CN117924822B - Dual-reinforced polyethylene reclaimed material composition, dual-reinforced reclaimed polyethylene and preparation method and application thereof - Google Patents
Dual-reinforced polyethylene reclaimed material composition, dual-reinforced reclaimed polyethylene and preparation method and application thereof Download PDFInfo
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- CN117924822B CN117924822B CN202410088362.4A CN202410088362A CN117924822B CN 117924822 B CN117924822 B CN 117924822B CN 202410088362 A CN202410088362 A CN 202410088362A CN 117924822 B CN117924822 B CN 117924822B
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- -1 polyethylene Polymers 0.000 title claims abstract description 118
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 103
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 103
- 239000000203 mixture Substances 0.000 title claims abstract description 66
- 239000000463 material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 51
- 239000003607 modifier Substances 0.000 claims abstract description 25
- 239000003381 stabilizer Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 20
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000945 filler Substances 0.000 claims abstract description 15
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 11
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004342 Benzoyl peroxide Substances 0.000 claims abstract description 7
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000019400 benzoyl peroxide Nutrition 0.000 claims abstract description 7
- 239000012985 polymerization agent Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 44
- 238000002156 mixing Methods 0.000 claims description 41
- 230000009977 dual effect Effects 0.000 claims description 30
- 239000001993 wax Substances 0.000 claims description 10
- 235000014676 Phragmites communis Nutrition 0.000 claims description 8
- 239000010902 straw Substances 0.000 claims description 8
- QRVSDVDFJFKYKA-UHFFFAOYSA-N dipropan-2-yl propanedioate Chemical compound CC(C)OC(=O)CC(=O)OC(C)C QRVSDVDFJFKYKA-UHFFFAOYSA-N 0.000 claims description 7
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 claims description 6
- 235000011037 adipic acid Nutrition 0.000 claims description 6
- 239000001361 adipic acid Substances 0.000 claims description 6
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N hexanedioic acid Natural products OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 6
- YACGMDXBNOZTFM-UHFFFAOYSA-N C(C)(C)(C)C1=CC=CC=C1.P(=O)(OC1=CC=CC=C1)(OC1=CC=CC=C1)O Chemical compound C(C)(C)(C)C1=CC=CC=C1.P(=O)(OC1=CC=CC=C1)(OC1=CC=CC=C1)O YACGMDXBNOZTFM-UHFFFAOYSA-N 0.000 claims description 5
- 239000012188 paraffin wax Substances 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 4
- 239000003623 enhancer Substances 0.000 claims description 4
- 230000002787 reinforcement Effects 0.000 claims description 4
- 239000000454 talc Substances 0.000 claims description 4
- 229910052623 talc Inorganic materials 0.000 claims description 4
- 229920000742 Cotton Polymers 0.000 claims description 2
- 229920000426 Microplastic Polymers 0.000 claims 1
- 238000011084 recovery Methods 0.000 claims 1
- 238000005452 bending Methods 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 3
- 230000002950 deficient Effects 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000001125 extrusion Methods 0.000 description 11
- 239000013067 intermediate product Substances 0.000 description 11
- 238000001816 cooling Methods 0.000 description 10
- 239000012535 impurity Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 239000002699 waste material Substances 0.000 description 4
- 238000009472 formulation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 235000012222 talc Nutrition 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- DIBUFQMCUZYQKN-UHFFFAOYSA-N butyl diphenyl phosphate Chemical group C=1C=CC=CC=1OP(=O)(OCCCC)OC1=CC=CC=C1 DIBUFQMCUZYQKN-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000001038 titanium pigment Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/20—Recycled plastic
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of modification of high polymer materials, and discloses a double-reinforced polyethylene reclaimed material composition, a double-reinforced reclaimed polyethylene and a preparation method and application thereof. The composition contains the following components which are stored independently or stored in a mixed way: polyethylene reclaimed materials, modifiers, polymerizers, reinforcing agents, stabilizers and fillers; the modifier comprises the following components in percentage by mass: 1-octene of 1-5 in combination with propylene; the polymerization agent is benzoyl peroxide; the content mass ratio of the reinforcing agent is 1:0.2-0.7 of a combination of reinforcing agents A and B. The dual-reinforcement recycled polyethylene prepared by the method has better tensile strength, bending strength and impact strength, and can ensure lower defective rate.
