CN115109194B - Polyethylene grafted maleic anhydride hot melt adhesive modified material and preparation method thereof - Google Patents
Polyethylene grafted maleic anhydride hot melt adhesive modified material and preparation method thereof Download PDFInfo
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- CN115109194B CN115109194B CN202210976445.8A CN202210976445A CN115109194B CN 115109194 B CN115109194 B CN 115109194B CN 202210976445 A CN202210976445 A CN 202210976445A CN 115109194 B CN115109194 B CN 115109194B
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- polyethylene
- maleic anhydride
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- hot melt
- carbon dioxide
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- 239000004698 Polyethylene Substances 0.000 title claims abstract description 110
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 109
- -1 Polyethylene Polymers 0.000 title claims abstract description 90
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 239000000463 material Substances 0.000 title claims abstract description 74
- 239000004831 Hot glue Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims description 16
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 92
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 46
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 46
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 30
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 27
- 239000000178 monomer Substances 0.000 claims abstract description 27
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 26
- 239000003999 initiator Substances 0.000 claims abstract description 22
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 20
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims description 21
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- 229920001903 high density polyethylene Polymers 0.000 claims description 11
- 239000004700 high-density polyethylene Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000002023 wood Substances 0.000 claims description 9
- 229920001587 Wood-plastic composite Polymers 0.000 claims description 8
- 239000011155 wood-plastic composite Substances 0.000 claims description 8
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 7
- 235000013539 calcium stearate Nutrition 0.000 claims description 7
- 239000008116 calcium stearate Substances 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 6
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 6
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 3
- 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 3
- GOKFBDXJQGPRML-UHFFFAOYSA-N 2-ethylperoxy-2-methylpropane Chemical compound CCOOC(C)(C)C GOKFBDXJQGPRML-UHFFFAOYSA-N 0.000 claims description 3
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims description 3
- 238000001746 injection moulding Methods 0.000 claims description 3
- 235000019359 magnesium stearate Nutrition 0.000 claims description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 3
- 150000007970 thio esters Chemical class 0.000 claims description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 3
- KVWLLOIEGKLBPA-UHFFFAOYSA-N 3,6,9-triethyl-3,6,9-trimethyl-1,2,4,5,7,8-hexaoxonane Chemical compound CCC1(C)OOC(C)(CC)OOC(C)(CC)OO1 KVWLLOIEGKLBPA-UHFFFAOYSA-N 0.000 claims description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N isopropyl-benzene Natural products CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims 1
- 239000002530 phenolic antioxidant Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 10
- 238000001125 extrusion Methods 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 4
- 229920001577 copolymer Polymers 0.000 abstract description 3
- 150000003254 radicals Chemical class 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 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 4
- 238000005303 weighing Methods 0.000 description 4
- 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 3
- 230000000694 effects Effects 0.000 description 3
- 229920013716 polyethylene resin Polymers 0.000 description 3
- DEKVAWHRMRNKMI-UHFFFAOYSA-N 1,2-bis(tert-butylperoxy)-3-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC(OOC(C)(C)C)=C1OOC(C)(C)C DEKVAWHRMRNKMI-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000005429 filling process Methods 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
- C08F255/026—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms on to ethylene-vinylester copolymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention provides a polyethylene grafted maleic anhydride hot melt adhesive modified material, which comprises the following components: 90-100 parts of polyethylene and 0-10 parts of ethylene-vinyl acetate copolymer; maleic anhydride 0.5-3 weight portions; 0.5 to 3 parts by weight of monomer; 0.1 to 1 weight portion of antioxidant; 0.1 to 1 weight portion of initiator; 0.01 to 1 weight portion of other auxiliary agents; 1-5 parts of carbon dioxide. The invention introduces supercritical carbon dioxide into PE melt extrusion process, fully utilizes the supercritical state of the supercritical carbon dioxide, plays a plasticizing role, reduces the viscosity of the system, improves the fluidity of substances in an extruder, increases the collision probability of free radical active sites and copolymers such as maleic anhydride monomers, EVA and the like, and improves the grafting rate and the bonding performance. Residual monomers in the material are carried out more effectively by utilizing carbon dioxide, the odor of a grafted product is reduced, and the environment-friendly polyethylene grafted maleic anhydride hot melt adhesive modified material is obtained.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a polyethylene grafted maleic anhydride hot melt adhesive modified material and a preparation method thereof.
