CN115703854B - Compatibilizer and application thereof in preparation of polyolefin/polysaccharide polymer composite material - Google Patents
Compatibilizer and application thereof in preparation of polyolefin/polysaccharide polymer composite material Download PDFInfo
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- CN115703854B CN115703854B CN202110907994.5A CN202110907994A CN115703854B CN 115703854 B CN115703854 B CN 115703854B CN 202110907994 A CN202110907994 A CN 202110907994A CN 115703854 B CN115703854 B CN 115703854B
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- 229920000098 polyolefin Polymers 0.000 title claims abstract description 61
- 229920000642 polymer Polymers 0.000 title claims abstract description 52
- 150000004676 glycans Chemical class 0.000 title claims abstract description 48
- 229920001282 polysaccharide Polymers 0.000 title claims abstract description 48
- 239000005017 polysaccharide Substances 0.000 title claims abstract description 48
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- -1 polyethylene Polymers 0.000 claims abstract description 52
- 238000002156 mixing Methods 0.000 claims abstract description 44
- 239000000203 mixture Substances 0.000 claims abstract description 40
- 239000004743 Polypropylene Substances 0.000 claims abstract description 35
- 229920001155 polypropylene Polymers 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000004698 Polyethylene Substances 0.000 claims abstract description 20
- 229920000573 polyethylene Polymers 0.000 claims abstract description 20
- 230000008569 process Effects 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 7
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 150000001336 alkenes Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
- 238000000643 oven drying Methods 0.000 claims description 3
- 239000002861 polymer material Substances 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 229920003023 plastic Polymers 0.000 abstract description 36
- 239000004033 plastic Substances 0.000 abstract description 36
- 229920002472 Starch Polymers 0.000 abstract description 20
- 239000008107 starch Substances 0.000 abstract description 20
- 235000019698 starch Nutrition 0.000 abstract description 20
- 229920002678 cellulose Polymers 0.000 abstract description 17
- 239000001913 cellulose Substances 0.000 abstract description 17
- 238000010907 mechanical stirring Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 230000004048 modification Effects 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 6
- 229920000704 biodegradable plastic Polymers 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 229920006238 degradable plastic Polymers 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 3
- 239000004014 plasticizer Substances 0.000 abstract description 3
- 229920002959 polymer blend Polymers 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 238000012512 characterization method Methods 0.000 description 19
- 229920001903 high density polyethylene Polymers 0.000 description 15
- 239000004700 high-density polyethylene Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 13
- 239000000843 powder Substances 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 238000009864 tensile test Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 238000004626 scanning electron microscopy Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000010998 test method Methods 0.000 description 6
- 229920006112 polar polymer Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- SYWIXHZXHQDFOO-UHFFFAOYSA-N methyl n-phenyliminocarbamate Chemical compound COC(=O)N=NC1=CC=CC=C1 SYWIXHZXHQDFOO-UHFFFAOYSA-N 0.000 description 3
- 229920006113 non-polar polymer Polymers 0.000 description 3
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the field of modification preparation of polyolefin/polysaccharide polymer blends, in particular to a compatibilizer and application thereof in preparation of polyolefin/polysaccharide polymer composite materials. Firstly preparing a compatibilizer, then uniformly mixing the compatibilizer and the polysaccharide polymer through mechanical stirring, adding polyolefin plastic into an internal mixer, adding a mixture of a plasticizer and the polysaccharide polymer after the compatibilizer and the polysaccharide polymer are completely melted, and carrying out internal mixing together to obtain the blended composite plastic after the internal mixing is finished. The method is particularly suitable for blending between polyethylene/polypropylene and starch/cellulose, so that a composite material with good dispersion is obtained, and the method can be applied to the production of biodegradable plastics. The blending method is simple to operate, wide in raw material sources, obvious in compatibilization effect, capable of effectively reducing the production cost of the degradable plastic, and great in social benefit.
Description
Technical Field
The invention relates to the field of modification preparation of polyolefin/polysaccharide polymer blends, in particular to a compatibilizer and application thereof in preparation of polyolefin/polysaccharide polymer composite materials.
Background
Polysaccharide polymers (starch, cellulose and the like) are good renewable natural resources, and can be blended with polyolefin high molecular compounds to prepare biodegradable plastics with excellent performance, so that wastes of industrial, agricultural and domestic plastic products are greatly reduced, environmental pollution is lightened, and ecological protection is promoted.