Description
Technical Field
The invention relates to the technical field of modification of high polymer materials, in particular to a double-reinforced polyethylene reclaimed material composition, double-reinforced reclaimed polyethylene and a preparation method and application thereof.
Background
Polyethylene is a thermoplastic plastic, has the characteristics of light specific gravity, large surface hardness of finished products and high elasticity, has good heat resistance, chemical stability and insulativity, and is widely applied to the fields of automobile parts, household appliances and the like. With the rapid development of industry, the waste amount of polyethylene is increased year by year, so that recycling of polyethylene is gaining attention.
The properties of the recycled polyethylene material are obviously attenuated, and in the process of re-granulating the recycled polyethylene material, a polyethylene chain segment is damaged and degraded again, so that in order to obtain the polyethylene material with high strength and good ageing resistance, researchers carry out re-modification on the recycled polyethylene material.
CN107973954a discloses a reinforced modified polyethylene reclaimed material and a preparation method thereof, wherein the reclaimed material is prepared from the following components in parts by weight: 30-75 parts of polyethylene reclaimed materials, 10-30 parts of low-density polyethylene, 5-15 parts of maleic anhydride grafted polypropylene wax, 10-25 parts of medium-alkali glass fiber, 0.01-0.02 part of antioxidant and 0.5-2 parts of di-tert-butylperoxy diisopropylbenzene. The reclaimed material composition has good dispersibility, compatibility and excellent rigidity-toughness balance.
CN102079836a discloses a blended profile of modified recycled polyethylene and polyvinyl chloride and a preparation method of the blended profile. The profile is prepared by blending 100 parts of polyvinyl chloride, 5-10 parts of silicone oil modified recycled polyethylene, 3-6 parts of stabilizer, 3-6 parts of titanium pigment, 6-10 parts of chlorinated polyethylene, 1-4 parts of acrylic ester impact modifier, 0.2-1.0 part of lubricant and 0-30 parts of active calcium carbonate. The blending profile disclosed by the invention has excellent performance, can effectively improve the recycling rate of waste plastics, saves resources, saves cost and is environment-friendly and safe.
However, in the above-mentioned studies, the quality of the recovered polyethylene obtained is not known. The impurity points are important factors affecting the quality of the recycled polyethylene, and it is difficult to avoid that the produced recycled polyethylene contains impurity points. In addition, the appearance, mechanical properties, ageing resistance and other properties of the recycled polyethylene can be seriously affected by impurity points.
Disclosure of Invention
The invention aims to solve the problem that the recycled polyethylene prepared in the prior art has poor comprehensive mechanical properties and overcome the defect of high defective rate.
In order to achieve the above object, a first aspect of the present invention provides a dual reinforced polyethylene regrind composition comprising the following components stored independently or in a mixture of two or more:
polyethylene reclaimed materials, modifiers, polymerizers, reinforcing agents, stabilizers and fillers;
The modifier comprises the following components in percentage by mass: 1-octene of 1-5 in combination with propylene;
The polymerization agent is benzoyl peroxide;
The content mass ratio of the reinforcing agent is 1:0.2-0.7 of a combination of reinforcing agents A and B; the reinforcing agent A is at least one selected from tert-butylbenzene diphenyl phosphate, dimethyl methylphosphonate and tributyl phosphate; the reinforcing agent B is at least one selected from adipic acid diester, diisopropyl malonate and dibutyl sebacate;
The content mass ratio of the stabilizer is 1:0.7-1 of a combination of natural paraffin wax and polyethylene wax;
In the composition, the content of the modifier is 0.5 to 1 part by weight, the content of the polymerizer is 1.6 to 3.5 parts by weight, the content of the reinforcing agent is 4.5 to 5.1 parts by weight, the content of the stabilizer is 1 to 1.8 parts by weight, and the content of the filler is 0.1 to 1 part by weight, relative to 100 parts by weight of the polyethylene reclaimed material.
