CN110564003B - Preparation method of zinc oxide with surface grafted with liquid rubber - Google Patents

Preparation method of zinc oxide with surface grafted with liquid rubber Download PDF

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CN110564003B
CN110564003B CN201910726354.7A CN201910726354A CN110564003B CN 110564003 B CN110564003 B CN 110564003B CN 201910726354 A CN201910726354 A CN 201910726354A CN 110564003 B CN110564003 B CN 110564003B
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zinc oxide
grafted
liquid rubber
rubber
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CN110564003A (en
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沈显荣
相益信
宋庆平
查冬旺
蒲斌
胡庆松
耿雅婷
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Xuancheng Institute Of Industrial Technology Anhui University Of Engineering Co ltd
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    • 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
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/04—Compounds of zinc
    • C09C1/043—Zinc oxide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/10—Treatment with macromolecular organic 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
    • C08K2003/2296—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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

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  • Health & Medical Sciences (AREA)
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Abstract

The invention relates to a preparation method of zinc oxide with liquid rubber grafted on the surface, which comprises the steps of dispersing zinc oxide particles in a solvent, adding a coupling agent with double bonds, an initiator and the liquid rubber, reacting at a certain temperature, washing with the solvent after the reaction is finished, and drying to obtain the zinc oxide with the liquid rubber grafted on the surface. The method is a one-step reaction, is simple to operate, has mild reaction conditions, and is convenient for large-scale production; the compatibility of the zinc oxide with the surface grafted with the liquid rubber and the rubber compound is obviously modified, and a better basis is provided for more effectively exerting the synergistic performance of different components in the rubber formula.

