CN116622197A - Degradable 3C electronic material and preparation method thereof - Google Patents
Degradable 3C electronic material and preparation method thereof Download PDFInfo
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- CN116622197A CN116622197A CN202310608424.5A CN202310608424A CN116622197A CN 116622197 A CN116622197 A CN 116622197A CN 202310608424 A CN202310608424 A CN 202310608424A CN 116622197 A CN116622197 A CN 116622197A
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- 239000012776 electronic material Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000003063 flame retardant Substances 0.000 claims abstract description 58
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims abstract description 41
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 41
- 239000002994 raw material Substances 0.000 claims abstract description 24
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 18
- 239000004626 polylactic acid Substances 0.000 claims abstract description 18
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims abstract description 16
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920005586 poly(adipic acid) Polymers 0.000 claims abstract description 14
- 229920001707 polybutylene terephthalate Polymers 0.000 claims abstract description 14
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 13
- 229920002725 thermoplastic elastomer Polymers 0.000 claims abstract description 13
- 239000000314 lubricant Substances 0.000 claims abstract description 10
- 239000006185 dispersion Substances 0.000 claims description 22
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 11
- 229920000570 polyether Polymers 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 238000005303 weighing Methods 0.000 claims description 11
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 9
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 claims description 9
- 229920003064 carboxyethyl cellulose Polymers 0.000 claims description 9
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 claims description 9
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 229920000728 polyester Polymers 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- -1 polypropylene Polymers 0.000 claims description 8
- 229940126062 Compound A Drugs 0.000 claims description 7
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 7
- 229920000881 Modified starch Polymers 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 claims description 6
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 6
- 239000000347 magnesium hydroxide Substances 0.000 claims description 6
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 6
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 claims description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 6
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 5
- 235000012424 soybean oil Nutrition 0.000 claims description 4
- 239000003549 soybean oil Substances 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 2
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 2
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract description 8
- 238000000576 coating method Methods 0.000 abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 7
- 238000009825 accumulation Methods 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- 238000002485 combustion reaction Methods 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 28
- 230000000694 effects Effects 0.000 description 18
- 239000000463 material Substances 0.000 description 12
- 238000012545 processing Methods 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- XSAOTYCWGCRGCP-UHFFFAOYSA-K aluminum;diethylphosphinate Chemical compound [Al+3].CCP([O-])(=O)CC.CCP([O-])(=O)CC.CCP([O-])(=O)CC XSAOTYCWGCRGCP-UHFFFAOYSA-K 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
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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)
- Biological Depolymerization Polymers (AREA)
Abstract
The application relates to the field of 3C electronic materials, in particular to a degradable 3C electronic material and a preparation method thereof. The composite material comprises the following raw materials in parts by weight: 30-50 parts of poly (adipic acid)/butylene terephthalate, 7-40 parts of thermoplastic elastomer, 10-20 parts of flame retardant, 3-10 parts of polylactic acid, 0.5-1.5 parts of lubricant and 5-10 parts of processing aid. The degradable 3C electronic material has better strength, toughness, flame retardance and degradability through the combination of thermoplastic polyurethane, styrene-ethylene-butadiene-styrene copolymer, polylactic acid and poly (adipic acid)/butylene terephthalate, when the degradable 3C electronic material is used for coating a copper core, the phenomena of fracture, combustion and the like of a cable for the 3C electronic product are not easy to occur, and the cable of the 3C electronic product after being abandoned is easy to degrade in the environment, so that the possibility of influencing the ecological environment is reduced due to accumulation of wastes.
Description
Technical Field
The application relates to the field of 3C products, in particular to a degradable 3C electronic material and a preparation method thereof.
Background
The 3C product refers to a common name of a computer product, a communication product and a consumer 3C electronic product, and is also called an information household appliance. Such as a computer, tablet, cell phone, or digital audio player, etc. The 3C electronic material is a material for producing 3C electronic products, such as products of computers, tablet computers, mobile phones, new energy sources and the like.
