CN112961411A - Heat-conducting graphene latex slurry and process and application thereof - Google Patents
Heat-conducting graphene latex slurry and process and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 146
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 97
- 239000004816 latex Substances 0.000 title claims abstract description 92
- 229920000126 latex Polymers 0.000 title claims abstract description 92
- 239000002002 slurry Substances 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims abstract description 33
- 229910052582 BN Inorganic materials 0.000 claims abstract description 48
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000002135 nanosheet Substances 0.000 claims abstract description 42
- 239000000203 mixture Substances 0.000 claims abstract description 41
- 238000002156 mixing Methods 0.000 claims abstract description 38
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 35
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 35
- 229920001194 natural rubber Polymers 0.000 claims abstract description 35
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 21
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 7
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 15
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical compound C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-UHFFFAOYSA-N 0.000 claims description 8
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 239000004576 sand Substances 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 5
- OXGOEZHUKDEEKS-UHFFFAOYSA-N 3-tert-butylperoxy-1,1,5-trimethylcyclohexane Chemical compound CC1CC(OOC(C)(C)C)CC(C)(C)C1 OXGOEZHUKDEEKS-UHFFFAOYSA-N 0.000 claims description 4
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 4
- 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 4
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- CCNDOQHYOIISTA-UHFFFAOYSA-N 1,2-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1C(C)(C)OOC(C)(C)C CCNDOQHYOIISTA-UHFFFAOYSA-N 0.000 claims description 2
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical group C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 239000000945 filler Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 16
- 239000002131 composite material Substances 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 10
- 229920001971 elastomer Polymers 0.000 description 10
- 239000005060 rubber Substances 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000013461 design Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- STSDHUBQQWBRBH-UHFFFAOYSA-N n-cyclohexyl-1,3-benzothiazole-2-sulfonamide Chemical compound N=1C2=CC=CC=C2SC=1S(=O)(=O)NC1CCCCC1 STSDHUBQQWBRBH-UHFFFAOYSA-N 0.000 description 4
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000004594 Masterbatch (MB) Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- AXWJKQDGIVWVEW-UHFFFAOYSA-N 2-(dimethylamino)butanedioic acid Chemical compound CN(C)C(C(O)=O)CC(O)=O AXWJKQDGIVWVEW-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006255 coating slurry Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000010074 rubber mixing Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000009044 synergistic interaction Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011787 zinc oxide 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
- C08L7/00—Compositions of natural rubber
-
- 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
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a heat-conducting graphene latex slurry and a process and application thereof. The graphene latex slurry comprises the following components in parts by weight: 60-80 parts of natural rubber, 4-8 parts of aminated graphene, 5-10 parts of boron nitride nanosheets, 1-5 parts of vulcanizing agent and 1-4 parts of polyvinyl alcohol. The process for preparing the graphene latex slurry comprises the following steps: (1) uniformly mixing the boron nitride nanosheets, a vulcanizing agent, polyvinyl alcohol, water and an optional accelerator and an antioxidant to obtain a mixture A; (2) uniformly mixing the mixture A obtained in the step (1) with aminated graphene to obtain a mixture B; (3) and (3) uniformly mixing the mixture B obtained in the step (2) with natural rubber to obtain the graphene latex slurry. The graphene latex slurry provided by the invention has better uniformity and higher thermal conductivity, and is suitable for preparing a back cushion or a mattress.
Description
Technical Field
The invention belongs to the field of natural rubber composite materials, and particularly relates to heat-conducting graphene latex slurry and a process and application thereof.
Background
Natural rubber, also called indian rubber or elastic rubber, such as the material originally produced, consisting of a polymer of the organic compound isoprene, small amounts of other organic compound impurities and water. Natural rubber is the most widely used variety in the rubber industry and plays a significant role in the rubber industry. However, natural rubber is a poor heat conductor, and heat generated under dynamic conditions cannot be rapidly transferred out, so that the temperature of the material is increased, the performance is deteriorated, and the service life is shortened, and therefore, it is necessary to improve the heat conductivity of the natural rubber composite material.
