CN112375267A - Modified zinc oxide/rubber composite material and preparation method thereof - Google Patents
Modified zinc oxide/rubber composite material and preparation method thereof Download PDFInfo
- Publication number
- CN112375267A CN112375267A CN202011303124.9A CN202011303124A CN112375267A CN 112375267 A CN112375267 A CN 112375267A CN 202011303124 A CN202011303124 A CN 202011303124A CN 112375267 A CN112375267 A CN 112375267A
- Authority
- CN
- China
- Prior art keywords
- parts
- zinc oxide
- composite material
- nano
- rubber composite
- 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
- 239000002131 composite material Substances 0.000 title claims abstract description 72
- 229920001971 elastomer Polymers 0.000 title claims abstract description 54
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000008367 deionised water Substances 0.000 claims abstract description 30
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003063 flame retardant Substances 0.000 claims abstract description 28
- 239000006184 cosolvent Substances 0.000 claims abstract description 26
- 239000002270 dispersing agent Substances 0.000 claims abstract description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 25
- 239000000945 filler Substances 0.000 claims abstract description 25
- 229920002635 polyurethane Polymers 0.000 claims abstract description 23
- 239000004814 polyurethane Substances 0.000 claims abstract description 23
- 239000002562 thickening agent Substances 0.000 claims abstract description 23
- 239000006229 carbon black Substances 0.000 claims abstract description 21
- 229920000126 latex Polymers 0.000 claims abstract description 21
- 239000011787 zinc oxide Substances 0.000 claims abstract description 21
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims abstract description 19
- 235000017491 Bambusa tulda Nutrition 0.000 claims abstract description 19
- 241001330002 Bambuseae Species 0.000 claims abstract description 19
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims abstract description 19
- 239000011425 bamboo Substances 0.000 claims abstract description 19
- 239000003610 charcoal Substances 0.000 claims abstract description 17
- 239000000835 fiber Substances 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims description 42
- 239000000203 mixture Substances 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 239000005543 nano-size silicon particle Substances 0.000 claims description 7
- 238000004806 packaging method and process Methods 0.000 claims description 7
- -1 polypropylene Polymers 0.000 claims description 7
- 230000001954 sterilising effect Effects 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 4
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 4
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 150000001639 boron compounds Chemical class 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical group CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 3
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N ortho-diethylbenzene Natural products CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- FYUVLZRRIRGSTE-DTORHVGOSA-N tert-butyl (3ar,6as)-2,3,3a,4,6,6a-hexahydro-1h-pyrrolo[3,4-c]pyrrole-5-carboxylate Chemical compound C1NC[C@@H]2CN(C(=O)OC(C)(C)C)C[C@@H]21 FYUVLZRRIRGSTE-DTORHVGOSA-N 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical group [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 2
- 238000009413 insulation Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 230000003115 biocidal effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012767 functional filler Substances 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 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
- C08L7/02—Latex
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6561—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing systems of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring or ring system, with or without other non-condensed hetero rings
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a modified zinc oxide/rubber composite material and a preparation method thereof, relates to the technical field of rubber composite materials, and is used for solving the problems of complex preparation method, poor fire resistance and thermal insulation, short service life cycle and limitation of the practical application field of the existing rubber composite material, and the following scheme is provided and comprises the following raw materials in parts by weight: 46-58 parts of nano zinc oxide, 22-38 parts of rubber latex, 16-24 parts of nano filler, 16-20 parts of white carbon black, 12-16 parts of composite flame retardant, 11-15 parts of bamboo charcoal fiber, 6-8 parts of polyurethane thickener, 6-8 parts of cosolvent, 1-5 parts of cross-linking agent, 1-3 parts of dispersant and 60-80 parts of deionized water. The modified zinc oxide/rubber composite material has the advantages of simple preparation process, low cost, high hardness, high tensile strength, flame retardance, antibiosis, harmful substance absorption and long service life.
Description
Technical Field
The invention relates to the technical field of rubber composite materials, in particular to a modified zinc oxide/rubber composite material and a preparation method thereof.
