CN110498957B - Modified basalt fiber/carboxylic styrene-butadiene latex composite foaming material and preparation method thereof - Google Patents
Modified basalt fiber/carboxylic styrene-butadiene latex composite foaming material and preparation method thereof Download PDFInfo
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- CN110498957B CN110498957B CN201910643735.9A CN201910643735A CN110498957B CN 110498957 B CN110498957 B CN 110498957B CN 201910643735 A CN201910643735 A CN 201910643735A CN 110498957 B CN110498957 B CN 110498957B
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- 229920002748 Basalt fiber Polymers 0.000 title claims abstract description 185
- 229920000126 latex Polymers 0.000 title claims abstract description 179
- 239000004816 latex Substances 0.000 title claims abstract description 177
- 229920003048 styrene butadiene rubber Polymers 0.000 title claims abstract description 82
- 239000002174 Styrene-butadiene Substances 0.000 title claims abstract description 81
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000011115 styrene butadiene Substances 0.000 title claims abstract description 81
- 239000000463 material Substances 0.000 title claims abstract description 63
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 238000005187 foaming Methods 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 36
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000004073 vulcanization Methods 0.000 claims abstract description 34
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 27
- 125000002091 cationic group Chemical group 0.000 claims abstract description 24
- 229920001084 poly(chloroprene) Polymers 0.000 claims abstract description 18
- 238000002791 soaking Methods 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000007598 dipping method Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 72
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 43
- 238000002156 mixing Methods 0.000 claims description 23
- 238000011049 filling Methods 0.000 claims description 22
- 238000005507 spraying Methods 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 18
- 238000009998 heat setting Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 11
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 claims description 8
- 229960002447 thiram Drugs 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 5
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- 238000002715 modification method Methods 0.000 abstract description 3
- 239000004088 foaming agent Substances 0.000 abstract 1
- 238000004321 preservation Methods 0.000 abstract 1
- 229920001971 elastomer Polymers 0.000 description 12
- 239000005060 rubber Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 9
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 7
- OTZWITHPRWRMMX-UHFFFAOYSA-N 2-butyl-1h-pyrrole Chemical compound CCCCC1=CC=CN1 OTZWITHPRWRMMX-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 244000043261 Hevea brasiliensis Species 0.000 description 4
- 239000006261 foam material Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 229920003052 natural elastomer Polymers 0.000 description 4
- 229920001194 natural rubber Polymers 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 102000007620 Pulmonary Surfactant-Associated Protein C Human genes 0.000 description 1
- 108010007125 Pulmonary Surfactant-Associated Protein C Proteins 0.000 description 1
- 229910000629 Rh alloy Inorganic materials 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- FDYSSWYQRTVFIS-UHFFFAOYSA-N buta-1,3-diene 3-phenylprop-2-enoic acid Chemical compound C=CC=C.C(=O)(O)C=CC1=CC=CC=C1 FDYSSWYQRTVFIS-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- REQPQFUJGGOFQL-UHFFFAOYSA-N dimethylcarbamothioyl n,n-dimethylcarbamodithioate Chemical compound CN(C)C(=S)SC(=S)N(C)C REQPQFUJGGOFQL-UHFFFAOYSA-N 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000010074 rubber mixing Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
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- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
-
- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/06—CO2, N2 or noble gases
-
- 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
- C08J2313/00—Characterised by the use of rubbers containing carboxyl groups
- C08J2313/02—Latex
-
- 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
- C08J2411/00—Characterised by the use of homopolymers or copolymers of chloroprene
- C08J2411/02—Latex
-
- 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
- C08K5/40—Thiurams, i.e. compounds containing groups
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/10—Silicon-containing 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
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic 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
- C08K9/04—Ingredients treated with organic substances
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Reinforced Plastic Materials (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses a modified basalt fiber/carboxylic styrene-butadiene latex composite foaming material and a preparation method thereof, wherein the preparation raw materials and the parts by weight comprise: 100 parts of carboxylic styrene-butadiene latex, 10-15 parts of cationic neoprene latex, 10-15 parts of butadiene-pyridine latex, 5-10 parts of modified basalt fiber, 3-7 parts of foaming agent, 2-5 parts of vulcanizing agent and 1-3 parts of vulcanization accelerator; the modification method of the modified basalt fiber comprises the following steps: dipping basalt fibers in concentrated sulfuric acid to obtain sulfonated basalt fibers; dissolving polyacrylamide in water to obtain a polyacrylamide solution; and (2) soaking the sulfonated basalt fiber in a polyacrylamide solution, and carrying out constant-temperature curing at 50-60 ℃ and heat preservation at 300-400 ℃ to obtain the modified basalt fiber. The modified basalt fiber/carboxylic styrene-butadiene latex composite foaming material disclosed by the invention is excellent in performance and good in product stability, and is expected to be widely applied in the field of sole materials and excellent in prospect.
Description
Technical Field
The invention relates to the technical field of polymer processing, in particular to a modified basalt fiber/carboxylic styrene-butadiene latex composite foaming material and a preparation method thereof.