For example, CN101942122A discloses a heat-conducting natural rubber composite material and a preparation method thereof. The preparation method comprises the following steps: (1) preparing a heat-conducting filler: immersing natural crystalline flake graphite in a mixed solution of concentrated sulfuric acid and concentrated nitric acid, performing ultrasonic treatment, filtering, washing with water, drying, crushing and performing expansion treatment; (2) surface treatment of the heat-conducting filler: soaking the heat-conducting filler into a surface treating agent solution, carrying out ultrasonic treatment, filtering and drying; (3) preparing a heat-conducting natural rubber composite material: firstly plasticating the natural rubber, adding other raw materials after the natural rubber is coated on a roller for mixing, and then vulcanizing and forming to obtain a finished product. In the technical scheme, the expanded graphite subjected to surface treatment is used as the heat-conducting filler, and the prepared heat-conducting rubber composite material is widely applied to heat-radiating elements (such as heat-radiating parts among heat-radiating fins) and components with large dynamic heat generation (such as loading wheels, shock absorbers and the like which are frequently used under the dynamic condition), and is not suitable for preparing living goods such as mattresses, cushions and the like.
CN102660056A discloses a preparation method of a novel heat-conducting natural rubber composite material, which comprises the following steps: (1) preparing fibrous heat-conducting filler: mixing powdery and fibrous heat-conducting particles with high heat conductivity coefficient with thermoplastic plastics, adding the mixture into a double-screw extruder for granulation to prepare a master batch, wherein the mass part of the heat-conducting particles accounts for 20-70% of the total mass of the master batch, and then spinning the master batch in a small double-screw extruder with a spinning machine head to prepare fibrous heat-conducting filler; (2) preparing a heat-conducting natural rubber composite material: firstly, adding natural rubber into an internal mixer for plasticating, then sequentially adding stearic acid, zinc oxide, an anti-aging agent, carbon black and fibrous heat-conducting filler, uniformly mixing, taking out, and adding an accelerator and a vulcanizing agent on an open rubber mixer, wherein the mass ratio of the natural rubber to the carbon black to the fibrous heat-conducting filler is 100: 20-80: 10-40, mixing, uniformly mixing, then discharging to obtain mixed rubber, standing the mixed rubber at room temperature for 24 hours, and then vulcanizing and forming to obtain a finished product. The heat-conducting rubber composite material prepared by the technical scheme is widely applied to heat-radiating elements (such as heat-radiating parts among heat-radiating fins) and components with large dynamic heat generation (such as load wheels, shock absorbers and the like which are frequently used under the dynamic condition), and is not suitable for preparing living goods such as mattresses, back cushions and the like.
CN110144067A discloses a preparation method of a heat-conducting composite material of natural rubber. The preparation method comprises the following steps: s1: pretreating a heat-conducting filler, wherein the heat-conducting filler is selected from heat-conducting fillers with different particle sizes of 1-2000 meshes; s2: carrying out surface treatment on the pretreated heat-conducting filler; s3: putting natural rubber into a rubber mixing machine for plastication; s4: after the natural rubber is wrapped by the roller, sequentially adding an activating agent, an anti-aging agent, a reinforcing agent, a heat-conducting filler, filling oil, an accelerator and a vulcanizing agent for mixing; s5: and (3) uniformly mixing, then discharging to obtain mixed rubber, standing at room temperature for 20-28 h, vulcanizing and molding, testing the heat-conducting property of the composite material, and obtaining the finished heat-conducting composite material after the composite material is qualified. In the technical scheme, the heat-conducting filler comprises the combination of aluminum oxide, silicon carbide and aluminum nitride, but the heat-conducting filler has poor compatibility with natural rubber and is not easy to disperse.
Therefore, how to provide a latex slurry with good thermal conductivity and suitable for preparing mattress products has become a technical problem to be solved urgently.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a heat-conducting graphene latex slurry and a process and application thereof. According to the invention, through the design of the components of the graphene latex slurry, the aminated graphene and the boron nitride nanosheet are further adopted as the heat-conducting filler, and the synergistic cooperation effect of the aminated graphene and the boron nitride nanosheet is adopted, so that the prepared graphene latex slurry has better uniformity and heat conductivity, and is suitable for preparing household articles such as back cushions or mattresses.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a thermally conductive graphene latex slurry, which comprises the following components in parts by weight: 60-80 parts of natural rubber, 4-8 parts of aminated graphene, 5-10 parts of boron nitride nanosheets, 1-5 parts of vulcanizing agent and 1-4 parts of polyvinyl alcohol.