Background
Rubber is used as an important industrial raw material and strategic resource, and the rubber is mainly derived from natural latex and industrial synthesis. The quality of the dry rubber obtained after the latex is demulsified and dried affects the performance of the dry rubber. Although the practicability of high mechanical strength and service life can be achieved by adjusting the proportion of the reinforcing filler and other functional fillers in the formula, particularly the proportion of the carbon nanotube material to the rubber, the filler has small size and self-agglomeration phenomenon, and is difficult to uniformly disperse in the rubber, so that the realization of uniform dispersion and uniform and rapid drying of the filler in the rubber becomes the key for improving the performance of rubber products.
The rubber composite material has wide application and large market demand, but the performance needs to be further improved. In the prior art, the white carbon black is used for preparing the rubber composite material, so that the product performance is improved, but other coagulants such as acid and the like and a precipitator are needed, the generated waste liquid causes burden to the environment, and the waste water treatment cost is increased. In addition, although the common rubber has better physical properties at room temperature, the properties such as tensile strength, elongation and wear resistance are easy to be deteriorated due to high-temperature or low-temperature environments or chemicals, and meanwhile, the existing rubber composite material is complex in preparation method, poor in fire resistance and heat insulation, short in service life cycle and limited in practical application field. Therefore, we propose a modified zinc oxide/rubber composite material and a preparation method to solve the problems.
Disclosure of Invention
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a modified zinc oxide/rubber composite material, which comprises the following raw materials in parts by weight: 46-58 parts of nano zinc oxide, 22-38 parts of rubber latex, 16-24 parts of nano filler, 16-20 parts of white carbon black, 12-16 parts of composite flame retardant, 11-15 parts of bamboo charcoal fiber, 6-8 parts of polyurethane thickener, 6-8 parts of cosolvent, 1-5 parts of cross-linking agent, 1-3 parts of dispersant and 60-80 parts of deionized water.
Preferably, the feed comprises the following raw materials in parts by weight: 48-56 parts of nano zinc oxide, 26-32 parts of rubber latex, 18-22 parts of nano filler, 17-19 parts of white carbon black, 13-15 parts of composite flame retardant, 12-14 parts of bamboo charcoal fiber, 6.5-7.5 parts of polyurethane thickener, 6.5-7.5 parts of cosolvent, 2-4 parts of cross-linking agent, 1.5-2.5 parts of dispersant and 65-75 parts of deionized water.
Preferably, the feed comprises the following raw materials in parts by weight: 52 parts of nano zinc oxide, 29 parts of rubber latex, 20 parts of nano filler, 18 parts of white carbon black, 14 parts of composite flame retardant, 13 parts of bamboo charcoal fiber, 7 parts of polyurethane thickener, 7 parts of cosolvent, 3 parts of cross-linking agent, 2 parts of dispersant and 70 parts of deionized water.
Preferably, the nano filler is one or a combination of more than two of nano polypropylene/montmorillonite composite material, nano calcium carbonate, nano silicon oxide or nano silicon carbide.
Preferably, the mass ratio of the cross-linking agent to the dispersing agent is 1-5: 1-3, and the cross-linking agent is di-tert-butyl hydroperoxide or diethylenetriamine.
Preferably, the composite flame retardant is a phosphorus-containing triazine oligomer, which is obtained by reacting a raw material compound (1) 2,4, 6-triphosphoric diethyl ester-1, 3, 5-triazine, a compound (2) cis-2-Boc-hexahydropyrrolo [3,4-c ] pyrrole and a compound (4) pentaerythritol through the following reaction processes:
preferably, the dispersant is one of methane, dichloromethane, acetone, absolute ethyl alcohol, absolute methyl alcohol, trichloropetroleum ether, diethyl ether or benzene.
Preferably, the mass ratio of the polyurethane thickener to the cosolvent is 1:1, and the cosolvent comprises high-melting-point glass powder and/or low-melting-point glass powder and/or boron compound and/or phosphate compound.
