CN117343532A - Core-shell structure modified nylon plastic and preparation method thereof - Google Patents
Core-shell structure modified nylon plastic and preparation method thereof Download PDFInfo
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- CN117343532A CN117343532A CN202311344171.1A CN202311344171A CN117343532A CN 117343532 A CN117343532 A CN 117343532A CN 202311344171 A CN202311344171 A CN 202311344171A CN 117343532 A CN117343532 A CN 117343532A
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- 239000011258 core-shell material Substances 0.000 title claims abstract description 92
- 239000004677 Nylon Substances 0.000 title claims abstract description 70
- 229920001778 nylon Polymers 0.000 title claims abstract description 70
- 229920003023 plastic Polymers 0.000 title claims abstract description 38
- 239000004033 plastic Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000003607 modifier Substances 0.000 claims abstract description 41
- 239000004005 microsphere Substances 0.000 claims abstract description 36
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 36
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 35
- 229920002545 silicone oil Polymers 0.000 claims abstract description 35
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 239000002270 dispersing agent Substances 0.000 claims abstract description 19
- -1 alkenyl silicon dioxide Chemical compound 0.000 claims abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 239000010703 silicon Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 43
- 238000002156 mixing Methods 0.000 claims description 29
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 claims description 24
- 239000011347 resin Substances 0.000 claims description 24
- 229920005989 resin Polymers 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 23
- 229920002292 Nylon 6 Polymers 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 14
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 12
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims description 12
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 12
- 229920001223 polyethylene glycol Polymers 0.000 claims description 12
- 229940037312 stearamide Drugs 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 8
- 238000005469 granulation Methods 0.000 claims description 8
- 230000003179 granulation Effects 0.000 claims description 8
- 238000004806 packaging method and process Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- AMTWCFIAVKBGOD-UHFFFAOYSA-N dioxosilane;methoxy-dimethyl-trimethylsilyloxysilane Chemical compound O=[Si]=O.CO[Si](C)(C)O[Si](C)(C)C AMTWCFIAVKBGOD-UHFFFAOYSA-N 0.000 claims description 6
- 229940083037 simethicone Drugs 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 3
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 claims description 2
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims description 2
- 229920000571 Nylon 11 Polymers 0.000 claims description 2
- 229920000299 Nylon 12 Polymers 0.000 claims description 2
- 229920000305 Nylon 6,10 Polymers 0.000 claims description 2
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 8
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 239000012745 toughening agent Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000012779 reinforcing material Substances 0.000 description 4
- 229920002379 silicone rubber Polymers 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920001470 polyketone Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 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
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
-
- 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
- C08L2207/53—Core-shell polymer
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
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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)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention relates to the technical field of nylon, in particular to a core-shell structure modified nylon plastic and a preparation method thereof, wherein the core-shell structure modified nylon plastic comprises the following raw materials in parts by weight: 100-150 parts of nylon, 20-40 parts of silicon copolycarbonate, 5-9 parts of dimethyl silicone oil, 10-15 parts of core-shell structure modifier, 0.5-1 part of vulcanizing agent and 0.5-1.5 parts of dispersing agent; the core-shell structure modifier is a core-shell structure with an alkenyl silicon dioxide microsphere as a core and single-end hydrogen-containing silicone oil as a shell, wherein the alkenyl silicon dioxide microsphere is obtained by grafting vinyl tri (beta-methoxyethoxy) silane with the silicon dioxide microsphere.
Description
Technical Field
The invention relates to the technical field of nylon, in particular to a core-shell structure modified nylon plastic and a preparation method thereof.
Background
Nylon is a plastic material widely used in the industry. Nylon has high strength, heat resistance and corrosion resistance, but it also has some limitations such as brittleness and low toughness. Therefore, nylon needs to be modified to improve its mechanical properties. Common nylon modification modes comprise composite modification, additive modification, chemical modification and the like, and the modification methods can obviously improve the mechanical properties of nylon, but have some defects, such as poor solidification, color change, performance loss and the like of the modified nylon. The core-shell structure is a layered structure formed at the interface of materials, and the materials can have good mechanical properties and toughness due to the special structure. Therefore, the core-shell structure is widely applied to the preparation of modified materials, in particular to high polymer materials.