At present, two preparation methods of polyolefin/polysaccharide polymers are mainly adopted, one is to carry out grafting modification on starch or cellulose so as to realize good fusion of the starch or cellulose and polyolefin materials, but the grafting modification of the starch/cellulose has complex process and higher cost, and the prepared degradable material has far higher price than the existing common plastic and is difficult to accept in the market; the other is to add a compatibilizer between the two to change the interfacial bonding property and the compatibility between the two so as to achieve a good blending effect.
CN 102719013 discloses a reactive compatibilizer containing flexible chains, which can be used for modifying interfacial compatibility of lignin and polypropylene, so that the comprehensive performance of the composite material is remarkably improved, but the compatibilizer takes lignin as a basic raw material, has no obvious compatibilizing effect with other types of polysaccharide materials, and limits wider application of the compatibilizer.
CN 109847066 discloses a chitosan-based compatibilizer, which can be applied to the compatibilization of insoluble drugs, but the preparation process of the compatibilizer is complex in process, high in operation condition requirement, not suitable for large-scale production, and is mainly applied to the dissolution of drugs in water, and has large limitation.
At present, a composite material formed by polyolefin and polysaccharide has greater application potential, and a novel environment-friendly compatibilizer with universality is urgently needed to be developed so as to effectively improve interfacial compatibility of the polyolefin and the polysaccharide, reduce production cost of the composite material and promote large-scale application of the composite material.
Disclosure of Invention
Aiming at the defect of poor compatibility of polyolefin and polysaccharide polymer, the invention provides a compatibilizer and application thereof in preparing polyolefin/polysaccharide polymer composite materials.
The aim of the invention can be achieved by the following technical scheme:
the invention provides a compatibilizer, which is characterized in that an azodicarbonate compound is grafted on an olefin oligomer main chain, so that the compatibility of polyolefin and other polymer materials can be improved.
In one embodiment of the present invention, the method for preparing the compatibilizer comprises the steps of: mixing polyolefin and azodicarbonate compound in solvent, adding tungsten catalyst, reacting under illumination, standing, cooling, separating precipitate in solvent, filtering and oven drying to obtain compatibilizer.
In one embodiment of the present invention, the structural general formula of the compatibilizer is shown in the following formula (I):
wherein R is 1 Is a hydrogen atom or an unbranched or branched alkyl radical having 1 to 3 carbon atoms, R 2 、R 3 Each independently is a linear C1-C4 alkyl group or a branched C1-C4 alkyl group. Wherein n has a value of 10 to 500, preferably 10 to 100.
For example, the compatibilizer having the above structure may employ one or more of the following structural formulas.
Wherein n has a value of 10 to 500, preferably 10 to 100.
In the invention, the main chain structure of the compatibilizer is a nonpolar polyolefin polymer, the lower polarity ensures that the compatibilizer has better compatibility with low-polarity polymers such as polyethylene, polypropylene and the like, and the introduction of the polar groups of the side groups can generate stronger interaction with the polar groups in the nonpolar polymer, so that the compatibility with the polar polymer is improved, and therefore, the structural compatibilizer can effectively improve the compatibility of the polar polymer and the nonpolar polymer through the introduction of the polar groups of the side groups.
The invention also provides an application of the compatibilizer in preparing polyolefin/polysaccharide polymer composite materials, which comprises the following specific steps: firstly, uniformly mixing a compatibilizer and a polysaccharide polymer through mechanical stirring, then adding polyolefin plastic into an internal mixer, adding a mixture of a plasticizer and the polysaccharide polymer after the polyolefin plastic is completely melted, and carrying out internal mixing together to obtain the blended composite plastic after the internal mixing is finished.
In one embodiment of the invention, the polyolefin is selected from one or more of polyethylene or polypropylene, preferably a single polyethylene or polypropylene.
In one embodiment of the invention, the polyethylene may be a high density polyethylene or a low density polyethylene and the polypropylene may be isotactic polypropylene, syndiotactic polypropylene or atactic polypropylene.
In one embodiment of the invention, the polyethylene or polypropylene has a number average molecular weight of 10000 to 50000, preferably 15000 to 25000.
In one embodiment of the invention, the polysaccharide polymer is selected from one of starch or cellulose.
