CN112500614A - Flame-retardant anti-static outsole rubber and preparation method thereof - Google Patents
Flame-retardant anti-static outsole rubber and preparation method thereof Download PDFInfo
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- CN112500614A CN112500614A CN202011202739.2A CN202011202739A CN112500614A CN 112500614 A CN112500614 A CN 112500614A CN 202011202739 A CN202011202739 A CN 202011202739A CN 112500614 A CN112500614 A CN 112500614A
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 81
- 239000005060 rubber Substances 0.000 title claims abstract description 81
- 239000003063 flame retardant Substances 0.000 title claims abstract description 80
- 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 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 37
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 30
- 239000012763 reinforcing filler Substances 0.000 claims abstract description 15
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 13
- 150000002367 halogens Chemical class 0.000 claims abstract description 13
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 12
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 11
- 239000011593 sulfur Substances 0.000 claims abstract description 11
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052796 boron Inorganic materials 0.000 claims abstract description 10
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012936 vulcanization activator Substances 0.000 claims abstract description 6
- 229920003051 synthetic elastomer Polymers 0.000 claims abstract description 4
- 239000005061 synthetic rubber Substances 0.000 claims abstract description 4
- 238000007670 refining Methods 0.000 claims description 21
- 238000010074 rubber mixing Methods 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 19
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 14
- 235000021355 Stearic acid Nutrition 0.000 claims description 13
- 239000006229 carbon black Substances 0.000 claims description 13
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 13
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 12
- 239000008117 stearic acid Substances 0.000 claims description 12
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 10
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 239000008036 rubber plasticizer Substances 0.000 claims description 8
- 239000011787 zinc oxide Substances 0.000 claims description 8
- 239000012188 paraffin wax Substances 0.000 claims description 7
- 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 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 5
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 claims description 5
- MZCHBOYMVBQHQC-UHFFFAOYSA-N n-(4-chloro-2-methylphenyl)-n'-methylmethanimidamide Chemical compound CN=CNC1=CC=C(Cl)C=C1C MZCHBOYMVBQHQC-UHFFFAOYSA-N 0.000 claims description 5
- 238000007790 scraping Methods 0.000 claims description 5
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims 2
- 230000001070 adhesive effect Effects 0.000 claims 2
- 239000004826 Synthetic adhesive Substances 0.000 claims 1
- 238000004073 vulcanization Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 5
- 244000043261 Hevea brasiliensis Species 0.000 abstract description 2
- 229920003052 natural elastomer Polymers 0.000 abstract description 2
- 229920001194 natural rubber Polymers 0.000 abstract description 2
- 230000000704 physical effect Effects 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 12
- 238000003825 pressing Methods 0.000 description 10
- 238000002485 combustion reaction Methods 0.000 description 6
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 4
- 239000006082 mold release agent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical group C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 235000021314 Palmitic acid Nutrition 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/02—Soles; Sole-and-heel integral units characterised by the material
- A43B13/04—Plastics, rubber or vulcanised fibre
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
-
- 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
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- 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
- C08L2201/00—Properties
- C08L2201/04—Antistatic
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses flame-retardant antistatic outsole rubber which comprises, by weight, 65-75 parts of No. 2 standard rubber, 25-35 synthetic rubber, 1-3 parts of sulfur, 3-4.8 parts of an accelerator, 6-10 parts of a vulcanization activator, 1-3 parts of an anti-aging agent, 0.5-0.7 part of a release agent, 45-55 parts of a reinforcing filler, 10-21 parts of a softening system, 9.8-11.8 parts of an antimony flame retardant, 44.66-48.66 parts of a halogen flame retardant and 17.75-19.75 parts of a boron flame retardant. The invention takes natural rubber and butadiene styrene rubber as main materials, ensures the physical properties of rubber materials by adding reinforcing filler and softening system, ensures the service life of rubber soles, and provides excellent flame retardant performance for products by using antimony, halogen and boron flame retardants as flame retardant systems. The method is simple, low in cost and good in using effect.
Description
Technical Field
The invention relates to rubber and a preparation method thereof, in particular to sole rubber and a preparation method thereof.