The core-shell structure modified nylon plastic is mainly realized by adding a core-shell structure reinforcing material into nylon. The core-shell structure reinforcing material may be a microparticle, nanoparticle or organic-inorganic hybrid, which can increase the strength and toughness of nylon. Meanwhile, the core-shell structure reinforcing material is added into the nylon molecular chain, so that the heat stability and corrosion resistance of the material can be improved. The method for preparing the core-shell structure modified nylon plastic comprises a solution blending method, a melt blending method, an in-situ polymerization method and the like. Among them, the melt blending method is the most common method for preparing a core-shell structure modified nylon plastic by mixing nylon and a core-shell structure reinforcing material at high temperature and melting the mixture into a pellet or sheet material.
The invention relates to a core-shell toughening agent and a preparation method thereof as well as toughened nylon applied by the invention, wherein the core-shell toughening agent adopts a core-shell structure with polyketone grafts as shells and ethylene propylene diene monomer grafts as cores, and the toughening agent prepared by the application and nylon are melt and co-extruded, so that the toughness of the nylon is improved, but the temperature of an extruder is up to 200 ℃ when the nylon and the toughening agent are mixed and prepared, and the core-shell toughening agent is molten at the temperature, so that the structure is deformed, and the toughening effect is reduced.
Disclosure of Invention
In view of the above, the invention aims to provide a modified nylon plastic with a core-shell structure and a preparation method thereof, so as to solve the problem that the core-shell structure of the traditional polymer is easy to deform when the core-shell structure and nylon are blended and melted, and the toughening effect is reduced.
Based on the purposes, the invention provides a core-shell structure modified nylon plastic which comprises the following raw materials in parts by weight: 100-150 parts of nylon, 20-40 parts of silicon copolycarbonate, 5-9 parts of dimethyl silicone oil, 10-15 parts of core-shell structure modifier, 0.5-1 part of vulcanizing agent and 0.5-1.5 parts of dispersing agent;
the core-shell structure modifier is a core-shell structure with an alkenyl silicon dioxide microsphere as a core and single-end hydrogen-containing silicone oil as a shell, wherein the alkenyl silicon dioxide microsphere is obtained by grafting vinyl tri (beta-methoxyethoxy) silane with the silicon dioxide microsphere.
The specific preparation method of the core-shell structure modifier comprises the following steps:
s1: dispersing the silicon dioxide microspheres into a mixed solution of absolute ethyl alcohol and water, then adding vinyl tri (beta-methoxyethoxy) silane, stirring and reacting for 5-8 hours at 60-80 ℃, washing and drying to obtain alkenyl silicon dioxide microspheres;
s2: at N 2 Under the protection, the alkenylation silicon dioxide microsphere is added into absolute ethyl alcohol, then single-end hydrogen-containing silicone oil is dropwise added at the temperature of 30-50 ℃ and the rpm of 80-120, the dropwise adding time is 30-45min, and after the dropwise adding is finished, the reaction is carried out for 2-4h at the temperature of 60-80 ℃ and the rpm of 80-120rpm, and the core-shell structure modifier is obtained after washing and drying.
Wherein the nylon is one or more of nylon 6, nylon 66, nylon 610, nylon 1010, nylon 11, nylon 12, nylon 9T or nylon 12T.
The model of the silicon copolycarbonate is EXL1414T.
Wherein the average molecular weight of the simethicone is 5000-10000.
Wherein the vulcanizing agent is one of benzoyl peroxide, 2, 4-dichloro benzoyl peroxide or tert-butyl perbenzoate.
Wherein the dispersing agent is a mixture of polyethylene glycol and stearamide according to the weight ratio of 1-3:1.
Wherein the model of the single-end hydrogen-containing silicone oil is one of RH-222-4 or RH-222-10.
Wherein the average diameter of the silica microsphere is 150-250nm.
Wherein, the weight ratio of the silicon dioxide microspheres, the absolute ethyl alcohol, the water and the vinyl tri (beta-methoxyethoxy) silane in the step S1 is 5-10:5-10:50-100:0.05-0.1; in the step S2, the weight ratio of the alkenyl silicon dioxide microspheres to the anhydrous ethanol to the single-end hydrogen-containing silicone oil is 5-10:50-100:1-3.