In one embodiment of the present invention, the polyolefin is mixed with the polysaccharide polymer in a mass ratio of (2 to 5): 1, preferably the mass ratio is (3.5-4.5): 1.
in one embodiment of the present invention, the compatibilizer is added in an amount of 0.5 to 5%, preferably 1 to 2.5%, based on the total mass of the polyolefin.
In one embodiment of the invention, the blending process is carried out in an internal mixer at a normal pressure and at a blending temperature of 170-190 ℃, preferably 175-180 ℃; the rotating speed of the internal mixer is 40-60r/min, preferably 48-53r/min; the blending time is 5-8min, preferably 6-7min.
The invention also provides a polyolefin/polysaccharide polymer composite material, which is obtained by the method.
In one embodiment of the invention, the tensile strength of the polyethylene-based blended plastic is >25Mpa and the tensile strength of the polypropylene-based blended plastic is >30Mpa.
The main chain structure of the short-chain polyolefin containing azo ester side groups is a nonpolar polyolefin oligomer, the low polarity ensures that the short-chain polyolefin containing azo ester side groups has better compatibility with low-polarity polymers such as polyethylene, polypropylene and the like, the introduction of the side group polar groups can interact with the polar groups in the polar polymers to increase the compatibility with the polar polymers, the polysaccharide polymers contain more polar groups such as hydroxyl groups and the like, so that stronger interaction can be generated with the side groups of the compatibilizer, the nonpolar structure of the main chain ensures the compatibility with the nonpolar polymers, and sufficient interaction is ensured for the compatibilizer and the two polymers at the same time, so that the compatibility of two-phase interfaces is effectively increased, and the compatibility effect between the polyolefin polymers and the polysaccharide polymer interfaces is increased. The method is particularly suitable for blending polyethylene/polypropylene and starch/cellulose, and the obtained composite material with good dispersion can be applied to the production of biodegradable plastics. The blending method is simple to operate, wide in raw material sources and obvious in compatibilization effect, can effectively reduce the production cost of the degradable plastic, and has huge social benefits.
Compared with the prior art, the invention has the following advantages:
(1) The compatibilizer has simple preparation process and low operation requirement, and can be used for mass production;
(2) The compatibilizer has obvious compatibilizer effect and wider application;
(3) The compatibilizer is used for the preparation process of the polyolefin/polysaccharide polymer composite material, and has simple process and lower cost;
(4) The process conditions greatly reduce the waste of industrial, agricultural and domestic plastic products, lighten the environmental pollution and promote the ecological protection.
Drawings
FIG. 1 is a scanning electron microscope characterization of a blend film: (A) comparative example 1; (B) example 2; (C) comparative example 2; (D) example 3; (E) comparative example 3; (F) example 4.
Detailed Description
The invention provides a compatibilizer, which is characterized in that an azodicarbonate compound is grafted on an olefin oligomer main chain, so that the compatibility of polyolefin and other polymer materials can be improved.
In one embodiment of the present invention, the method for preparing the compatibilizer comprises the steps of: mixing polyolefin and azodicarbonate compound in solvent, adding tungsten catalyst, reacting under illumination, standing, cooling, separating precipitate in solvent, filtering and oven drying to obtain compatibilizer.
In one embodiment of the present invention, the structural general formula of the compatibilizer is shown in the following formula (I):
wherein R is 1 Is a hydrogen atom or an unbranched or branched alkyl radical having 1 to 3 carbon atoms, R 2 、R 3 Each independently is a linear C1-C4 alkyl group or a branched C1-C4 alkyl group.
For example, the compatibilizer having the above structure may employ one or more of the following structural formulas.
Wherein n has a value of 10 to 500, preferably 10 to 100.
The invention also provides an application of the compatibilizer in preparing polyolefin/polysaccharide polymer composite materials, which comprises the following specific steps: firstly, uniformly mixing a compatibilizer and a polysaccharide polymer through mechanical stirring, then adding polyolefin plastic into an internal mixer, adding a mixture of a plasticizer and the polysaccharide polymer after the polyolefin plastic is completely melted, and carrying out internal mixing together to obtain the blended composite plastic after the internal mixing is finished.
In one embodiment of the invention, the polyolefin is selected from one or more of polyethylene or polypropylene, preferably a single polyethylene or polypropylene.