According to the invention, through the design of the components of the graphene latex slurry, the aminated graphene and the boron nitride nanosheets are further adopted as the heat-conducting filler, wherein the aminated graphene can be uniformly dispersed in natural rubber, the heat conductivity of the graphene latex slurry can be effectively improved, and the boron nitride nanosheets play a bridging role between adjacent aminated graphene lamella, so that the aminated graphene and the boron nitride nanosheets form a heat-conducting network in direct contact, therefore, the prepared graphene latex slurry has better heat conductivity and is suitable for household articles such as cushions or mattresses.
According to the invention, the adopted aminated graphene has a large number of amino groups, and the amino groups have high activity, so that the compatibility of graphene and natural rubber can be improved, and the thermal conductivity of the graphene latex slurry is improved; meanwhile, through Van der Waals force between hydroxyl in a polyvinyl alcohol molecular chain and the boron nitride nanosheets, the hexagonal boron nitride nanosheets can be stably dispersed in the graphene latex slurry, and the boron nitride nanosheets can be effectively prevented from being agglomerated.
In the present invention, the natural rubber may be 60 parts, 62 parts, 64 parts, 66 parts, 68 parts, 70 parts, 72 parts, 74 parts, 76 parts, 78 parts, 80 parts, or the like by weight.
The aminated graphene can be 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts or 8 parts by weight.
The weight portion of the boron nitride nanosheet can be 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts, 9.5 parts, 10 parts and the like.
The vulcanizing agent can be 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts or 5 parts by weight and the like.
The polyvinyl alcohol may be present in an amount of 1 part, 1.2 parts, 1.5 parts, 1.8 parts, 2 parts, 2.3 parts, 2.5 parts, 2.7 parts, 3 parts, 3.2 parts, 3.5 parts, 3.7 parts, 4 parts, or the like, by weight.
The following is a preferred technical solution of the present invention, but not a limitation to the technical solution provided by the present invention, and the object and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solution.
In a preferred embodiment of the present invention, the number of layers of the boron nitride nanosheet is 1 to 20, and may be, for example, 1 layer, 2 layers, 4 layers, 6 layers, 8 layers, 10 layers, 12 layers, 14 layers, 16 layers, 18 layers, 20 layers, or the like.
Preferably, the mass ratio of the aminated graphene to the boron nitride nanosheets is 1 (1-1.5).
According to the invention, through the matching use of the aminated graphene and the boron nitride nanosheets, the thermal conductivity of the graphene latex slurry can be effectively improved. If the mass ratio of the aminated graphene to the boron nitride nanosheets is too large or too small, the thermal conductivity of the graphene latex slurry is reduced.
In a preferred embodiment of the present invention, the vulcanizing agent is selected from any one or a combination of at least two of benzoyl peroxide, N' -m-phenylene bismaleimide, sulfur, 1-bis (t-butylperoxy) -3,3, 5-trimethylcyclohexane or bis (t-butylperoxyisopropyl) benzene.
The polymerization degree of the polyvinyl alcohol is preferably 350 to 4500 (for example, 350, 500, 1000, 1500, 2000, 2500, 3000, 3500, 4000, or 4500), and more preferably 500 to 2000.
In a preferred embodiment of the present invention, the graphene latex slurry further comprises 1 to 3 parts of an accelerator, which may be, for example, 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.4 parts, 2.6 parts, 2.8 parts, or 3 parts.
Preferably, the accelerator is selected from N-cyclohexyl-2-benzothiazolesulfenamide and/or N-oxydiethylene-2-benzothiophenesulfinamide.
As a preferred embodiment of the present invention, the graphene latex slurry further comprises 1 to 3 parts of an antioxidant, which may be, for example, 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.4 parts, 2.6 parts, 2.8 parts or 3 parts.
Preferably, the antioxidant is selected from any one or a combination of at least two of 2, 6-di-tert-butyl-4-methylphenol, N-isopropyl-N' -phenyl-p-phenylenediamine or 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer.
In a preferred embodiment of the present invention, the graphene latex slurry further includes 10 to 30 parts of water, which may be, for example, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, 20 parts, 22 parts, 24 parts, 26 parts, 28 parts, 30 parts, or the like.
Preferably, the graphene latex slurry has a viscosity of 1.5 to 2.5Pa · s, and may be, for example, 1.5Pa · s, 1.6Pa · s, 1.7Pa · s, 1.8Pa · s, 1.9Pa · s, 2Pa · s, 2.1Pa · s, 2.2Pa · s, 2.3Pa · s, 2.4Pa · s, or 2.5Pa · s.