Background
Polyethylene (PE) is the simplest resin variety with molecular composition and structure, has flexible molecular chains, is easy to crystallize, is in a semitransparent state, has excellent film forming property, chemical stability, and good mechanical strength and air permeability, and is widely applied to the fields of agriculture, food packaging and the like as one of thermoplastic plastics. However, due to the low surface energy of PE and the nonpolar nature of molecular chains, the PE has poor compatibility and cohesiveness with materials, and the application direction of the PE is greatly limited, so that the functional modification of polyethylene has profound research significance.
At present, polyethylene is functionalized to mainly graft polyethylene, and functional groups are introduced into molecular chains. Among them, maleic Anhydride (MAH) has a symmetrical molecular structure as an unsaturated compound containing a polar group, has high reactivity and hardly forms long-chain branches in PE molecules, and is often used as a grafting monomer. The grafted PE-g-MAH product can be used as an adhesive layer and a hot melt adhesive of an extruded composite film, and can also be used as a compatilizer for blending PE and various polar polymers. However, the grafting efficiency of the polyethylene grafted maleic anhydride product industrialized at the present stage is low, residual monomers cannot be separated sufficiently, so that pungent odor can be generated in the production process, the grafting rate of the product is low, and the effect of improving the compatibility of the polyethylene is not ideal.
Therefore, the preparation method of the green environment-friendly polyethylene grafted maleic anhydride hot melt adhesive modified material is provided, so that the compatibility with other matched components is good, the grafting rate is high, and the VOC content is low.
Disclosure of Invention
In view of the above, the technical problem to be solved by the invention is to provide a polyethylene grafted maleic anhydride hot melt adhesive modified material which has high grafting rate and good cohesiveness, and has good blending compatibility with polyethylene and wood powder.
The invention provides a polyethylene grafted maleic anhydride hot melt adhesive modified material, which comprises the following components:
90-100 parts of polyethylene and 0-10 parts of ethylene-vinyl acetate copolymer; maleic anhydride 0.5-3 weight portions; 0.5 to 3 parts by weight of monomer; 0.1 to 1 weight portion of antioxidant; 0.1 to 1 weight portion of initiator; 0.01 to 1 weight portion of other auxiliary agents; 1-5 parts of carbon dioxide.
Preferably, the polyethylene grafted maleic anhydride hot melt adhesive modified material comprises:
90-100 parts of polyethylene and 2-10 parts of ethylene-vinyl acetate copolymer; 1-3 parts by weight of maleic anhydride; 1-3 parts by weight of monomer; 0.1 to 0.8 weight portion of antioxidant; 0.1 to 0.8 weight portion of initiator; 0.01 to 0.8 weight portion of other auxiliary agents; 1-4 parts of carbon dioxide.
Preferably, the polyethylene is selected from high density polyethylene, and the melt flow index is 1g/10 min-10 g/10min; the ethylene-vinyl acetate copolymer is selected from VA with 30-40%.
Preferably, the antioxidant is selected from one or more of hindered phenol antioxidants, phosphite antioxidants and thioester antioxidants;
the monomer is selected from one or more of styrene, divinylbenzene, 1, 6-hexanediol diacrylate and dicyclopentadiene;
the initiator is selected from one or more of di-tert-butyl peroxide, dicumyl peroxide, 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxynonane (301), 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) ethane (101), and bis-tert-butylperoxyisopropylbenzene;
the other auxiliary agent is selected from one or more of calcium stearate, magnesium stearate and zinc stearate.