In one embodiment of the invention, the polyethylene may be a high density polyethylene or a low density polyethylene and the polypropylene may be isotactic polypropylene, syndiotactic polypropylene or atactic polypropylene.
In one embodiment of the invention, the polyethylene or polypropylene has a number average molecular weight of 100000 ～ 500000, preferably a number average molecular weight of 150000-250000.
In one embodiment of the invention, the polysaccharide polymer is selected from one of starch or cellulose.
In one embodiment of the present invention, the compatibilizer is added in an amount of 0.5 to 5%, preferably 1 to 2.5%, based on the total mass of the polyolefin.
In one embodiment of the present invention, the polyolefin is mixed with the polysaccharide polymer in a mass ratio of (2 to 5): 1, preferably the mass ratio is (3.5-4.5): 1.
in one embodiment of the present invention, the compatibilizer is added in an amount of 0.5 to 5%, preferably 1 to 2.5%, based on the total mass of the polyolefin.
In one embodiment of the invention, the blending process is carried out in an internal mixer at a normal pressure and at a blending temperature of 170-190 ℃, preferably 175-180 ℃; the rotating speed of the internal mixer is 40-60r/min, preferably 48-53r/min; the blending time is 5-8min, preferably 6-7min.
The invention also provides a polyolefin/polysaccharide polymer composite material, which is obtained by the preparation method.
In one embodiment of the invention, the tensile strength of the polyethylene-based blended plastic is >25Mpa and the tensile strength of the polypropylene-based blended plastic is >30Mpa.
Short-chain polyolefin containing azo ester side groups is used as a compatibilizer, so that the compatibility effect between the polyolefin polymer and the polysaccharide polymer interface is effectively improved. The method is particularly suitable for blending polyethylene/polypropylene and starch/cellulose, and the obtained composite material with good dispersion can be applied to the production of biodegradable plastics. The blending method is simple to operate, wide in raw material sources and obvious in compatibilization effect, can effectively reduce the production cost of the degradable plastic, and has huge social benefits.
The invention will now be described in detail with reference to the drawings and specific examples.
Analytical instrument:
internal mixer Rheomix 600, rotor type: roller Rotors, rotor speed ratio 3:2, cavity volume (without rotor): 120cm 3 The feeding mode is as follows: manual, temperature control mode: program automatic temperature control, temperature control thermocouple: 3, temperature control: electric heating, air cooling, three-zone heating: back plate/middle plate/front plate.
Scanning electron microscope Ultra55, germany Zeiss
Reagent:
high density polyethylene, beijing Yanshan division, china petrochemical Co., ltd;
polypropylene, beijing Yanshan division of China petrochemical Co., ltd;
starch, shanghai microphone Biochemical technologies Co., ltd;
cellulose, shanghai microphone Biochemical technology Co., ltd;
diisopropyl azodicarboxylate, shanghai Taitan technologies Co., ltd;
POE-g-MAH, a good polymer of easy to use (Shanghai) Co., ltd;
the catalyst TBADT was prepared as described in reference chem.Commun.,2009,41 (47), 7351-7353.
Example 1
The embodiment provides a preparation method of a compatibilizer.
Into a 10mL reaction flask, 56mg of polyethylene powder, 808mg of diisopropyl azodicarboxylate, 166mg of TBADT and 5mL of 1, 2-tetrachloroethane were added, and the mixture was stirred well.
The mixture was purged with nitrogen at room temperature for 1.5h, then light was applied at 110 ℃ and stirred for 48h. The mixture was then cooled to room temperature and the resulting mixture was precipitated by dropwise addition to 100mL of methanol. The precipitated solids were washed 3 times with methanol and acetonitrile, respectively. Finally, the product is dried under vacuum overnight to obtain the product compatibilizer (I).
Example 2
The embodiment provides a blending compatibilization test method.
400mg of the compatibilizer prepared in example 1 was taken, 8g of starch was added, and uniformly mixed by mechanical stirring, then 32g of high-density polyethylene powder (molecular weight: 200000) was fed into an internal mixer for plasticization, and after the high-density polyethylene was completely melted, the starch and compatibilizer mixture was fed into the internal mixer. The blend was blended at 180℃for 6 minutes at 60 rpm. The resulting composite plastic material was kept dry under vacuum at 50 ℃ overnight.