Background
The carboxylic styrene-butadiene latex is a copolymer produced by emulsion polymerization of butadiene, styrene, a small amount of carboxylic acid and other auxiliary agents. Due to the introduction of carboxyl, the polarity of the latex is increased, and the carboxyl styrene-butadiene latex product has better wear resistance, heat resistance and aging resistance than a styrene-butadiene latex product, can be used together with natural rubber and various synthetic rubbers, and is expected to be widely applied as a sole material. At present, the research on the carboxylic styrene-butadiene latex foaming material is rarely reported.
However, the carboxylated styrene-butadiene latex still has the defects of poor tensile resistance, wear resistance, poor compatibility with ingredients and the like, and needs to be solved urgently, so that in practical application, the carboxylated styrene-butadiene latex is generally required to be modified to improve the product performance of a latex product. Common modification methods include: filler modification and chemical modification.
The cationic neoprene latex has better oil resistance, aging resistance and corrosion resistance, also has better tensile resistance, and can be used together with the carboxylic styrene-butadiene latex to enhance the product performance of the carboxylic styrene-butadiene latex product.
The basalt fiber is a continuous fiber which is formed by melting basalt stone at 1450-1500 ℃ and drawing the basalt stone at high speed through a platinum-rhodium alloy wire drawing bushing, has various excellent performances of high tensile strength, good insulativity, wear resistance, corrosion resistance and the like, and is a good rubber reinforcing material. However, because the basalt fiber has a smooth surface, low surface activity and poor compatibility with rubber materials, the application of the basalt fiber in the rubber field is limited, and the basalt fiber needs to be modified.
At present, the common basalt fiber modification method aims at improving the surface roughness or surface activity of basalt fibers, and the most common method is a method for modifying the basalt fibers by using a coupling agent. However, the method of modifying a coupling agent also has a problem of poor modification effect due to unstable coupling effect.
Chinese patent CN201711222315.0 discloses a basalt fiber rubber sole and a preparation method thereof, wherein the rubber sole is prepared from the following raw materials in parts by weight: 20-30 parts of natural rubber, 40-60 parts of chloroprene rubber, 20-29 parts of styrene-butadiene rubber, 1.5-2.0 parts of sulfur, 35-46 parts of basalt fiber, 4-5 parts of calcium carbonate, 0.6-1.2 parts of stearic acid, 0.5-1.1 parts of after-effect accelerator, 3-6 parts of nano calcium, 0.22-0.35 part of accelerator TMTM, 1.7-2.6 parts of diethylene glycol, 22-29 parts of superfine active calcium carbonate, 6-8 parts of white factice, 0.7-1.1 parts of silane coupling agent, 6-9 parts of naphthenic oil, 0.35-0.45 part of antioxidant, 0.6-1.0 part of anti-aging agent SP-C, 0.5-0.9 part of paraffin and 0.5-1.1 part of rosin modified resin. However, the basalt fiber adopted in the patent is not modified, so that the surface activity is poor, the compatibility with a rubber material is poor, and the reinforcing effect is poor.
Chinese patent CN201811575761.4 discloses a preparation method of a modified basalt fiber rubber composite material, which comprises the following steps: weighing basalt fibers, putting the basalt fibers into a large beaker, slowly pouring glacial acetic acid, stirring by using an electric stirrer to disperse the basalt fibers, stopping stirring to take the basalt fibers out of the beaker, performing suction filtration, cleaning, and then performing vacuum drying to obtain modified basalt fibers; weighing natural rubber, plasticating by adopting an open rubber mixing mill, sequentially adding modified basalt fiber, zinc oxide, stearic acid, an anti-aging agent 4020NA, an accelerator NS, carbon black, an accelerator TMTD and sulfur, and mixing and standing to obtain a rubber compound; and vulcanizing the prepared rubber compound by adopting a flat vulcanizing machine to obtain the modified basalt fiber/natural rubber composite material. However, the basalt in the patent is only subjected to acid etching, so that the surface roughness of the basalt fiber is increased, but the effect of improving the compatibility of the basalt fiber and a rubber material is limited.
Therefore, a composite foam material of modified basalt fiber reinforced styrene-butadiene latex is needed, and the tensile property, the wear resistance, the corrosion resistance and other properties of the composite foam material are improved.
Disclosure of Invention
Aiming at the problems, the invention provides a modified basalt fiber/carboxylic styrene-butadiene latex composite foaming material and a preparation method thereof.
The technical scheme adopted by the invention for solving the problems is as follows: the modified basalt fiber/carboxylic styrene-butadiene latex composite foaming material is prepared from the following raw materials in parts by weight: 100 parts of carboxylic styrene-butadiene latex, 10-15 parts of cationic neoprene latex, 10-15 parts of butadiene-pyridine latex, 5-10 parts of modified basalt fiber, 2-5 parts of vulcanizing agent and 1-3 parts of vulcanization accelerator;
the method for modifying the modified basalt fiber comprises the following steps:
step I, soaking basalt fibers in concentrated sulfuric acid to obtain sulfonated basalt fibers;
step II, dissolving polyacrylamide in water to obtain a polyacrylamide solution with the mass fraction of 0.5-3%;
step III, dipping the sulfonated basalt fiber obtained in the step I into the polyacrylamide solution obtained in the step II, heating to 50-60 ℃, and curing at constant temperature for 1-12 h; taking out the obtained product, washing, drying, preserving heat for 1-2 h at the temperature of 300-400 ℃, and grinding the obtained product to obtain the modified basalt fiber.