The invention provides a preparation method of a polyethylene grafted maleic anhydride hot melt adhesive modified material, which is characterized by comprising the following steps:
mixing polyethylene, ethylene-vinyl acetate copolymer, maleic anhydride, monomer, antioxidant, initiator and other assistants, adding carbon dioxide into a double-screw extruder, vacuumizing, extruding to form strips, cooling, air-cooling to remove water, and granulating.
Preferably, the carbon dioxide is supercritical carbon dioxide;
the carbon dioxide is added at 1-5% of the feeding speed of the polyethylene;
the carbon dioxide adding pressure is 3-8 MPa, and the temperature is 20-40 ℃.
Preferably, the heating area from the feed opening to the machine head of the double-screw extruder is provided with 12 sections, sequentially set at 120-150 ℃, 135-180 ℃, 160-200 ℃ and 160-200 ℃, 160-200 ℃ and 160-200 ℃, the rotating speed of the screw is 150-400 r/min, and the feeding rotating speed is 4-10 kg/h.
The invention provides a polyethylene-based wood-plastic composite material, which comprises the polyethylene grafted maleic anhydride hot melt adhesive modified material prepared by any one of the technical schemes or the preparation method of any one of the technical schemes.
Preferably, the polyethylene grafted maleic anhydride hot melt adhesive modified material is added in an amount of 5-10% wt.
The invention provides a preparation method of a polyethylene-based wood-plastic composite material, which comprises the following steps:
the polyethylene, wood powder and the polyethylene grafted maleic anhydride hot melt adhesive modified material prepared by the technical scheme or the preparation method of the technical scheme are blended, extruded and granulated in a double screw extruder and injection molded to obtain the polyethylene grafted maleic anhydride hot melt adhesive modified material.
Compared with the prior art, the invention provides a polyethylene grafted maleic anhydride hot melt adhesive modified material, which comprises the following components: 90-100 parts of polyethylene and 0-10 parts of ethylene-vinyl acetate copolymer; maleic anhydride 0.5-3 weight portions; 0.5 to 3 parts by weight of monomer; 0.1 to 1 weight portion of antioxidant; 0.1 to 1 weight portion of initiator; 0.01 to 1 weight portion of other auxiliary agents; 1-5 parts of carbon dioxide. The invention uses supercritical carbon dioxide (SC-CO) 2 ) The PE melt extrusion process is introduced, the supercritical state of the PE melt extrusion process is fully utilized, the plasticization effect is exerted, the system viscosity is reduced, the fluidity of substances in an extruder is improved, the collision probability of free radical active sites and copolymers such as maleic anhydride monomers and EVA is increased, and the grafting rate and the bonding performance are improved. And a vacuumizing device is added at the position close to the machine head, and the supercritical carbon dioxide filling process is combined, so that residual monomers in the material are carried out more effectively by utilizing carbon dioxide, the odor of a grafted product is reduced, and the environment-friendly polyethylene grafted maleic anhydride hot melt adhesive modified material is obtained.
Detailed Description
The invention provides a polyethylene grafted maleic anhydride hot melt adhesive modified material and a preparation method thereof, and the technical parameters can be properly improved by the person skilled in the art by referring to the content of the material. It is expressly noted that all such similar substitutions and modifications will be apparent to those skilled in the art, and they are intended to be within the scope of the present invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those skilled in the relevant art that the invention can be practiced and practiced with modification and alteration and combination of the methods and applications herein without departing from the spirit and scope of the invention.
The invention provides a polyethylene grafted maleic anhydride hot melt adhesive modified material, which comprises the following components:
90-100 parts of polyethylene and 0-10 parts of ethylene-vinyl acetate copolymer; maleic anhydride 0.5-3 weight portions; 0.5 to 3 parts by weight of monomer; 0.1 to 1 weight portion of antioxidant; 0.1 to 1 weight portion of initiator; 0.01 to 1 weight portion of other auxiliary agents; 1-5 parts of carbon dioxide.