The 3C electronic material may be a plastic material for producing a housing, a part, a wiring board, an electric wire, etc. of a 3C product. According to different purposes, the 3C electronic material has different functions, such as a coating material used on a cable of a 3C product, generally has better flame retardance, coating property, mechanical property and the like, and the coating material is easy to coat on the surface of a copper core to form the cable, so that the possibility of burning of the 3C product is reduced, and meanwhile, the phenomena of breakage, damage and the like in the process of pulling and using the cable are reduced due to mechanical properties such as tensile strength, flexibility and the like.
However, most of the current 3C electronic materials are difficult to degrade or have long degradation time, so that the materials are easy to accumulate after being discarded, and the ecological environment is affected. Therefore, photosensitizer, degradable material and the like are added into the 3C electronic material to accelerate the degradation of the material and reduce the accumulation of waste materials, but the addition of the materials also affects the flame retardance, cladding property, mechanical property and the like of the 3C electronic material, and affects the use of the 3C electronic material.
Disclosure of Invention
On the basis of ensuring that the 3C electronic material has better degradability, better flame retardance, cladding property and mechanical property are further obtained. The application provides a degradable 3C electronic material and a preparation method thereof.
In a first aspect, the application provides a degradable 3C electronic material, which comprises the following raw materials in parts by weight:
30-50 parts of poly (adipic acid)/butylene terephthalate
7-40 parts of thermoplastic elastomer
10 to 20 parts of flame retardant
Polylactic acid 3-10 parts
0.5 to 1.5 portions of lubricant
5-10 parts of processing aid.
The composition of the raw materials and the weight range of the raw materials are all the preferred choices of the application, wherein the poly (adipic acid)/butylene terephthalate has better ductility, elongation at break, heat resistance and impact property, and also has excellent biodegradability; polylactic acid is a biodegradable material, has good softness, good heat resistance and the like, but has poor impact property and is easy to break and tear; therefore, the properties of the polybutylene adipate/terephthalate and polylactic acid are combined, so that the polybutylene adipate/terephthalate has better degradability and mechanical properties.
The degradable 3C electronic material is mainly used as a sheath, and the copper core used for cladding forms a 3C electronic product cable and an electric wire; for example, when the mechanical properties are poor, it is difficult to coat them, and the phenomena of breakage and tearing are easily caused after the coating.
Therefore, the application further adds the thermoplastic elastomer, and the thermoplastic elastomer has better elasticity and toughness, so that the mechanical property of the degradable 3C electronic material can be further improved.
In addition, the flame retardant has a flame retardant effect, so that the degradable 3C electronic material has a flame retardant effect, and when the flame retardant is used on a 3C electronic product, the possibility of burning of cables and wires of the 3C electronic is reduced; the lubricant has a lubricating effect, so that the raw material system of the degradable 3C electronic material is convenient to process; other auxiliary agents have the function of assisting in processing, and the processing convenience of the degradable 3C electronic material is further improved.
In summary, the application combines the performances of polylactic acid and polybutylene adipate/terephthalate, further improves the mechanical performance under the action of the thermoplastic elastomer, improves the flame retardant effect of the flame retardant, and ensures that the obtained degradable 3C electronic material has better mechanical performance, flame retardance and degradability under the auxiliary processing of the lubricant and other processing aids. The degradable 3C electronic material is easy to cover the copper core, a cable for the 3C electronic product is formed, the phenomenon of combustion is not easy to occur, and the cable of the 3C electronic product after being abandoned is easy to degrade in the environment, so that the possibility of influencing the ecological environment due to accumulation of wastes is reduced.
Preferably, the thermoplastic elastomer comprises the following raw materials in parts by weight:
5-10 parts of styrene-ethylene-butadiene-styrene copolymer
2-30 parts of thermoplastic polyurethane.