In a second aspect of the invention, a preparation method of a modified zinc oxide/rubber composite material is provided, which comprises the following preparation steps:
s1, adding the nano zinc oxide, the rubber latex, the nano filler and a part of deionized water into a mixer in parts by weight, setting the stirring speed at 1200-1600r/min, stirring for 20-40min, sequentially adding the white carbon black, the bamboo carbon fiber, the composite flame retardant and the cosolvent while stirring, heating to 65-85 ℃, and stirring for 1-3h at 160-r/min to prepare a mixture A;
s2, naturally cooling the mixture A to normal temperature, adding the dispersing agent and the rest deionized water, adjusting the rotating speed to 1800-2200r/min, stirring for 20-40min, adding the polyurethane thickening agent and the cross-linking agent, and continuously stirring for 25-45min to obtain a mixture B;
s3, adding the mixture B into a kneader, mixing for 14-18min, heating to keep high vacuum of-0.07 +/-0.005 MPa for 20-40min, defoaming, sterilizing, placing in a drying oven, drying at 60-80 ℃ for 15-20min, taking out, standing for 1-2h, cooling at normal temperature, and packaging to obtain the modified zinc oxide/rubber composite material.
Preferably, the volume ratio of the deionized water in S1 to the deionized water in S2 is 2-5: 1.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, nano zinc oxide and rubber latex are taken as base materials, nano fillers such as nano polypropylene/montmorillonite, nano silicon oxide and nano zinc oxide are added, through reasonable proportioning, the finally obtained nano rubber composite material has excellent mechanical properties, white carbon black, a composite flame retardant and a polyurethane thickener are added in a matching manner, a modified zinc oxide material with higher hardness can be gradually formed at a lower temperature, the thermal property and the mechanical property are improved, the nano rubber composite material is safe and harmless, the good heat insulation, heat insulation and fire blocking effects can be achieved, in addition, the preparation efficiency of the rubber composite material is improved by utilizing the synergistic effect of a cosolvent and a dispersing agent, and the raw materials are dispersed more uniformly and are harmless to the environment. The modified zinc oxide/rubber composite material has the advantages of simple preparation process, low cost, high hardness, high tensile strength, flame retardance, antibiosis, harmful substance absorption and long service life.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to specific embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
Example one
A modified zinc oxide/rubber composite material comprises the following raw materials in parts by weight: 46 parts of nano zinc oxide, 22 parts of rubber latex, 16 parts of nano filler, 16 parts of white carbon black, 12 parts of composite flame retardant, 11 parts of bamboo charcoal fiber, 6 parts of polyurethane thickener, 6 parts of cosolvent, 1 part of cross-linking agent, 1 part of dispersant and 60 parts of deionized water;
the preparation method comprises the following steps:
s1, adding the nano zinc oxide, the rubber latex, the nano filler and a part of deionized water into a mixer in parts by weight, setting the stirring speed to 1200r/min, stirring for 20min, sequentially adding the white carbon black, the bamboo charcoal fiber, the composite flame retardant and the cosolvent while stirring, heating to 65 ℃, and stirring for 1h at 120r/min to obtain a mixture A;
s2, naturally cooling the mixture A to normal temperature, adding the dispersing agent and the rest deionized water, adjusting the rotating speed to 1800r/min, stirring for 20min, adding the polyurethane thickening agent and the cross-linking agent, and continuously stirring for 25min to obtain a mixture B;
and S3, adding the mixture B into a kneader, mixing for 14min, heating to keep high vacuum of-0.065 MPa for 20min, defoaming, sterilizing, placing in a drying oven, drying at 60 ℃ for 15min, taking out, standing for 1h, cooling at normal temperature, and packaging to obtain the modified zinc oxide/rubber composite material.