The method comprises the following steps of carrying out sulfonation treatment on basalt fibers, increasing the surface roughness of the basalt fibers, and improving the surface activity of the basalt fibers so as to be combined with polyacrylamide, so that a polyacrylamide high-molecular chain segment is added on the surface of the basalt fibers. The polyacrylamide is a linear high molecular polymer, and a large number of amide groups are arranged on the main chain of the polyacrylamide, so that the chemical activity is high. Therefore, the sulfonated basalt fiber is combined with the polyacrylamide, so that the surface activity of the basalt fiber is greatly improved, the surface polarity of the basalt fiber is improved, the compatibility of the basalt fiber and rubber latex is enhanced, the dispersibility of the basalt fiber in a latex material is improved, and the mechanical property of the latex material is enhanced. And the modified basalt fiber is mixed with the butadiene-pyridine latex firstly, and because the butadiene-pyridine latex has higher polarity, the modified basalt fiber has higher compatibility with the butadiene-pyridine latex and better compatibility with the butadiene-pyridine latex, the modified basalt fiber is uniformly dispersed in the butadiene-pyridine latex and then is mixed with the cationic chloroprene latex and the carboxylic styrene-butadiene latex, the dispersibility of the modified basalt fiber in the latex material is further improved, the reinforcing effect of the modified basalt fiber is improved, and the prepared composite rubber foaming material has good mechanical strength and product properties.
Further, the vulcanizing agents include: tetramethylthiuram disulfide or sulfur.
Further, the vulcanization accelerator includes: one or more of vulcanization accelerator TT, vulcanization accelerator D and vulcanization accelerator CZ.
Furthermore, in the step I, the dipping time is 6-12 h.
Further, in step II, the number average molecular weight of the polyacrylamide is: 80 to 100 ten thousand.
Another object of the present invention is to provide a preparation method of the modified basalt fiber/carboxylated styrene-butadiene latex composite foam material, which comprises the following steps:
step S1, adding the modified basalt fiber in parts by weight into the butadiene-pyridine latex in parts by weight, stirring for 1 min-2 min at the rotating speed of 300 rpm-400 rpm, and then stirring for 2 min-5 min at the rotating speed of 1000 rpm-3000 rpm to obtain the butadiene-pyridine latex with the modified basalt fiber;
step S2, adding the cationic neoprene latex in parts by weight into the butadiene-pyridine latex with the modified basalt fibers obtained in the step S1, stirring for 1 min-3 min at the rotating speed of 300 rpm-500 rpm, then adding the carboxylic styrene-butadiene latex in parts by weight, stirring for 2 min-4 min at the rotating speed of 400 rpm-600 rpm, and stirring for 5 min-10 min at the rotating speed of 1500 rpm-4000 rpm to obtain mixed latex with the modified basalt fibers;
step S3, adding the vulcanizing agent and the vulcanization accelerator in parts by weight into the mixed latex with the modified basalt fiber obtained in the step S2, stirring and mixing, filling nitrogen while stirring, uniformly mixing, and spraying by a spraying gun to obtain a sheet;
and S4, conveying the sheet obtained in the step S3 to an oven for processing, then carrying out heat setting processing, cooling and placing the obtained product for 12-18 h, and obtaining the modified basalt fiber/carboxylic styrene-butadiene latex composite foaming material.
Further, in step S3, the filling pressure of nitrogen is 0.6MPa to 1.2 MPa.
Further, in step S3, the sheet has a thickness of 1mm to 5 mm.
Further, in step S4, the process conditions of the processing in the oven are as follows: the treatment is carried out for 1min to 3min under the condition that the temperature is 120 ℃ to 150 ℃.
Further, in step S4, the process conditions of the heat setting treatment are: heat setting treatment is carried out for 20min to 60min under the temperature condition of 60 ℃ to 80 ℃.
The invention has the advantages that:
1. the invention carries out sulfonation treatment on the basalt fiber so as to be combined with polyacrylamide, so that a polyacrylamide high-molecular chain segment is added on the surface of the basalt fiber, the surface activity of the basalt fiber is greatly improved, the compatibility of the basalt fiber and rubber latex is enhanced, the dispersibility of the basalt fiber in the latex material is improved, and the mechanical property of the latex material is enhanced; the modified basalt fiber is firstly mixed with the butadiene-pyridine latex, the modified basalt fiber is uniformly dispersed in the butadiene-pyridine latex and then mixed with the cationic chloroprene latex and the carboxylic styrene-butadiene latex, so that the dispersibility of the modified basalt fiber in the latex material is further improved, the reinforcing effect of the modified basalt fiber is improved, and the prepared composite rubber foaming material has good mechanical strength and product properties;
2. the modified basalt fiber/carboxylic styrene-butadiene latex composite foaming material prepared by the invention has the advantages of excellent mechanical strength performance, high product comfort level, strong size stability, simple and convenient preparation method, easy large-scale operation and contribution to enhancing the market competitiveness.