The thermoplastic polyurethane is a thermoplastic elastomer, and particularly has better high strength and high toughness; the styrene-ethylene-butadiene-styrene copolymer is called SEBS for short, is a thermoplastic elastomer, and has high elasticity and better toughness; the thermoplastic polyurethane and the styrene-ethylene-butadiene-styrene copolymer are compounded in the above dosage, so that a synergistic effect can be achieved, the degradable 3C electronic material has better mechanical properties, and when the thermoplastic polyurethane and the styrene-ethylene-butadiene-styrene copolymer are used in 3C electronic products, the thermoplastic polyurethane and the styrene-ethylene-butadiene-styrene copolymer can be well coated on a copper core, and the obtained cable has better mechanical properties such as tear resistance, strength and the like.
Preferably, the thermoplastic polyurethane is a polyether TPU and/or a polyester TPU.
Polyether type TPU has high strength, hydrolysis resistance and high rebound resilience, and can further strengthen the mechanical property of the degradable 3C electronic material.
The polyester TPU has better tensile property, flexural property, abrasion resistance and higher temperature resistance, and can further enhance the mechanical property when being used in the degradable 3C electronic material.
When the polyether TPU and the polyester TPU are used in a composite mode, the comprehensive mechanical property of the degradable 3C electronic material is better.
For example, when only polyether TPU is used, the tensile strength of the degradable 3C electronic material is 30.1MPa and elongation at break is 615%; when the polyether TPU and the polyester TPU are used in a compounding way according to the weight part ratio of (1.3-1.8): 1, the tensile strength of the degradable 3C electronic material is up to 39.5MPa, and the elongation at break is up to 635%.
Preferably, the lubricant is one or more of PE wax, low molecular weight polypropylene, butyl stearate, oleamide and ethylene bis stearamide.
The lubricant has good lubricating effect, is used for degradable 3C electronic materials, is convenient for processing a raw material system, and improves processing efficiency.
The PE wax or the low-molecular polypropylene is preferably adopted, so that the processing efficiency can be improved, the phenomenon of adhesion of a raw material system of the degradable 3C electronic material in the processing process can be prevented, and meanwhile, the dispersibility of the flame retardant in the raw material system of the degradable 3C electronic material can be improved.
Preferably, the processing aid is epoxidized soybean oil or tributyl citrate.
The epoxidized soybean oil and the tributyl citrate are environment-friendly plasticizers, can play a better plasticizing role, and improve the processing efficiency of the degradable 3C electronic material.
Preferably, the flame retardant is one or more of diethyl aluminum hypophosphite, melamine phosphate and magnesium hydroxide.
The diethyl aluminum hypophosphite has good fluidity and flame retardance, and has good flame retardance effect when used in 3C electronic products, so that the possibility of burning of cables of the 3C electronic products is reduced.
The melamine phosphate is a flame retardant with good flame retardant effect, so that the common 3C electronic material is flame retardant, and the magnesium hydroxide is a common flame retardant with good flame retardant effect. The flame retardant effect of the 3C electronic material can be improved by compounding one or more flame retardants.
Preferably, the flame retardant is a modified flame retardant, and the preparation of the modified flame retardant comprises the following steps:
1) Weighing 1-3 parts by weight of sodium dodecyl benzene sulfonate, and dissolving in 40-60 parts by weight of water to obtain a dispersion; 50-80 parts of flame retardant is added into the dispersion liquid, and the dispersion liquid is obtained after shaking for 10-20 min.
2) Weighing 10.8-16.5 parts by weight of compatilizer, dripping the compatilizer into the dispersion obtained in the step 1), stirring the dispersion for 10-30 min at the rotating speed of 100-300 r/min, filtering the mixture, and drying the mixture to obtain the modified flame retardant.
In order to obtain the degradable 3C electronic material with better performance, the application further researches the flame retardant property and the mechanical property of the degradable 3C electronic material; in the research process, the inventor finds that the larger the adding amount of the flame retardant is, the better the flame retardant effect is; however, the addition of a large amount of flame retardant also results in a decrease in mechanical properties, for example, the larger the amount of aluminum diethylphosphinate, the better the flame retardant effect, but the addition of a large amount of aluminum diethylphosphinate also results in a decrease in mechanical properties of the material due to the large amount of aluminum diethylphosphinate, which results in poor compatibility with the degradable 3C electronic material.