Furthermore, the invention also provides a preparation method of the core-shell structure modified nylon plastic, which comprises the following steps:
s3: weighing 100-150 parts of nylon, 20-40 parts of silicon copolycarbonate, 5-9 parts of dimethyl silicone oil, 10-15 parts of core-shell structure modifier, 0.5-1 part of vulcanizing agent and 0.5-1.5 parts of dispersing agent for standby according to parts by weight;
s4: placing nylon and silicon copolycarbonate into a vacuum oven at 90-120 ℃ for drying for 1-2h to obtain pretreatment resin;
s5: adding the pretreatment resin, the core-shell structure modifier and the dimethyl silicone oil into a mixer, stirring and mixing for 1-2h under the condition that the stirring rate is 800-1200r/min, and then adding the vulcanizing agent and the dispersing agent, and continuously stirring and mixing for 30-50min to obtain a mixture;
s6: adding the mixture into a double-screw extruder for melt extrusion, wherein the temperature from a feed inlet of the extruder to a machine head is 180 ℃, 200 ℃, 220 ℃, 240 ℃, 220 ℃ and the screw speed is 200-300r/min, performing water cooling granulation, and packaging to obtain the core-shell structure modified nylon plastic.
The invention has the beneficial effects that:
the invention provides a nylon plastic with a core-shell structure modification, wherein a layer of silicon rubber is formed on the surface of a core-shell structure modifier, the silicon rubber with thermosetting property solves the problem that the traditional polymer core-shell structure and nylon are easy to deform when being blended and melted, and the silicon rubber has relatively high toughness, so that the toughening effect is improved. The invention also provides a method for preparing the core-shell structure modified nylon plastic, which has the characteristics of simplicity, convenience and high efficiency. The core-shell structure modified nylon plastic can be used for manufacturing high-performance engineering plastics, such as automobile parts, electronic devices and the like, and has wide market application prospects.
The invention provides a nylon plastic with a core-shell structure modification, wherein the core-shell structure modifier takes an alkenyl silicon dioxide microsphere as a core and single-end hydrogen-containing silicone oil as a shell, the single-end hydrogen-containing silicone oil can perform addition reaction with alkenyl groups on the surface of the alkenyl silicon dioxide microsphere, and the single-end hydrogen-containing silicone oil on the surface of the core-shell structure modifier can further generate cross-linking with the dimethyl silicone oil and the silicon copolycarbonate in the subsequent melt mixing process with the silicon copolycarbonate, the dimethyl silicone oil and the vulcanizing agent, so that the dispersion and compatibility of the core-shell structure modifier in the nylon plastic are promoted.
Detailed Description
The present invention will be further described in detail with reference to specific embodiments in order to make the objects, technical solutions and advantages of the present invention more apparent.
The raw materials in the specific embodiment of the invention have the following properties:
the average molecular weight of the simethicone is 8000; the average diameter of the silica microspheres was 190nm.
Example 1
S1: dispersing 5g of silicon dioxide microspheres into a mixed solution of 5g of absolute ethyl alcohol and 50g of water, then adding 0.05g of vinyl tri (beta-methoxyethoxy) silane, stirring at 60 ℃ for reaction for 5 hours, washing and drying to obtain alkenylation silicon dioxide microspheres;
s2: at N 2 Under the protection, adding 5g of alkenyl silicon dioxide microspheres into 50g of absolute ethyl alcohol, then dropwise adding 1g of RH-222-4 at 3 ℃ and 80rpm for 30min, reacting for 2h at 60 ℃ and 80rpm after the dropwise adding, washing, and drying to obtain a core-shell structure modifier;
s3: weighing 100g of nylon 6, 20g of EXL1414T, 5g of dimethyl silicone oil, 10g of a core-shell structure modifier, 0.5g of benzoyl peroxide, 0.25g of polyethylene glycol and 0.25g of stearamide for later use;
s4: nylon 6 and EXL1414T are placed in a vacuum oven at 90 ℃ to be dried for 1h, so as to obtain pretreatment resin;
s5: adding the pretreatment resin, the core-shell structure modifier and the dimethyl silicone oil into a mixer, stirring and mixing for 1h under the condition of stirring speed of 800r/min, and then adding the vulcanizing agent and the dispersing agent, and continuing stirring and mixing for 30min to obtain a mixture;
s6: and adding the mixture into a double-screw extruder for melt extrusion, wherein the temperature from a feed inlet of the extruder to a machine head is 180 ℃, 200 ℃, 220 ℃, 240 ℃, 220 ℃ and 200r/min of screw speed, performing water-cooling granulation, and packaging to obtain the core-shell structure modified nylon plastic.