Detailed Description
The following detailed description of embodiments of the invention, but the invention can be practiced in many different ways, as defined and covered by the claims.
Example 1
The modified basalt fiber/carboxylic styrene-butadiene latex composite foaming material is prepared from the following raw materials in parts by weight: 100 parts of carboxylic styrene-butadiene latex, 10 parts of cationic neoprene latex, 10 parts of butadiene-pyridine latex, 5 parts of modified basalt fiber, 2 parts of vulcanizing agent tetramethyl thiuram disulfide and 1 part of vulcanization accelerator TT;
the method for modifying the modified basalt fiber comprises the following steps:
step I, soaking basalt fibers in concentrated sulfuric acid for 6 hours to obtain sulfonated basalt fibers;
step II, dissolving polyacrylamide with the number average molecular weight of 80 ten thousand in water to obtain a polyacrylamide solution with the mass fraction of 0.5%;
step III, soaking the sulfonated basalt fiber obtained in the step I in the polyacrylamide solution obtained in the step II, heating to 50 ℃, and curing at constant temperature for 1 h; and taking out the obtained product, cleaning, drying, preserving heat for 1h at the temperature of 300 ℃, and grinding the obtained product to obtain the modified basalt fiber.
The preparation method of the modified basalt fiber/carboxylic styrene-butadiene latex composite foaming material comprises the following steps:
step S1, adding the modified basalt fiber in parts by weight into the butadiene-pyridine latex in parts by weight, stirring for 1min at the rotating speed of 300rpm, and then stirring for 2min at the rotating speed of 1000rpm to obtain the butadiene-pyridine latex with the modified basalt fiber;
step S2, adding the cationic neoprene latex in parts by weight into the butadiene-pyridine latex with the modified basalt fibers obtained in the step S1, stirring for 1min at the rotating speed of 300rpm, then adding the carboxylic styrene-butadiene latex in parts by weight, stirring for 2min at the rotating speed of 400rpm, and stirring for 5min at the rotating speed of 1500rpm to obtain mixed latex with the modified basalt fibers;
step S3, adding the vulcanizing agent and the vulcanization accelerator in parts by weight into the mixed latex with the modified basalt fiber obtained in the step S2, stirring and mixing, filling nitrogen while stirring, wherein the filling pressure of the nitrogen is 0.6MPa, uniformly mixing, and spraying by using a spraying gun to obtain a sheet with the thickness of 1 mm;
and S4, conveying the sheet obtained in the step S3 into an oven, treating the sheet at the temperature of 120 ℃ for 1min, then carrying out heat setting treatment at the temperature of 60 ℃ for 20min, and cooling and standing the obtained product for 12h to obtain the modified basalt fiber/carboxylic styrene-butadiene latex composite foaming material.
Example 2
The modified basalt fiber/carboxylic styrene-butadiene latex composite foaming material is prepared from the following raw materials in parts by weight: 100 parts of carboxylic styrene-butadiene latex, 15 parts of cationic neoprene latex, 15 parts of butadiene-pyridine latex, 10 parts of modified basalt fiber, 5 parts of vulcanizing agent sulfur and 3 parts of vulcanization accelerator D;
the method for modifying the modified basalt fiber comprises the following steps:
step I, soaking basalt fibers in concentrated sulfuric acid for 12 hours to obtain sulfonated basalt fibers;
step II, dissolving polyacrylamide with the number average molecular weight of 100 ten thousand in water to obtain a polyacrylamide solution with the mass fraction of 3%;
step III, soaking the sulfonated basalt fiber obtained in the step I in the polyacrylamide solution obtained in the step II, heating to 60 ℃, and curing at constant temperature for 12 hours; and taking out the obtained product, cleaning, drying, preserving heat for 2 hours at the temperature of 400 ℃, and grinding the obtained product to obtain the modified basalt fiber.
The preparation method of the modified basalt fiber/carboxylic styrene-butadiene latex composite foaming material comprises the following steps:
step S1, adding the modified basalt fiber in parts by weight into the butadiene-pyridine latex in parts by weight, stirring for 2min at the rotating speed of 400rpm, and then stirring for 5min at the rotating speed of 3000rpm to obtain the butadiene-pyridine latex with the modified basalt fiber;
step S2, adding the cationic neoprene latex in parts by weight into the butadiene-pyridine latex with the modified basalt fibers obtained in the step S1, stirring for 3min at the rotating speed of 500rpm, then adding the carboxylic styrene-butadiene latex in parts by weight, stirring for 4min at the rotating speed of 600rpm, and stirring for 10min at the rotating speed of 4000rpm to obtain mixed latex with the modified basalt fibers;
step S3, adding the vulcanizing agent and the vulcanization accelerator in parts by weight into the mixed latex with the modified basalt fiber obtained in the step S2, stirring and mixing, filling nitrogen while stirring, wherein the filling pressure of the nitrogen is 1.2MPa, uniformly mixing, and spraying by using a spraying gun to obtain a sheet with the thickness of 5 mm;
and S4, conveying the sheet obtained in the step S3 into an oven, treating for 3min at the temperature of 150 ℃, then carrying out heat setting treatment for 60min at the temperature of 80 ℃, and cooling and standing the obtained product for 18h to obtain the modified basalt fiber/carboxylic styrene-butadiene latex composite foaming material.