In a second aspect the present invention provides a process for the preparation of a dual reinforced recycled polyethylene using the components of the composition according to the first aspect of the invention comprising:
(1) Firstly mixing a modifier, a polymerizer and an enhancer to obtain a mixture I;
(2) Carrying out second mixing on the polyethylene reclaimed material and the mixture I to obtain a mixture II;
(3) Thirdly, mixing the stabilizer and the mixture II to obtain a mixture III;
(4) And fourth mixing the filler and the mixture III to obtain the double reinforced recycled polyethylene.
A third aspect of the present invention provides a dual reinforced recycled polyethylene produced by the process of the second aspect of the present invention.
The fourth aspect of the invention provides an application of the dual reinforced recycled polyethylene in recycling of recycled plastic pelletization.
In the invention, 1-octene and propylene with specific contents are selected as modifiers, and reinforcing agents A and B with specific contents are introduced into materials such as polyethylene reclaimed materials, polymerization agents, stabilizers, fillers and the like to form a composition system, so that the prepared dual-reinforced reclaimed polyethylene has better tensile strength, bending strength and impact strength, and the prepared dual-reinforced reclaimed polyethylene contains lower impurity points.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In the invention, the molecular formula of benzoyl peroxide is C 14H10O4.
In the invention, the molecular formula of the tertiary butyl diphenyl phosphate is C 22H23O4 P; the molecular formula of the methyl dimethyl phosphonate is C 3H9O3 P; the molecular formula of tributyl phosphate is C 12H27O4 P; the molecular formula of the adipic acid diester is C 22H42O4; the molecular formula of the diisopropyl malonate is C 9H16O4, and the molecular formula of the dibutyl sebacate is C 18H34O4.
It should be noted that, in the aspects of the present invention, the present invention is described only once in one aspect thereof for the same components in the aspects and is not repeated, and those skilled in the art should not understand the limitation of the present invention.
As previously described, the first aspect of the present invention provides a dual reinforced polyethylene regrind composition comprising the following components, each independently stored or stored in admixture with two or more:
polyethylene reclaimed materials, modifiers, polymerizers, reinforcing agents, stabilizers and fillers;
The modifier comprises the following components in percentage by mass: 1-octene of 1-5 in combination with propylene;
The polymerization agent is benzoyl peroxide;
The content mass ratio of the reinforcing agent is 1:0.2-0.7 of a combination of reinforcing agents A and B; the reinforcing agent A is at least one selected from tert-butylbenzene diphenyl phosphate, dimethyl methylphosphonate and tributyl phosphate; the reinforcing agent B is at least one selected from adipic acid diester, diisopropyl malonate and dibutyl sebacate;
The content mass ratio of the stabilizer is 1:0.7-1 of a combination of natural paraffin wax and polyethylene wax;
In the composition, the content of the modifier is 0.5 to 1 part by weight, the content of the polymerizer is 1.6 to 3.5 parts by weight, the content of the reinforcing agent is 4.5 to 5.1 parts by weight, the content of the stabilizer is 1 to 1.8 parts by weight, and the content of the filler is 0.1 to 1 part by weight, relative to 100 parts by weight of the polyethylene reclaimed material.
In the present invention, there is no particular limitation on the source of the polyethylene reclaimed material, which is obtained by subjecting a polyethylene plastic bag recovered from a waste station to crushing treatment and melting treatment in this order, and which can be obtained commercially or by the present invention in combination with known knowledge in the art. The invention is not described in detail herein, and those skilled in the art should not understand the limitation of the invention.
Preferably, the content mass ratio of the modifier is 1:2-4 and propylene. The inventor of the present invention found that under the preferred conditions, the obtained double reinforced recycled polyethylene has better mechanical properties.
Further preferably, the enhancer is 1:0.3-0.67 of a combination of reinforcing agents A and B. The inventor of the present invention found that under the preferred conditions, the obtained double reinforced recycled polyethylene has better toughness and mechanical properties.
Further preferably, in the stabilizer, the polyethylene wax has a bulk density of 400 to 483kg/m 3 and a softening point of 104 to 106 ℃.
Preferably, the filler is selected from reed straw, talc, sericite or cotton.
Preferably, the filler is reed straw or talcum powder.
Further preferably, the average diameter of the reed straw is 2.5-3mm, and the average length is 15-20mm.
More preferably, the talc has a particle average diameter of 3 to 4 μm.
