CN111978570A - Method for vulcanizing and packaging graphene modified natural latex - Google Patents
Method for vulcanizing and packaging graphene modified natural latex Download PDFInfo
- Publication number
- CN111978570A CN111978570A CN202010901089.4A CN202010901089A CN111978570A CN 111978570 A CN111978570 A CN 111978570A CN 202010901089 A CN202010901089 A CN 202010901089A CN 111978570 A CN111978570 A CN 111978570A
- Authority
- CN
- China
- Prior art keywords
- latex
- graphene
- natural latex
- nano
- vulcanizing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 112
- -1 graphene modified natural latex Chemical class 0.000 title claims description 35
- 238000000034 method Methods 0.000 title claims description 16
- 238000004806 packaging method and process Methods 0.000 title description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 83
- 238000004073 vulcanization Methods 0.000 claims abstract description 57
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229920000642 polymer Polymers 0.000 claims abstract description 26
- 229920000126 latex Polymers 0.000 claims description 61
- 239000004816 latex Substances 0.000 claims description 61
- 238000003756 stirring Methods 0.000 claims description 27
- 239000006185 dispersion Substances 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 21
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 16
- 239000002270 dispersing agent Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000000227 grinding Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- RKQOSDAEEGPRER-UHFFFAOYSA-L zinc diethyldithiocarbamate Chemical compound [Zn+2].CCN(CC)C([S-])=S.CCN(CC)C([S-])=S RKQOSDAEEGPRER-UHFFFAOYSA-L 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 9
- 239000005018 casein Substances 0.000 claims description 8
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 claims description 8
- 235000021240 caseins Nutrition 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 239000011787 zinc oxide Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 claims description 7
- 239000003381 stabilizer Substances 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- 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 3
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 3
- HEBRGEBJCIKEKX-UHFFFAOYSA-M sodium;2-hexadecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HEBRGEBJCIKEKX-UHFFFAOYSA-M 0.000 claims description 3
- KMNUDJAXRXUZQS-UHFFFAOYSA-L zinc;n-ethyl-n-phenylcarbamodithioate Chemical compound [Zn+2].CCN(C([S-])=S)C1=CC=CC=C1.CCN(C([S-])=S)C1=CC=CC=C1 KMNUDJAXRXUZQS-UHFFFAOYSA-L 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 2
- 244000043261 Hevea brasiliensis Species 0.000 abstract description 4
- 229920003052 natural elastomer Polymers 0.000 abstract description 4
- 229920001194 natural rubber Polymers 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000004576 sand Substances 0.000 description 7
- 238000002715 modification method Methods 0.000 description 5
- 239000011324 bead Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229920006173 natural rubber latex Polymers 0.000 description 4
- 238000005987 sulfurization reaction Methods 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 241000207961 Sesamum Species 0.000 description 2
- 235000003434 Sesamum indicum Nutrition 0.000 description 2
- 241000700605 Viruses Species 0.000 description 2
- 239000002313 adhesive film Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- DWHOIYXAMUMQTI-UHFFFAOYSA-L disodium;2-[(1-sulfonatonaphthalen-2-yl)methyl]naphthalene-1-sulfonate Chemical compound [Na+].[Na+].C1=CC2=CC=CC=C2C(S(=O)(=O)[O-])=C1CC1=CC=C(C=CC=C2)C2=C1S([O-])(=O)=O DWHOIYXAMUMQTI-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- LCRMGUFGEDUSOG-UHFFFAOYSA-N naphthalen-1-ylsulfonyloxymethyl naphthalene-1-sulfonate;sodium Chemical compound [Na].C1=CC=C2C(S(=O)(OCOS(=O)(=O)C=3C4=CC=CC=C4C=CC=3)=O)=CC=CC2=C1 LCRMGUFGEDUSOG-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/242—Applying crosslinking or accelerating agent onto compounding ingredients such as fillers, reinforcements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
- C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
- C08J3/215—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase at least one additive being also premixed with a liquid phase
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2307/00—Characterised by the use of natural rubber
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2489/00—Characterised by the use of proteins; Derivatives thereof
-
- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- 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
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- 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
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- 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
- C08K3/02—Elements
- C08K3/06—Sulfur
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/39—Thiocarbamic acids; Derivatives thereof, e.g. dithiocarbamates
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention aims to provide a graphene modified vulcanization package technology, which solves the problem that graphene and a vulcanizing agent are not uniformly dispersed in natural rubber, and further improves the performance of natural latex polymers.