Example 2
S1: dispersing 7.5g of silicon dioxide microspheres into a mixed solution of 7.5g of absolute ethyl alcohol and 75g of water, then adding 0.08g of vinyl tri (beta-methoxyethoxy) silane, stirring and reacting for 6.5 hours at 70 ℃, washing and drying to obtain alkenylation silicon dioxide microspheres;
s2: at N 2 Under the protection, adding 7.5g of alkenyl silicon dioxide microspheres into 75g of absolute ethyl alcohol, then dropwise adding 2gRH-222-4 at 40 ℃ and 100rpm for 40min, reacting for 3h at 70 ℃ and 100rpm after the dropwise adding, washing and drying to obtain the core-shell structure modifier;
s3: 125g of nylon 6, 30g of EXL1414T, 7g of dimethyl silicone oil, 12.5g of core-shell structure modifier, 0.75g of benzoyl peroxide, 0.6g of polyethylene glycol and 0.3g of stearamide are weighed for standby;
s4: nylon 6 and EXL1414T are placed in a vacuum oven at the temperature of 100 ℃ to be dried for 1.5 hours, so as to obtain pretreatment resin;
s5: adding the pretreatment resin, the core-shell structure modifier and the dimethyl silicone oil into a mixer, stirring and mixing for 1.5h under the condition of stirring speed of 1000r/min, and then adding the vulcanizing agent and the dispersing agent, and continuing stirring and mixing for 40min to obtain a mixture;
s6: and adding the mixture into a double-screw extruder for melt extrusion, wherein the temperature from a feed inlet of the extruder to a machine head is 180 ℃, 200 ℃, 220 ℃, 240 ℃, 220 ℃ and the rotating speed of a screw rod is 250r/min, performing water-cooling granulation, and packaging to obtain the core-shell structure modified nylon plastic.
Example 3
S1: dispersing 10g of silicon dioxide microspheres into a mixed solution of 10g of absolute ethyl alcohol and 100g of water, then adding 0.1g of vinyl tri (beta-methoxyethoxy) silane, stirring at 80 ℃ for reaction for 8 hours, washing and drying to obtain alkenylation silicon dioxide microspheres;
s2: at N 2 Under the protection, adding 10g of alkenyl silicon dioxide microspheres into 100g of absolute ethyl alcohol, then dropwise adding 3gRH-222-4 at 50 ℃ and 120rpm for 45min, reacting for 4h at 80 ℃ and 120rpm after the dropwise adding, washing, and drying to obtain the core-shell structure modifier;
s3: 150g of nylon 6, 40g of EXL1414T, 9g of dimethyl silicone oil, 15g of core-shell structure modifier, 1g of benzoyl peroxide, 1g of polyethylene glycol and 0.5g of stearamide are weighed for standby;
s4: nylon 6 and EXL1414T are placed in a vacuum oven at the temperature of 120 ℃ for drying for 2 hours, so as to obtain pretreatment resin;
s5: adding the pretreatment resin, the core-shell structure modifier and the dimethyl silicone oil into a mixer, stirring and mixing for 2 hours under the condition of the stirring rate of 1200r/min, and then adding the vulcanizing agent and the dispersing agent, and continuing stirring and mixing for 50 minutes to obtain a mixture;
s6: and adding the mixture into a double-screw extruder for melt extrusion, wherein the temperature from a feed inlet of the extruder to a machine head is 180 ℃, 200 ℃, 220 ℃, 240 ℃, 220 ℃ and 300r/min of screw speed, performing water-cooling granulation, and packaging to obtain the core-shell structure modified nylon plastic.