As previously mentioned, the second aspect of the present invention provides a process for preparing a dual reinforced recycled polyethylene using the components of the composition of the first aspect of the present invention comprising:
(1) Firstly mixing a modifier, a polymerizer and an enhancer to obtain a mixture I;
(2) Carrying out second mixing on the polyethylene reclaimed material and the mixture I to obtain a mixture II;
(3) Thirdly, mixing the stabilizer and the mixture II to obtain a mixture III;
(4) And fourth mixing the filler and the mixture III to obtain the double reinforced recycled polyethylene.
Preferably, the method further comprises: after said fourth mixing, the resulting intermediate product needs to be subjected to an extrusion process.
In the present invention, there is no particular limitation on the manner of the extrusion molding process, and the extrusion molding process is exemplified by placing the intermediate in an extrusion granulator having a cylindrical hole, shearing the excess part to obtain a granular intermediate product, and cooling the intermediate product in water at 25 ℃; the diameter of the cylindrical pore canal is 3mm.
Preferably, the whole process of preparing the dual reinforced recycled polyethylene using the components of the composition is under agitation.
Preferably, in step (1), the conditions of the first mixing at least satisfy: the pressure is 6-8MPa, the temperature is 250-270 ℃, and the time is 7-9min.
Preferably, in step (1), the first mixing is performed under stirring and the stirring speed is 140-180rpm.
Further preferably, in step (1), the conditions of the first mixing further include: the temperature rising rate is 15-30 ℃/min.
More preferably, the method further comprises: the pressure in the reaction apparatus was reduced to normal pressure before the second mixing was performed.
Preferably, in step (2), the second mixing is performed under stirring, and the conditions of the second mixing at least satisfy: the stirring speed is 330-390rpm, the temperature is 180-200 ℃ and the time is 18-26min.
Preferably, in step (2), the conditions of the second mixing further include: the cooling rate is 15-20 ℃/min.
Further preferably, in step (3), the third mixing is performed under stirring, and the conditions of the third mixing at least satisfy: the stirring speed is 240-280rpm, the temperature is 130-155 ℃ and the time is 6-8min.
Preferably, in step (3), the conditions of the third mixing further include: the cooling rate is 10-20 ℃/min.
Preferably, in step (4), the fourth mixing is performed under stirring, and the conditions of the fourth mixing at least satisfy: the stirring speed is 70-90rpm, the temperature is 140-155 ℃ and the time is 7-9min.
As previously mentioned, a third aspect of the present invention provides a dual reinforced recycled polyethylene produced by the process of the second aspect of the present invention.
As previously mentioned, a fourth aspect of the present invention provides the use of the dual reinforced recycled polyethylene of the third aspect of the present invention in recycling of recycled plastics pelletization.
The present invention will be described in detail by examples. In the following examples, unless otherwise specified, all of the raw materials are commercially available.
In the examples to be given below,
The polyethylene reclaimed material is obtained by crushing and melting polyethylene plastic bags reclaimed from a waste station in sequence;
Reinforcing agent:
t-butylbenzene diphenyl phosphate, available from aladine Biotechnology Co., ltd;
dimethyl methylphosphonate, available from marcanuno technologies, inc;
tributyl phosphate, available from Alatine Biochemical technologies Co., ltd;
adipic acid diester, available from merck company;
diisopropyl malonate, available from the international trade company of pan (Shanghai);
Dibutyl sebacate, purchased from aladine biochemistry technologies, inc;
Stabilizing agent:
Polyethylene wax with bulk density of 483kg/m 3 and softening point of 106 ℃;
Filler:
reed straw I has an average diameter of 2.5mm and an average length of 20mm;
Reed straw II has an average diameter of 3mm and an average length of 15mm;
talc powder with an average particle diameter of 3.25 μm.
In the following examples, the extrusion molding treatment is extrusion by adopting an extrusion granulator, wherein the extrusion granulator comprises a cylindrical pore canal, and the excess part is sheared to obtain a granular intermediate product, and then the intermediate product is placed in water with the temperature of 25 ℃ for cooling molding; the diameter of the cylindrical pore canal is 3mm.