Description
Technical Field
The invention belongs to the technical field of natural rubber, and particularly relates to a graphene modified vulcanization package for preparing a graphene composite natural latex polymer.
Background
The natural latex has excellent comprehensive performance, and the obtained product has excellent elasticity, higher strength, larger elongation, smaller creep deformation and other performances, and is widely applied to the chemical industry and life. However, natural latex cannot meet many actual requirements in terms of physical and mechanical properties such as pure rubber hardness and tensile strength, and modification is urgently needed to improve the properties such as strength, wear resistance and aging resistance and widen the application field of the natural latex.
In the rubber industry, compounding research on traditional nano reinforced particles such as carbon black, white carbon black, clay and the like has been widely carried out, and natural rubber nano composite materials with excellent performance are developed. With the development of technology and the application of new nano materials such as nano zinc oxide, nano calcium carbonate, carbon nano tubes, nano fibers and the like, the properties of the natural rubber nano composite material are improved to a certain degree, but the current research results show that the effect of improving the physical properties of the composite material is limited due to poor dispersion level, the process is complex, and the stability is poor.
Graphene is a two-dimensional carbon nanomaterial with a single atom thickness, and has excellent optical, electrical, thermal and mechanical properties and a huge specific surface area. The graphene and the polymer can be compounded through covalent or non-covalent actions (hydrogen bonds, pi-pi actions, electrostatic actions and the like). the interactions not only increase the solubility or the dispersibility of the graphene in the polymer, but also can improve the performance of the composite material or expand the functions of the composite material.
Disclosure of Invention
The invention aims to provide a method for vulcanizing graphene modified natural latex bags, which is characterized by comprising the following steps:
1) and grinding and dispersing the graphene oxide into a graphene oxide dispersion liquid A.
2) Preparing a vulcanization bag from a natural latex vulcanization system according to a ratio, and grinding and dispersing the natural latex vulcanization system into a nano vulcanization bag B by using a nano sand mill or a circulating grinder.
3) Adding the nano-vulcanization package B prepared in the step 2) into the graphene oxide dispersion liquid A in a continuous stirring state. And uniformly mixing to prepare the graphene modified nano vulcanization bag.
4) And under the stirring state, sequentially adding a stabilizer and the graphene modified nano vulcanization package prepared in the step 3) into the natural latex solution to obtain a latex mixed solution C.
5) And (3) carrying out pre-vulcanization treatment on the latex mixed solution C to prepare semi-vulcanized latex D.
6) Separating the refined semi-vulcanized latex E from the semi-vulcanized latex D.
7) And after the refined semi-vulcanized latex E is formed, obtaining the graphene modified natural latex polymer.
Further, in the step 1), the graphene oxide is washed, then deionized water is added, then a dispersing agent with the content of 0.5-2 times that of the graphene oxide is added, the pH value is adjusted to 8-10, and the graphene oxide dispersion liquid A is dispersed and ground.
Further, in the step 1), the dispersant is a mixed solution of at least one of peregal, dispersant NF and sodium hexadecylbenzene sulfonate. In the graphene oxide nano dispersion liquid A, the concentration of graphene oxide is 0.2-2%.
Further, in the step 2), the nano-sized vulcanization process package B is a mixture of sulfur (S), ZDC (zinc diethyldithiocarbamate), PX (zinc ethylphenyldithiocarbamate), casein, peregal, 264(2, 6-di-tert-butyl-4-methylphenol), zinc oxide, a dispersant NF (sodium methylenedinaphthalene sulfonate), and the like.