In order to maintain the better flame retardant effect and mechanical property, the inventor further modifies the flame retardant, adopts sodium dodecyl benzene sulfonate to be dissolved in water to form dispersion liquid, wherein the sodium dodecyl benzene sulfonate is a cationic surfactant, and can improve the dispersing effect of the flame retardant to obtain the dispersion liquid with better surface activity.
And (3) dropwise adding a compatilizer into the dispersion liquid to enable the compatilizer to coat the particle surfaces of the flame retardant, so that a coating film is formed on the surfaces of the flame retardant to obtain the modified flame retardant, and when the modified flame retardant is used in the degradable 3C electronic material, the modified flame retardant is easily compatible with a raw material system of the degradable 3C electronic material, so that the flame retardance and the mechanical property of the degradable 3C electronic material are further improved.
Preferably, the compatilizer is prepared from the following raw materials in parts by weight:
sodium carboxyethyl cellulose 0.5-0.8 part
1.3 to 2.5 portions of ethylene glycol dimethacrylate
1-3 parts of 1-vinyl-2-pyrrolidone
1.5 to 2.7 parts of pregelatinized starch
0.01 to 0.03 portion of potassium persulfate
5-8 parts of water.
Preferably, the compatibilizing agent is prepared by the following method:
1) According to the weight portions, the pregelatinized starch is weighed and mixed with water, and is heated to 65-75 ℃ while being stirred, and then ethylene glycol dimethacrylate and potassium persulfate are added and stirred for 1-2 hours to obtain a compound A;
2) Weighing 1-vinyl-2-pyrrolidone according to parts by weight, adding the 1-vinyl-2-pyrrolidone into the compound A obtained in the step 1), and stirring for 35-45 min to obtain a compound B;
3) And weighing sodium carboxyethyl cellulose according to parts by weight, adding the sodium carboxyethyl cellulose into the compound B obtained in the step 2), and stirring for 40-70 min to obtain the compatilizer.
The pregelatinized starch is obtained by gelatinizing natural starch, is easy to dissolve in water to form paste, saves the process of heating and gelatinizing starch, has a degradable effect, and has good adhesion as well as degradability.
Ethylene glycol dimethacrylate is a cross-linking agent containing double functional groups, and can be subjected to grafting composite reaction with pregelatinized starch under the catalysis of potassium persulfate, and the added vinyl-2-pyrrolidone (NVP), also called N-vinyl-2-pyrrolidone, is an organic compound, can be mixed with water, ethanol, diethyl ether and other organic solvents, is easy to copolymerize with other vinyl compounds, and can be further reacted with the compound A after being added into a compatilizer raw material system to obtain a macromolecular compound B.
The added sodium carboxyethylcellulose can further improve the degradability, film forming property, adhesiveness and compatibility with polymers of the compound B, so that the obtained compatilizer is used for preparing the modified flame retardant, a coating film can be formed on the surface of the flame retardant, the compatibility of the flame retardant with the polymers is improved, the mechanical property and flame retardant effect of the degradable 3C electronic material can be further improved, and the degradability of the degradable 3C electronic material can be further improved due to the fact that the compatilizer also has degradability.
In a second aspect, the application provides a preparation method of a degradable 3C electronic material, which adopts the following technical scheme:
the method comprises the following steps: according to the weight portions, the poly (adipic acid)/butylene terephthalate, the thermoplastic elastomer, the flame retardant, the polylactic acid, the PE wax and the processing aid are weighed, uniformly mixed, extruded and granulated to obtain the degradable 3C electronic material.
The preparation method is simple to operate and high in production efficiency, and the obtained degradable 3C electronic material has better flame retardance, degradability and mechanical property.
