CN115109194A - 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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- CN115109194A CN115109194A CN202210976445.8A CN202210976445A CN115109194A CN 115109194 A CN115109194 A CN 115109194A CN 202210976445 A CN202210976445 A CN 202210976445A CN 115109194 A CN115109194 A CN 115109194A
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- 239000004698 Polyethylene Substances 0.000 title claims abstract description 115
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 113
- 239000000463 material Substances 0.000 title claims abstract description 93
- -1 Polyethylene Polymers 0.000 title claims abstract description 91
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000004831 Hot glue Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims description 18
- 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
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 35
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 34
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 33
- 239000000178 monomer Substances 0.000 claims abstract description 28
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 27
- 239000003999 initiator Substances 0.000 claims abstract description 23
- 239000000654 additive Substances 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 14
- 239000012752 auxiliary agent Substances 0.000 claims description 11
- 229920001903 high density polyethylene Polymers 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 229920001587 Wood-plastic composite Polymers 0.000 claims description 9
- 239000002023 wood Substances 0.000 claims description 9
- 239000011155 wood-plastic composite Substances 0.000 claims description 9
- 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
- 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
- 239000000155 melt Substances 0.000 claims description 6
- 238000001746 injection moulding Methods 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 4
- 239000000203 mixture 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
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 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
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000002530 phenolic antioxidant Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 13
- 238000001125 extrusion Methods 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 4
- 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
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 15
- 239000004700 high-density polyethylene Substances 0.000 description 10
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 235000013339 cereals Nutrition 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000005429 filling process Methods 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- 229920013716 polyethylene resin Polymers 0.000 description 2
- 239000010421 standard material Substances 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 238000000861 blow drying Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007613 environmental effect Effects 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
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 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
- 230000006872 improvement Effects 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
- Adhesives Or Adhesive Processes (AREA)
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; 0.5-3 parts by weight of maleic anhydride; 0.5-3 parts by weight of a monomer; 0.1-1 part by weight of an antioxidant; 0.1-1 part by weight of an initiator; 0.01-1 part by weight of other additives; 1-5 parts by weight of carbon dioxide. According to the invention, supercritical carbon dioxide is introduced into the PE melt extrusion process, the supercritical state of the PE melt extrusion process is fully utilized, the plasticizing effect is exerted, the system viscosity is reduced, the fluidity of the substance 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. Residual monomers in the materials are carried out more effectively by using carbon dioxide, the odor of a grafted product is reduced, and the green 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 a resin variety with the simplest molecular composition and structure, has a smooth molecular chain, is easily crystallized, is in a translucent state, has excellent film-forming properties, chemical stability, and good mechanical strength and air permeability, and is widely used in 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 non-polarity of molecular chains, the compatibility and the cohesiveness of PE and materials are poor, and the application direction of PE is greatly limited, so that the polyethylene functionalized modification 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), which is an unsaturated compound containing a polar group, has a symmetrical molecular structure, has high reactivity, hardly forms a long chain branch in a PE molecule, and is often used as a graft 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 polyethylene grafted maleic anhydride product industrialized at present has low grafting efficiency, residual monomers can not be sufficiently removed, so that an irritant odor can be generated in the production process, the product grafting rate is low, and the effect of improving the polyethylene compatibility 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 green environment-friendly polyethylene grafted maleic anhydride hot melt adhesive modified material is good in compatibility with other matching components, high in grafting rate and low in VOC content.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a polyethylene grafted maleic anhydride hot melt adhesive modified material, which has high grafting ratio, good adhesion, and 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; 0.5 to 3 parts by weight of maleic anhydride; 0.5-3 parts by weight of a monomer; 0.1-1 part by weight of an antioxidant; 0.1-1 part by weight of an initiator; 0.01-1 part by weight of other additives; 1-5 parts by weight 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 a monomer; 0.1-0.8 part by weight of antioxidant; 0.1-0.8 part by weight of an initiator; 0.01-0.8 part by weight of other additives; 1-4 parts by weight of carbon dioxide.