Example two
A modified zinc oxide/rubber composite material comprises the following raw materials in parts by weight: 49 parts of nano zinc oxide, 25 parts of rubber latex, 18 parts of nano filler, 17 parts of white carbon black, 13 parts of composite flame retardant, 12 parts of bamboo charcoal fiber, 6.5 parts of polyurethane thickener, 6.5 parts of cosolvent, 2 parts of cross-linking agent, 1.5 parts of dispersant and 65 parts of deionized water;
the preparation method comprises the following steps:
s1, adding the nano zinc oxide, the rubber latex, the nano filler and a part of deionized water into a mixer in parts by weight, setting the stirring speed to 1300r/min, stirring for 25min, sequentially adding the white carbon black, the bamboo charcoal fiber, the composite flame retardant and the cosolvent while stirring, heating to 70 ℃, and stirring for 1.5h at 130r/min to obtain a mixture A;
s2, naturally cooling the mixture A to normal temperature, adding the dispersing agent and the rest deionized water, adjusting the rotating speed to 1900r/min, stirring for 25min, adding the polyurethane thickening agent and the cross-linking agent, and continuously stirring for 30min to obtain a mixture B;
and S3, adding the mixture B into a kneader, mixing for 15min, heating to keep high vacuum of-0.067 MPa for 25min, defoaming, sterilizing, placing in a drying oven, drying at 65 ℃ for 16min, taking out, standing for 1.2h, cooling at normal temperature, and packaging to obtain the modified zinc oxide/rubber composite material.
EXAMPLE III
A modified zinc oxide/rubber composite material comprises the following raw materials in parts by weight: 52 parts of nano zinc oxide, 29 parts of rubber latex, 20 parts of nano filler, 18 parts of white carbon black, 14 parts of composite flame retardant, 13 parts of bamboo charcoal fiber, 7 parts of polyurethane thickener, 7 parts of cosolvent, 3 parts of cross-linking agent, 2 parts of dispersant and 70 parts of deionized water;
the preparation method comprises the following steps:
s1, adding the nano zinc oxide, the rubber latex, the nano filler and a part of deionized water into a mixer in parts by weight, setting the stirring speed at 1400r/min, stirring for 30min, sequentially adding the white carbon black, the bamboo charcoal fiber, the composite flame retardant and the cosolvent while stirring, heating to 75 ℃, and stirring for 2h at 140r/min to obtain a mixture A;
s2, naturally cooling the mixture A to normal temperature, adding the dispersing agent and the rest deionized water, adjusting the rotating speed to 2000r/min, stirring for 30min, adding the polyurethane thickening agent and the cross-linking agent, and continuously stirring for 35min to obtain a mixture B;
and S3, adding the mixture B into a kneader, mixing for 14-18min, heating to keep high vacuum of-0.07 MPa for 30min, defoaming, sterilizing, placing in a drying oven, drying at 70 ℃ for 18min, taking out, standing for 1.5h, cooling at normal temperature, and packaging to obtain the modified zinc oxide/rubber composite material.
Example four
A modified zinc oxide/rubber composite material comprises the following raw materials in parts by weight: 54 parts of nano zinc oxide, 34 parts of rubber latex, 22 parts of nano filler, 19 parts of white carbon black, 15 parts of composite flame retardant, 14 parts of bamboo charcoal fiber, 7.5 parts of polyurethane thickener, 7.5 parts of cosolvent, 4 parts of cross-linking agent, 2.5 parts of dispersant and 75 parts of deionized water;
the preparation method comprises the following steps:
s1, adding the nano zinc oxide, the rubber latex, the nano filler and a part of deionized water into a mixer in parts by weight, setting the stirring speed to be 1500r/min, stirring for 35min, sequentially adding the white carbon black, the bamboo charcoal fiber, the composite flame retardant and the cosolvent while stirring, heating to 80 ℃, and stirring for 2.5h at 150r/min to obtain a mixture A;
s2, naturally cooling the mixture A to normal temperature, adding the dispersing agent and the rest deionized water, adjusting the rotating speed to 2100r/min, stirring for 35min, adding the polyurethane thickening agent and the cross-linking agent, and continuously stirring for 40min to obtain a mixture B;
and S3, adding the mixture B into a kneader, mixing for 17min, heating to keep high vacuum of-0.073 MPa, keeping for 35min, defoaming, sterilizing, placing in a drying oven, drying at 75 ℃ for 19min, taking out, standing for 1.8h, cooling at normal temperature, and packaging to obtain the modified zinc oxide/rubber composite material.