In summary, the application has the following beneficial effects:
1. according to the application, through compounding polylactic acid and poly (adipic acid)/butylene terephthalate, the performances are combined, the mechanical properties are further improved under the action of a thermoplastic elastomer, the flame retardant effect is improved by adding the flame retardant, and the obtained degradable 3C electronic material has better mechanical properties, flame retardance and degradability under the auxiliary processing of a lubricant and other processing aids. The degradable 3C electronic material is easy to cover the copper core, the possibility that the cable for the 3C electronic product is not easy to burn is formed, and the cable of the discarded 3C electronic product is easy to degrade in the environment, so that the accumulation of wastes is reduced, and the ecological environment is influenced;
2. the thermoplastic polyurethane and the styrene-ethylene-butadiene-styrene copolymer are compounded to play a synergistic effect, so that the degradable 3C electronic material has better mechanical property, and when the material is used in a 3C electronic product, the material can be better coated on a copper core, and the obtained cable has better mechanical property.
3. The adoption of the modified flame retardant can further improve the compatibility of the flame retardant and a raw material system of the degradable 3C electronic material, so that the degradable 3C electronic material has better flame retardant effect and mechanical property.
4. The compatilizer prepared from starch, ethylene glycol dimethacrylate, 1-vinyl-2-pyrrolidone and sodium carboxyethyl cellulose has better degradability, adhesiveness and film forming property, and the compatilizer is used for treating the flame retardant, so that the compatibility and degradability of the flame retardant can be further improved, the compatibility of the flame retardant and a raw material system of the degradable 3C electronic material can be further improved, and the obtained degradable 3C electronic material has better degradability, flame retardance and mechanical property.
Detailed Description
The present application will be described in further detail with reference to examples.
Sources or parameters of part of the raw materials;
the density of the poly (adipic acid)/butylene terephthalate is 1.2-1.3 g/cm < 3 >; the elongation at break is 500-700%;
the average molecular weight of the polylactic acid is 80000-12000;
the polyether TPU is TPU U.S. road-run 2103-70A;
the polyester TPU is US Lubo run ETE60DS3;
the average molecular weight of the styrene-ethylene-butadiene-styrene copolymer is 6 to 15 ten thousand.
Examples
Example 1
A preparation method of a degradable 3C electronic material comprises the following steps: 3kg of poly (adipic acid)/butylene terephthalate, 0.7kg of styrene-ethylene-butadiene-styrene copolymer, 0.2kg of thermoplastic polyurethane, 1kg of flame retardant, 0.3kg of polylactic acid, 0.05kg of PE wax and 0.5kg of processing aid are weighed, put into a high-speed mixer, uniformly mixed, transferred to a double-screw extruder for extrusion, cooled by a cold water tank in the extrusion process, and the obtained filaments are granulated by a granulator to obtain the degradable 3C electronic material.
Wherein the thermoplastic polyurethane is composed of polyether TPU and polyester TPU with the weight (kg) ratio of 1.3:1; the processing aid is epoxidized soybean oil, and the lubricant is PE wax; the flame retardant is diethyl aluminum hypophosphite.
Temperature setting of the twin-screw extruder: first 180 ℃, second 195 ℃, third 210 ℃, fourth 210 ℃, fifth 200 ℃, sixth 195 ℃ and extrusion die 190 ℃.
Example 2
Example 2 differs from example 1 in that: the amounts of the raw materials varied, specifically 4kg of poly (adipic acid)/butylene terephthalate, 0.8kg of styrene-ethylene-butadiene-styrene copolymer, 0.2kg of thermoplastic polyurethane, 1kg of diethyl aluminum hypophosphite, 0.6kg of polylactic acid, 0.1kg of PE wax, and 0.8kg of processing aid.
Example 3
Example 3 differs from example 1 in that: the amounts of the raw materials varied, specifically 5kg of poly (adipic acid)/butylene terephthalate, 1kg of styrene-ethylene-butadiene-styrene copolymer, 0.2kg of thermoplastic polyurethane, 1kg of diethyl aluminum hypophosphite, 1kg of polylactic acid, 0.15kg of PE wax, 1kg of processing aid.