Background
As is well known, rubber shoes are always flammable and insulating, but with the progress and development of modern society, various potential safety hazards caused by static electricity and working rubber shoes with good flame retardant performance need to be eliminated in partial workplaces, so that the partial markets need rubber shoes with antistatic performance and have different requirements on the electric conductivity and the flame retardant performance of the rubber shoes, and therefore a series of flame retardant and antistatic rubber shoes gradually enter the rubber shoe market. In the process of manufacturing shoes, particularly flame-retardant and anti-static rubber shoes, the sole is the most important part because the sole is in direct contact with a burning object and a human body, so that the flame-retardant and anti-static sole is the most important part of the flame-retardant and anti-static rubber shoes and must have good flame-retardant performance and electrical conductivity. Meanwhile, the flame-retardant and anti-static sole is simple in manufacturing process and low in cost, and can better meet the requirements of the market. Therefore, the invention of the antistatic substrate rubber with simple process and low cost has practical significance.
Disclosure of Invention
The purpose of the invention is: the flame-retardant antistatic outsole rubber and the preparation method thereof have the advantages of good flame-retardant property, good smoke suppression effect, no toxicity in smoke and long service life of products, can prevent liquid drops from transmitting fire and overcome the defects of the prior art.
The invention is realized by the following steps: the flame-retardant antistatic outsole rubber comprises, by weight, 65-75 parts of No. 2 standard rubber, 25-35 parts of synthetic rubber, 1-3 parts of sulfur, 3-4.8 parts of an accelerator, 6-10 parts of a vulcanization activator, 1-3 parts of an anti-aging agent, 0.5-0.7 part of a mold release agent, 45-55 parts of a reinforcing filler, 10-20 parts of a softening system, 9.8-11.8 parts of an antimony flame retardant, 44.66-48.66 parts of a halogen flame retardant and 17.75-19.75 parts of a boron flame retardant
The more preferable technical scheme is that the flame retardant comprises, by weight, 70 parts of No. 2 standard rubber, 30 parts of styrene-butadiene rubber, 2 parts of sulfur, 3.9 parts of an accelerator, 3 parts of stearic acid, 5 parts of nano zinc oxide, 0.6 part of a release agent, 45 parts of carbon black, 5 parts of conductive carbon black, 15 parts of a liquid environment-friendly rubber plasticizer, 10.8 parts of an antimony flame retardant, 46.66 parts of a halogen flame retardant and 18.75 parts of a boron flame retardant.
The synthetic rubber is styrene butadiene rubber.
Every 3.9 parts of accelerator consists of 0.9 part of accelerator DCDM, 1.1 parts of accelerator DCM, 0.7 part of accelerator CZ and 1.2 parts of accelerator D.
Every 8 parts of vulcanization activator comprises 3 parts of tertiary stearic acid and 5 parts of nano zinc oxide.
Every 2 parts of the anti-aging agent consists of 0.3 part of anti-aging agent RD and 1.7 parts of anti-aging agent 4010 NA.
15 parts of environment-friendly rubber plasticizer per 15 parts of softening system
Each 50 parts of reinforcing filler is composed of 45 parts of carbon black and 5 parts of conductive carbon black.
Every 46.66 parts of halogen flame retardant consists of 25 parts of chlorinated paraffin and 21.66 parts of decabromodiphenyl ether
Adding 2# standard rubber, butadiene styrene rubber, light magnesium oxide, a flame retardant, an anti-aging agent and carbon black into an internal mixer, pressurizing and mixing rubber for 4-6 minutes, lifting a top bolt to scrape rubber when the load of a rubber mixing machine is reduced to 240, conveying the material at the mouth of the internal mixer into an internal mixing chamber, scraping the material in 15-25 seconds, returning the top bolt to the right position, continuing to press and mixing, and then pressing and mixing for 2-4 minutes after the load of the rubber mixing machine is lifted, so that the load of the rubber mixing machine is increased to more than 160 to discharge, thus obtaining the rubber mixing belt; standing the master batch for 12 hours, adding the master batch, conductive carbon black, chlorinated paraffin, aluminum hydroxide and a medium material into an internal mixer, performing pressure refining for 2-3 minutes, putting into a softening system, performing pressure refining for 3-5 minutes, lifting a top bolt to scrape the rubber, performing pressure refining for 2 minutes, and performing rubber refining for 1 minute after the rubber is lifted to load when the internal of the internal mixer generates a muffling sound due to the friction of the rubber material, thus obtaining a finished product.
The medium materials comprise sulfur, an accelerator, stearic acid, nano zinc oxide, a release agent and a reinforcing filler.