EXAMPLE five
A modified zinc oxide/rubber composite material comprises the following raw materials in parts by weight: 46-58 parts of nano zinc oxide, 38 parts of rubber latex, 24 parts of nano filler, 20 parts of white carbon black, 16 parts of composite flame retardant, 15 parts of bamboo charcoal fiber, 8 parts of polyurethane thickener, 8 parts of cosolvent, 8 parts of cross-linking agent, 5 parts of dispersing agent, 3 parts of deionized water and 80 parts of nano flame retardant;
the preparation method comprises the following steps:
s1, adding the nano zinc oxide, the rubber latex, the nano filler and a part of deionized water into a mixer in parts by weight, setting the stirring speed to 1600r/min, stirring for 40min, sequentially adding the white carbon black, the bamboo charcoal fiber, the composite flame retardant and the cosolvent while stirring, heating to 85 ℃, and stirring for 3h at 160r/min to obtain a mixture A;
s2, naturally cooling the mixture A to normal temperature, adding the dispersing agent and the rest deionized water, adjusting the rotating speed to 2200r/min, stirring for 40min, adding the polyurethane thickening agent and the cross-linking agent, and continuously stirring for 45min to obtain a mixture B;
and S3, adding the mixture B into a kneader, mixing for 18min, heating to keep high vacuum of-0.075 MPa for 40min, defoaming, sterilizing, placing in a drying oven, drying at 80 ℃ for 20min, taking out, standing for 2h, cooling at normal temperature, and packaging to obtain the modified zinc oxide/rubber composite material.
In the above five embodiments, the nano filler is one or a combination of two or more of a nano polypropylene/montmorillonite composite material, nano calcium carbonate, nano silicon oxide and nano silicon carbide, and the mass ratio of the cross-linking agent to the dispersing agent is 1-5: 1-3, wherein the cross-linking agent is di-tert-butyl hydroperoxide or diethylenetriamine, the composite flame retardant is a phosphorous triazine oligomer, and the composite flame retardant is obtained by reacting a raw material compound (1) 2,4, 6-triphosphoric diethyl ester-1, 3, 5-triazine, a compound (2) cis-2-Boc-hexahydropyrrolo [3,4-c ] pyrrole and a compound (4) pentaerythritol through the following reaction processes:
Comparative example
Commercially available rubber composites.
The rubber composite materials prepared in the first to fifth examples and the rubber composite material obtained in the comparative example are respectively subjected to flame retardance and breaking strength performance detection, and the detection results are detailed in table 1.
TABLE 1
| Detecting items | Example one | Example two | EXAMPLE III | Example four | EXAMPLE five | Comparative example |
| Elongation at break% | 798 | 812 | 809 | 803 | 799 | 755 |
| Tensile strength Mpa | 29 | 29 | 31 | 30 | 29 | 24 |
| Breaking strength (N/5 cm) | 51.31 | 52.56 | 49.98 | 50.27 | 52.33 | 38.26 |
| Flame retardant properties | Ⅴ | Ⅴ | Ⅴ | Ⅴ | Ⅴ | Ⅲ |
From the results in table 1, it can be seen that the elongation at break and tensile strength of the modified zinc oxide/rubber composite material prepared in the first to fifth embodiments of the present invention are both significantly improved, the flame retardant property thereof reaches level v, the breaking strength thereof is significantly better than that of the commercially available product, the modified zinc oxide/rubber composite material has excellent flame retardant effect, large breaking strength, stable thermal properties and mechanical properties, and further the service life thereof is prolonged.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. The modified zinc oxide/rubber composite material is characterized by comprising the following raw materials in parts by weight: 46-58 parts of nano zinc oxide, 22-38 parts of rubber latex, 16-24 parts of nano filler, 16-20 parts of white carbon black, 12-16 parts of composite flame retardant, 11-15 parts of bamboo charcoal fiber, 6-8 parts of polyurethane thickener, 6-8 parts of cosolvent, 1-5 parts of cross-linking agent, 1-3 parts of dispersant and 60-80 parts of deionized water.