The dried plastic was cut into small particles and pressurized by a press vulcanizer to obtain a blend film. The plate temperature was set to 200 ℃, the pressure was set to 20T and held for 10 minutes to obtain the final film. The pressed film was broken in liquid nitrogen and sent for scanning electron microscopy characterization, the characterization results are shown in fig. 1B. The pressed film was cut simultaneously for tensile testing, and its tensile strength was measured to be 27.80MPa.
Example 3
The embodiment provides a blending compatibilization test method.
400mg of the compatibilizer prepared in example 1 was taken, 8g of cellulose was added, and uniformly mixed by mechanical stirring, then 32g of high-density polyethylene powder (molecular weight: 200000) was fed into an internal mixer for plasticization, and after the high-density polyethylene was completely melted, the mixture of cellulose and compatibilizer was added into the internal mixer. The blend was blended at 180℃for 6 minutes at 60 rpm. The resulting composite plastic material was kept dry under vacuum at 50 ℃ overnight.
The dried plastic was cut into small particles and pressurized by a press vulcanizer to obtain a blend film. The plate temperature was set to 200 ℃, the pressure was set to 20T and held for 10 minutes to obtain the final film. The pressed film was broken in liquid nitrogen and sent for scanning electron microscopy characterization, the characterization results are shown in fig. 1D. The pressed film was cut simultaneously for tensile testing, and its tensile strength was measured to be 26.15MPa.
Example 4
The embodiment provides a blending compatibilization test method.
400mg of the compatibilizer prepared in example 1 was taken, 8g of starch was added, and mixed well by mechanical stirring, then 32g of polypropylene powder (molecular weight 100000) was fed into an internal mixer for plasticization, and after the polypropylene was completely melted, the mixture of the fibril starch and the compatibilizer was fed into the internal mixer. The blend was blended at 180℃for 6 minutes at 60 rpm. The resulting composite plastic material was kept dry under vacuum at 50 ℃ overnight.
The dried plastic was cut into small particles and pressurized by a press vulcanizer to obtain a blend film. The plate temperature was set to 200 ℃, the pressure was set to 20T and held for 10 minutes to obtain the final film. The pressed film was broken in liquid nitrogen and sent for scanning electron microscopy characterization, the characterization results are shown in fig. 1F. The pressed film was cut simultaneously for tensile test, and its tensile strength was measured to be 31.8MPa.
Example 5
The embodiment provides a blending compatibilization test method.
400mg of compatibilizer prepared in example 1 was taken, 8g of starch was added, and mixed well by mechanical stirring, then 32g of high-density polyethylene powder (molecular weight 100000) was fed into an internal mixer for plasticization, and after the polypropylene was completely melted, the mixture of the fibril starch and the compatibilizer was added into the internal mixer. The blend was blended at 170℃for 8 minutes at a speed of 40 rpm. The resulting composite plastic material was kept dry under vacuum at 50 ℃ overnight.
The dried plastic was cut into small particles and pressurized by a press vulcanizer to obtain a blend film. The plate temperature was set to 200 ℃, the pressure was set to 20T and held for 10 minutes to obtain the final film. The pressed film was broken in liquid nitrogen and sent for scanning electron microscopy characterization, the characterization results are shown in fig. 1F. The pressed film was cut simultaneously for tensile testing, and its tensile strength was measured to be 27.5MPa.
Example 6
The embodiment provides a blending compatibilization test method.
300mg of the compatibilizer prepared in example 1 was taken, 8g of cellulose was added, and uniformly mixed by mechanical stirring, then 32g of high-density polyethylene powder (molecular weight: 300000) was fed into an internal mixer for plasticization, and after the polypropylene was completely melted, the fiber starch and compatibilizer mixture was fed into the internal mixer. The blend was blended at 190℃for 5 minutes at 60 rpm. The resulting composite plastic material was kept dry under vacuum at 50 ℃ overnight.
The dried plastic was cut into small particles and pressurized by a press vulcanizer to obtain a blend film. The plate temperature was set to 200 ℃, the pressure was set to 20T and held for 10 minutes to obtain the final film. The pressed film was broken in liquid nitrogen and sent for scanning electron microscopy characterization, the characterization results are shown in fig. 1F. The pressed film was cut simultaneously for tensile testing, and its tensile strength was measured to be 26.9MPa.