The flame retardant property detection method comprises the following steps: according to a vertical method in GB/T10707-2008, refining rubber materials on an open mill, wrapping rollers to discharge bubbles, discharging sheets, wherein the thickness of the discharged sheets is about 3.0mm, then putting a film into a special rubber flame-retardant detection adhesive tape die, and manufacturing a rubber flame-retardant strip under the condition of 150 ℃ multiplied by 4min, wherein the specification of the flame-retardant strip is as follows: 130mm long, 13mm wide and 3mm thick, then vertically burning the sample on an alcohol lamp, simultaneously timing by a stopwatch, moving the flame after burning for 10 seconds for the first time, recording the flaming burning time, then returning the stopwatch to zero, then burning for 10 seconds for the second time, simultaneously timing, moving the flame after 10 seconds, simultaneously recording the flaming burning time and flameless burning time of the sample, and requiring that the flame retardant property reaches FV-0 level.
And (3) judging the flame retardant grade:
the standard glue is classified according to international uniform physical and chemical properties and indexes, the physical and chemical properties comprise seven items of impurity content, initial plastic value, plastic retention rate, nitrogen content, volatile matter content, ash content, color index and the like, wherein the impurity content is taken as a main index, and the standard glue is divided into five grades of 5L, 5, 10, 20, 50 and the like according to the amount of impurities.
The stearic acid industry is in white or yellowish granules or chunks, a mixture of 45% stearic acid and 55% palmitic acid, and contains a small amount of oleic acid, with a slight fatty odour. The industrial product is divided into a first grade (old called three-pressing, and subjected to three-pressing), a second grade (old called two-pressing, and subjected to two-pressing), and a third grade (old called one-pressing, and subjected to one-pressing or not). Is a mixed acid mainly comprising stearic acid and palmitic acid. The primary and secondary stearic acids are white waxy solids with a gloss or grain. Tertiary stearic acid is a light yellow waxy solid.
The chemical name of the anti-aging agent RD is 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer; the chemical name of the anti-aging agent 4010NA is N-phenyl-N' -yl-p-phenylenediamine.
The working principle of the invention is that the antimony, halogen and boron flame retardants can form gas, a carbonized layer and partial water vapor which have higher density than air and can stay on a combustion object for a long time at high temperature, so as to achieve the flame retardant effect under the action of diluting oxygen and isolating air.
The UL94 fire rating is 94HB, 94V, 94-5V.
A) Grade 94 HB: i.e. when the test piece is ignited in a horizontal mode, 1) the thickness of the test piece is less than 3.05mm, and the burning speed is less than 76.2 mm/min; 2) the thickness of the test piece is 3.05-12.7 mm, and the burning speed is less than 38.1 mm/min; this is a 94HB level minimum requirement.
B)94V level: the test piece can reach the following standard when being vertically burnt, and can be divided into three stages of V-0, V-1 and V-2. Wherein
V-0 level: when each flame was removed, the test piece ignited no more than 10 seconds and no sparks dropped to surgical cotton 305mm from the test piece to ignite the ignition point and no residual flame for more than 30 seconds.
V-1 grade: the same as V-0, except that the test piece had to be extinguished within 30 seconds and had no residual combustion after 60 seconds.
V-2 level: same as V-0 except that there are starred drops that catch fire on the dried cotton.
94V-0 level: the flame does not support combustion for 15 seconds (1000BTU) and can be automatically fried and extinguished;
94V-1 level: the flame dropped for 30 seconds (1000BTU), but no flame was generated.
94V-2 level: the flame man will drop in 30 seconds (1000BTU), has flame, but will not ignite cotton, and will self-extinguish.
94 HB: OBTU is almost non-fire-resistant.
The flame retardant grade is gradually increased from HB, V-2, V-1 to V-0:
1) HB: the lowest flame retardant rating in the UL94 standard. Requiring a burn rate of less than 40 mm per minute for samples 3 to 13mm thick; a sample less than 3mm thick with a burning rate less than 70 mm per minute; or extinguished before the 100 mm mark.
2) V-2: after two 10 second burn tests on the samples, the flame extinguished within 60 seconds. There may be combustion products falling.
3) V-1: after two 10 second burn tests on the samples, the flame extinguished within 60 seconds. No combustible material can fall off.