Further, in the step 2), the weight ratio of the nano vulcanization process package B is as follows:
100-120 parts of sulfur (S)
60-80 parts of zinc oxide
1-40 parts of ZDC (zinc diethyldithiocarbamate)
1 to 40 portions of PX (zinc ethyl phenyl dithiocarbamate)
75-100 parts of casein
1-10 parts of peregal
264 to 100 parts of (2, 6-di-tert-butyl-4-methylphenol)
5-10 parts of dispersing agent NF (sodium methylene dinaphthalene sulfonate)
Further, in the step 4), a stabilizer is added to the natural latex solution in a state of being continuously stirred, and the mixture is stirred. And slowly adding the graphene modified nano vulcanization bag, and continuously stirring to obtain a latex mixed solution C.
Further, in the step 4), the mass concentration of the natural latex solution is 40-60%, and the dry mass content of the graphene oxide in the latex mixed solution C is 0.1-2%.
Further, in the step 5), the pre-vulcanizing treatment of the latex mixed solution C is to heat the latex mixed solution C in a water bath and stir the latex mixed solution C at a high speed. Heating the mixture at the temperature of between 40 and 80 ℃ for 2 to 4 hours to prepare semi-vulcanized latex D.
Further, in the step 6), after the semi-vulcanized latex D is parked, high-speed centrifugal separation treatment is carried out on the semi-vulcanized latex D, so as to obtain refined semi-vulcanized latex E.
Further, in the step 7), the refined semi-vulcanized latex E is dipped and molded by a mold, and then heated and dried to obtain the graphene modified natural latex polymer, wherein the temperature of the drying treatment is 90-130 ℃.
Further, the size of the graphene oxide dispersion liquid A is 2-5 micrometers, and the thickness of the graphene oxide dispersion liquid A is 3-5 nm. The size of the nano vulcanization process package B is 30-50 nm.
The invention has the beneficial effects that:
according to the method for modifying the graphene modified natural latex, a large-size graphene modified natural latex vulcanization bag is applied, the natural latex vulcanization bag is prepared into a nano vulcanization bag, and the nano particle size of the nano vulcanization bag is 30-50nm, so that the nano particle effect is achieved. Then mixing with 2-5 μm graphene, and loading nanometer sulfide coated particles on two sides of the graphene sheet layer to form a sesame cake structure. When the pre-vulcanization is carried out, the graphene nano vulcanization coated particles enter the linear chain segment of the natural latex to carry out a crosslinking reaction, so as to form a crosslinking network structure. Graphene is uniformly dispersed in a natural latex cross-linked network. The problem of uneven dispersion of graphene in natural latex is solved, and the modified natural latex is obtained. The mechanical property of the graphene modified natural latex polymer obtained by the invention is improved by 50-200%, the natural pore problem of natural latex is effectively improved, the barrier property of an adhesive film is improved, various viruses can be blocked, and the raw materials adopted by the graphene modified natural latex polymer modification method are easy to obtain and are easy for large-scale production.
Detailed Description
The present invention is further illustrated by the following examples, but it should not be construed that the scope of the above-described subject matter is limited to the following examples. Various substitutions and alterations can be made without departing from the technical idea of the invention and the scope of the invention is covered by the present invention according to the common technical knowledge and the conventional means in the field.
The method for modifying the graphene modified natural latex polymer comprises the following steps:
1) firstly, adding graphene oxide into deionized water, and uniformly stirring. Then, centrifugation was carried out to remove the supernatant. And repeatedly washing for 3-5 times, and testing the solid content of the graphene oxide. Then preparing a solution with the solid content of 0.2-2 percent. Then adding a dispersing agent with the graphene content of 0.5-2 times, wherein the dispersing agent is a mixed solution of at least one of peregal, a dispersing agent NF and sodium hexadecylbenzene sulfonate. And simultaneously adding KOH, NaOH, ammonia water and the like to adjust the pH value to 8-10. Pre-dispersing for 10min by a high-speed stirrer. And finally, grinding and dispersing the graphene dispersion liquid A into the graphene dispersion liquid A by using a nano sand mill, a circulating grinder and a high-pressure homogenizer.