Example 3
The modified basalt fiber/carboxylic styrene-butadiene latex composite foaming material is prepared from the following raw materials in parts by weight: 100 parts of carboxylic styrene-butadiene latex, 12.5 parts of cationic chloroprene latex, 12.5 parts of butadiene-pyridine latex, 7.5 parts of modified basalt fiber, 3.5 parts of vulcanizing agent tetramethyl thiuram disulfide and 2 parts of vulcanization accelerator CZ;
the method for modifying the modified basalt fiber comprises the following steps:
step I, soaking basalt fibers in concentrated sulfuric acid for 9 hours to obtain sulfonated basalt fibers;
step II, dissolving polyacrylamide with the number average molecular weight of 90 ten thousand in water to obtain a polyacrylamide solution with the mass fraction of 1.75%;
step III, soaking the sulfonated basalt fiber obtained in the step I in the polyacrylamide solution obtained in the step II, heating to 55 ℃, and curing at constant temperature for 6.5 hours; and taking out the obtained product, cleaning, drying, preserving heat for 1.5 hours at the temperature of 350 ℃, and grinding the obtained product to obtain the modified basalt fiber.
The preparation method of the modified basalt fiber/carboxylic styrene-butadiene latex composite foaming material comprises the following steps:
step S1, adding the modified basalt fiber in parts by weight into the butyl pyrrole latex in parts by weight, stirring for 1.5min at the rotating speed of 350rpm, and then stirring for 3.5min at the rotating speed of 2000rpm to obtain the butyl pyrrole latex with the modified basalt fiber;
step S2, adding the cationic neoprene latex in parts by weight into the butadiene-pyridine latex with the modified basalt fibers obtained in the step S1, stirring for 2min at the rotation speed of 400rpm, then adding the carboxylic styrene-butadiene latex in parts by weight, stirring for 3min at the rotation speed of 500rpm, and then stirring for 7.5min at the rotation speed of 2700rpm to obtain mixed latex with the modified basalt fibers;
step S3, adding the vulcanizing agent and the vulcanization accelerator in parts by weight into the mixed latex with the modified basalt fiber obtained in the step S2, stirring and mixing, filling nitrogen while stirring, wherein the filling pressure of the nitrogen is 0.9MPa, uniformly mixing, and spraying by using a spraying gun to obtain a sheet with the thickness of 3 mm;
and S4, conveying the sheet obtained in the step S3 into an oven, treating for 2min at the temperature of 135 ℃, then carrying out heat setting treatment for 40min at the temperature of 70 ℃, and cooling and standing the obtained product for 15h to obtain the modified basalt fiber/carboxylic styrene-butadiene latex composite foaming material.
Example 4
The modified basalt fiber/carboxylic styrene-butadiene latex composite foaming material is prepared from the following raw materials in parts by weight: 100 parts of carboxylic styrene-butadiene latex, 11 parts of cationic neoprene latex, 14 parts of butadiene-pyridine latex, 6 parts of modified basalt fiber, 2.8 parts of vulcanizing agent sulfur, 1 part of vulcanization accelerator TT and 0.5 part of vulcanization accelerator D;
the method for modifying the modified basalt fiber comprises the following steps:
step I, soaking basalt fibers in concentrated sulfuric acid for 7.5 hours to obtain sulfonated basalt fibers;
step II, dissolving polyacrylamide with the number average molecular weight of 85 ten thousand in water to obtain a polyacrylamide solution with the mass fraction of 1%;
step III, soaking the sulfonated basalt fiber obtained in the step I in the polyacrylamide solution obtained in the step II, heating to 52 ℃, and curing at constant temperature for 3 hours; and taking out the obtained product, cleaning, drying, preserving heat for 1.2 hours at the temperature of 320 ℃, and grinding the obtained product to obtain the modified basalt fiber.
The preparation method of the modified basalt fiber/carboxylic styrene-butadiene latex composite foaming material comprises the following steps:
step S1, adding the modified basalt fiber in parts by weight into the butyl pyrrole latex in parts by weight, stirring for 1.2min at the rotating speed of 320rpm, and then stirring for 3min at the rotating speed of 1500rpm to obtain the butyl pyrrole latex with the modified basalt fiber;
step S2, adding the cationic neoprene latex in parts by weight into the butadiene-pyridine latex with the modified basalt fibers obtained in the step S1, stirring for 1.5min at the rotating speed of 350rpm, then adding the carboxylic styrene-butadiene latex in parts by weight, stirring for 2.5min at the rotating speed of 450rpm, and stirring for 6min at the rotating speed of 2000rpm to obtain mixed latex with the modified basalt fibers;
step S3, adding the vulcanizing agent and the vulcanization accelerator in parts by weight into the mixed latex with the modified basalt fiber obtained in the step S2, stirring and mixing, filling nitrogen while stirring, wherein the filling pressure of the nitrogen is 0.8MPa, uniformly mixing, and spraying by using a spraying gun to obtain a sheet with the thickness of 4 mm;
and S4, conveying the sheet obtained in the step S3 into an oven, treating for 2.5min at the temperature of 125 ℃, then carrying out heat setting treatment for 50min at the temperature of 65 ℃, cooling and standing the obtained product for 14h to obtain the modified basalt fiber/carboxylic styrene-butadiene latex composite foaming material.