Example 4
S1: dispersing 7.5g of silicon dioxide microspheres into a mixed solution of 7.5g of absolute ethyl alcohol and 75g of water, then adding 0.05g of vinyltri (beta-methoxyethoxy) silane, stirring at 70 ℃ for reaction for 6.5 hours, washing, and drying to obtain alkenylation silicon dioxide microspheres;
s2: at N 2 Under the protection, adding 7.5g of alkenyl silicon dioxide microspheres into 75g of absolute ethyl alcohol, then dropwise adding 1gRH-222-4 at 40 ℃ and 100rpm for 40min, reacting for 3h at 70 ℃ and 100rpm after the dropwise adding, washing and drying to obtain the core-shell structure modifier;
s3: 125g of nylon 6, 20g of EXL1414T, 5g of dimethyl silicone oil, 10g of core-shell structure modifier, 0.75g of benzoyl peroxide, 0.6g of polyethylene glycol and 0.3g of stearamide are weighed for standby;
s4: nylon 6 and EXL1414T are placed in a vacuum oven at the temperature of 100 ℃ to be dried for 1.5 hours, so as to obtain pretreatment resin;
s5: adding the pretreatment resin, the core-shell structure modifier and the dimethyl silicone oil into a mixer, stirring and mixing for 1.5h under the condition of stirring speed of 1000r/min, and then adding the vulcanizing agent and the dispersing agent, and continuing stirring and mixing for 40min to obtain a mixture;
s6: and adding the mixture into a double-screw extruder for melt extrusion, wherein the temperature from a feed inlet of the extruder to a machine head is 180 ℃, 200 ℃, 220 ℃, 240 ℃, 220 ℃ and the rotating speed of a screw rod is 250r/min, performing water-cooling granulation, and packaging to obtain the core-shell structure modified nylon plastic.
Example 5
S1: dispersing 7.5g of silicon dioxide microspheres into a mixed solution of 7.5g of absolute ethyl alcohol and 75g of water, then adding 0.1g of vinyltri (beta-methoxyethoxy) silane, stirring and reacting for 6.5 hours at 70 ℃, washing, and drying to obtain alkenylation silicon dioxide microspheres;
s2: at N 2 Under the protection, adding 7.5g of alkenyl silicon dioxide microspheres into 75g of absolute ethyl alcohol, then dropwise adding 3gRH-222-4 at 40 ℃ and 100rpm for 40min, reacting for 3h at 70 ℃ and 100rpm after the dropwise adding is finished, washing, and drying to obtain the core-shell structure modifier;
s3: 125g of nylon 6, 40g of EXL1414T, 9g of dimethyl silicone oil, 15g of core-shell structure modifier, 0.75g of benzoyl peroxide, 0.6g of polyethylene glycol and 0.3g of stearamide are weighed for standby;
s4: nylon 6 and EXL1414T are placed in a vacuum oven at the temperature of 100 ℃ to be dried for 1.5 hours, so as to obtain pretreatment resin;
s5: adding the pretreatment resin, the core-shell structure modifier and the dimethyl silicone oil into a mixer, stirring and mixing for 1.5h under the condition of stirring speed of 1000r/min, and then adding the vulcanizing agent and the dispersing agent, and continuing stirring and mixing for 40min to obtain a mixture;
s6: and adding the mixture into a double-screw extruder for melt extrusion, wherein the temperature from a feed inlet of the extruder to a machine head is 180 ℃, 200 ℃, 220 ℃, 240 ℃, 220 ℃ and the rotating speed of a screw rod is 250r/min, performing water-cooling granulation, and packaging to obtain the core-shell structure modified nylon plastic.
Comparative example 1
S1: 125g of nylon 6, 30g of EXL1414T, 7g of dimethyl silicone oil, 12.5g of silica microspheres, 0.75g of benzoyl peroxide, 0.6g of polyethylene glycol and 0.3g of stearamide are weighed for standby;
s2: nylon 6 and EXL1414T are placed in a vacuum oven at the temperature of 100 ℃ to be dried for 1.5 hours, so as to obtain pretreatment resin;
s3: adding the pretreatment resin, the core-shell structure modifier and the dimethyl silicone oil into a mixer, stirring and mixing for 1.5h under the condition of stirring speed of 1000r/min, and then adding the vulcanizing agent and the dispersing agent, and continuing stirring and mixing for 40min to obtain a mixture;
s4: and adding the mixture into a double-screw extruder for melt extrusion, wherein the temperature from a feed inlet of the extruder to a machine head is 180 ℃, 200 ℃, 220 ℃, 240 ℃, 220 ℃ and the rotating speed of a screw rod is 250r/min, performing water-cooling granulation, and packaging to obtain the core-shell structure modified nylon plastic.