2) Preparing a vulcanization bag from a natural latex vulcanization system according to a ratio. And then grinding and dispersing the mixture into the nano vulcanized bag B by using a nano sand mill or a circulating mill.
3) And adding a certain amount of nano-vulcanization package B into the graphene dispersion liquid A under the continuous stirring state. And uniformly mixing to prepare the graphene modified nano vulcanization bag.
4) Adding stabilizer into the natural latex solution under continuous stirring, and stirring for 5 min. And slowly adding the graphene modified nano vulcanization bag, and continuously stirring for 5-10 min. To obtain a latex mixture C. Pre-vulcanizing the latex mixed solution C: namely, the latex mixed solution C is subjected to water bath heating and slow stirring treatment at the heating temperature of 40-80 ℃ for 2-4 hours to prepare semi-vulcanized latex D. Further, the added parts are as follows: based on 60% natural rubber latex as 100 phr. The dosage of the stabilizer is 0.5 to 5phr, and the stabilizer is ammonia water, KOH and casein. The dosage of the nano vulcanized package B is 5-8phr, and the nano vulcanized package B is a mixture of S, ZDC, PX, casein, peregal, 264, zinc oxide and a dispersing agent NF.
5) Standing the semi-vulcanized latex D for 12-24h, and then carrying out high-speed centrifugal treatment and filtration on the semi-vulcanized latex D to obtain refined semi-vulcanized latex E.
6) Dipping and molding the refined semi-vulcanized latex D by using a mold, and then heating and drying at the drying temperature of 90-130 ℃. And obtaining the graphene modified natural latex polymer.
The graphene modification and sulfurization package technology disclosed by the invention is characterized in that the size of a sulfurization package particle is 30-50nm, then the sulfurization package particle is compounded with graphene with the particle size of 2-5 microns, and nano sulfurization package particles are loaded on two sides of a graphene sheet layer to form a sesame cake structure. When the pre-vulcanization is carried out, the graphene and the nano vulcanization coated particles enter the linear chain segment of the natural latex to carry out a crosslinking reaction, so as to form a crosslinking network structure. Graphene is uniformly dispersed in a natural latex cross-linked network. The problem of uneven dispersion of graphene in natural latex is solved, and the modified natural latex is obtained. The mechanical property of the graphene modified natural latex polymer obtained by the invention is improved by 50-200%, the natural pore problem of natural latex is effectively improved, the barrier property of an adhesive film is improved, various viruses can be blocked, and the raw materials adopted by the graphene modified natural latex polymer modification method are easy to obtain and are easy for large-scale production.
Example 1
The graphene modified natural latex vulcanization coating method of the embodiment comprises the following steps:
1) firstly, 20g of graphene oxide is dissolved in 300g of deionized water, the mixture is uniformly stirred, and then the supernatant is removed by centrifugation. Washing was repeated 5 times. Most of the water-soluble impurities are removed. The washed graphite oxide was tested for solid content. Preparing a part of the graphene oxide aqueous solution into 500ml of graphene oxide aqueous solution with the solid content of 0.5%, adding 0.5% of dispersing agent NF, and then adding a small amount of KOH to adjust the pH value to 9-10. And pre-dispersing for 10min by using a high-speed stirrer (the rotating speed is 15000 r/min). Finally grinding and dispersing the graphene into the graphene dispersion liquid A by using a high-pressure homogenizer (the pressure is 1200 bar).
2) Preparing a vulcanization bag from a natural latex vulcanization system according to a ratio. 60g of nano sulfur, 35g of nano zinc oxide, 20g of ZDC, 3g of NF (sodium methylenedinaphthalene sulfonate), 40g of 10% casein emulsion, 4g of 25% KOH aqueous solution and 125.5g of water are prepared into a vulcanization bag. Then grinding and dispersing into a nano vulcanized bag B by using a nano sand mill (the diameter of zirconia beads is 0.7-0.8mm, and the rotating speed is 2500 rpm).