Preferably, the polyethylene is selected from high-density polyethylene, and the melt flow index is 1g/10 min-10 g/10 min; the ethylene-vinyl acetate copolymer has VA content of 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, divinyl benzene, 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-triperoxonane (301), 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) ethane (101), and di-tert-butylperoxyisopropyl benzene;
the other auxiliary agents are 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 comprises the following steps:
mixing polyethylene, ethylene-vinyl acetate copolymer, maleic anhydride, monomer, antioxidant, initiator and other auxiliaries, adding the mixture into a double-screw extruder, introducing carbon dioxide, vacuumizing, extruding and drawing strips, and sequentially cooling, air-cooling to remove water and granulating to obtain the polyethylene-vinyl acetate copolymer.
Preferably, the carbon dioxide is supercritical carbon dioxide;
the carbon dioxide is added at 1-5% of the feeding speed of the polyethylene;
the adding pressure of the carbon dioxide is 3-8 MPa, and the temperature is 20-40 ℃.
Preferably, the double-screw extruder has 12 sections from the feed opening to the heating zone of the head, and the sections are sequentially set to be 120-150 ℃, 135-180 ℃, 160-200 ℃, the screw rotation speed is 150-400 r/min, and the feeding rotation 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 above technical schemes or the polyethylene-grafted maleic anhydride hot melt adhesive modified material prepared by the preparation method of any one of the above technical schemes.
Preferably, the addition amount of the polyethylene grafted maleic anhydride hot melt adhesive modified material is 5-10 wt%.
The invention provides a preparation method of a polyethylene-based wood-plastic composite material, which comprises the following steps:
polyethylene, wood powder and the polyethylene grafted maleic anhydride hot melt adhesive modified material prepared by any one of the above technical schemes or the polyethylene grafted maleic anhydride hot melt adhesive modified material prepared by any one of the above technical schemes, blending, extruding and granulating in a double-screw extruder, and performing injection molding 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 in percentage by weight: 90-100 parts of polyethylene and 0-10 parts of ethylene-vinyl acetate copolymer; 0.5-3 parts by weight of maleic anhydride; 0.5-3 parts by weight of a monomer; 0.1-1 part by weight of an antioxidant; 0.1-1 part by weight of an initiator; 0.01-1 part by weight of other additives; 1-5 parts by weight of carbon dioxide. The invention uses supercritical carbon dioxide (SC-CO) 2 ) The PE is introduced into a melt extrusion process, the supercritical state of the PE is fully utilized, the plasticizing 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, EVA and the like is increased, and the grafting rate and the bonding performance are improved. A vacuumizing device is added at a position close to a machine head, a supercritical carbon dioxide filling process is combined, residual monomers in the materials are effectively carried out by using carbon dioxide, the odor of a grafting 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 a person skilled in the art can use the content for reference and appropriately improve the process parameters to realize the modification. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the scope of the invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the methods and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of this invention 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; 0.5-3 parts by weight of maleic anhydride; 0.5-3 parts by weight of a monomer; 0.1-1 part by weight of an antioxidant; 0.1-1 part by weight of an initiator; 0.01-1 part by weight of other additives; 1-5 parts by weight 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/10 min;
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 2 to 10 parts by weight; more preferably 4 to 10 parts by weight; specifically, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, or 10 parts by weight; or a point value between any of the above.
The ethylene-vinyl acetate copolymer of the invention has a 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 1 to 3 parts by weight of maleic anhydride; specifically, the amount of the compound is 1 part by weight, 2 parts by weight or 3 parts by weight; or a point value between any 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 a monomer; preferably 1-3 parts by weight of monomer; specifically, the amount of the compound is 1 part by weight, 2 parts by weight or 3 parts by weight; or a point value between any of the above.