The polyethylene grafted maleic anhydride hot melt adhesive modified material provided by the invention comprises 90-100 parts by weight of polyethylene; the polyethylene is selected from high-density polyethylene, and the melt flow index is 1g/10 min-10 g/10min;
the polyethylene grafted maleic anhydride hot melt adhesive modified material provided by the invention comprises 0-10 parts by weight of ethylene-vinyl acetate copolymer; preferably comprises 2 to 10 parts by weight; more preferably from 4 to 10 parts by weight; specifically, the weight of the composition can be 4 weight parts, 5 weight parts, 6 weight parts, 7 weight parts, 8 weight parts, 9 weight parts or 10 weight parts; or a point value between any two of the above.
The ethylene-vinyl acetate copolymer of the invention is selected from VA content of 30% -40%.
The polyethylene grafted maleic anhydride hot melt adhesive modified material provided by the invention comprises 0.5-3 parts by weight of maleic anhydride; preferably comprises 1 to 3 parts by weight of maleic anhydride; specifically, 1 part by weight, 2 parts by weight and 3 parts by weight can be used; or a point value between any two of the above.
The polyethylene grafted maleic anhydride hot melt adhesive modified material provided by the invention comprises 0.5-3 parts by weight of monomer; preferably comprising 1 to 3 parts by weight of monomers; specifically, 1 part by weight, 2 parts by weight and 3 parts by weight can be used; or a point value between any two of the above.
According to the invention, the monomer is selected from one or more of styrene, divinylbenzene, 1, 6-hexanediol diacrylate and dicyclopentadiene; the source of the present invention is not limited, and those skilled in the art can well know the source.
The polyethylene grafted maleic anhydride hot melt adhesive modified material provided by the invention comprises 0.1-1 part by weight of antioxidant; preferably comprises 0.1 to 0.8 weight part of antioxidant; more preferably 0.1 to 0.6 parts by weight.
Specifically, the antioxidant is one or more selected from hindered phenol antioxidants, phosphite antioxidants and thioester antioxidants.
The polyethylene grafted maleic anhydride hot melt adhesive modified material provided by the invention comprises 0.1-1 part by weight of initiator; preferably comprises 0.1 to 0.8 part by weight of initiator; more preferably 0.1 to 0.6 parts by weight.
Specifically, the initiator is selected from one or more of di-tert-butyl peroxide, dicumyl peroxide, 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane (301), 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) ethane (101), and bis-tert-butylperoxy isopropyl benzene; the source of the present invention is not limited, and those skilled in the art can well know the source.
The polyethylene grafted maleic anhydride hot melt adhesive modified material provided by the invention comprises 0.01-1 part by weight of other auxiliary agents; preferably comprises 0.01 to 0.8 weight part of other auxiliary agents; more preferably, 0.01 to 0.5 parts by weight of other auxiliary agents are included. Wherein the other auxiliary agent is selected from one or more of calcium stearate, magnesium stearate and zinc stearate.
The polyethylene grafted maleic anhydride hot melt adhesive modified material provided by the invention comprises 1-5 parts by weight of carbon dioxide; preferably comprises 1 to 4 parts by weight of carbon dioxide. The carbon dioxide is supercritical carbon dioxide.
In a preferred embodiment of a part of the present invention, the polyethylene grafted maleic anhydride hot melt adhesive modified material comprises:
90-100 parts of polyethylene and 2-10 parts of ethylene-vinyl acetate copolymer; 1-3 parts by weight of maleic anhydride; 1-3 parts by weight of monomer; 0.1 to 0.8 weight portion of antioxidant; 0.1 to 0.8 weight portion of initiator; 0.01 to 0.8 weight portion of other auxiliary agents; 1-4 parts of carbon dioxide.