Example 4
Example 4 differs from example 2 in that: the thermoplastic polyurethane was used in an amount of 1.5kg and the ratio by weight (kg) of polyether TPU to polyester TPU was 1.5:1.
Example 5
Example 5 differs from example 2 in that: the thermoplastic polyurethane was used in an amount of 3kg, the ratio by weight (kg) of polyether TPU to polyester TPU being 1.8:1.
example 6
Example 6 differs from example 4 in that: the amount of flame retardant used was 2kg.
Example 7
Example 7 differs from example 6 in that: the flame retardant is obtained by mixing 0.5kg of diethyl aluminum hypophosphite, 0.5kg of melamine phosphate and 1kg of magnesium hydroxide.
Example 8
Example 8 differs from example 6 in that: the flame retardant is a modified flame retardant, and the modified flame retardant is prepared by the following method: 1) Weighing 0.1kg of sodium dodecyl benzene sulfonate, and dissolving in 4kg of water to obtain a dispersion liquid; 1.25kg of diethyl aluminum hypophosphite, 1.25kg of melamine phosphate and 2.5kg of magnesium hydroxide are weighed and uniformly mixed to obtain a flame retardant; adding 5kg of flame retardant into the dispersion liquid, putting into ultrasonic waves for oscillation for 10min, wherein the oscillation frequency of the ultrasonic waves is 30 MHz, and obtaining a dispersion;
2) Weighing 1.08kg of compatilizer, dripping the compatilizer into the dispersion obtained in 1), putting the dispersion into a stirrer to stir the dispersion while dripping the compatilizer, stirring the dispersion for 30min again after the compatilizer is completely added, filtering the dispersion, and putting the dispersion into a 50 ℃ oven to dry the dispersion for 6h to obtain the modified flame retardant.
The compatilizer is prepared by the following method:
1. 3.5kg of pregelatinized starch is weighed and mixed with 5kg of water, and is heated to 70 ℃ while stirring, 1.3kg of ethylene glycol dimethacrylate and 0.01kg of potassium persulfate are added, and stirring is carried out for 2 hours, so as to obtain a compound A;
2) Weighing 1kg of 1-vinyl-2-pyrrolidone, adding the 1kg of 1-vinyl-2-pyrrolidone into the compound A obtained in the step 1), and stirring for 40min to obtain a compound B;
3) 0.5kg of sodium carboxyethyl cellulose is weighed and added into the compound B obtained in the step 2), and the mixture is stirred for 50 minutes to obtain the compatilizer.
Examples 9 to 10
Examples 9 to 10 differ from example 8 in that: the amounts of the raw materials of the modified flame retardant and the compatibilizing agent are different, and are shown in tables 1 and 2:
table 1 raw material amounts (kg) of modified flame retardants of examples 8 to 10
TABLE 2 raw material amounts (kg) of compatibilizers for examples 8 to 10
Example 11
Example 11 differs from example 5 in that: the thermoplastic polyurethane is a polyether TPU.
Comparative example
Comparative example 1
Comparative example 1 differs from example 1 in that: the polylactic acid is replaced with poly (adipic acid)/butylene terephthalate in equal amount.
Comparative example 2
Comparative example 2 is different from example 1 in that: the equivalent amount of poly (adipic acid)/butylene terephthalate is replaced by polylactic acid.
Comparative example 3
Comparative example 3 is different from example 1 in that: the thermoplastic polyurethane is replaced equally with a styrene-ethylene-butadiene-styrene copolymer.
Comparative example 4
Comparative example 4 differs from example 1 in that: the styrene-ethylene-butadiene-styrene copolymer was replaced equally with a thermoplastic polyurethane.
Comparative example 5
Comparative example 5 is different from example 1 in that: the amount of aluminum diethylphosphinate used was 3kg.
Comparative example 6
Comparative example 6 differs from example 8 in that: the equivalent amount of 1-vinyl-2-pyrrolidone is replaced by ethylene glycol dimethacrylate.