According to the invention, the monomer is selected from one or more of styrene, divinyl benzene, 1, 6-hexanediol diacrylate and dicyclopentadiene; the present invention is not limited in its origin, as is well known to those skilled in the art.
The polyethylene grafted maleic anhydride hot melt adhesive modified material provided by the invention comprises 0.1-1 part by weight of antioxidant; preferably 0.1-0.8 part by weight of antioxidant; more preferably 0.1 to 0.6 parts by weight.
Specifically, the antioxidant is selected from one or more of 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 an initiator; preferably comprises 0.1 to 0.8 weight part 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 di-tert-butylperoxyisopropyl benzene; the present invention is not limited in its origin, as is well known to those skilled in the art.
The polyethylene grafted maleic anhydride hot melt adhesive modified material provided by the invention comprises 0.01-1 part by weight of other additives; preferably, the additive comprises 0.01-0.8 weight part of other additives; more preferably, the additive comprises 0.01 to 0.5 weight part of other additives. Wherein the other auxiliary agents are 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, the carbon dioxide is included in an amount of 1 to 4 parts by weight. The carbon dioxide is supercritical carbon dioxide.
In some of the preferred embodiments 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 a monomer; 0.1-0.8 part by weight of antioxidant; 0.1-0.8 part by weight of an initiator; 0.01-0.8 part by weight of other additives; 1-4 parts by weight of carbon dioxide.
According to the invention, through the blending, grafting and modification of polyethylene, the addition of 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 functionally support each other, and the overall scheme is matched to act, so that the prepared polyethylene-grafted maleic anhydride hot melt adhesive modified material is added into PE/wood powder, and the compatibility is good, meanwhile, the grafting rate is high, the VOC content is low, and the bonding performance of a grafted product is good.
The invention provides a preparation method of a polyethylene grafted maleic anhydride hot melt adhesive modified material, which comprises the following steps:
mixing polyethylene, ethylene-vinyl acetate copolymer, maleic anhydride, monomer, antioxidant, initiator and other auxiliaries, adding the mixture into a double-screw extruder, introducing carbon dioxide, vacuumizing, extruding and drawing strips, and sequentially cooling, air-cooling to remove water and granulating to obtain the polyethylene-vinyl acetate copolymer.
The preparation method of the polyethylene grafted maleic anhydride hot melt adhesive modified material provided by the invention comprises the steps of mixing polyethylene, ethylene-vinyl acetate copolymer, maleic anhydride, monomer, antioxidant, initiator and other auxiliaries. The present invention has been described clearly with respect to the above components and equipment, and will not be described in detail herein.
The present invention is not limited to the specific operation of mixing as described above, and those skilled in the art will be familiar with the operation. The mixing time is preferably 5-10 min.
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% to 4% of the polyethylene feed rate; the adding pressure of the carbon dioxide is 3-8 MPa, and the temperature is 20-40 ℃; more preferably, the adding pressure of the carbon dioxide is 4-7 MPa, and the temperature is 25-38 ℃.
The vacuum degree of the vacuum pumping is-0.06 MPa.
And after vacuumizing, cooling, air-cooling to remove water and granulating to obtain the finished product.
The cooling is specifically that the brace is cooled by a water tank, water is removed by air cooling of a blow-drying machine, and the traction speed and the rotating speed of a cutter are adjusted to obtain granules with the length of about 5 mm.
According to the invention, the double-screw extruder has 12 sections from the feed opening to the heating zone of the head, and the sections are sequentially set to be 120-150 ℃, 135-180 ℃, 160-200 ℃, the screw rotation speed is 150-400 r/min, and the feeding rotation speed is 4-10 kg/h.
The PE/EVA-g-MAH product provided by the invention has the advantages of low odor, environmental protection, high grafting rate, product polarity increase and adhesion improvement, and can be 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 above technical schemes or the polyethylene-grafted maleic anhydride hot melt adhesive modified material prepared by the preparation method of any one of the above 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 flour, wherein the ratio of the polyethylene to the wood flour is 5:4 optionally.