Example 5
The modified basalt fiber/carboxylic styrene-butadiene latex composite foaming material is prepared from the following raw materials in parts by weight: 100 parts of carboxylic styrene-butadiene latex, 14 parts of cationic neoprene latex, 14 parts of butadiene-pyridine latex, 9 parts of modified basalt fiber, 4 parts of vulcanizing agent sulfur, 0.5 part of vulcanization accelerator TT, 78 parts of vulcanization accelerator D1 and 1 part of vulcanization accelerator CZ;
the method for modifying the modified basalt fiber comprises the following steps:
step I, soaking basalt fibers in concentrated sulfuric acid for 11 hours to obtain sulfonated basalt fibers;
step II, dissolving polyacrylamide with the number average molecular weight of 95 ten thousand in water to obtain a polyacrylamide solution with the mass fraction of 2.5%;
step III, soaking the sulfonated basalt fiber obtained in the step I in the polyacrylamide solution obtained in the step II, heating to 58 ℃, and curing at constant temperature for 10 hours; and taking out the obtained product, cleaning, drying, preserving heat for 1.8 hours at the temperature of 380 ℃, and grinding the obtained product to obtain the modified basalt fiber.
The preparation method of the modified basalt fiber/carboxylic styrene-butadiene latex composite foaming material comprises the following steps:
step S1, adding the modified basalt fiber in parts by weight into the butyl pyrrole latex in parts by weight, stirring at the rotating speed of 380rpm for 1.8min, and then stirring at the rotating speed of 2500rpm for 4min to obtain the butyl pyrrole latex with the modified basalt fiber;
step S2, adding the cationic neoprene latex in parts by weight into the butadiene-pyridine latex with the modified basalt fibers obtained in the step S1, stirring for 2.5min at the rotating speed of 450rpm, then adding the carboxylic styrene-butadiene latex in parts by weight, stirring for 3.5min at the rotating speed of 550rpm, and stirring for 9min at the rotating speed of 3500rpm to obtain mixed latex with the modified basalt fibers;
step S3, adding the vulcanizing agent and the vulcanization accelerator in parts by weight into the mixed latex with the modified basalt fiber obtained in the step S2, stirring and mixing, filling nitrogen while stirring, wherein the filling pressure of the nitrogen is 1.1MPa, uniformly mixing, and spraying by using a spraying gun to obtain a sheet with the thickness of 2 mm;
and S4, conveying the sheet obtained in the step S3 into an oven, treating for 1.5min at the temperature of 145 ℃, then carrying out heat setting treatment for 25min at the temperature of 75 ℃, cooling and standing the obtained product for 17h to obtain the modified basalt fiber/carboxylic styrene-butadiene latex composite foaming material.
Comparative example 1
The styrene-butadiene latex foaming material is prepared from the following raw materials in parts by weight: 100 parts of carboxylic styrene-butadiene latex, 3.5 parts of vulcanizing agent tetramethyl thiuram disulfide and 2 parts of vulcanization accelerator CZ;
the preparation method of the styrene-butadiene latex foaming material comprises the following steps:
step S1, adding the parts by weight of carboxylic styrene-butadiene latex, stirring for 3min at the rotating speed of 500rpm, then stirring for 7.5min at the rotating speed of 2700rpm, then adding the parts by weight of vulcanizing agent and vulcanization accelerator, stirring and mixing, filling nitrogen while stirring, wherein the filling pressure of the nitrogen is 0.9MPa, and spraying by a spraying gun after uniform mixing to obtain a sheet with the thickness of 3 mm;
and S2, conveying the sheet obtained in the step S1 into an oven, treating for 2min at the temperature of 135 ℃, then carrying out heat setting treatment for 40min at the temperature of 70 ℃, cooling and standing the obtained product for 15h to obtain the styrene-butadiene latex foaming material.
Comparative example 2
The styrene-butadiene latex composite foaming material is prepared from the following raw materials in parts by weight: 100 parts of carboxylic styrene-butadiene latex, 12.5 parts of cationic chloroprene latex, 12.5 parts of butadiene-pyridine latex, 3.5 parts of vulcanizing agent tetramethyl thiuram disulfide and 2 parts of vulcanization accelerator CZ;
the preparation method of the styrene-butadiene latex composite foaming material comprises the following steps:
step S1, adding the cationic chloroprene latex in parts by weight into the butadiene-pyridine latex, stirring for 2min at the rotating speed of 400rpm, then adding the carboxylic butylbenzene latex in parts by weight, stirring for 3min at the rotating speed of 500rpm, and stirring for 7.5min at the rotating speed of 2700rpm to obtain mixed latex;
step S2, adding the vulcanizing agent and the vulcanization accelerator in parts by weight into the mixed latex obtained in the step S1, stirring and mixing, filling nitrogen while stirring, wherein the filling pressure of the nitrogen is 0.9MPa, and spraying by a spraying gun after uniformly mixing to obtain a sheet with the thickness of 3 mm;
and S4, conveying the sheet obtained in the step S3 into an oven, treating for 2min at the temperature of 135 ℃, then carrying out heat setting treatment for 40min at the temperature of 70 ℃, cooling and standing the obtained product for 15h to obtain the styrene-butadiene latex composite foaming material.