According to the invention, the polyethylene grafted maleic anhydride hot melt adhesive modified material is added into PE/wood powder through the above-mentioned blending grafting modification of polyethylene, added ethylene-vinyl acetate copolymer (EVA) and maleic anhydride, including the addition of other monomers, antioxidant, initiator and auxiliary agent, the components interact with each other and support each other functionally, and the above-mentioned integral scheme cooperates with each other, so that the compatibility is good, the grafting rate is high, the VOC content is low, and the bonding property of the grafted product is good.
The invention provides a preparation method of a polyethylene grafted maleic anhydride hot melt adhesive modified material, which is characterized by comprising the following steps:
mixing polyethylene, ethylene-vinyl acetate copolymer, maleic anhydride, monomer, antioxidant, initiator and other assistants, adding carbon dioxide into a double-screw extruder, vacuumizing, extruding to form strips, cooling, air-cooling to remove water, and granulating.
The preparation method of the polyethylene grafted maleic anhydride hot melt adhesive modified material comprises the steps of firstly mixing polyethylene, ethylene-vinyl acetate copolymer, maleic anhydride, monomers, an antioxidant, an initiator and other auxiliary agents. The present invention has been clearly described with respect to the above components and arrangements, and will not be described in detail herein.
The present invention is not limited to the specific operation of the above mixing, and may be well known to those skilled in the art. The mixing time is preferably 5 to 10 minutes.
Mixing, adding into a double-screw extruder, and introducing carbon dioxide. The carbon dioxide is supercritical carbon dioxide; the carbon dioxide is added at 1-5% of the feeding speed of the polyethylene; preferably at 1% -4% of the polyethylene feeding speed; the carbon dioxide adding pressure is 3-8 MPa, and the temperature is 20-40 ℃; more preferably, the carbon dioxide addition pressure is 4-7 MPa and the temperature is 25-38 ℃.
The bracing is extruded after vacuumizing, and the vacuumizing degree of the invention is minus 0.06MPa.
And (5) cooling, air-cooling, dewatering and granulating after vacuumizing.
The cooling method specifically comprises the steps of cooling the braces through a water tank, performing air cooling and water removal through a blow dryer, and adjusting the traction rate and the rotating speed of a cutter to obtain granules with the length of about 5 mm.
According to the invention, the heating zone from the feed opening to the machine head of the double-screw extruder is provided with 12 sections, sequentially set at 120-150 ℃, 135-180 ℃, 160-200 ℃ and 160-200 ℃, 160-200 ℃ and 160-200 ℃, the rotating speed of the screw is 150-400 r/min, and the feeding rotating speed is 4-10 kg/h.
The PE/EVA-g-MAH product provided by the invention has the advantages of low odor, environment friendliness, high grafting rate, increased product polarity and improved binding force, and is widely applied to the fields of steel-plastic composite pipes, glue coating, composite materials and the like as a hot melt adhesive.
The invention provides a polyethylene-based wood-plastic composite material, which comprises the polyethylene grafted maleic anhydride hot melt adhesive modified material prepared by any one of the technical schemes or the preparation method of any one of the technical schemes.
Specifically, the addition amount of the polyethylene grafted maleic anhydride hot melt adhesive modified material is 5-10% wt.
The polyethylene-based wood-plastic composite material comprises polyethylene and wood powder, wherein the ratio of the polyethylene to the wood powder is 5:4.
The invention provides a preparation method of a polyethylene-based wood-plastic composite material, which comprises the following steps:
the polyethylene, wood powder and the polyethylene grafted maleic anhydride hot melt adhesive modified material prepared by the technical scheme or the preparation method of the technical scheme are blended, extruded and granulated in a double screw extruder and injection molded to obtain the polyethylene grafted maleic anhydride hot melt adhesive modified material.
The invention is not limited to the specific extrusion pelletization, injection molding steps and parameters, and those skilled in the art will recognize.