3) And adding the graphene dispersion liquid A240g into the nano vulcanization bag B36g while stirring, and uniformly mixing to prepare the graphene modified nano vulcanization bag.
4) 1000g of 60% natural rubber latex was added with 2.4g of KOH under stirring, and stirred for 5 min. Then 276g of graphene modified nano-sulfide package was slowly added. Stirring for 5-10 min. To obtain a latex mixture C. And (3) carrying out pre-vulcanization treatment on the latex mixed solution C. Heating in water bath while stirring at 60 deg.C for 4 hr to obtain semi-vulcanized latex D
5) And standing the semi-vulcanized latex D for 12 hours, and carrying out high-speed centrifugal treatment and filtration on the semi-vulcanized latex D to obtain refined semi-vulcanized latex E.
6) And dipping and molding the refined semi-vulcanized latex E by using a mold, and then heating and drying to obtain the graphene modified natural latex polymer.
7) And carrying out curing and forming treatment on the graphene modified natural latex polymer, wherein the temperature of the curing and forming treatment is 110 ℃.
The graphene-modified natural latex polymer of this embodiment is prepared by using the graphene-modified natural latex polymer modification method of this embodiment.
Example 2
The graphene modified natural latex vulcanization coating method of the embodiment comprises the following steps:
1) firstly, 20g of graphene oxide is dissolved in 300g of deionized water, the mixture is uniformly stirred, and then the supernatant is removed by centrifugation. Washing was repeated 5 times. Most of the water-soluble impurities are removed. The washed graphite oxide was tested for solid content. Preparing a part of the graphene oxide aqueous solution with the solid content of 1% into 500ml, adding 0.5% of dispersing agent NF, and then adding a small amount of KOH to adjust the pH value to 9-10. Pre-dispersing for 10min by a high speed mixer (the rotating speed is 10000 r/min). Finally grinding and dispersing the mixture into graphene dispersion liquid A by using a nano sand mill (the diameter of zirconia beads is 0.3-0.4mm, the rotating speed is 2500 rpm)
2) Preparing a vulcanization bag from a natural latex vulcanization system according to a ratio. 60g of nano sulfur, 35g of nano zinc oxide, 20g of ZDC, 3g of NF, 40g of 10% casein emulsion, 4g of 25% KOH aqueous solution and 125.5g of water are prepared into a vulcanization bag. Then grinding and dispersing into a nano vulcanized bag B by using a nano sand mill (the diameter of zirconia beads is 0.3-0.4mm, the rotating speed is 2500 rpm).
3) And adding the graphene dispersion liquid A300g into the nano vulcanization bag B30g while stirring, and uniformly mixing to prepare the graphene modified nano vulcanization bag.
4) 1000g of 60% natural rubber latex was stirred while adding 2.4g of KOH, and the mixture was stirred for 5 minutes. Then, 330g of graphene modified nano-sulfide package is slowly added. Stirring for 5-10 min. To obtain a latex mixture C. And (3) carrying out pre-vulcanization treatment on the latex mixed solution C. And heating in a water bath while stirring at a low speed, wherein the heating temperature is 60 ℃, and the heating time is 4 hours, so as to prepare the semi-vulcanized latex D.
5) And standing the semi-vulcanized latex D for 12 hours, and carrying out high-speed centrifugal treatment and filtration on the semi-vulcanized latex D to obtain refined semi-vulcanized latex E.
6) And dipping and molding the refined semi-vulcanized latex E by using a mold, and then heating and drying to obtain the graphene modified natural latex polymer.
7) And carrying out curing and forming treatment on the graphene modified natural latex polymer, wherein the temperature of the curing and forming treatment is 110 ℃.
The graphene-modified natural latex polymer of this embodiment is prepared by using the graphene-modified natural latex polymer modification method of this embodiment.