Comparative example 2
S1: same as in example 2;
s2: same as in example 2;
s3: 155g of nylon 6, 7g of simethicone, 12.5g of core-shell structure modifier, 0.75g of benzoyl peroxide, 0.6g of polyethylene glycol and 0.3g of stearamide are weighed for standby;
s4: placing nylon 6 in a vacuum oven at 100 ℃ for drying for 1.5 hours to obtain pretreated resin;
s5: adding the pretreatment resin, the core-shell structure modifier and the dimethyl silicone oil into a mixer, stirring and mixing for 1.5h under the condition of stirring speed of 1000r/min, and then adding the vulcanizing agent and the dispersing agent, and continuing stirring and mixing for 40min to obtain a mixture;
s6: as in example 2.
Comparative example 3
S1: same as in example 2;
s2: same as in example 2;
s3: 125g of nylon 6, 30g of EXL1414T, 12.5g of core-shell structure modifier, 0.75g of benzoyl peroxide, 0.6g of polyethylene glycol and 0.3g of stearamide are weighed for standby;
s4: nylon 6 and EXL1414T are placed in a vacuum oven at the temperature of 100 ℃ to be dried for 1.5 hours, so as to obtain pretreatment resin;
s5: adding the pretreated resin and the core-shell structure modifier into a mixer, stirring and mixing for 1.5h under the condition of stirring speed of 1000r/min, and then adding the vulcanizing agent and the dispersing agent, and continuously stirring and mixing for 40min to obtain a mixture;
s6: as in example 2.
Comparative example 4
S1: same as in example 2;
s2: same as in example 2;
s3: 125g nylon 6, 30g EXL1414T, 7g dimethyl silicone oil, 0.75g benzoyl peroxide, 0.6g polyethylene glycol and 0.3g stearamide are weighed for later use;
s4: nylon 6 and EXL1414T are placed in a vacuum oven at the temperature of 100 ℃ to be dried for 1.5 hours, so as to obtain pretreatment resin;
s5: adding the pretreated resin and the simethicone into a mixer, stirring and mixing for 1.5h under the condition of stirring speed of 1000r/min, and then adding the vulcanizing agent and the dispersing agent, and continuing stirring and mixing for 40min to obtain a mixture;
s6: as in example 2.
Comparative example 5
S1: same as in example 2;
s2: same as in example 2;
s3: 155g of nylon 6, 12.5g of core-shell structure modifier, 0.75g of benzoyl peroxide, 0.6g of polyethylene glycol and 0.3g of stearamide are weighed for standby;
s4: placing nylon 6 in a vacuum oven at 100 ℃ for drying for 1.5 hours to obtain pretreated resin;
s5: adding the pretreated resin and the core-shell structure modifier into a mixer, stirring and mixing for 1.5h under the condition of stirring speed of 1000r/min, and then adding the vulcanizing agent and the dispersing agent, and continuously stirring and mixing for 40min to obtain a mixture;
s6: as in example 2.
Performance testing
Examples 1 to 5 and comparative examples 1 to 5 were tested for tensile strength and elongation at break according to the ISO-527/2 standard, impact strength according to the ISO-180 standard, flexural strength and flexural modulus according to the ISO-178 standard, and the results are shown in the following table;
data analysis: it can be seen from examples 1-5 that the core-shell structure modified nylon plastic prepared by the invention has excellent mechanical properties, and from example 2 and comparative example 1, the construction of the core-shell structure has a dominant effect on the mechanical properties of the nylon plastic, and from time 2 and comparative examples 2-5, the silicon copolycarbonate, the simethicone and the core-shell structure modifier synergistically promote the improvement of the mechanical properties of the nylon plastic.
Those of ordinary skill in the art will appreciate that: the discussion of any of the embodiments above is merely exemplary and is not intended to suggest that the scope of the invention (including the claims) is limited to these examples; the technical features of the above embodiments or in the different embodiments may also be combined within the idea of the invention, the steps may be implemented in any order and there are many other variations of the different aspects of the invention as described above, which are not provided in detail for the sake of brevity.
The present invention is intended to embrace all such alternatives, modifications and variances which fall within the broad scope of the appended claims. Therefore, any omission, modification, equivalent replacement, improvement, etc. of the present invention should be included in the scope of the present invention.