Example 7
The embodiment provides a blending compatibilization test method.
800mg of the compatibilizer prepared in example 1 was taken, 8g of cellulose was added, and uniformly mixed by mechanical stirring, then 32g of polypropylene powder (molecular weight: 150000) was fed into an internal mixer for plasticization, and after the polypropylene was completely melted, the mixture of the fibril starch and the compatibilizer was fed into the internal mixer. The blend was blended at 190℃for 7 minutes at 50 rpm. The resulting composite plastic material was kept dry under vacuum at 50 ℃ overnight.
The dried plastic was cut into small particles and pressurized by a press vulcanizer to obtain a blend film. The plate temperature was set to 200 ℃, the pressure was set to 20T and held for 10 minutes to obtain the final film. The pressed film was broken in liquid nitrogen and sent for scanning electron microscopy characterization, the characterization results are shown in fig. 1F. The pressed film was cut simultaneously for tensile testing, and its tensile strength was measured to be 34.7MPa.
Comparative example 1
32g of high-density polyethylene powder was fed into an internal mixer for plasticization, and after the high-density polyethylene was completely melted, 8g of starch was fed into the internal mixer. The blend was blended at 180℃for 6 minutes at 60 rpm. The resulting composite plastic material was kept dry under vacuum at 50 ℃ overnight.
The dried plastic was cut into small particles and pressurized by a press vulcanizer to obtain a blend film. The plate temperature was set to 200 ℃, the pressure was set to 20T and held for 10 minutes to obtain the final film. The pressed film was broken in liquid nitrogen and sent for scanning electron microscopy characterization, the characterization results are shown in fig. 1A. The pressed film was cut simultaneously for tensile testing, and its tensile strength was measured to be 20.66MPa.
Comparative example 2
32g of high-density polyethylene powder was fed into an internal mixer for plasticization, and after the high-density polyethylene was completely melted, 8g of cellulose was fed into the internal mixer. The blend was blended at 180℃for 6 minutes at 60 rpm. The resulting composite plastic material was kept dry under vacuum at 50 ℃ overnight.
The dried plastic was cut into small particles and pressurized by a press vulcanizer to obtain a blend film. The plate temperature was set to 200 ℃, the pressure was set to 20T and held for 10 minutes to obtain the final film. The pressed film was broken in liquid nitrogen and sent for scanning electron microscopy characterization, the characterization results are shown in fig. 1C. The pressed film was cut simultaneously for tensile testing, and its tensile strength was measured to be 18.69MPa.
Comparative example 3
32g of polypropylene powder was fed into an internal mixer for plasticization and after the polypropylene was completely melted, 8g of starch was added to the internal mixer. The blend was blended at 180℃for 6 minutes at 60 rpm. The resulting composite plastic material was kept dry under vacuum at 50 ℃ overnight.
The dried plastic was cut into small particles and pressurized by a press vulcanizer to obtain a blend film. The plate temperature was set to 200 ℃, the pressure was set to 20T and held for 10 minutes to obtain the final film. The pressed film was broken in liquid nitrogen and sent for scanning electron microscopy characterization, the characterization results are shown in fig. 1E. The pressed film was cut simultaneously for tensile testing, and its tensile strength was measured to be 25.36MPa.
Comparative example 4
400mg of commercial compatibilizer POE-g-MAH is taken, 8g of cellulose is added, the mixture is uniformly mixed through mechanical stirring, then 32g of high-density polyethylene powder is sent into an internal mixer for plasticizing, and after the high-density polyethylene is completely melted, the mixture of the cellulose and the compatibilizer is added into the internal mixer. The blend was blended at 180℃for 6 minutes at 60 rpm. The resulting composite plastic material was kept dry under vacuum at 50 ℃ overnight.
The dried plastic was cut into small particles and pressurized by a press vulcanizer to obtain a blend film. The plate temperature was set to 200 ℃, the pressure was set to 20T and held for 10 minutes to obtain the final film. The pressed film was cut for tensile testing and found to have a tensile strength of 21.45MPa.