Description

Preparation method of zinc oxide with surface grafted with liquid rubber
Technical Field
The invention belongs to the technical field of rubber, and particularly relates to a preparation method of zinc oxide with liquid rubber grafted on the surface.
Background
Zinc oxide (ZnO) and stearic acid are commonly used as the active systems in the vulcanization system of rubber materials. The production and use process of zinc oxide can have great influence on the environment. On the premise of improving the performance of rubber materials, the trend of the development of the rubber industry at present is to reduce the consumption of zinc oxide. The particle size, shape, specific surface area and degree of agglomeration of the zinc oxide all affect its active properties. The zinc oxide has extremely large specific surface area and higher specific surface energy, and is not easy to disperse in an organic medium, which directly influences the actual efficacy of the nano zinc oxide. In order to improve the dispersibility and affinity of inorganic particles in organic media and expand the application range of nano materials, the surface of ZnO needs to be modified.
The ZnO surface modification is reported less, and the modification method can refer to the surface modification method of silicon dioxide. Chinese patent CN101220177 and the like disclose a preparation method of a white carbon black/solution polymerized styrene butadiene rubber nano composite material. The method comprises the following steps ofAfter fully mixing the silicon oxide and the silane coupling agent, carrying out condensation reaction by heat treatment at high temperature to obtain organic modified nano silicon dioxide powder, adding the organic modified nano silicon dioxide powder into the solution of the solution polymerized styrene-butadiene rubber, stirring, removing the solvent, and drying to obtain the white carbon black/solution polymerized styrene-butadiene rubber nano composite material. Prucker (Macromolecules,1998,3(31):592-601) modifies silica by conventional free radical polymerization by grafting a nitrogen-containing free radical initiator onto the silica surface and then initiating free radical polymerization by such modified silica particles with polymer chains grafted onto the silica surface. Huck summarizes in SiO2Methods for grafting polymer molecular brushes onto the surface of spheres include Atom Transfer Radical Polymerization (ATRP), nitroxide-stabilized radical polymerization, reversible addition-fragmentation chain transfer polymerization (RAFT), activated anionic surface initiated polymerization (LASIP), and the like (Chemical Society Reviews,2004,33, 14-22). Chinese patent CN 107501486A discloses a preparation method and application of nano-silica with polyisoprene grafted on the surface, in the method, silica reacts with RAFT reagent to initiate RAFT polymerization of isoprene, and the nano-silica with polyisoprene grafted on the surface is obtained after washing and drying.
Taghvaei-Ganjali (Journal of Applied Polymer Science,2011,122,249-256.) uses polyethylene glycol (PEG) and polypropylene glycol (PPG) to respectively modify ZnO and nZnO, and the zinc oxide modified particles have larger improvement on the performance of NR/SBR. Wang (Journal of Applied Polymer Science,2011,119, 1144-. Abbasic (Polymer Engineering & Science,2016,56, 187-.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a preparation method of zinc oxide with liquid rubber grafted on the surface. The invention solves the problems that the zinc oxide is easy to agglomerate and disperse unevenly in the rubber compound, and the liquid rubber material is grafted on the surface of the zinc oxide only by a one-step method, so that the dispersibility of the zinc oxide material in the rubber material can be improved by the method; the zinc oxide material after surface grafting is improved in dispersibility in rubber, the vulcanization time of chloroprene rubber is shortened by 5-30%, and the tensile strength is improved by 10-30%.
In order to achieve the purpose, the invention adopts the technical scheme that:
a process for preparing the zinc oxide grafted with liquid rubber on its surface includes such steps as dispersing zinc oxide particles in solvent, adding coupling agent with double bond, trigger and liquid rubber, reaction at a certain temp, washing with solvent, and drying.
The invention grafts the liquid rubber on the nano zinc oxide by a one-step method and through the reaction of the coupling agent under the traditional free radical polymerization condition, has obvious grafting effect and is suitable for large-scale production.
Preferably, the zinc oxide is micron-sized zinc oxide or nano-sized zinc oxide.
Preferably, the solvent is any one of dichloromethane, toluene, 1,4 dioxane, tetrahydrofuran, N dimethylformamide and water.
Preferably, the coupling agent with double bonds is maleic anhydride or methacrylic anhydride.
Preferably, the initiator is any one of azobisisobutyronitrile, 1' -azo (cyanocyclohexane), dimethyl azobisisobutyrate, benzoyl peroxide and di-tert-butyl peroxide.
Preferably, the liquid rubber is any one of liquid natural rubber, liquid butadiene rubber, liquid styrene butadiene rubber and liquid nitrile butadiene rubber.
Preferably, the mass ratio of the zinc oxide particles, the liquid rubber, the coupling agent with double bonds, the initiator and the solvent is 1: 0.1-1: 0.01-0.2: 0.005-0.1: 1 to 10.
Preferably, the reaction temperature is 40-150 ℃, and the reaction time is 5-40 h.
Preferably, after the reaction is finished, washing the reaction product for three to five times by using dichloromethane, and drying the reaction product for 5 to 36 hours in a vacuum oven at the temperature of 40 to 100 ℃.
Preferably, the grafted liquid rubber accounts for 0.1-20% of the weight of the zinc oxide particles.
The surface-modified zinc oxide powder is successfully prepared by a one-step method, and the material has good dispersion stability and good compatibility with a rubber compound matrix material; the zinc oxide powder after surface modification is used as a good vulcanization activator, and the mechanical property of vulcanized rubber can be improved, and the mechanical property of a rubber material can also be improved. The preparation method has the advantages of simplicity, convenience, practicability, easy industrialization and the like, and can be directly combined with the existing production process of the inorganic nanoparticles.
Drawings
FIG. 1 is an infrared spectrum of zinc oxide (ZnO), liquid natural rubber (PIP), zinc oxide-grafted liquid rubber (ZnO-g-PIP) of the present invention;
FIG. 2 is a graph showing the thermogravimetric curves of zinc oxide grafted liquid rubbers according to examples 1 to 3 of the present invention;
FIG. 3 is a graph showing the thermogravimetric curves of zinc oxide grafted liquid rubbers of examples 4 to 6 of the present invention.
Detailed Description
The present invention is further described with reference to the following specific examples, which are not intended to be limiting, but are intended to be exemplary only in light of the teachings of the present invention and are not intended to be limiting.
Example 1