Example 1
This example is used to provide the dual reinforced polyethylene regrind composition of the present invention according to the following formulation and process parameters and to prepare the dual reinforced regrind polyethylene according to the method described below:
(1) Placing 0.5kg of modifier, 1.6kg of benzoyl peroxide and 5kg of reinforcing agent into a pressure tank, sealing, setting the pressure to 6MPa, starting stirring (the stirring speed is 140 rpm), setting the temperature to 250 ℃ (the heating rate is 15 ℃/min), and mixing and reacting for 7min at the temperature to obtain a mixture I;
The mass ratio of the modifier is 1:2, and propylene; the mass ratio of the reinforcing agent is 1:0.3 of a reinforcing agent A and a reinforcing agent B, wherein the reinforcing agent A is dimethyl methylphosphonate and the reinforcing agent B is diisopropyl malonate.
(2) The pressure in the pressure tank was reduced to normal pressure with stirring (stirring speed: 140 rpm), 100kg of polyethylene reclaimed material was added to the mixture I, the stirring speed was set at 330rpm, and the temperature was set at 180 ℃ (cooling rate: 15 ℃/min), and the mixture was mixed and reacted at that temperature for 18min to obtain a mixture II.
(3) Adding 1.4kg of stabilizer into the mixture II under stirring (stirring speed is 330 rpm), setting the temperature to 130 ℃ (cooling speed is 10 ℃/min), setting the stirring speed to 240rpm, and mixing and reacting at the temperature for 6min to obtain a mixture III;
the mass ratio of the stabilizer is 1:1 and polyethylene wax.
(4) Under stirring (stirring speed 240 rpm), 0.1kg of reed straw I was added to the mixture III, the stirring speed was set to 70rpm, the temperature was set to 140 ℃, and the mixture was mixed at the temperature for 7min to obtain an intermediate product.
(5) And (3) carrying out extrusion molding treatment on the intermediate product to obtain the dual-reinforcement recycled polyethylene.
Example 2
This example is used to provide the dual reinforced polyethylene regrind composition of the present invention according to the following formulation and process parameters and to prepare the dual reinforced regrind polyethylene according to the method described below:
(1) Placing 0.5kg of modifier, 2.3kg of benzoyl peroxide and 5.1kg of reinforcing agent into a pressure tank, sealing, setting the pressure to 7MPa, starting stirring (the stirring speed is 160 rpm), setting the temperature to 260 ℃ (the heating rate is 30 ℃/min), and mixing and reacting for 8min at the temperature to obtain a mixture I;
The mass ratio of the modifier is 1:3, and propylene; the mass ratio of the reinforcing agent is 1:0.4 of a reinforcing agent A and a reinforcing agent B, wherein the reinforcing agent A is prepared from the following components in percentage by mass: 1, wherein the reinforcing agent B is prepared from tert-butylbenzene diphenyl phosphate and dimethyl methylphosphonate according to the mass ratio of 1:1.2 adipic acid diester and diisopropyl malonate.
(2) The pressure in the pressure tank was reduced to normal pressure with stirring (stirring speed: 160 rpm), 100kg of polyethylene reclaimed material was added to the mixture I, the stirring speed was set at 360rpm, the temperature was set at 190 ℃ (cooling speed: 20 ℃/min), and the mixture was mixed and reacted at that temperature for 22min to obtain a mixture II.
(3) Adding 1.4kg of stabilizer into the mixture II under stirring (stirring speed is 360 rpm), setting the stirring speed to 260rpm, setting the temperature to 150 ℃ (cooling speed is 20 ℃/min), and mixing and reacting for 7min at the temperature to obtain a mixture III;
the mass ratio of the stabilizer is 1:0.75 of a combination of natural paraffin wax and polyethylene wax.
(4) Under stirring (stirring speed: 260 rpm), 0.1kg of reed straw II was added to the mixture III, the stirring speed was set at 80rpm, the temperature was set at 150 ℃, and the mixture was mixed and reacted at the temperature for 8 minutes to obtain an intermediate product.
(5) And (3) carrying out extrusion molding treatment on the intermediate product to obtain the dual-reinforcement recycled polyethylene.