Comparative example 3
The modified basalt fiber/carboxylic styrene-butadiene latex composite foaming material is prepared from the following raw materials in parts by weight: 100 parts of carboxylic styrene-butadiene latex, 12.5 parts of cationic chloroprene latex, 7.5 parts of modified basalt fiber, 3.5 parts of vulcanizing agent tetramethyl thiuram disulfide and 2 parts of vulcanization accelerator CZ;
the method for modifying the modified basalt fiber comprises the following steps:
step I, soaking basalt fibers in concentrated sulfuric acid for 9 hours to obtain sulfonated basalt fibers;
step II, dissolving polyacrylamide with the number average molecular weight of 90 ten thousand in water to obtain a polyacrylamide solution with the mass fraction of 1.75%;
step III, soaking the sulfonated basalt fiber obtained in the step I in the polyacrylamide solution obtained in the step II, heating to 55 ℃, and curing at constant temperature for 6.5 hours; and taking out the obtained product, cleaning, drying, preserving heat for 1.5 hours at the temperature of 350 ℃, and grinding the obtained product to obtain the modified basalt fiber.
The preparation method of the modified basalt fiber/carboxylic styrene-butadiene latex composite foaming material comprises the following steps:
step S1, adding the modified basalt fiber in parts by weight into the cationic neoprene latex in parts by weight, stirring for 2min at the rotating speed of 400rpm, then adding the carboxylic styrene-butadiene latex in parts by weight, stirring for 3min at the rotating speed of 500rpm, and stirring for 7.5min at the rotating speed of 2700rpm to obtain mixed latex with the modified basalt fiber;
step S2, adding the vulcanizing agent and the vulcanization accelerator in parts by weight into the mixed latex with the modified basalt fiber obtained in the step S1, stirring and mixing, filling nitrogen while stirring, wherein the filling pressure of the nitrogen is 0.9MPa, uniformly mixing, and spraying by using a spraying gun to obtain a sheet with the thickness of 3 mm;
and S4, conveying the sheet obtained in the step S3 into an oven, treating for 2min at the temperature of 135 ℃, then carrying out heat setting treatment for 40min at the temperature of 70 ℃, and cooling and standing the obtained product for 15h to obtain the modified basalt fiber/carboxylic styrene-butadiene latex composite foaming material.
Comparative example 4
The basalt fiber/styrene-butadiene latex composite foaming material is prepared from the following raw materials in parts by weight: 100 parts of carboxylic styrene-butadiene latex, 12.5 parts of cationic chloroprene latex, 12.5 parts of butadiene-pyridine latex, 7.5 parts of basalt fiber, 3.5 parts of vulcanizing agent tetramethyl thiuram disulfide and 2 parts of vulcanization accelerator CZ;
the preparation method of the basalt fiber/styrene-butadiene latex composite foaming material comprises the following steps:
step S1, adding the basalt fibers in parts by weight into the butadiene-pyridine latex in parts by weight, stirring for 1.5min at the rotating speed of 350rpm, and then stirring for 3.5min at the rotating speed of 2000rpm to obtain the butadiene-pyridine latex with the basalt fibers;
step S2, adding the cationic neoprene latex in parts by weight into the butadiene-pyridine latex with basalt fibers obtained in the step S1, stirring for 2min at the rotating speed of 400rpm, then adding the carboxylic styrene-butadiene latex in parts by weight, stirring for 3min at the rotating speed of 500rpm, and then stirring for 7.5min at the rotating speed of 2700rpm to obtain mixed latex with basalt fibers;
step S3, adding the vulcanizing agent and the vulcanization accelerator in parts by weight into the mixed latex with basalt fibers obtained in the step S2, stirring and mixing, filling nitrogen while stirring, wherein the filling pressure of the nitrogen is 0.9MPa, uniformly mixing, and spraying by using a spraying gun to obtain a sheet with the thickness of 3 mm;
and S4, conveying the sheet obtained in the step S3 into an oven, treating for 2min at the temperature of 135 ℃, then carrying out heat setting treatment for 40min at the temperature of 70 ℃, cooling and standing the obtained product for 15h to obtain the basalt fiber/styrene-butadiene latex composite foaming material.
Examples of the experiments
To further illustrate the technological advancement of the present invention, experiments are now taken to further illustrate it.
The modified basalt fiber/carboxylic styrene-butadiene latex composite foaming materials produced in the embodiments 1 to 5 of the invention are subjected to performance tests on the hardness, stress at definite elongation, tear strength and compression set of various materials under the same condition, and the test results are shown in table 1. Wherein, the tearing performance is tested according to GB/T528-2009, and the hardness is tested according to GB/T531.1-2008.