Example 3
The graphene modified natural latex vulcanization coating method of the embodiment comprises the following steps:
1) firstly, 20g of graphene oxide is put into 300g of deionized water, stirred uniformly and then centrifuged to remove supernatant. Washing was repeated 5 times. Most of the water-soluble impurities are removed. The washed graphite oxide was tested for solid content. Preparing a part of the graphene oxide aqueous solution into 500ml of graphene oxide aqueous solution with the solid content of 0.5%, adding 0.5% of dispersing agent NF, and then adding a small amount of KOH to adjust the pH value to 9-10. And pre-dispersing for 10min by a high-speed stirrer (rotating speed: 12000 r/min). Finally, grinding and dispersing the graphene into the graphene dispersion liquid A by using a circulating grinding machine (the rotating speed is 9000 r/min).
2) Preparing a vulcanization bag from a natural latex vulcanization system according to a proportion. 60g of nano sulfur, 35g of nano zinc oxide, 20g of ZDC, 3g of NF, 40g of 10% casein emulsion, 4g of 25% KOH aqueous solution and 125.5g of water are prepared into a vulcanization bag. Then grinding and dispersing into a nano vulcanized bag B by using a nano sand mill (the diameter of zirconia beads is 0.3-0.4mm, and the rotating speed is 2500 rpm).
3) And adding the graphene dispersion liquid A240g into the nano vulcanization bag B36g while stirring, and uniformly mixing to prepare the graphene modified nano vulcanization bag.
4) 1000g of 60% natural rubber latex was added with 2.4g of KOH under stirring, and stirred for 5 min. Then 276g of graphene modified nano-sulfide package was slowly added. Stirring for 5-10 min. To obtain a latex mixture C. And (3) carrying out pre-vulcanization treatment on the latex mixed solution C. Heating in water bath while stirring at 60 deg.C for 4 hr to obtain semi-vulcanized latex D
5) And standing the semi-vulcanized latex D for 12 hours, and carrying out high-speed centrifugal treatment and filtration on the semi-vulcanized latex D to obtain refined semi-vulcanized latex E.
6) And dipping and molding the refined semi-vulcanized latex E by using a mold, and then heating and drying to obtain the graphene modified natural latex polymer.
7) And carrying out curing and forming treatment on the graphene modified natural latex polymer, wherein the temperature of the curing and forming treatment is 110 ℃.
The graphene-modified natural latex polymer of this embodiment is prepared by using the graphene-modified natural latex polymer modification method of this embodiment.
Claims (10)
1. A method for vulcanizing graphene modified natural latex bags is characterized by comprising the following steps:
1) grinding and dispersing the graphene oxide into a graphene oxide dispersion liquid A;
2) mixing all components of a vulcanization system of natural latex, grinding and dispersing to prepare a nano vulcanization bag B;
3) adding the nano-vulcanization package B prepared in the step 2) into the graphene oxide dispersion liquid A in a continuous stirring state. Uniformly mixing to prepare a graphene modified nano vulcanization bag;
4) sequentially adding a stabilizer and the graphene modified nano vulcanization package prepared in the step 3) into the natural latex solution under a stirring state to obtain a latex mixed solution C;
5) pre-vulcanizing the latex mixed solution C to prepare semi-vulcanized latex D;
6) separating a refined semi-vulcanized latex E from the semi-vulcanized latex D;
7) and after the refined semi-vulcanized latex E is formed, obtaining the graphene modified natural latex polymer.
2. The method for vulcanizing graphene modified natural latex according to claim 1, wherein: in the step 1), the graphene oxide is washed, then deionized water is added, then 0.5-2 times of dispersant of the solid content of the graphene oxide is added, the PH value is adjusted to 8-10, and the graphene oxide dispersion liquid A is dispersed and ground.
3. The method for vulcanizing graphene modified natural latex according to claim 1 or 2, wherein: in the step 1), the dispersant is a mixed solution of at least one of peregal, dispersant NF and sodium hexadecylbenzene sulfonate. In the graphene oxide nano dispersion liquid A, the concentration of graphene oxide is 0.2-2%.
4. The method for vulcanizing graphene modified natural latex according to claim 1, wherein: in the step 2), the nano-vulcanization process package B is a mixture of sulfur (S), ZDC (zinc diethyldithiocarbamate), PX (zinc ethylphenyldithiocarbamate), casein, peregal, 264(2, 6-di-tert-butyl-4-methylphenol), zinc oxide and a dispersing agent NF.