4) V-0: after two 10 second burn tests on the samples, the flame extinguished within 30 seconds. No combustible material can fall off.
By adopting the technical scheme, compared with the prior art, the natural rubber and the styrene-butadiene rubber are used as main materials, the physical properties of the rubber material are ensured by adding the reinforcing filler and the softening system, so that the product has the advantages of wear resistance, skid resistance, wear resistance and the like, the service life of the rubber sole is ensured, and excellent flame retardant property and antistatic property are provided for the product by using the antimony, halogen and boron flame retardants as a flame retardant system and conductive carbon black; the product also generates a carbon layer during combustion to adsorb melted and ignited polymers, can prevent liquid drops from transmitting fire, has good flame retardant effect and electric conductivity, overcomes the defect of non-conductivity of NR + SBR rubber compound which is extremely easy to combust, has the flame retardant grade reaching FV-0 grade, meets the self-extinguishing requirement in a vertical combustion test, and has the resistance value of 0.1-100K omega at the bottom of the rubber sole. The method is simple, low in cost and good in using effect.
To further verify the effect of the present invention, the following experiment was performed:
first, research on optimum mixture ratio of raw materials
Table 1: research on optimum ratio of skeleton material
Table 2: research on optimal proportion of filling reinforcing agent, softening agent and flame-retardant material
According to the test results in tables 1 and 2, the optimal formula is as follows: the flame retardant coating comprises 70 parts of No. 2 standard rubber, 30 parts of butadiene styrene rubber, 2 parts of sulfur, 3.9 parts of an accelerator, 3 parts of stearic acid, 5 parts of nano zinc oxide, 0.6 part of a release agent, 2 parts of an anti-aging agent, 45 parts of carbon black, 5 parts of conductive carbon black, 15 parts of a liquid environment-friendly rubber plasticizer, 10.8 parts of an antimony flame retardant, 46.66 parts of a halogen flame retardant and 18.75 parts of a boron flame retardant.
Detailed Description
Example 1 of the invention: the flame-retardant antistatic rubber comprises, by weight, 65 parts of No. 2 standard rubber, 35 parts of styrene-butadiene rubber, 2 parts of sulfur, 3 parts of an accelerator (each 3 parts of the accelerator consists of 0.8 part of an accelerator DCDM, 1 part of an accelerator DCM, 0.4 part of an accelerator CZ and 0.8 part of an accelerator D), 3 parts of tertiary stearic acid, 5 parts of nano zinc oxide, 0.6 part of a mold release agent, 2 parts of an anti-aging agent (each 2 parts of the anti-aging agent consists of 0.3 part of an anti-aging agent RD and 1.7 parts of an anti-aging agent 4010 NA), 50 parts of a reinforcing filler (each 50 parts of the reinforcing filler consists of 45 parts of carbon black and 5 parts of conductive carbon black), 15 parts of a softening system (each 18 parts of the softening system consists of 15 parts of a liquid environment-friendly rubber plasticizer), 9.8 parts of an antimony flame retardant, 44.66 parts of a halogen-series flame retardant.
Adding 2# standard rubber, butadiene styrene rubber, light magnesium oxide, a flame retardant, an anti-aging agent and carbon black into an internal mixer, pressurizing and mixing rubber for 4-6 minutes, lifting a top bolt to scrape rubber when the load of a rubber mixing machine is reduced to 240, conveying the material at the mouth of the internal mixer into an internal mixing chamber, scraping the material in 15-25 seconds, returning the top bolt to the right position, continuing to press and mixing, and then pressing and mixing for 2-4 minutes after the load of the rubber mixing machine is lifted, so that the load of the rubber mixing machine is increased to more than 160 to discharge, thus obtaining the rubber mixing belt; standing the master batch for 12 hours, adding the master batch, conductive carbon black, chlorinated paraffin, aluminum hydroxide and a medium material into an internal mixer, performing pressure refining for 2-3 minutes, putting into a softening system, performing pressure refining for 3-5 minutes, lifting a top bolt to scrape the rubber, performing pressure refining for 2 minutes, and performing rubber refining for 1 minute after the rubber is lifted to load when the internal of the internal mixer generates a muffling sound due to the friction of the rubber material, thus obtaining a finished product.