The invention provides a polyethylene grafted maleic anhydride hot melt adhesive modified material, which comprises the following components: 90-100 parts of polyethylene and 0-10 parts of ethylene-vinyl acetate copolymer; maleic anhydride 0.5-3 weight portions; 0.5 to 3 parts by weight of monomer; 0.1 to 1 weight portion of antioxidant; 0.1 to 1 weight portion of initiator; 0.01 to 1 weight portion of other auxiliary agents; 1-5 parts of carbon dioxide. The invention uses supercritical carbon dioxide (SC-CO) 2 ) The PE melt extrusion process is introduced, the supercritical state of the PE melt extrusion process is fully utilized, the plasticization effect is exerted, the system viscosity is reduced, the fluidity of substances in an extruder is improved, the collision probability of free radical active sites and copolymers such as maleic anhydride monomers and EVA is increased, and the grafting rate and the bonding performance are improved. At the proximity headAnd a vacuumizing device is added at the position, and the supercritical carbon dioxide filling process is combined, so that residual monomers in the material are carried out more effectively by utilizing carbon dioxide, the odor of a grafted product is reduced, and the environment-friendly polyethylene grafted maleic anhydride hot melt adhesive modified material is obtained.
In order to further illustrate the invention, the following describes in detail a polyethylene grafted maleic anhydride hot melt adhesive modified material and a preparation method thereof.
Example 1:
weighing PE, EVA base stock and auxiliary agent according to a proportion, wherein 90 parts of high-density polyethylene resin (HDPE 6080) and 10 parts of EVA (VA content of 32%) are calculated by weight relative to the polyethylene resin, 0.1 part of antioxidant 1010, 0.1 part of antioxidant 168, 1.2 parts of maleic anhydride, 1.2 parts of styrene, 0.05 part of calcium stearate and 0.15 part of initiator BIPB are placed in a high-speed mixer, and stirred for 5min to be mixed uniformly; adding the mixed material into a parallel co-directional double-screw extruder, wherein 12 sections are arranged from a feed opening to a heating zone of a machine head, sequentially setting 135 ℃, 150 ℃, 170 ℃, 195 ℃ and 195 ℃, the screw speed is set to 350r/min, the feeding speed is 6.5kg/h, introducing supercritical carbon dioxide with the pressure of 4.5MPa and the temperature of 30 ℃ into the middle section of the screw, vacuumizing at a position close to a machine head, extruding, bracing, cooling, air-cooling, removing water and granulating to obtain the environment-friendly polyethylene grafted maleic anhydride hot melt adhesive modified material (PE/EVA-g-MAH).
Example 2:
weighing PE, EVA base stock and auxiliary agent according to a proportion, wherein, based on the weight of polyethylene resin, 95 parts of high-density polyethylene resin (HDPE 6080), 5 parts of EVA (VA content of 32%), 0.1 part of antioxidant 1010, 0.1 part of antioxidant 168, 1.2 parts of maleic anhydride, 1.2 parts of styrene, 0.05 part of calcium stearate and 0.15 part of initiator BIPB are placed in a high-speed mixer, and stirred for 5min to be mixed uniformly; adding the mixed material into a parallel co-directional double-screw extruder, wherein 12 sections are arranged from a feed opening to a heating zone of a machine head, sequentially setting 135 ℃, 150 ℃, 170 ℃, 195 ℃ and 195 ℃, the screw speed is set to 350r/min, the feeding speed is 6.5kg/h, introducing supercritical carbon dioxide with the pressure of 4.5MPa and the temperature of 30 ℃ into the middle section of the screw, vacuumizing at a position close to a machine head, extruding, bracing, cooling, air-cooling, removing water and granulating to obtain the environment-friendly polyethylene grafted maleic anhydride hot melt adhesive modified material (PE/EVA-g-MAH).