Claims (10)
1. The modified nylon plastic with the core-shell structure is characterized by comprising the following raw materials in parts by weight: 100-150 parts of nylon, 20-40 parts of silicon copolycarbonate, 5-9 parts of dimethyl silicone oil, 10-15 parts of core-shell structure modifier, 0.5-1 part of vulcanizing agent and 0.5-1.5 parts of dispersing agent;
the core-shell structure modifier is a core-shell structure with an alkenyl silicon dioxide microsphere as a core and single-end hydrogen-containing silicone oil as a shell, wherein the alkenyl silicon dioxide microsphere is obtained by grafting vinyl tri (beta-methoxyethoxy) silane with the silicon dioxide microsphere.
2. The modified nylon plastic with the core-shell structure according to claim 1, wherein the specific preparation method of the modifier with the core-shell structure is as follows:
s1: dispersing the silicon dioxide microspheres into a mixed solution of absolute ethyl alcohol and water, then adding vinyl tri (beta-methoxyethoxy) silane, stirring and reacting for 5-8 hours at 60-80 ℃, washing and drying to obtain alkenyl silicon dioxide microspheres;
s2: at N 2 Under the protection, the alkenylation silicon dioxide microsphere is added into absolute ethyl alcohol, then single-end hydrogen-containing silicone oil is dropwise added at the temperature of 30-50 ℃ and the rpm of 80-120, the dropwise adding time is 30-45min, and after the dropwise adding is finished, the reaction is carried out for 2-4h at the temperature of 60-80 ℃ and the rpm of 80-120rpm, and the core-shell structure modifier is obtained after washing and drying.
3. The core-shell structure modified nylon plastic of claim 1, wherein the nylon is one or more of nylon 6, nylon 66, nylon 610, nylon 1010, nylon 11, nylon 12, nylon 9T, or nylon 12T.
4. The core-shell structure modified nylon plastic of claim 1, wherein the silicon copolycarbonate is model EXL1414T.
5. The core-shell structure modified nylon plastic of claim 1, wherein the simethicone has an average molecular weight of 5000-10000.
6. The modified nylon plastic with the core-shell structure according to claim 1, wherein the vulcanizing agent is one of benzoyl peroxide, 2, 4-dichloro benzoyl peroxide and tert-butyl perbenzoate; the dispersing agent is a mixture of polyethylene glycol and stearamide in a weight ratio of 1-3:1.
7. The core-shell structured modified nylon plastic of claim 1, wherein the single-ended hydrogen-containing silicone oil is one of RH-222-4 or RH-222-10.
8. The core-shell structure modified nylon plastic of claim 1, wherein the silica microspheres have an average diameter of 150-250nm.
9. The modified nylon plastic with the core-shell structure according to claim 1, wherein the weight ratio of the silica microspheres, the absolute ethyl alcohol, the water and the vinyltris (beta-methoxyethoxy) silane in the step S1 is 5-10:5-10:50-100:0.05-0.1; in the step S2, the weight ratio of the alkenyl silicon dioxide microspheres to the anhydrous ethanol to the single-end hydrogen-containing silicone oil is 5-10:50-100:1-3.
10. The method for preparing the modified nylon plastic with the core-shell structure according to any one of claims 1 to 9, which is characterized by comprising the following specific preparation method:
s3: weighing 100-150 parts of nylon, 20-40 parts of silicon copolycarbonate, 5-9 parts of dimethyl silicone oil, 10-15 parts of core-shell structure modifier, 0.5-1 part of vulcanizing agent and 0.5-1.5 parts of dispersing agent for standby according to parts by weight;
s4: placing nylon and silicon copolycarbonate into a vacuum oven at 90-120 ℃ for drying for 1-2h to obtain pretreatment resin;
s5: adding the pretreatment resin, the core-shell structure modifier and the dimethyl silicone oil into a mixer, stirring and mixing for 1-2h under the condition that the stirring rate is 800-1200r/min, and then adding the vulcanizing agent and the dispersing agent, and continuously stirring and mixing for 30-50min to obtain a mixture;
s6: adding the mixture into a double-screw extruder for melt extrusion, wherein the temperature from a feed inlet of the extruder to a machine head is 180 ℃, 200 ℃, 220 ℃, 240 ℃, 220 ℃ and the screw speed is 200-300r/min, performing water cooling granulation, and packaging to obtain the core-shell structure modified nylon plastic.
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| CN117659696B (en) * | 2024-02-01 | 2024-05-07 | 河北铁科翼辰新材科技有限公司 | Anti-fatigue low-temperature-resistant nylon composite material and preparation method and application thereof |
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