5. The method for vulcanizing graphene modified natural latex according to claim 1 or 3, wherein: in the step 4), a stabilizer is added into the natural latex solution in a continuous stirring state, and stirring is carried out; and slowly adding the graphene modified nano vulcanization bag, and continuously stirring to obtain a latex mixed solution C.
6. The method for vulcanizing graphene modified natural latex according to claim 1 or 5, wherein: in the step 4), the mass concentration of the natural latex solution is 40-60%, and the dry mass content of the graphene oxide in the latex mixed solution C is 0.1-2%.
7. The method for vulcanizing graphene modified natural latex according to claim 1, wherein: in the step 5), the pre-vulcanization treatment of the latex mixed solution C is to heat the latex mixed solution C in a water bath and stir the latex mixed solution C quickly; heating the mixture at the temperature of between 40 and 80 ℃ for 2 to 4 hours to prepare semi-vulcanized latex D.
8. The method for vulcanizing graphene modified natural latex according to claim 1, wherein: and in the step 6), after the semi-vulcanized latex D is parked, carrying out high-speed centrifugal separation treatment on the semi-vulcanized latex D to obtain refined semi-vulcanized latex E.
9. The method for vulcanizing graphene modified natural latex according to claim 1, wherein: in the step 7), the refined semi-vulcanized latex E is dipped and molded by a mold, and then heated and dried to obtain the graphene modified natural latex polymer, wherein the drying temperature is 90-130 ℃.
10. The method for vulcanizing graphene modified natural latex according to claim 1, wherein: the size of the graphene oxide in the graphene oxide dispersion liquid A is 2-5 micrometers, and the thickness of the graphene oxide in the graphene oxide dispersion liquid A is 3-5 nm; the size of the nano vulcanization process package B is 30-50 nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010901089.4A CN111978570A (en) | 2020-09-01 | 2020-09-01 | Method for vulcanizing and packaging graphene modified natural latex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010901089.4A CN111978570A (en) | 2020-09-01 | 2020-09-01 | Method for vulcanizing and packaging graphene modified natural latex |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111978570A true CN111978570A (en) | 2020-11-24 |
Family
ID=73448583
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010901089.4A Pending CN111978570A (en) | 2020-09-01 | 2020-09-01 | Method for vulcanizing and packaging graphene modified natural latex |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111978570A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112501716A (en) * | 2020-12-04 | 2021-03-16 | 广东国兴乳胶丝有限公司 | Preparation method of magnetic graphene composite latex yarn |
| CN118895019A (en) * | 2024-07-26 | 2024-11-05 | 江苏爱德福乳胶制品有限公司 | A high-performance graphene/natural latex composite material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11172042A (en) * | 1997-12-12 | 1999-06-29 | Japan Atom Energy Res Inst | Molding method from mixture of prevulcanized natural rubber latex and water-soluble polymer and molded article thereof |
| CN105542248A (en) * | 2016-02-02 | 2016-05-04 | 重庆墨希科技有限公司 | Graphene modified natural emulsion preparation method and high barrier condom |
| CN105906854A (en) * | 2016-02-02 | 2016-08-31 | 重庆墨希科技有限公司 | Graphene-modified natural latex polymer and modification method thereof |
| CN106832453A (en) * | 2017-02-24 | 2017-06-13 | 山东圣泉新材料股份有限公司 | A kind of Graphene modified natural emulsion material and its preparation method and application |
-
2020
- 2020-09-01 CN CN202010901089.4A patent/CN111978570A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11172042A (en) * | 1997-12-12 | 1999-06-29 | Japan Atom Energy Res Inst | Molding method from mixture of prevulcanized natural rubber latex and water-soluble polymer and molded article thereof |
| CN105542248A (en) * | 2016-02-02 | 2016-05-04 | 重庆墨希科技有限公司 | Graphene modified natural emulsion preparation method and high barrier condom |