Example 2 of the invention: the flame-retardant antistatic rubber comprises, by weight, 70 parts of No. 2 standard rubber, 30 parts of styrene-butadiene rubber, 2 parts of sulfur, 3 parts of an accelerator (each 3.9 parts of the accelerator consists of 0.9 part of an accelerator DCDM, 1.1 parts of an accelerator DCM, 0.7 part of an accelerator CZ and 1.2 parts of an accelerator D), 3 parts of tertiary stearic acid, 5 parts of nano zinc oxide, 0.6 part of a mold release agent, 2 parts of an anti-aging agent (each 2 parts of the anti-aging agent consists of 0.3 part of an anti-aging agent RD and 1.7 parts of an anti-aging agent 4010 NA), 50 parts of a reinforcing filler (each 50 parts of the reinforcing filler consists of 45 parts of carbon black and 5 parts of conductive carbon black), 15 parts of a softening system (each 18 parts of the softening system consists of 15 parts of a liquid environment-friendly rubber plasticizer), 10.8 parts of an antimony flame retardant, 46.66 parts of a halogen flame retardant and 18.
Adding 2# standard rubber, butadiene styrene rubber, light magnesium oxide, a flame retardant, an anti-aging agent and carbon black into an internal mixer, pressurizing and mixing rubber for 4-6 minutes, lifting a top bolt to scrape rubber when the load of a rubber mixing machine is reduced to 240, conveying the material at the mouth of the internal mixer into an internal mixing chamber, scraping the material in 15-25 seconds, returning the top bolt to the right position, continuing to press and mixing, and then pressing and mixing for 2-4 minutes after the load of the rubber mixing machine is lifted, so that the load of the rubber mixing machine is increased to more than 160 to discharge, thus obtaining the rubber mixing belt; standing the master batch for 12 hours, adding the master batch, conductive carbon black, chlorinated paraffin, aluminum hydroxide and a medium material into an internal mixer, performing pressure refining for 2-3 minutes, putting into a softening system, performing pressure refining for 3-5 minutes, lifting a top bolt to scrape the rubber, performing pressure refining for 2 minutes, and performing rubber refining for 1 minute after the rubber is lifted to load when the internal of the internal mixer generates a muffling sound due to the friction of the rubber material, thus obtaining a finished product.
Example 3 of the invention: the flame-retardant antistatic rubber comprises, by weight, 75 parts of No. 2 standard rubber, 25 parts of styrene-butadiene rubber, 2 parts of sulfur, 3 parts of an accelerator (4.8 parts of the accelerator comprises 1.2 parts of an accelerator DCDM, 1.5 parts of an accelerator DCM, 1.2 parts of an accelerator CZ and 0.9 part of an accelerator D), 3 parts of tertiary stearic acid, 5 parts of nano zinc oxide, 0.6 part of a mold release agent, 2 parts of an anti-aging agent (2 parts of the anti-aging agent comprises 0.3 part of an anti-aging agent RD and 1.7 parts of an anti-aging agent 4010 NA), 50 parts of a reinforcing filler (50 parts of the reinforcing filler comprises 45 parts of carbon black and 5 parts of conductive carbon black), 15 parts of a softening system (18 parts of the softening system comprises 15 parts of a liquid environment-friendly rubber plasticizer), 11.8 parts of an antimony flame retardant, 38.92 parts of a halogen flame retardant and 19.75 parts of a boron flame.
Adding 2# standard rubber, butadiene styrene rubber, light magnesium oxide, a flame retardant, an anti-aging agent and carbon black into an internal mixer, pressurizing and mixing rubber for 4-6 minutes, lifting a top bolt to scrape rubber when the load of a rubber mixing machine is reduced to 240, conveying the material at the mouth of the internal mixer into an internal mixing chamber, scraping the material in 15-25 seconds, returning the top bolt to the right position, continuing to press and mixing, and then pressing and mixing for 2-4 minutes after the load of the rubber mixing machine is lifted, so that the load of the rubber mixing machine is increased to more than 160 to discharge, thus obtaining the rubber mixing belt; standing the master batch for 12 hours, adding the master batch, conductive carbon black, chlorinated paraffin, aluminum hydroxide and a medium material into an internal mixer, performing pressure refining for 2-3 minutes, putting into a softening system, performing pressure refining for 3-5 minutes, lifting a top bolt to scrape the rubber, performing pressure refining for 2 minutes, and performing rubber refining for 1 minute after the rubber is lifted to load when the internal of the internal mixer generates a muffling sound due to the friction of the rubber material, thus obtaining a finished product.
