reinforcing master batch is 10% of the mass of the HDPE, and the temperatures of all sections from a feeding port to an outlet in the double-screw extruder are respectively controlled to be 170 ℃, 185 ℃, 200 ℃,180 ℃ and 175 ℃ to obtain the reinforced polyethylene plastic.
The tensile strength of the polyethylene plastic obtained in the comparative example is 53.8MPa, and the impact strength is 69.0KJ/m 2; the retention of tensile strength after heat aging is 90.6% and the retention of impact strength is 91.4%; the retention of tensile strength by ultraviolet aging is 92.2%, and the retention of impact strength is 89.5%.
As can be seen from the comparison between the present comparative example and example 1, the reinforcing effect of VMQ can be significantly improved by performing chemical grafting reaction on VMQ and polyolefin material under VPDMS compatibilization in advance.
Comparative example 4
This comparative example was the same as example 1, except that instead of octene-terminated modified polysiloxane (VPDMS), a terminal vinyl polydimethylsiloxane (commercially available, average molecular weight 6000, vinyl content 0.92wt.%, viscosity 100mpa.s at 25 ℃ C.) was used having the same vinyl content.
The polyethylene plastic obtained in this comparative example has a tensile strength of 62.1MPa and an impact strength of 60.3KJ/m 2; the retention of tensile strength after heat aging is 84.7%, and the retention of impact strength is 84.5%; the retention of tensile strength by ultraviolet aging is 85.6%, and the retention of impact strength is 88.2%.
As can be seen from the comparison of the comparative example and the example 1, VPDMS used for grafting modification has too short carbon chain, poor compatibility with polyolefin, and poor compatibilization effect on VMQ, so that the mechanical property and ageing resistance of the obtained polyolefin material are obviously reduced.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the anti-aging toughened and reinforced polyolefin plastic is characterized by comprising the following preparation steps:
(1) Adding hydrogen-terminated silicone oil and alpha, omega-diene into an organic solvent according to the mol ratio of 1:2-2.2, stirring and dissolving uniformly, adding a chloroplatinic acid catalyst after deoxidizing nitrogen, heating to 70-90 ℃ for stirring and reacting, and removing the solvent by reduced pressure distillation after the reaction is completed to obtain olefin end-capped modified polysiloxane;
(2) Adding polyolefin, olefin end-capped modified polysiloxane, vinyl MQ silicon resin and an initiator into an extruder, carrying out melt blending reaction, and then extruding and granulating to obtain anti-aging toughening reinforcing master batch;
(3) And (3) adding the anti-aging toughening and reinforcing master batch obtained in the step (2) and the polyolefin base material into an extruder, and carrying out melt blending, extrusion and granulation to obtain the anti-aging toughening and reinforcing polyolefin plastic.
2. The method for preparing the anti-aging toughened and reinforced polyolefin plastic according to claim 1, wherein the hydrogen terminated silicone oil in the step (1) has a weight average molecular weight of 1000-20000 and a viscosity of 10-600 mpa.s at 25 ℃; the alpha, omega-diene is alpha, omega-diene with carbon number more than or equal to 6.
3. The method for preparing the anti-aging, toughening and reinforcing polyolefin plastic according to claim 1, wherein the organic solvent in the step (1) is one or more than two of toluene, xylene, petroleum ether, isopropanol and butanol.
4. The method for producing an anti-aging, toughening and reinforcing polyolefin plastic according to claim 1, wherein the polyolefin in the step (2) is polyethylene or polypropylene.
5. The method for preparing the anti-aging toughened and reinforced polyolefin plastic according to claim 1, wherein the vinyl MQ silicone resin in the step (2) is vinyl MQ silicone resin with a molecular weight of 3000-8000 g/mol and a vinyl content of 0.5-3.0 wt%.
6. The method for preparing the anti-aging toughened and reinforced polyolefin plastic according to claim 1, wherein the mass ratio of the polyolefin, the olefin end-capped modified polysiloxane and the vinyl MQ silicone resin added in the step (2) is 100:2-10:2-10.
7. The method for preparing the anti-aging, toughening and reinforcing polyolefin plastic according to claim 1, wherein the initiator in the step (2) is dicumyl peroxide, benzoyl peroxide or azobisisobutyronitrile; the addition amount of the initiator is 0.1 to 0.5 percent of the mass of the polyolefin; the temperature of the melt blending reaction is 180-220 ℃ and the time is 15-90 min.
8. The method for producing an anti-aging, toughening and reinforcing polyolefin plastic according to claim 1, wherein the polyolefin substrate in the step (3) is polyethylene, polypropylene, polyolefin elastomer or ethylene-vinyl acetate copolymer.
9. The method for preparing the anti-aging, toughening and reinforcing polyolefin plastic according to claim 1, wherein the addition amount of the anti-aging, toughening and reinforcing master batch in the step (3) is 5-15% of the mass of the polyolefin base material.
10. An anti-aging toughened and reinforced polyolefin plastic, characterized in that it is prepared by the method of any one of claims 1 to 9.
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