Performance test
The degradable 3C electronic materials obtained in examples 1 to 11 and comparative examples 1 to 6 were put into an injection molding machine for injection molding, and test bars were obtained.
Detection method/test method
1. Flame retardancy
Flame retardant rating: the detection is carried out with reference to GB 31247-2014.
Oxygen index: the oxygen index is detected by referring to the national standard GB/T2406-93, and the higher the oxygen index is, the more difficult the combustion is.
2. The degradation rate test is carried out by referring to the national standard GB/T41010-2021, the test condition is that the degradable soil is referred to GB/T22047, the soil is buried for 100 days, and the quality loss is calculated.
3. Mechanical properties
The elongation at break and the tensile strength are detected by referring to the national standard GB/T1040.1-2018, and are specifically shown in the table 3;
TABLE 3 Experimental data for examples 1-11 and comparative examples 1-6
As can be seen from the combination of example 1 and comparative examples 1 to 2 and the combination of table 2, the degradation rate and oxygen index of example 1 are higher than those of comparative example 1 and lower than those of comparative example 2; the elongation at break and tensile strength of example 1 are lower than those of comparative example 1 and higher than those of comparative example 2. The polylactic acid and the polybutylene adipate/terephthalate are combined, so that the properties of the polylactic acid and polybutylene adipate/terephthalate can be combined, and the 3C electronic material can obtain better degradability and mechanical properties.
As can be seen from comparative examples 1 and comparative examples 3 to 4, the elongation at break and tensile strength of example 1 are both higher than those of comparative examples 3 to 4, indicating that the mechanical properties of the thermoplastic polyurethane and the styrene-ethylene-butadiene-styrene copolymer used in combination are better.
As can be seen from comparative examples 1 and 5, the elongation at break and tensile strength of example 1 are both higher than those of comparative example 5, indicating that the mechanical properties are greatly affected when the amount of aluminum diethylphosphinate is increased.
As can be seen from comparative examples 6 and 7, the flame retardant effect is better when diethyl aluminum hypophosphite, melamine phosphate, magnesium hydroxide are used in combination.
As can be seen from the comparison of the examples 7 and 8, the degradation rate, tensile strength, elongation at break and oxygen index of the example 8 are higher than those of the example 7, which shows that the modified flame retardant is adopted in the application, so that the flame retardant effect, the degradation property and the mechanical property of the 3C electronic material are improved, and the 3C electronic material has better performance.
As can be seen from comparative examples 8 and 6, the oxygen index, elongation at break and tensile strength of example 8 are all higher than those of comparative example 6, which means that the compatilizer obtained from 1-vinyl-2-pyrrolidone and ethylene glycol dimethacrylate has better coating property and compatibility, and can better coat the flame retardant, so that the flame retardant is easy to be compatible with the raw material system of the 3C electronic material, and the 3C electronic material has better mechanical property and flame retardance.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (10)
1. The degradable 3C electronic material is characterized by comprising the following raw materials in parts by weight:
30-50 parts of poly (adipic acid)/butylene terephthalate
7-40 parts of thermoplastic elastomer
10-20 parts of flame retardant
3-10 parts of polylactic acid
0.5-1.5 parts of lubricant
5-10 parts of processing aid.
2. A degradable 3C electronic material according to claim 1, characterized in that: the thermoplastic elastomer comprises the following raw materials in parts by weight:
5-10 parts of styrene-ethylene-butadiene-styrene copolymer
2-30 parts of thermoplastic polyurethane.
3. A degradable 3C electronic material according to claim 2, characterized in that: the thermoplastic polyurethane is polyether TPU and/or polyester TPU.
4. A degradable 3C electronic material according to claim 1, characterized in that: the lubricant is one or more of PE wax, low molecular weight polypropylene, butyl stearate, oleamide and ethylene bis stearamide.
5. A degradable 3C electronic material according to claim 1, characterized in that: the processing aid is epoxidized soybean oil or tributyl citrate.