In a second aspect, the present invention provides a process for preparing the graphene latex slurry according to the first aspect, the process comprising the steps of:
(1) uniformly mixing the boron nitride nanosheets, a vulcanizing agent, polyvinyl alcohol, water and an optional accelerator and an antioxidant to obtain a mixture A;
(2) uniformly mixing the mixture A obtained in the step (1) with aminated graphene to obtain a mixture B;
(3) and (3) uniformly mixing the mixture B obtained in the step (2) with natural rubber to obtain the graphene latex slurry.
As a preferred embodiment of the present invention, the temperature of the mixing in the step (1) is 10 to 25 ℃, and may be, for example, 10 ℃, 11 ℃, 12 ℃, 13 ℃, 14 ℃, 15 ℃, 16 ℃, 17 ℃, 18 ℃, 19 ℃, 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃ or 25 ℃.
Preferably, the step (1) further comprises a post-treatment step after the mixing.
Preferably, the method of post-treatment is grinding by a nano sand mill.
Preferably, the particle size of D90 in the mixture A is 60-100 nm, such as 60nm, 64nm, 68nm, 72nm, 76nm, 80nm, 84nm, 88nm, 92nm, 96nm or 100 nm.
As a preferred embodiment of the present invention, the temperature of the mixing in the step (2) is 10 to 25 ℃, and may be, for example, 10 ℃, 11 ℃, 12 ℃, 13 ℃, 14 ℃, 15 ℃, 16 ℃, 17 ℃, 18 ℃, 19 ℃, 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃ or 25 ℃.
Preferably, the step (2) further comprises a post-treatment step after the mixing.
Preferably, the post-treatment method is to perform dispersion by a high-speed fluted disc dispersion machine.
Preferably, the particle size of D90 in the mixture B is 1-10 μm, such as 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm or 10 μm.
Preferably, the mixing temperature in step (3) is 10-25 ℃, for example, 10 ℃, 11 ℃, 12 ℃, 13 ℃, 14 ℃, 15 ℃, 16 ℃, 17 ℃, 18 ℃, 19 ℃, 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃ or 25 ℃.
In a third aspect, the present invention provides a use of the graphene latex slurry according to the first aspect, for preparing a back cushion or a mattress.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, through the design of the components of the graphene latex slurry, the aminated graphene and the boron nitride nanosheet are further adopted as the heat-conducting filler, and the mass ratio of the aminated graphene to the boron nitride is controlled within a specific proportion range, so that the prepared graphene latex slurry has good uniformity, is still uniform after standing for 48 hours, does not agglomerate, has good heat conductivity, has a heat conductivity coefficient of 0.498-0.524W/(m.K), and is suitable for preparing household articles such as a back cushion or a mattress.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Some of the component sources in the examples and comparative examples are as follows:
natural rubber: internationally for neutralization;
aminated graphene: chongqing Yuanshi graphene technology development, Inc.;
boron nitride nanosheets: new Material incubator, Inc. of the institute of thawing Industrial, Tianyuan military;
polyvinyl alcohol: shanxi three-dimensional Shengtai New materials science and technology Co., Ltd;
carboxylated graphene: nanjing Xiancheng nanomaterial science and technology Co., Ltd.
Example 1
The embodiment provides a heat-conducting graphene latex slurry and a process thereof, wherein the graphene latex slurry comprises the following components in parts by weight: 70 parts of natural rubber, 5 parts of aminated graphene, 7 parts of boron nitride nanosheets, 3 parts of sulfur, 2 parts of polyvinyl alcohol, 2 parts of N-cyclohexyl-2-benzothiazole sulfonamide, 2 parts of 2, 6-di-tert-butyl-4-methylphenol and 18 parts of water.
The process of the graphene latex slurry comprises the following steps:
(1) uniformly mixing boron nitride nanosheets, sulfur, polyvinyl alcohol, water, N-cyclohexyl-2-benzothiazole sulfonamide and 2, 6-di-tert-butyl-4-methylphenol at 20 ℃, and then grinding the mixture in a nano sand mill to obtain a mixture A with the particle size of D90 being 80 nm;
(2) uniformly mixing the mixture A obtained in the step (1) with the aminated graphene at 20 ℃, and then placing the mixture A into a high-speed fluted disc dispersion machine for dispersion to obtain a mixture B with the particle size of D90 being 8 microns;
(3) and (3) uniformly mixing the mixture B obtained in the step (2) with natural rubber at 20 ℃ to obtain the graphene latex slurry.