Claims (10)
1. The flame-retardant antistatic outsole rubber is characterized in that: the adhesive comprises, by weight, 65-75 parts of No. 2 standard adhesive, 25-35 parts of synthetic adhesive, 1-3 parts of sulfur, 3-4.8 parts of an accelerator, 6-10 parts of a vulcanization activator, 1-3 parts of an anti-aging agent, 0.5-0.7 part of a release agent, 45-55 parts of a reinforcing filler, 10-20 parts of a softening system, 9.8-11.8 parts of an antimony flame retardant, 44.66-48.66 parts of a halogen flame retardant and 17.75-19.75 parts of a boron flame retardant.
2. The flame-retardant antistatic outsole rubber as claimed in claim 1, wherein: the flame retardant rubber comprises, by weight, 70 parts of No. 2 standard rubber, 30 parts of styrene-butadiene rubber, 2 parts of sulfur, 3.9 parts of an accelerator, 8 parts of a vulcanization activator, 0.6 part of a release agent, 2 parts of an anti-aging agent, 45 parts of carbon black, 5 parts of conductive carbon black, 15 parts of a liquid environment-friendly rubber plasticizer, 10.8 parts of an antimony flame retardant, 46.66 parts of a halogen flame retardant and 18.75 parts of a boron flame retardant.
3. The flame-retardant antistatic outsole rubber according to claim 1 or 2, characterized in that: the synthetic rubber is styrene butadiene rubber.
4. The flame-retardant antistatic outsole rubber according to claim 1 or 2, characterized in that: every 3.9 parts of accelerator consists of 0.9 part of accelerator DCDM, 1.1 parts of accelerator DCM, 0.7 part of accelerator CZ and 1.2 parts of accelerator D.
5. The flame-retardant antistatic outsole rubber according to claim 1 or 2, characterized in that: every 8 parts of vulcanization activator comprises 3 parts of third-grade stearic acid and 5 parts of nano zinc oxide.
6. The flame-retardant antistatic outsole rubber according to claim 1 or 2, characterized in that: every 2 parts of the anti-aging agent consists of 0.3 part of anti-aging agent RD and 1.7 parts of anti-aging agent 4010 NA.
7. The flame-retardant antistatic outsole rubber according to claim 1 or 2, characterized in that: the softening system is an environment-friendly rubber plasticizer.
8. The flame-retardant antistatic outsole rubber according to claim 1 or 2, characterized in that: each 50 parts of reinforcing filler is composed of 45 parts of carbon black and 5 parts of conductive carbon black.
9. The flame-retardant antistatic outsole rubber according to claim 1 or 2, characterized in that: each 46.66 parts of the halogen flame retardant comprises 25 parts of chlorinated paraffin and 21.66 parts of decabromodiphenyl ether.
10. The preparation method of the flame-retardant antistatic outsole rubber is characterized by comprising the following steps of: taking the components according to the weight parts, adding 2# standard rubber, butadiene styrene rubber, light magnesium oxide, a flame retardant, an anti-aging agent and carbon black into an internal mixer, carrying out pressurized rubber mixing for 4-6 minutes, lifting a top bolt to scrape rubber when the load of the rubber mixing machine is reduced to 240, conveying the material at the mouth of the internal mixer into an internal mixing chamber, scraping the top bolt in 15-25 seconds, returning the top bolt to the right position, continuing to carry out pressure mixing, carrying out pressure mixing for 2-4 minutes after the load of the rubber mixing machine is lifted, and returning the load of the rubber mixing machine to more than 160 for discharging to obtain the rubber mixing belt; standing the master batch for 12 hours, adding the master batch, conductive carbon black, chlorinated paraffin, aluminum hydroxide and a medium material into an internal mixer, performing pressure refining for 2-3 minutes, putting into a softening system, performing pressure refining for 3-5 minutes, lifting a top bolt to scrape the rubber, performing pressure refining for 2 minutes, and performing rubber refining for 1 minute after the rubber is lifted to load when the sound of pounding is generated in the internal mixer due to the friction of the rubber material, thus obtaining a finished product; wherein the medium materials comprise sulfur, an accelerator, a vulcanization accelerator, a release agent and a reinforcing filler.
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Application publication date: 20210316 |