Example 3:
weighing PE base stock and auxiliary agent according to a proportion, wherein the materials are placed in a high-speed mixer for stirring for 5min and uniformly mixed by calculating 100 parts of high-density polyethylene resin (HDPE 6080), 0.1 part of antioxidant 1010, 168.1 parts of antioxidant, 1.2 parts of maleic anhydride, 1.2 parts of styrene, 0.05 part of calcium stearate and 0.15 part of initiator BIPB; adding the mixed material into a parallel co-directional double-screw extruder, wherein 12 sections are arranged from a feed opening to a heating zone of a machine head, sequentially setting 135 ℃, 150 ℃, 170 ℃, 195 ℃ and 195 ℃, the screw speed is set to 350r/min, the feeding speed is 6.5kg/h, introducing supercritical carbon dioxide with the pressure of 4.5MPa and the temperature of 30 ℃ into the middle section of the screw, vacuumizing at a position close to the machine head, extruding, bracing, cooling, air-cooling, removing water and granulating to obtain the environment-friendly polyethylene grafted maleic anhydride hot melt adhesive modified material (PE-g-MAH).
Comparative example 1:
weighing PE, EVA base stock and auxiliary agent according to a proportion, wherein 90 parts of high-density polyethylene resin (HDPE 6080) and 10 parts of EVA (VA content of 32%) are calculated by weight relative to the polyethylene resin, 0.1 part of antioxidant 1010, 0.1 part of antioxidant 168, 1.2 parts of maleic anhydride, 1.2 parts of styrene, 0.05 part of calcium stearate and 0.15 part of initiator BIPB are placed in a high-speed mixer, and stirred for 5min to be mixed uniformly; adding the mixed material into a parallel co-directional double-screw extruder, wherein 12 sections are arranged from a feed opening to a heating zone of a machine head, sequentially setting 135 ℃, 150 ℃, 170 ℃, 195 ℃ and 195 ℃, the screw speed was set at 350r/min, the feeding speed is 6.5kg/h, the vacuum pumping operation is carried out at the position close to the machine head, and the polyethylene grafted maleic anhydride hot melt adhesive modified material (PE/EVA-g-MAH) under the process of not adding supercritical carbon dioxide is obtained through extrusion bracing, cooling, air cooling for dewatering and granulating.
The invention discloses a process flow for preparing a green environment-friendly polyethylene grafted maleic anhydride hot melt adhesive modified material, which comprises the steps of mixing materials, adding supercritical carbon dioxide, vacuumizing at a position close to a machine head, extruding a bracing piece, cooling, air-cooling to remove water and granulating to obtain a low-odor high-grafting-rate polyethylene grafted maleic anhydride hot melt adhesive modified material PE/EVA-g-MAH under the process of adding the supercritical carbon dioxide.
Table 1 shows the comparison of the properties of the polyethylene-grafted maleic anhydride hot melt adhesive modified materials prepared in example 1, example 2, example 3 and comparative example 1 according to the invention and the comparison of the properties of the standard WP128, as can be seen from the table:
comparative examples 1, 2 and 3 show that the tensile strength and impact strength of the product obtained by adding EVA for blending modification grafting and increasing the addition amount of EVA in the application of the polyethylene-based wood-plastic composite material are respectively improved, because the EVA contains a vinyl acetate unit, an oxygen atom on an ester bond can form an intermolecular hydrogen bond with an active hydrogen atom in a hydroxyl group on the surface of the wood-plastic material, and the compatibility is improved; the process of filling supercritical carbon dioxide in comparative example 1 and comparative example 1 obviously shows that the odor level can be effectively reduced and is below 3.5, which means that the supercritical carbon dioxide can effectively carry residual monomers in the materials out in the melt extrusion process, the odor of grafted products is reduced, the materials can be fully reacted, the grafting efficiency is improved, and finally, the polyethylene grafted maleic anhydride hot melt adhesive modified material product with low odor and high grafting rate is obtained and is superior to the standard WP128.