Example 2
The embodiment provides a heat-conducting graphene latex slurry and a process thereof, wherein the graphene latex slurry comprises the following components in parts by weight: 75 parts of natural rubber, 4 parts of aminated graphene, 6 parts of boron nitride nanosheets, 1 part of benzoyl peroxide, 1.5 parts of polyvinyl alcohol, 3 parts of N-oxydiethylene-2-benzothiophene sulfenamide, 1 part of N-isopropyl-N' -phenyl-p-phenylenediamine and 24 parts of water.
The process of the graphene latex slurry comprises the following steps:
(1) uniformly mixing boron nitride nanosheets, benzoyl peroxide, polyvinyl alcohol, water, N-oxydiethylene-2-benzothiophene sulfenamide and N-isopropyl-N' -phenyl p-phenylenediamine at 10 ℃, and then grinding the mixture in a nano sand mill to obtain a mixture A with the particle size of D90 being 60 nm;
(2) uniformly mixing the mixture A obtained in the step (1) with the aminated graphene at 10 ℃, and then placing the mixture A into a high-speed fluted disc dispersion machine for dispersion to obtain a mixture B with the particle size of D90 being 10 microns;
(3) and (3) uniformly mixing the mixture B obtained in the step (2) with natural rubber at 10 ℃ to obtain the graphene latex slurry.
Example 3
The embodiment provides a heat-conducting graphene latex slurry and a process thereof, wherein the graphene latex slurry comprises the following components in parts by weight: 80 parts of natural rubber, 8 parts of aminated graphene, 10 parts of boron nitride nanosheets, 5 parts of 1-bis (tert-butylperoxy) -3,3, 5-trimethylcyclohexane, 4 parts of polyvinyl alcohol, 1 part of N-cyclohexyl-2-benzothiazole sulfonamide, 1.5 parts of 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer and 30 parts of water.
The process of the graphene latex slurry comprises the following steps:
(1) uniformly mixing boron nitride nanosheets, 1-bis (tert-butylperoxy) -3,3, 5-trimethylcyclohexane, polyvinyl alcohol, water, N-cyclohexyl-2-benzothiazole sulfonamide and 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer at 25 ℃, and then placing the mixture in a nano sand mill for grinding to obtain a mixture A with the particle size of D90 being 60 nm;
(2) uniformly mixing the mixture A obtained in the step (1) with the aminated graphene at 25 ℃, and then placing the mixture A into a high-speed fluted disc dispersion machine for dispersion to obtain a mixture B with the particle size of D90 being 1 mu m;
(3) and (3) uniformly mixing the mixture B obtained in the step (2) with natural rubber at 25 ℃ to obtain the graphene latex slurry.
Example 4
The embodiment provides a heat-conducting graphene latex slurry and a process thereof, wherein the graphene latex slurry comprises the following components in parts by weight: 60 parts of natural rubber, 5 parts of aminated graphene, 5 parts of boron nitride nanosheets, 4 parts of bis (tert-butylperoxyisopropyl) benzene, 1 part of polyvinyl alcohol, 1.5 parts of N-oxydiethylene-2-benzothiophene sulfenamide, 3 parts of N-isopropyl-N' -phenyl-p-phenylenediamine and 10 parts of water.
The process of the graphene latex slurry comprises the following steps:
(1) uniformly mixing boron nitride nanosheets, vulcanizing agents, polyvinyl alcohol, water, N-oxydiethylene-2-benzothiophene sulfenamide and N-isopropyl-N' -phenyl p-phenylenediamine at 15 ℃, and then placing the mixture in a nano sand mill for grinding to obtain a mixture A with the particle size of D90 being 70 nm;
(2) uniformly mixing the mixture A obtained in the step (1) with the aminated graphene at 15 ℃, and then placing the mixture A into a high-speed fluted disc dispersion machine for dispersion to obtain a mixture B with the particle size of D90 being 5 microns;
(3) and (3) uniformly mixing the mixture B obtained in the step (2) with natural rubber at 15 ℃ to obtain the graphene latex slurry.