As can be seen from comparison of comparative examples and examples, the compatibilizer of the invention can effectively improve the compatibility between polyolefin and polysaccharide polymer, and obviously improve the tensile strength of the blended plastic, thereby providing an effective solution for the preparation and large-scale application of biodegradable plastics.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (13)
1. The compatibilizer is characterized in that the compatibilizer is an olefin oligomer type compatibilizer with an azo-diformate compound grafted on the main chain, and can improve the compatibility of polyolefin and other polymer materials;
the preparation method of the compatibilizer comprises the following steps: mixing polyolefin and azodicarbonate compound in solvent, adding tungsten metal catalyst, reacting under illumination condition, standing for cooling, separating precipitate in solvent, filtering and oven drying to obtain compatibilizer;
the structural general formula of the compatibilizer is shown in the following formula (I):
wherein R1 is a hydrogen atom or an unbranched or branched alkyl group having 1 to 3 carbon atoms, R2, R3 are each independently a straight-chain C1-C4 alkyl group or a branched C1-C4 alkyl group; n has a value of 10 to 500.
2. A compatibilizer according to claim 1 wherein the compatibilizer has one or more of the following formulas:
wherein n has a value of 10 to 500.
3. A method for blending and compatibilizing polyolefin and polysaccharide polymer, which is characterized by mainly comprising the following steps: the polyolefin and the polysaccharide polymer are subjected to banburying and blending under the action of the compatibilizer as claimed in claim 1 or 2, so as to obtain the polyolefin/polysaccharide polymer composite material.
4. A method of compatibilizing a polyolefin and a polysaccharide polymer according to claim 3, wherein the polyolefin is a single polymer or a mixture of both polyethylene and polypropylene;
the number average molecular weight of the polyethylene or the polypropylene is 100000 ～ 500000.
5. The method of claim 4, wherein the polyolefin is a single polyethylene or polypropylene polymer;
the number average molecular weight of the polyethylene or the polypropylene is 150000-250000.
6. A method of compatibilizing a polyolefin and a polysaccharide polymer according to claim 3, wherein the polyolefin is mixed with the polysaccharide polymer in a mass ratio of (2 to 5): 1.
7. the method for blending and compatibilizing a polyolefin and a polysaccharide polymer according to claim 6, wherein the mass ratio of the polyolefin to the polysaccharide polymer is (3.5-4.5): 1.
8. a method of compatibilizing a blend of a polyolefin and a polysaccharide polymer according to claim 3 wherein the compatibilizer is added in an amount of 0.5% to 5% based on the total mass of the blend.
9. The method for blending and compatibilizing a polyolefin and a polysaccharide polymer according to claim 8, wherein the compatibilizer is added in an amount of 1% to 2.5% based on the total mass of the blend.
10. A method of compatibilizing a polyolefin and a polysaccharide polymer according to claim 3, wherein the blending process is carried out in an internal mixer at a blending pressure of normal pressure, a blending temperature of 170-190 ℃, a rotational speed of the internal mixer of 40-60r/min, and a blending time of 5-8min.
11. The method for blending and compatibilizing polyolefin and polysaccharide polymer according to claim 10, wherein the blending process is carried out in an internal mixer, the blending pressure is normal pressure, and the blending temperature is 175-180 ℃; the rotating speed of the internal mixer is 48-53r/min; the blending time is 6-7min.
12. A polyolefin/polysaccharide polymer composite, characterized in that it is prepared by the process according to claim 3.
13. The polyolefin/polysaccharide polymer composite according to claim 12, wherein the tensile strength of the polyolefin/polysaccharide polymer composite is >25Mpa.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013158225A1 (en) * | 2012-04-18 | 2013-10-24 | Exxonmobil Chemical Patents Inc. | Polyolefin compositions and methods of production thereof |
| CN106995508A (en) * | 2016-11-25 | 2017-08-01 | 中山大学 | A kind of preparation method of hydrazides graft-modified polyolefin |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013158225A1 (en) * | 2012-04-18 | 2013-10-24 | Exxonmobil Chemical Patents Inc. | Polyolefin compositions and methods of production thereof |
| CN106995508A (en) * | 2016-11-25 | 2017-08-01 | 中山大学 | A kind of preparation method of hydrazides graft-modified polyolefin |
Non-Patent Citations (1)
| Title |
|---|
| 增容剂对微晶纤维素增强淀粉塑料的影响;郭斌;王礼建;董亚强;李本刚;范磊;李盘欣;高分子材料科学与工程(第006期);摘要，第1.2节内容 * |
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