Table 1 test results of modified basalt fiber/carboxylated styrene-butadiene latex composite foam materials prepared in examples 1 to 5
Experimental results show that compared with a comparative example, the modified basalt fiber/carboxylic styrene-butadiene latex composite foaming material prepared in the embodiments 1-5 has the advantages that the hardness and the mechanical strength are greatly improved, the compression permanent deformation is greatly reduced, and the composite foaming material prepared by adopting the modified basalt fiber reinforced carboxylic styrene-butadiene latex has excellent performance and good product stability, is expected to be widely applied to the field of sole materials, and has an excellent prospect.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The modified basalt fiber/carboxylic styrene-butadiene latex composite foaming material is characterized in that the raw materials for preparing the modified basalt fiber/carboxylic styrene-butadiene latex composite foaming material and the parts by weight of the raw materials comprise: 100 parts of carboxylic styrene-butadiene latex, 10-15 parts of cationic neoprene latex, 10-15 parts of butadiene-pyridine latex, 5-10 parts of modified basalt fiber, 2-5 parts of vulcanizing agent and 1-3 parts of vulcanization accelerator;
the method for modifying the modified basalt fiber comprises the following steps:
step I, soaking basalt fibers in concentrated sulfuric acid to obtain sulfonated basalt fibers;
step II, dissolving polyacrylamide in water to obtain a polyacrylamide solution with the mass fraction of 0.5-3%;
step III, dipping the sulfonated basalt fiber obtained in the step I into the polyacrylamide solution obtained in the step II, heating to 50-60 ℃, and curing at constant temperature for 1-12 h; taking out the obtained product, washing, drying, preserving heat for 1-2 h at the temperature of 300-400 ℃, and grinding the obtained product to obtain the modified basalt fiber.
2. The modified basalt fiber/carboxylated styrene-butadiene latex composite foamed material according to claim 1, wherein the vulcanizing agent comprises: tetramethylthiuram disulfide or sulfur.
3. The modified basalt fiber/carboxylated styrene-butadiene latex composite foamed material according to claim 1, wherein the vulcanization accelerator comprises: one or more of vulcanization accelerator TT, vulcanization accelerator D and vulcanization accelerator CZ.
4. The modified basalt fiber/carboxylic styrene-butadiene latex composite foaming material according to claim 1, wherein the dipping time in the step I is 6 to 12 hours.
5. The modified basalt fiber/carboxylic styrene-butadiene latex composite foaming material according to claim 1, wherein in the step II, the number average molecular weight of the polyacrylamide is as follows: 80 to 100 ten thousand.
6. The preparation method of the modified basalt fiber/carboxylic styrene-butadiene latex composite foaming material according to any one of claims 1 to 5, characterized by comprising the following steps:
step S1, adding the modified basalt fiber in parts by weight into the butadiene-pyridine latex in parts by weight, stirring for 1 min-2 min at the rotating speed of 300 rpm-400 rpm, and then stirring for 2 min-5 min at the rotating speed of 1000 rpm-3000 rpm to obtain the butadiene-pyridine latex with the modified basalt fiber;
step S2, adding the cationic neoprene latex in parts by weight into the butadiene-pyridine latex with the modified basalt fibers obtained in the step S1, stirring for 1 min-3 min at the rotating speed of 300 rpm-500 rpm, then adding the carboxylic styrene-butadiene latex in parts by weight, stirring for 2 min-4 min at the rotating speed of 400 rpm-600 rpm, and stirring for 5 min-10 min at the rotating speed of 1500 rpm-4000 rpm to obtain mixed latex with the modified basalt fibers;
step S3, adding the vulcanizing agent and the vulcanization accelerator in parts by weight into the mixed latex with the modified basalt fiber obtained in the step S2, stirring and mixing, filling nitrogen while stirring, uniformly mixing, and spraying by a spraying gun to obtain a sheet;
and S4, conveying the sheet obtained in the step S3 to an oven for processing, then carrying out heat setting processing, cooling and placing the obtained product for 12-18 h, and obtaining the modified basalt fiber/carboxylic styrene-butadiene latex composite foaming material.
7. The production method according to claim 6, wherein in step S3, the filling pressure of the nitrogen gas is 0.6MPa to 1.2 MPa.
8. The production method according to claim 6, wherein in step S3, the sheet has a thickness of 1mm to 5 mm.
9. The method according to claim 6, wherein in step S4, the process conditions for the treatment in the oven are as follows: the treatment is carried out for 1min to 3min under the condition that the temperature is 120 ℃ to 150 ℃.
10. The method according to claim 6, wherein in step S4, the heat-setting treatment process conditions are as follows: heat setting treatment is carried out for 20min to 60min under the temperature condition of 60 ℃ to 80 ℃.
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Effective date of registration: 20230404 Address after: No. 1466, Haining Road, Haibin Street, Longwan District, Wenzhou City, Zhejiang Province 325,024 Patentee after: WENZHOU YIHE SHOE MATERIAL Co.,Ltd. Address before: 325000 Wenzhou City National University Science Park incubator, No. 38 Dongfang South Road, Ouhai District, Wenzhou, Zhejiang Patentee before: WENZHOU VOCATIONAL & TECHNICAL College |