2. The modified zinc oxide/rubber composite material as claimed in claim 1, which is characterized by comprising the following raw materials in parts by weight: 48-56 parts of nano zinc oxide, 26-32 parts of rubber latex, 18-22 parts of nano filler, 17-19 parts of white carbon black, 13-15 parts of composite flame retardant, 12-14 parts of bamboo charcoal fiber, 6.5-7.5 parts of polyurethane thickener, 6.5-7.5 parts of cosolvent, 2-4 parts of cross-linking agent, 1.5-2.5 parts of dispersant and 65-75 parts of deionized water.
3. The modified zinc oxide/rubber composite material as claimed in claim 1, which is characterized by comprising the following raw materials in parts by weight: 52 parts of nano zinc oxide, 29 parts of rubber latex, 20 parts of nano filler, 18 parts of white carbon black, 14 parts of composite flame retardant, 13 parts of bamboo charcoal fiber, 7 parts of polyurethane thickener, 7 parts of cosolvent, 3 parts of cross-linking agent, 2 parts of dispersant and 70 parts of deionized water.
4. The modified zinc oxide/rubber composite material of claim 1, wherein the nano filler is one or a combination of more than two of nano polypropylene/montmorillonite composite material, nano calcium carbonate, nano silicon oxide or nano silicon carbide.
5. The modified zinc oxide/rubber composite material as claimed in claim 1, wherein the mass ratio of the cross-linking agent to the dispersing agent is 1-5: 1-3, and the cross-linking agent is di-tert-butyl hydroperoxide or diethylenetriamine.
6. The modified zinc oxide/rubber composite material as claimed in claim 1, wherein the composite flame retardant is a phosphorous triazine oligomer, and is obtained by subjecting a raw material compound (1) 2,4, 6-triphosphoric diethyl ester-1, 3, 5-triazine, a compound (2) cis-2-Boc-hexahydropyrrolo [3,4-c ] pyrrole and a compound (4) pentaerythritol to the following reaction processes:
7. the modified zinc oxide/rubber composite material of claim 1, wherein the dispersant is one of methane, dichloromethane, acetone, absolute ethanol, absolute methanol, trichloropetroleum ether, diethyl ether or benzene.
8. The modified zinc oxide/rubber composite material as claimed in claim 1, wherein the mass ratio of the polyurethane thickener to the cosolvent is 1:1, and the cosolvent comprises high-melting-point glass powder and/or low-melting-point glass powder and/or boron compound and/or phosphate compound.
9. A process for the preparation of a modified zinc oxide/rubber composite according to any one of claims 1 to 8, characterized in that it comprises the following preparation steps:
s1, adding the nano zinc oxide, the rubber latex, the nano filler and a part of deionized water into a mixer in parts by weight, setting the stirring speed at 1200-1600r/min, stirring for 20-40min, sequentially adding the white carbon black, the bamboo carbon fiber, the composite flame retardant and the cosolvent while stirring, heating to 65-85 ℃, and stirring for 1-3h at 160-r/min to prepare a mixture A;
s2, naturally cooling the mixture A to normal temperature, adding the dispersing agent and the rest deionized water, adjusting the rotating speed to 1800-2200r/min, stirring for 20-40min, adding the polyurethane thickening agent and the cross-linking agent, and continuously stirring for 25-45min to obtain a mixture B;
s3, adding the mixture B into a kneader, mixing for 14-18min, heating to keep high vacuum of-0.07 +/-0.005 MPa for 20-40min, defoaming, sterilizing, placing in a drying oven, drying at 60-80 ℃ for 15-20min, taking out, standing for 1-2h, cooling at normal temperature, and packaging to obtain the modified zinc oxide/rubber composite material.