Example 3
This example is used to provide the dual reinforced polyethylene regrind composition of the present invention according to the following formulation and process parameters and to prepare the dual reinforced regrind polyethylene according to the method described below:
(1) Placing 1kg of modifier, 3.5kg of diaryl peroxide and 5kg of reinforcing agent into a pressure tank, sealing, setting the pressure to 8MPa, starting stirring (the stirring speed is 180 rpm), setting the temperature to 270 ℃ (the heating rate is 25 ℃/min), and mixing and reacting for 9min at the temperature to obtain a mixture I;
The mass ratio of the modifier is 1: 1-octene and propylene combination of 1.5; the mass ratio of the reinforcing agent is 1:0.667 of a combination of a reinforcing agent A and a reinforcing agent B, wherein the reinforcing agent A is tributyl phosphate and the reinforcing agent B is dibutyl sebacate.
(2) The pressure in the pressure tank was reduced to normal pressure with stirring (stirring speed: 180 rpm), 100kg of polyethylene reclaimed material was added to the mixture I, the stirring speed was set to 390rpm, the temperature was set to 200 ℃ (cooling speed: 15 ℃/min), and the mixture was mixed and reacted at that temperature for 26 minutes to obtain a mixture II.
(3) Adding 1.8kg of stabilizer into the mixture II under stirring (stirring speed is 390 rpm), setting the stirring speed to 280rpm, setting the temperature to 155 ℃ (cooling speed is 15 ℃/min), and mixing and reacting for 8min at the temperature to obtain a mixture III;
the mass ratio of the stabilizer is 1:0.75 of a combination of natural paraffin wax and polyethylene wax.
(4) 1Kg of talc was added to the mixture III with stirring (stirring speed: 280 rpm), stirring speed: 90rpm was set, and temperature: 155℃was set, and the mixture was reacted at this temperature for 9 minutes with mixing to obtain an intermediate product.
(5) And (3) carrying out extrusion molding treatment on the intermediate product to obtain the dual-reinforcement recycled polyethylene.
Example 4
A dual reinforced recycled polyethylene was prepared as in example 1, except that in step (1), the modifier was 1:5, and the rest of the steps and parameters are the same as in example 1.
Example 5
A dual reinforced recycled polyethylene was prepared as in example 1, except that in step (1), the reinforcing agent was 1:0.7 of reinforcing agent A and reinforcing agent B, the rest of the procedure and parameters being the same as in example 1.
Comparative example 1
A dual reinforcement recycled polyethylene was prepared as in example 1, except that in step (1) the same amount of 1-butene was used in place of 1-octene, with the remainder of the steps and parameters being the same as in example 1.
Comparative example 2
A dual reinforced recycled polyethylene was prepared as in example 1, except that in step (1) the amount of polymerization agent was 4kg, the remaining steps and parameters were the same as in example 1.
Comparative example 3
A dual reinforced recycled polyethylene was prepared as in example 1, except that in step (1), the reinforcing agent was present in a mass ratio of 1:0.8 of reinforcing agent A and reinforcing agent B, the rest of the procedure and parameters being the same as in example 1.
Test case
The double-reinforced recycled polyethylene prepared in the above examples and comparative examples was subjected to performance test, and the tensile strength and elongation of the double-reinforced recycled polyethylene were measured according to GB/T1040, the bending strength of the double-reinforced recycled polyethylene was measured according to GB/T9341, and the impact strength of the double-reinforced recycled polyethylene was measured according to GB/T1843, to obtain the results shown in Table 1.
TABLE 1
As can be seen from the results in Table 1, the dual-reinforcement recycled polyethylene prepared by the embodiment of the invention has obviously better tensile strength, bending strength and impact strength, which indicates that the dual-reinforcement recycled polyethylene has better mechanical properties; and the impurity points are obviously fewer, which indicates that the quality of the dual reinforced recycled polyethylene obtained by the embodiment of the invention is better.
As can be seen from a comparison of example 1 and comparative example 1, respectively, the obtained double reinforced recycled polyethylene has better mechanical properties and contains fewer impurity points by adopting 1-octene and propylene as modifiers and matching with the composition system of the invention.
As can be seen from the comparison of example 1 and comparative example 2, the obtained double reinforced recycled polyethylene has better mechanical properties and contains fewer impurity points by adopting the amount of the polymerization agent disclosed by the invention and matching with the composition system disclosed by the invention.