| CN105906854A (en) * | 2016-02-02 | 2016-08-31 | 重庆墨希科技有限公司 | Graphene-modified natural latex polymer and modification method thereof |
| CN106832453A (en) * | 2017-02-24 | 2017-06-13 | 山东圣泉新材料股份有限公司 | A kind of Graphene modified natural emulsion material and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| 陈利水等: "石墨烯/氧化锌复合填充剂对天然胶乳及其制品性能的影响", 《合成橡胶工业》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112501716A (en) * | 2020-12-04 | 2021-03-16 | 广东国兴乳胶丝有限公司 | Preparation method of magnetic graphene composite latex yarn |
| CN118895019A (en) * | 2024-07-26 | 2024-11-05 | 江苏爱德福乳胶制品有限公司 | A high-performance graphene/natural latex composite material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105906854B (en) | Graphene modified natural emulsion polymer and its method of modifying | |
| CN103203810B (en) | Rubber masterbatch and rubber prepared by the method for continuously producing and the method for rubber masterbatch | |
| WO2016029798A1 (en) | Liquid phase continuous mixing process for highly dispersed carbon nanotube masterbatch and rubber product thereof | |
| CN114591545B (en) | Forming method for preparing graphene masterbatch and long-service-life heavy vehicle road wheel tire through water phase cooperative coagulation process | |
| WO2012080160A1 (en) | Improved elastomer formulations | |
| CN104927298A (en) | Polyetheretherketone-base composite, preparing method thereof and application thereof in friction reduction and wear resistance | |
| CN106589922B (en) | A kind of preparation method of Fanglun slurry cake composite master batch | |
| CN103756079B (en) | Composite modified cerium oxide improves the method for kiss-coating grip-pad rubber performance | |
| CN113861459B (en) | A kind of helical nano carbon fiber reinforced rubber composite material and preparation method thereof | |
| CN111978570A (en) | Method for vulcanizing and packaging graphene modified natural latex | |
| CN103419291B (en) | Rubber masterbatch prepared by the method for continuously producing of rubber masterbatch and the method | |
| CN104558711A (en) | Rubber composite material and preparation method thereof | |
| CN103554563B (en) | Room-temperature sulfurization preparation method for carbon nanotube-filled natural rubber composite material | |
| CN109627502B (en) | A kind of Tianjia rubber and natural rubber composite material and preparation method thereof | |
| US20170121511A1 (en) | A process to prepare high-quality natural rubber silica masterbatch by liquid phase mixing | |
| CN105524297A (en) | Preparation method of attapulgite/hydrotalcite composite filler used in rubber reinforcement | |
| CN105694144A (en) | A preparing method of a nitrile butadiene rubber/attapulgite/hydrotalcite composite material | |
| WO2016014037A1 (en) | A process to prepare high-quality natural rubber-silica masterbatch by liquid phase mixing | |
| CN106554528A (en) | Butadiene-styrene rubber/white carbon/lignocellulose/montmorillonite rubber composite and preparation method thereof | |
| CN107189122B (en) | A kind of carbon fiber-based puncture resistant rubber composite material and preparation method thereof | |
| CN108410041A (en) | A kind of preparation method of white carbon wet masterbatch | |
| CN117467204A (en) | MXene/rubber composite material with high wear resistance and preparation method thereof | |
| CN112500619A (en) | Aramid fiber reinforced nitrile rubber composite material and preparation method thereof | |
| CN114921008B (en) | Production method of reinforced carboxylic acrylonitrile butadiene latex | |
| CN103539977B (en) | The preparation method that the strong prestige powder of a kind of modified natural rubber graft modification strengthens native rubber composite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20230731 Address after: 401329 No. 15-6, Fengsheng Road, Jiulongpo District, Chongqing Applicant after: CHONGQING INSTITUTE OF GRAPHENE Address before: No. 15-6 Fengsheng Road, Jiulongpo District, Chongqing, 404100 Applicant before: CHONGQING ZHONGKE XIWEI TECHNOLOGY Co.,Ltd. Applicant before: CHONGQING INSTITUTE OF GRAPHENE |
|
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201124 |