Weighing 12g of micron-sized zinc oxide, 3.6g of liquid natural rubber (molecular weight is 3w), 0.36g of maleic anhydride and 0.18g of azodiisobutyronitrile, and 40ml of 1, 4-dioxane, adding into a flask, and mechanically stirring for 24 hours at the reaction temperature of 60 ℃ to obtain a product.
And adding 10ml of dichloromethane to dissolve the obtained product, washing away unreacted liquid rubber, performing suction filtration, repeating the operation for four times, and drying in a vacuum drying oven at 70 ℃ to obtain the final product, namely the zinc oxide with the surface grafted with the liquid rubber. The grafting ratio of the zinc oxide grafted liquid rubber (liquid rubber in weight percent of zinc oxide particles) is shown in Table 1.
The infrared spectrogram of the zinc oxide (ZnO), the liquid natural rubber (PIP) and the zinc oxide grafted liquid rubber (ZnO-g-PIP) is shown in figure 1.
Example 2
Weighing 12g of micron-sized zinc oxide, 9.6g of liquid natural rubber (molecular weight is 3w), 0.96g of maleic anhydride and 0.48g of azobisisobutyronitrile, and 40ml of 1, 4-dioxane, adding into a flask, and mechanically stirring for 24 hours at the reaction temperature of 60 ℃ to obtain the product.
And adding 10ml of dichloromethane to the obtained product for dissolving, washing away unreacted liquid rubber, performing suction filtration, repeating the operation for four times, and drying in a vacuum drying oven at 70 ℃ to obtain the final product. The grafting ratio of the zinc oxide grafted liquid rubber is shown in Table 1.
Example 3
Weighing 12g of micron-sized zinc oxide, 12g of liquid natural rubber (molecular weight is 3w), 1.2g of maleic anhydride and 0.6g of azodiisobutyronitrile and 50ml of 1, 4-dioxane, adding the mixture into a flask, and mechanically stirring the mixture for 24 hours at the reaction temperature of 60 ℃ to obtain a product.
And adding 10ml of dichloromethane to the obtained product for dissolving, washing away unreacted liquid rubber, performing suction filtration, repeating the operation for four times, and drying in a vacuum drying oven at 60 ℃ to obtain the final product. The grafting ratio of the zinc oxide grafted liquid rubber is shown in Table 1.
The thermogravimetric curves of the zinc oxide grafted liquid rubbers of examples 1 to 3 are shown in FIG. 2.
Example 4
Weighing 8g of nanoscale zinc oxide, 2.4g of liquid natural rubber (molecular weight is 5w), 0.24g of maleic anhydride, 0.12g of azodiisobutyronitrile and 50ml of 1, 4-dioxane, adding the materials into a flask, and mechanically stirring the materials for 24 hours at the reaction temperature of 60 ℃ to obtain a product.
And adding 15ml of dichloromethane to the obtained product for dissolving, washing away unreacted liquid rubber, performing suction filtration, repeating the operation for four times, and drying in a vacuum drying oven at 70 ℃ to obtain the final product. The grafting ratio of the zinc oxide grafted liquid rubber is shown in Table 1.
Example 5
Weighing 8g of nanoscale zinc oxide, 5.6g of liquid natural rubber (molecular weight is 5w), 0.56g of maleic anhydride, 0.28g of azodiisobutyronitrile and 50ml of 1, 4-dioxane, adding the materials into a flask, and mechanically stirring the materials for 20 hours at the reaction temperature of 70 ℃ to obtain a product.
And adding 10ml of dichloromethane to the obtained product for dissolving, washing away unreacted liquid rubber, performing suction filtration, repeating the operation for four times, and drying in a vacuum drying oven at the temperature of 80 ℃ to obtain the final product. The grafting ratio of the zinc oxide grafted liquid rubber is shown in Table 1.
Example 6
Weighing 150g of nano-scale zinc oxide, 45g of liquid natural rubber (molecular weight is 5w), 4.5g of maleic anhydride, 2.25g of azodiisobutyronitrile and 1000ml of 1, 4-dioxane, adding into a reaction kettle, and mechanically stirring for 24 hours at the reaction temperature of 60 ℃ to obtain a product.
And adding 1000ml of dichloromethane to the obtained product for dissolving, washing away unreacted liquid rubber, performing suction filtration, repeating the operation for four times, and drying in a vacuum drying oven at 70 ℃ to obtain the final product. The grafting ratio of the zinc oxide grafted liquid rubber is shown in Table 1.
The thermogravimetric curves of the zinc oxide grafted liquid rubbers of examples 4 to 6 are shown in FIG. 3.
TABLE 1
Example 1 Example 2 Example 3 Example 4 Example 5 Example 6
Graft ratio (%) 2.57 5.15 5.82 4.78 11.25 12.16
The invention can design the grafting rate according to the requirement to obtain the corresponding performance.
Performance testing
Research on vulcanization and mechanical properties of chloroprene rubber
Drying the provided ZnO before mixing, wherein the conditions are as follows: 70 ℃ for 5 h. Mixing on an open mill, plasticating raw rubber CR, wrapping rollers, adding stearic acid and MgO for left and right rubber tapping, adding accelerators NA-22 and ZnO, thinly wrapping in a triangular bag, and cooling and standing the lower piece; the formula of the chloroprene rubber comprises the following components: 100 parts of CR, 1 part of stearic acid, 4 parts of MgO, 5 parts of ZnO and 0.6 part of accelerator. Vulcanizing a sample by a flat vulcanizing machine under the conditions of 180 ℃ multiplied by 10MPa multiplied by t90min; the total number of the groups is 6. The vulcanization and tensile properties of the material are shown in Table 2.
TABLE 2 vulcanization and mechanical Properties of Neoprene
Species of ZnO Nano meter Example 4 Example 5 Micron meter Example 1 Example 2
MH/(dN·m) 3.90 4.08 3.86 4.17 4.13 4.04
ML/(dN·m) 0.37 0.40 0.48 0.46 0.49 0.48
Scorching time t10/min 0.59 0.62 0.60 0.62 0.55 0.55
Positive vulcanization time t90/min 15.81 15.28 14.20 15.56 15.13 14.23
Tensile strength/MPa 9.83 11.62 11.35 8.61 9.78 11.36
Elongation at break/% 783 784 780 771 690 781
300% stress at definite elongation/%) 1.09 1.16 1.19 1.12 1.48 1.26
As can be seen from Table 2, the ZnO grafted on the chloroprene rubber can obviously shorten the vulcanization time of the chloroprene rubber and can improve the tensile strength.
Example 7
Adding 8g of nano-grade zinc oxide, 5.6g of liquid butadiene rubber (molecular weight 3k), 0.56g of maleic anhydride, 0.28g of azodiisobutyronitrile and 50ml of tetrahydrofuran into a pressure-resistant flask, and mechanically stirring for 20 hours at the reaction temperature of 60 ℃ to obtain a product.
And adding 10ml of dichloromethane to the obtained product for dissolving, washing away unreacted liquid butadiene rubber, performing suction filtration, repeating the operation for four times, and drying in a vacuum drying oven at the temperature of 80 ℃ to obtain the final product. The grafting rate of the zinc oxide grafted butadiene liquid rubber is 6.32 percent.
The method is a one-step reaction, is simple to operate, has mild reaction conditions, and is convenient for large-scale production; the compatibility of the zinc oxide with the surface grafted with the liquid rubber and the rubber compound is obviously modified, and a better basis is provided for more effectively exerting the synergistic performance of different components in the rubber formula.