As can be seen from a comparison of example 1 and comparative example 3, the obtained double reinforced recycled polyethylene has better mechanical properties and contains fewer impurity points by adopting the reinforcing agent disclosed by the invention and matching with the composition system disclosed by the invention.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. The double reinforced recovery polyethylene is characterized by comprising the following components:
polyethylene reclaimed materials, modifiers, polymerizers, reinforcing agents, stabilizers and fillers;
The modifier comprises the following components in percentage by mass: 1-octene of 1-5 in combination with propylene;
The polymerization agent is benzoyl peroxide;
The content mass ratio of the reinforcing agent is 1:0.2-0.7 of a combination of reinforcing agents A and B; the reinforcing agent A is at least one selected from tert-butylbenzene diphenyl phosphate, dimethyl methylphosphonate and tributyl phosphate; the reinforcing agent B is at least one selected from adipic acid diester, diisopropyl malonate and dibutyl sebacate;
The content mass ratio of the stabilizer is 1:0.7-1 of a combination of natural paraffin wax and polyethylene wax;
The content of the modifier is 0.5-1 weight part, the content of the polymerizer is 1.6-3.5 weight parts, the content of the reinforcing agent is 4.5-5.1 weight parts, the content of the stabilizer is 1-1.8 weight parts, and the content of the filler is 0.1-1 weight part relative to 100 weight parts of polyethylene reclaimed materials;
The method for preparing the double reinforced recycled polyethylene by adopting the components comprises the following steps:
(1) Firstly mixing a modifier, a polymerizer and an enhancer to obtain a mixture I;
(2) Carrying out second mixing on the polyethylene reclaimed material and the mixture I to obtain a mixture II;
(3) Thirdly, mixing the stabilizer and the mixture II to obtain a mixture III;
(4) And fourth mixing the filler and the mixture III to obtain the double reinforced recycled polyethylene.
2. The dual reinforced recycled polyethylene according to claim 1, wherein the modifier is present in an amount of 1 by mass: 2-4 and propylene.
3. The dual reinforced recycled polyethylene according to claim 1 or 2, wherein the reinforcing agent is 1:0.3-0.67 of a combination of reinforcing agents A and B.
4. The dual reinforced recycled polyethylene according to claim 1 or 2, wherein in the stabilizer, the polyethylene wax has a bulk density of 400-483kg/m 3 and a softening point of 104-106 ℃.
5. The dual reinforced recycled polyethylene according to claim 1 or 2, wherein the filler is selected from reed straw, talc, sericite or cotton.
6. The dual reinforced recycled polyethylene according to claim 1 or 2, wherein in step (1), the conditions of the first mixing at least satisfy: the pressure is 6-8MPa, the temperature is 250-270 ℃, and the time is 7-9min.
7. The dual reinforcement recycled polyethylene according to claim 1 or 2, wherein in step (2), the second mixing is performed under agitation, and the conditions of the second mixing at least satisfy: the stirring speed is 330-390rpm, the temperature is 180-200 ℃ and the time is 18-26min.
8. The dual reinforcement recycled polyethylene according to claim 1 or 2, wherein in step (3), the third mixing is performed under agitation, and the conditions of the third mixing at least satisfy: the stirring speed is 240-280rpm, the temperature is 130-155 ℃ and the time is 6-8min.
9. The dual reinforcement recycled polyethylene according to claim 1 or 2, wherein in step (4), the fourth mixing is performed under agitation, and the conditions of the fourth mixing are at least: the stirring speed is 70-90rpm, the temperature is 140-155 ℃ and the time is 7-9min.
10. Use of the dual reinforced recycled polyethylene of any one of claims 1-9 in recycling of recycled plastic pellets.
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| CN102863678A (en) * | 2012-09-28 | 2013-01-09 | 四川塑金科技有限公司 | Special modified recycled polyethylene material for cables and preparation method of special modified recycled polyethylene material |
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| CN103059376B (en) * | 2012-12-24 | 2015-01-28 | 常州南京大学高新技术研究院 | Enhanced toughening recycled polyethylene material and preparation method thereof |
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| CN102863678A (en) * | 2012-09-28 | 2013-01-09 | 四川塑金科技有限公司 | Special modified recycled polyethylene material for cables and preparation method of special modified recycled polyethylene material |
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