The invention provides a preparation method of a polyethylene-based wood-plastic composite material, which comprises the following steps:
polyethylene, wood powder and the polyethylene grafted maleic anhydride hot melt adhesive modified material prepared by any one of the above technical schemes or the polyethylene grafted maleic anhydride hot melt adhesive modified material prepared by any one of the above technical schemes, blending, extruding and granulating in a double-screw extruder, and performing injection molding to obtain the polyethylene-grafted maleic anhydride hot melt adhesive modified material.
The present invention is not limited to the specific extrusion granulation and injection molding steps and parameters, and those skilled in the art will be familiar with them.
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; 0.5-3 parts by weight of maleic anhydride; 0.5-3 parts by weight of a monomer; 0.1-1 part by weight of an antioxidant; 0.1-1 part by weight of an initiator; 0.01-1 part by weight of other additives; 1-5 parts by weight of carbon dioxide. The invention uses supercritical carbon dioxide (SC-CO) 2 ) The PE is introduced into a melt extrusion process, the supercritical state of the PE is fully utilized, the plasticizing 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, EVA and the like is increased, and the grafting rate and the bonding performance are improved. A vacuumizing device is added at a position close to a machine head, a supercritical carbon dioxide filling process is combined, residual monomers in the materials are effectively carried out by using carbon dioxide, the odor of a grafting 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 provided by the invention with reference to examples.
Example 1:
weighing PE, EVA base material and auxiliary agent according to a proportion, wherein the weight of the high-density polyethylene resin (HDPE 6080), EVA (VA content 32%) 10 parts, antioxidant 10100.1 parts, antioxidant 1680.1 parts, maleic anhydride 1.2 parts, styrene 1.2 parts, calcium stearate 0.05 parts and initiator BIPB 0.15 parts, and placing the materials in a high-speed mixer, stirring for 5min and uniformly mixing; adding the mixed material into a parallel co-rotating twin-screw extruder, wherein 12 sections are arranged in a heating zone from a feed opening to a machine head, the heating zone is sequentially set to be 135 ℃, 150 ℃, 170 ℃, 195 ℃, the screw rotation speed is set to be 350r/min, the feeding rotation speed is 6.5kg/h, supercritical carbon dioxide with the pressure of 4.5MPa and the temperature of 30 ℃ is introduced into the middle section of the screw, the vacuumizing operation is carried out at a position close to the machine head, and the green environment-friendly polyethylene grafted maleic anhydride hot melt adhesive modified material (PE/EVA-g-MAH) is obtained through extrusion, bracing, cooling, air cooling, water removal and grain cutting.
Example 2:
weighing PE, EVA base material and auxiliary agent according to a proportion, wherein the weight of the PE, EVA base material and auxiliary agent is calculated according to the weight of the polyethylene resin, 95 parts of high-density polyethylene resin (HDPE 6080), 5 parts of EVA (ethylene vinyl acetate) (32 percent of VA content), 10100.1 parts of antioxidant, 1680.1 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, placing the materials in a high-speed mixer, stirring for 5min and uniformly mixing; adding the mixed material into a parallel co-rotating twin-screw extruder, wherein 12 sections are arranged in a heating zone from a feed opening to a machine head, the heating zone is sequentially set to be 135 ℃, 150 ℃, 170 ℃, 195 ℃, the screw rotation speed is set to be 350r/min, the feeding rotation speed is 6.5kg/h, supercritical carbon dioxide with the pressure of 4.5MPa and the temperature of 30 ℃ is introduced into the middle section of the screw, the vacuumizing operation is carried out at a position close to the machine head, and the green environment-friendly polyethylene grafted maleic anhydride hot melt adhesive modified material (PE/EVA-g-MAH) is obtained through extrusion, bracing, cooling, air cooling, water removal and grain cutting.