Claims (9)

1. A preparation method of zinc oxide with liquid rubber grafted on the surface is characterized by comprising the following steps: dispersing zinc oxide particles in a solvent, adding a coupling agent with double bonds, an initiator and liquid rubber, reacting at a certain temperature, washing with the solvent after the reaction is finished, and drying to obtain zinc oxide with the surface grafted with the liquid rubber; the mass ratio of the zinc oxide particles, the liquid rubber, the coupling agent with double bonds, the initiator to the solvent is 1: 0.1-1: 0.01-0.2: 0.005-0.1: 1 to 10.
2. The method for preparing zinc oxide surface-grafted with liquid rubber according to claim 1, wherein: the zinc oxide is micron-sized zinc oxide or nano-sized zinc oxide.
3. The method for preparing zinc oxide surface-grafted with liquid rubber according to claim 1, wherein: the solvent is any one of dichloromethane, toluene, 1,4 dioxane, tetrahydrofuran, N dimethylformamide and water.
4. The method for preparing zinc oxide surface-grafted with liquid rubber according to claim 1, wherein: the coupling agent with double bonds is maleic anhydride or methacrylic anhydride.
5. The method for preparing zinc oxide surface-grafted with liquid rubber according to claim 1, wherein: the initiator is any one of azobisisobutyronitrile, 1' -azo (cyanocyclohexane), dimethyl azobisisobutyrate, benzoyl peroxide and di-tert-butyl peroxide.
6. The method for preparing zinc oxide surface-grafted with liquid rubber according to claim 1, wherein: the liquid rubber is any one of liquid natural rubber, liquid butadiene rubber, liquid styrene butadiene rubber and liquid nitrile butadiene rubber.
7. The method for preparing zinc oxide surface-grafted with liquid rubber according to claim 1, wherein: the reaction temperature is 40-150 ℃, and the reaction time is 5-40 h.
8. The method for preparing zinc oxide with liquid rubber grafted on the surface according to claim 1, wherein: and after the reaction is finished, washing the reaction product for three to five times by using dichloromethane, and drying the reaction product for 5 to 36 hours in a vacuum oven at the temperature of 40 to 100 ℃.
9. The method for preparing zinc oxide with liquid rubber grafted on the surface according to claim 1, wherein: the grafted liquid rubber accounts for 0.1-20% of the weight of the zinc oxide particles.
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Effects of ZnO content on microstructure and properties of maleated EPDMzinc oxide composites;Yeowool Kim,et al.;《Polym. Bull.》;20150210;第72卷;正文第1163-1175页 *
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X-Ray Diffraction and X-Ray Photoelectron Spectroscopy Characterization of Maleic Anhydride-Grafted Ethylene-Propylene-diene Terpolymer Based Thermoplastic Elastomers;YEOWOOL KIM,et al.;《Asian Journal of Chemistry》;20131231;第25卷(第9期);正文第5277-5283页 *
聚丙烯接枝马来酸酐改性纳米ZnO_省略_复合材料的成核结晶行为及力学性能;刘晶如等;《复合材料学报》;20170731;第34卷(第7期);正文第1526-1530页 *

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