Example 5
The present embodiment provides a thermally conductive graphene latex slurry and a process thereof, which are different from embodiment 1 only in that the graphene latex slurry contains 6 parts by weight of aminated graphene and 6 parts by weight of boron nitride nanosheets, and other conditions are the same as those in embodiment 1.
Example 6
The present embodiment provides a thermally conductive graphene latex slurry and a process thereof, which are different from embodiment 1 only in that the weight part of aminated graphene in the graphene latex slurry is 4.8 parts, the weight part of boron nitride nanosheet is 7.2 parts, and other conditions are the same as those in embodiment 1.
Example 7
The present embodiment provides a thermally conductive graphene latex slurry and a process thereof, which are different from embodiment 1 only in that the graphene latex slurry contains 4 parts by weight of aminated graphene and 8 parts by weight of boron nitride nanosheets, and other conditions are the same as those in embodiment 1.
Example 8
The present embodiment provides a thermally conductive graphene latex slurry and a process thereof, which are different from embodiment 1 only in that the weight part of aminated graphene in the graphene latex slurry is 6.5 parts, the weight part of boron nitride nanosheet is 5.5 parts, and other conditions are the same as those in embodiment 1.
Comparative example 1
The comparative example provides graphene latex slurry and a process thereof, and only differs from example 1 in that the graphene latex slurry does not contain boron nitride nanosheets, the weight part of aminated graphene is 12 parts, and other conditions are the same as those in example 1.
Comparative example 2
The comparative example provides graphene latex slurry and a process thereof, and only the difference from example 1 is that the graphene latex slurry does not contain aminated graphene, the weight part of boron nitride nanosheets is 12 parts, and other conditions are the same as those in example 1.
Comparative example 3
This comparative example provides a graphene latex slurry and a process thereof, which are different from example 1 only in that aminated graphene is replaced with carboxylated graphene, and the other conditions are the same as example 1.
Comparative example 4
The present comparative example provides a graphene latex slurry and a process thereof, which is different from example 1 only in that the graphene latex slurry does not contain polyvinyl alcohol, and the other conditions are the same as example 1.
The graphene latex slurries provided in the above examples and comparative examples were tested for their performance according to the following test criteria:
appearance: standing the graphene glue coating slurry provided by the embodiment and the comparative example for 48 hours, and observing whether the graphene latex slurry is uniform or not and whether aggregation occurs or not;
coefficient of thermal conductivity: the method comprises the steps of uniformly coating graphene latex slurry on a continuous circulating rotating conveying belt (the coating thickness is 2mm) through a scraper by adopting continuous transfer type extrusion coating, placing conductive polyurethane sponge on the graphene latex slurry, extruding the graphene latex slurry into the sponge through a double-roller extruder, conveying the sponge into a blast oven for drying after extrusion impregnation, and testing the heat conductivity coefficient of the sponge according to GB/T10294 and 2008, wherein the pressure of the extruder is 10kPa, the distance between two rollers is 3.5mm, and the temperature of the oven is 80 ℃.
The test results of the performance of the graphene latex slurry provided in the above examples and comparative examples are shown in table 1:
TABLE 1
As can be seen from table 1, by designing the components of the graphene latex slurry, further adopting the aminated graphene and the boron nitride nanosheet as the heat-conducting filler, and controlling the mass ratio of the aminated graphene to the boron nitride within a specific proportion range, the prepared graphene latex slurry is still uniform and does not agglomerate after standing for 48 hours, has good heat conductivity, has a heat conductivity coefficient of 0.498-0.524W/(m · K), and is suitable for preparing household articles such as a back cushion or a mattress.
If the mass of the aminated graphene is smaller than that of boron nitride compared with example 1 (example 7), the prepared graphene latex slurry has poor thermal conductivity and a thermal conductivity of 0.412W/(m · K); if the mass ratio of the aminated graphene to the boron nitride is large (example 8), the prepared graphene latex slurry has poor thermal conductivity and the thermal conductivity coefficient is 0.418W/(m · K). It can be seen that if the mass ratio of the aminated graphene to the boron nitride is not within the specific ratio range, the thermal conductivity of the prepared graphene latex slurry is poor.