Example 3:
weighing the PE base material and the auxiliary agent according to a proportion, wherein the PE base material and the auxiliary agent are uniformly mixed by placing 100 parts of high-density polyethylene resin (HDPE 6080), 10100.1 parts of antioxidant, 1680.1 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 in a high-speed mixer for stirring for 5 min; adding the mixed material into a parallel co-rotating twin-screw extruder, wherein 12 sections are arranged from a feed opening to a heating zone of a machine head, the sections are sequentially set to be 135 ℃, 150 ℃, 170 ℃, 195 ℃, the screw rotation speed is set to be 350r/min, the feeding rotation speed is 6.5kg/h, supercritical carbon dioxide with the pressure of 4.5MPa and the temperature of 30 ℃ is introduced into the middle section of the screw, the vacuumizing operation is carried out at the position close to the machine head, and the green environment-friendly polyethylene grafted maleic anhydride hot melt adhesive modified material (PE-g-MAH) is obtained through extrusion, bracing, cooling, air cooling, water removal and grain cutting.
Comparative example 1:
weighing PE, EVA base material and auxiliary agent according to a proportion, wherein the weight of the PE, EVA base material and auxiliary agent is calculated according to the weight of polyethylene resin, the weight of high density polyethylene resin (HDPE 6080) is 90 parts, the weight of EVA (VA content is 32%) is 10 parts, the weight of antioxidant 10100.1 parts, the weight of antioxidant 1680.1 parts, the weight of maleic anhydride is 1.2 parts, the weight of styrene is 1.2 parts, the weight of calcium stearate is 0.05 part, and the weight of initiator BIPB is 0.15 part, putting the materials into a high-speed mixer, stirring for 5min, and uniformly mixing; adding the mixed material into a parallel co-rotating twin-screw extruder, wherein 12 sections are arranged in a heating zone from a feed opening to a machine head, the heating zone is sequentially set to be 135 ℃, 150 ℃, 170 ℃, 195 ℃, the screw rotation speed is set to be 350r/min, the feeding rotation speed is 6.5kg/h, vacuumizing operation is carried out at a position close to the machine head, and the polyethylene grafted maleic anhydride hot melt adhesive modified material (PE/EVA-g-MAH) under the process without injecting supercritical carbon dioxide is obtained through extrusion bracing, cooling, air cooling, water removal and grain cutting.
The invention relates to 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 the position close to a machine head, extruding and bracing, cooling, air-cooling to remove water, and granulating to obtain the polyethylene grafted maleic anhydride hot melt adhesive modified material PE/EVA-g-MAH with low odor and high grafting rate under the supercritical carbon dioxide adding process.
Table 1 shows the comparison of the properties of the polyethylene grafted maleic anhydride hot melt adhesive modified materials prepared in the inventive example 1, example 2, example 3 and comparative example 1 with the standard WP128, and it can be seen from the table that:
comparing example 1, example 2 and example 3, it is found that adding EVA for blending modification grafting increases tensile strength and impact strength of the product obtained by increasing the addition amount of EVA in the application of the polyethylene-based wood-plastic composite material, respectively, because EVA contains a vinyl acetate unit, oxygen atoms on ester bonds can form intermolecular hydrogen bonds with active hydrogen atoms in hydroxyl groups on the surface of the wood-plastic composite material, and compatibility is improved; compared with the comparative example 1, the obvious discovery of the comparative example 1 shows that the odor grade can be effectively reduced by the process of adding the supercritical carbon dioxide, and the odor grade is below 3.5, which indicates that the residual monomers in the materials can be effectively carried away by the supercritical carbon dioxide in the melt extrusion process, the odor of the grafted product 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 material WP 128.