10. The method for preparing the modified zinc oxide/rubber composite material as claimed in claim 9, wherein the volume ratio of the deionized water in S1 to the deionized water in S2 is 2-5: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011303124.9A CN112375267A (en) | 2020-11-19 | 2020-11-19 | Modified zinc oxide/rubber composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011303124.9A CN112375267A (en) | 2020-11-19 | 2020-11-19 | Modified zinc oxide/rubber composite material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112375267A true CN112375267A (en) | 2021-02-19 |
Family
ID=74584579
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011303124.9A Pending CN112375267A (en) | 2020-11-19 | 2020-11-19 | Modified zinc oxide/rubber composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112375267A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111944289A (en) * | 2020-08-24 | 2020-11-17 | 张文俊 | PBAT/PLA composite material for degradable garbage bag and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111454495A (en) * | 2020-05-13 | 2020-07-28 | 王智辉 | Composite material prepared from recycled rubber sole and preparation method thereof |
| CN111808322A (en) * | 2020-07-03 | 2020-10-23 | 浙江红励卓纺织有限公司 | Modified ammonium polyphosphate material for antibacterial flame-retardant carpet and preparation method thereof |
-
2020
- 2020-11-19 CN CN202011303124.9A patent/CN112375267A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111454495A (en) * | 2020-05-13 | 2020-07-28 | 王智辉 | Composite material prepared from recycled rubber sole and preparation method thereof |
| CN111808322A (en) * | 2020-07-03 | 2020-10-23 | 浙江红励卓纺织有限公司 | Modified ammonium polyphosphate material for antibacterial flame-retardant carpet and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111944289A (en) * | 2020-08-24 | 2020-11-17 | 张文俊 | PBAT/PLA composite material for degradable garbage bag and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106519239A (en) | Preparation method and application of phosphorus-nitrogen-carbon-containing aggregate and intumescent flame retardant | |
| CN101717514B (en) | Modified phenolic resin, foamed material thereof and method for preparing same | |
| Wang et al. | Double-layered co-microencapsulated ammonium polyphosphate and mesoporous MCM-41 in intumescent flame-retardant natural rubber composites | |
| CN109705634B (en) | Attapulgite-based composite flame retardant modified by nitrogen-phosphorus-containing organic matter and preparation and application thereof | |
| WO2020173018A1 (en) | Modified expandable graphite and flame retardant, preparation method therefor, and use thereof in polyurethane foam | |
| CN112375267A (en) | Modified zinc oxide/rubber composite material and preparation method thereof | |
| CN113308118A (en) | Environment-friendly foaming flame-retardant silicon rubber material and preparation method thereof | |
| CN109776865B (en) | Toughened flame-retardant polylactic acid composite material and preparation method thereof | |
| CN105907087A (en) | Flame retardant nylon material and preparation method thereof | |
| CN107459492A (en) | A kind of organically-modified melamine polyphosphate and preparation method thereof | |
| CN107446368B (en) | Using silane-modified boehmite as wood plastic composite of fire retardant and preparation method thereof | |
| CN106751469B (en) | A kind of fluorine titanium Hybrid fire retardant and the preparation method and application thereof | |
| CN110540707B (en) | Multi-element flame-retardant polypropylene material and preparation method thereof | |
| CN108084660B (en) | A kind of expansion type fire retarding epoxide resin and preparation method thereof | |
| CN106519421A (en) | Flame-retardant composite sheet and preparation method thereof | |
| CN107177130B (en) | A kind of preparation method of the high thermal conductivity polyvinyl chloride composite materials modified based on boron nitride nanosheet | |
| CN113292823B (en) | Preparation method of terephthalonitrile derivative flame-retardant epoxy resin composite material | |
| CN114891293A (en) | Halogen-free low-smoke flame-retardant cable material and preparation method thereof | |
| CN113512301A (en) | Functionalized graphene modified polypropylene wood-plastic plate and preparation method thereof | |
| CN114133734A (en) | Low-filling efficient synergistic flame-retardant nylon 66 and preparation method thereof | |
| CN113278215A (en) | Polyethylene foam material and preparation method thereof | |
| CN111662432A (en) | Epoxy resin curing agent and preparation method and application thereof | |
| CN105524353A (en) | Fire retardant containing allyl substituted triazine carbon-forming agent and preparation method of same | |
| CN110903546A (en) | Flame-retardant high polymer material and preparation method and application thereof | |
| CN115028984B (en) | Conductive foam material with good flame retardance and preparation method thereof |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210219 |