TABLE 1 comparison of different properties
| Example 1 | Example 2 | Example 3 | Comparative example 1 | To standard WP128 | |
| Grafting percentage% | 1.07 | 0.93 | 0.81 | 1.01 | 0.82 |
| Melt finger g/10min | 1.19 | 0.79 | 0.82 | 1.07 | 0.43 |
| Odor grade/grade | 3.3 | 3.4 | 3.4 | 4.5 | 4.2 |
| Gel content/% | 1.57 | 1.29 | 1.17 | 1.28 | 1.68 |
| Tensile strength Mpa | 89 | 41 | 36 | 79 | 57 |
| Impact strength kJ/square meter | 67 | 58 | 46 | 64 | 62 |
Remarks: the PE/EVA-g-MAH products prepared were added with 10% of PE/wood flour (PE/wood flour=5/4), extruded and granulated in a twin screw extruder, and the mechanical properties were tested by injection molding standard bars.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (7)
1. The polyethylene-based wood-plastic composite material comprises a polyethylene grafted maleic anhydride hot melt adhesive modified material, wherein the polyethylene grafted maleic anhydride hot melt adhesive modified material comprises the following components:
90-100 parts of polyethylene and 2-10 parts of ethylene-vinyl acetate copolymer; 1-3 parts of maleic anhydride; 1-3 parts of monomer; 0.1-0.8 part by weight of an antioxidant; 0.1-0.8 parts by weight of an initiator; 0.01-0.8 parts by weight of other auxiliary agents; 1-4 parts by weight of supercritical carbon dioxide;
the monomer is selected from one or more of styrene, divinylbenzene, 1, 6-hexanediol diacrylate and dicyclopentadiene;
the polyethylene is selected from high-density polyethylene, and the melt flow index is 1g/10 min-10 g/10min; the ethylene-vinyl acetate copolymer is selected from the VA content of 30% -40%.
2. The material according to claim 1, wherein the antioxidant is selected from one or more of hindered phenolic antioxidants, phosphite antioxidants and thioester antioxidants;
the initiator is selected from one or more of di-tert-butyl peroxide, dicumyl peroxide, 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxynonane, 2, 5-dimethyl-2, 5-bis (tert-butyl peroxy) ethane and di-tert-butyl peroxy isopropyl benzene;
the other auxiliary agent is selected from one or more of calcium stearate, magnesium stearate and zinc stearate.
3. The composite material according to claim 1, wherein the polyethylene grafted maleic anhydride hot melt adhesive modified material is added in an amount of 5% wt% to 10% wt%.
4. The composite material according to claim 1, wherein the preparation method of the polyethylene grafted maleic anhydride hot melt adhesive modified material comprises the following steps:
mixing polyethylene, ethylene-vinyl acetate copolymer, maleic anhydride, monomer, antioxidant, initiator and other assistants, adding carbon dioxide into a double-screw extruder, vacuumizing, extruding to form strips, cooling, air-cooling to remove water, and granulating.
5. The composite of claim 4, wherein the carbon dioxide is supercritical carbon dioxide;
the carbon dioxide is added at a feeding speed of polyethylene of 1% -5%;
the carbon dioxide adding pressure is 3-8 MPa, and the temperature is 20-40 ℃.
6. The composite material according to claim 4, wherein the twin-screw extruder has 12 sections from the feed opening to the heating zone of the head, sequentially set at 120-150 ℃, 135-180 ℃, 160-200 DEG 160-200 ℃, the screw rotating speed is 150 r/min-400 r/min, and the feeding rotating speed is 4 kg/h-10 kg/h.
7. A method for preparing the polyethylene-based wood-plastic composite material according to any one of claims 1 to 6, which is characterized by comprising the following steps:
and (3) blending polyethylene, wood powder and the polyethylene grafted maleic anhydride hot melt adhesive modified material, extruding and granulating in a double-screw extruder, and performing injection molding to obtain the modified polyethylene-grafted maleic anhydride hot melt adhesive.
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