TABLE 1 comparison of the Properties of the different samples
| Example 1 | Example 2 | Example 3 | Comparative example 1 | For standard material WP128 | |
| Graft ratio% | 1.07 | 0.93 | 0.81 | 1.01 | 0.82 |
| Melt index 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 |
Remarking: respectively adding 10% of the prepared PE/EVA-g-MAH product into PE/wood powder (PE/wood powder is 5/4), extruding and granulating in a double-screw extruder, and testing mechanical properties by injection molding standard sample strips.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The polyethylene grafted maleic anhydride hot melt adhesive modified material is characterized by comprising the following components in parts by weight:
90-100 parts of polyethylene and 0-10 parts of ethylene-vinyl acetate copolymer; 0.5-3 parts by weight of maleic anhydride; 0.5-3 parts by weight of a monomer; 0.1-1 part by weight of an antioxidant; 0.1-1 part by weight of an initiator; 0.01-1 part by weight of other additives; 1-5 parts by weight of carbon dioxide.
2. The material of claim 1, wherein 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 a monomer; 0.1-0.8 part by weight of antioxidant; 0.1-0.8 part by weight of an initiator; 0.01-0.8 part by weight of other additives; 1-4 parts by weight of carbon dioxide.
3. The material according to claim 1 or 2, characterized in that the polyethylene is chosen from high density polyethylenes, having a melt flow index comprised between 1g/10min and 10g/10 min; the ethylene-vinyl acetate copolymer has VA content of 30-40%.
4. The material according to claim 1 or 2, wherein the antioxidant is selected from one or more of hindered phenolic antioxidants, phosphite antioxidants and thioester antioxidants;
the monomer is selected from one or more of styrene, divinyl benzene, 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-triperoxonane (301), 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) ethane (101), and di-tert-butylperoxyisopropyl benzene;
the other auxiliary agents are selected from one or more of calcium stearate, magnesium stearate and zinc stearate.
5. The preparation method of the polyethylene grafted maleic anhydride hot melt adhesive modified material as claimed in any one of claims 1 to 4, characterized by comprising the following steps:
mixing polyethylene, ethylene-vinyl acetate copolymer, maleic anhydride, monomer, antioxidant, initiator and other auxiliaries, adding the mixture into a double-screw extruder, introducing carbon dioxide, vacuumizing, extruding and drawing strips, and sequentially cooling, air-cooling to remove water and granulating to obtain the polyethylene-vinyl acetate copolymer.
6. The production method according to claim 5, wherein the carbon dioxide is supercritical carbon dioxide;
the carbon dioxide is added at 1-5% of the feeding speed of the polyethylene;
the adding pressure of the carbon dioxide is 3-8 MPa, and the temperature is 20-40 ℃.
7. The preparation method of claim 5, wherein the twin-screw extruder has 12 sections from the feed opening to the heating zone of the head, which are sequentially arranged at 120 ℃ to 150 ℃, 135 ℃ to 180 ℃, 160 ℃ to 200 ℃, the screw rotation speed is 150r/min to 400r/min, and the feed rotation speed is 4kg/h to 10 kg/h.
8. A polyethylene-based wood-plastic composite material is characterized by comprising the polyethylene-grafted maleic anhydride hot melt adhesive modified material of any one of claims 1 to 4 or the polyethylene-grafted maleic anhydride hot melt adhesive modified material prepared by the preparation method of any one of claims 5 to 7.
9. The composite material of claim 8, wherein the polyethylene grafted maleic anhydride hot melt adhesive modified material is added in an amount of 5-10% by weight.
10. The preparation method of the polyethylene-based wood-plastic composite material is characterized by comprising the following steps:
blending polyethylene, wood powder and the polyethylene grafted maleic anhydride hot melt adhesive modified material as claimed in any one of claims 1 to 4 or the polyethylene grafted maleic anhydride hot melt adhesive modified material prepared by the preparation method as claimed in any one of claims 5 to 7, extruding and granulating in a double-screw extruder, and performing injection molding to obtain the polyethylene-grafted maleic anhydride hot melt adhesive modified material.
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| CN116655989A (en) * | 2023-05-08 | 2023-08-29 | 浙江祥邦科技股份有限公司 | Preparation method of silane-functionalized polyolefin material |
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