6. A degradable 3C electronic material according to claim 1, characterized in that: the flame retardant is one or more of diethyl aluminum hypophosphite, melamine phosphate and magnesium hydroxide.
7. The degradable 3C electronic material according to any one of claims 1-6, wherein the flame retardant is a modified flame retardant, and the preparation of the modified flame retardant comprises the following steps:
1) Weighing 1-3 parts by weight of sodium dodecyl benzene sulfonate, and dissolving in 40-60 parts by weight of water to obtain a dispersion liquid; adding 50-80 parts of flame retardant into the dispersion liquid, and oscillating for 10-20 min to obtain a dispersion;
2) Weighing 10.8-16.5 parts by weight of compatilizer, dripping the compatilizer into the dispersion obtained in the step 1), stirring for 10-30 min at the rotating speed of 100-300 r/min, filtering and drying to obtain the modified flame retardant.
8. The degradable 3C electronic material according to claim 7, wherein the compatilizer is prepared from the following raw materials in parts by weight:
0.5-0.8 part of sodium carboxyethyl cellulose
1.5-2.7 parts of ethylene glycol dimethacrylate
1-3 parts of 1-vinyl-2-pyrrolidone
1.3-2.5 parts of pregelatinized starch
0.01 to 0.03 part of potassium persulfate
5-8 parts of water.
9. The degradable 3C electronic material of claim 8, wherein the compatibilizer is prepared by the method comprising:
1) According to the weight parts, the pregelatinized starch is weighed and mixed with water, the mixture is heated to 65-75 ℃ while being stirred, and then ethylene glycol dimethacrylate and potassium persulfate are added and stirred for 1-2 hours to obtain a compound A;
2) Weighing 1-vinyl-2-pyrrolidone according to parts by weight, adding the 1-vinyl-2-pyrrolidone into the compound A obtained in the step 1), and stirring for 35-45 min to obtain a compound B;
3) And weighing sodium carboxyethyl cellulose according to parts by weight, adding the sodium carboxyethyl cellulose into the compound B obtained in the step 2), and stirring for 40-70 min to obtain the compatilizer.
10. A method for preparing the degradable 3C electronic material according to any one of claims 1 to 9, comprising the steps of: according to the weight portions, the poly (adipic acid)/butylene terephthalate, the thermoplastic elastomer, the flame retardant, the polylactic acid, the PE wax and the processing aid are weighed, uniformly mixed, extruded and granulated to obtain the degradable 3C electronic material.
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| CN107501881A (en) * | 2017-09-06 | 2017-12-22 | 青岛百佳创想新材料有限公司 | The composite of trapping environmental protection, preparation method and applications |
| CN109486083A (en) * | 2018-12-20 | 2019-03-19 | 吉林中粮生化有限公司 | A kind of biodegradable blend film and preparation method thereof |
| CN112262695A (en) * | 2020-10-24 | 2021-01-26 | 山东清田塑工有限公司 | Three-layer composite high-barrier controllable full-biodegradable mulching film and preparation method thereof |
| CN114230989A (en) * | 2022-01-14 | 2022-03-25 | 珠海市四唯包装材料有限公司 | Preparation method of environment-friendly biodegradable PBAT (poly (butylene adipate-co-terephthalate)) foaming material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107501881A (en) * | 2017-09-06 | 2017-12-22 | 青岛百佳创想新材料有限公司 | The composite of trapping environmental protection, preparation method and applications |
| CN109486083A (en) * | 2018-12-20 | 2019-03-19 | 吉林中粮生化有限公司 | A kind of biodegradable blend film and preparation method thereof |
| CN112262695A (en) * | 2020-10-24 | 2021-01-26 | 山东清田塑工有限公司 | Three-layer composite high-barrier controllable full-biodegradable mulching film and preparation method thereof |
| CN114230989A (en) * | 2022-01-14 | 2022-03-25 | 珠海市四唯包装材料有限公司 | Preparation method of environment-friendly biodegradable PBAT (poly (butylene adipate-co-terephthalate)) foaming material |
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