Compared with example 1, if the graphene latex slurry does not contain boron nitride nanosheets (comparative example 1), the prepared graphene latex slurry has poor thermal conductivity and the thermal conductivity coefficient is 0.302W/(m.K); if the graphene latex slurry does not contain aminated graphene (comparative example 2), the prepared graphene latex slurry has poor thermal conductivity and the thermal conductivity coefficient is 0.278W/(m.K). Therefore, a synergistic interaction effect exists between the aminated graphene and the boron nitride nanosheet, and the graphene latex slurry prepared by using the aminated graphene and the boron nitride nanosheet in a matched manner has good thermal conductivity.
Compared with example 1, if the aminated graphene in the graphene latex slurry is replaced by carboxylated graphene (comparative example 3), the prepared graphene latex slurry is easy to agglomerate and poor in thermal conductivity; if the graphene latex slurry does not contain polyvinyl alcohol (comparative example 4), the prepared graphene latex slurry is easy to agglomerate and poor in thermal conductivity.
In summary, through the design of the components of the graphene latex slurry, the aminated graphene and the boron nitride nanosheet are further adopted as the heat conducting filler, and the mass ratio of the aminated graphene to the boron nitride is controlled within a specific proportion range, so that the prepared graphene latex slurry is uniform, has good heat conductivity, and is suitable for preparing household articles such as back cushions or mattresses.
The applicant states that the present invention is illustrated by the detailed process flow of the present invention through the above examples, but the present invention is not limited to the above detailed process flow, that is, it does not mean that the present invention must rely on the above detailed process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The heat-conducting graphene latex slurry is characterized by comprising the following components in parts by weight: 60-80 parts of natural rubber, 4-8 parts of aminated graphene, 5-10 parts of boron nitride nanosheets, 1-5 parts of vulcanizing agent and 1-4 parts of polyvinyl alcohol.
2. The graphene latex slurry according to claim 1, wherein the number of layers of the boron nitride nanosheets is 1-20;
preferably, the mass ratio of the aminated graphene to the boron nitride nanosheets is 1 (1-1.5).
3. The graphene latex slurry according to claim 1 or 2, wherein the vulcanizing agent is selected from any one of or a combination of at least two of benzoyl peroxide, N' -m-phenylene bismaleimide, sulfur, 1-bis (t-butylperoxy) -3,3, 5-trimethylcyclohexane or bis (t-butylperoxyisopropyl) benzene;
preferably, the polymerization degree of the polyvinyl alcohol is 350 to 4500, and more preferably 500 to 2000.
4. The graphene latex slurry according to any one of claims 1 to 3, further comprising 1 to 3 parts of an accelerator;
preferably, the accelerator is selected from N-cyclohexyl-2-benzothiazolesulfenamide and/or N-oxydiethylene-2-benzothiophenesulfinamide.
5. The graphene latex slurry according to any one of claims 1 to 4, further comprising 1 to 3 parts of an antioxidant;
preferably, the antioxidant is selected from any one or a combination of at least two of 2, 6-di-tert-butyl-4-methylphenol, N-isopropyl-N' -phenyl-p-phenylenediamine or 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer.
6. The graphene latex slurry according to any one of claims 1 to 5, further comprising 10 to 30 parts of water;
preferably, the viscosity of the graphene latex slurry is 1.5 to 2.5 pas.
7. A process for preparing the graphene latex slurry according to any one of claims 1 to 6, wherein the process comprises the steps of:
(1) uniformly mixing the boron nitride nanosheets, a vulcanizing agent, polyvinyl alcohol, water and an optional accelerator and an antioxidant to obtain a mixture A;
(2) uniformly mixing the mixture A obtained in the step (1) with aminated graphene to obtain a mixture B;
(3) and (3) uniformly mixing the mixture B obtained in the step (2) with natural rubber to obtain the graphene latex slurry.
8. The process according to claim 7, wherein the temperature of the mixing in the step (1) is 10-25 ℃;
preferably, the step (1) further comprises a post-treatment step after the mixing;
preferably, the post-treatment method is grinding by a nano sand mill;
preferably, the D90 particle size of the mixture A is 60-100 nm.
9. The process according to claim 7 or 8, wherein the temperature of the mixing in the step (2) is 10-25 ℃;
preferably, the step (2) further comprises a post-treatment step after the mixing;
preferably, the post-treatment method is to disperse by a high-speed fluted disc disperser;
preferably, the D90 particle size of the mixture B is 1-10 μm;
preferably, the mixing temperature in the step (3) is 10-25 ℃.
10. Use of the graphene latex slurry according to any one of claims 1 to 6, for preparing a back cushion or a mattress.
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