CN107540897B - Preparation method of flame-retardant softener for styrene butadiene rubber - Google Patents
Preparation method of flame-retardant softener for styrene butadiene rubber Download PDFInfo
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- CN107540897B CN107540897B CN201610474918.9A CN201610474918A CN107540897B CN 107540897 B CN107540897 B CN 107540897B CN 201610474918 A CN201610474918 A CN 201610474918A CN 107540897 B CN107540897 B CN 107540897B
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 77
- 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 70
- 229920003048 styrene butadiene rubber Polymers 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000005060 rubber Substances 0.000 claims abstract description 62
- 229920001971 elastomer Polymers 0.000 claims abstract description 56
- 239000002904 solvent Substances 0.000 claims description 28
- 239000003054 catalyst Substances 0.000 claims description 23
- -1 isopentenyl Chemical group 0.000 claims description 22
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 21
- 238000005865 alkene metathesis reaction Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000003292 glue Substances 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 11
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 239000012327 Ruthenium complex Substances 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims description 2
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 claims 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 26
- 229910052760 oxygen Inorganic materials 0.000 abstract description 26
- 239000001301 oxygen Substances 0.000 abstract description 26
- 241001441571 Hiodontidae Species 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 19
- 238000012360 testing method Methods 0.000 description 14
- 238000002156 mixing Methods 0.000 description 10
- 239000004902 Softening Agent Substances 0.000 description 9
- 239000010692 aromatic oil Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- UWTUEMKLYAGTNQ-OWOJBTEDSA-N (e)-1,2-dibromoethene Chemical group Br\C=C\Br UWTUEMKLYAGTNQ-OWOJBTEDSA-N 0.000 description 4
- APQIUTYORBAGEZ-UHFFFAOYSA-N 1,1-dibromoethane Chemical group CC(Br)Br APQIUTYORBAGEZ-UHFFFAOYSA-N 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000012433 hydrogen halide Substances 0.000 description 4
- 229910000039 hydrogen halide Inorganic materials 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000000779 smoke Substances 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- 239000002174 Styrene-butadiene Substances 0.000 description 3
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 3
- 239000010426 asphalt Substances 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000012796 inorganic flame retardant Substances 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000010057 rubber processing Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- LGXVIGDEPROXKC-UHFFFAOYSA-N 1,1-dichloroethene Chemical group ClC(Cl)=C LGXVIGDEPROXKC-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- BBZZUDQCNMQSSE-UHFFFAOYSA-L [Ru](Cl)Cl.C(C)(C)OC1=C(C=C2C(CCCC2)P(C2CCCCC2)C2CCCCC2)C=CC=C1 Chemical compound [Ru](Cl)Cl.C(C)(C)OC1=C(C=C2C(CCCC2)P(C2CCCCC2)C2CCCCC2)C=CC=C1 BBZZUDQCNMQSSE-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 150000001638 boron Chemical class 0.000 description 1
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920005558 epichlorohydrin rubber Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 229920002681 hypalon Polymers 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229940099259 vaseline Drugs 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a preparation method of a styrene butadiene rubber flame-retardant softener. The flame-retardant softener can reduce the Mooney index of base rubber by 0.2-2.0 units/part and improve the oxygen index by 0.1-1.0%/part by adding styrene butadiene rubber into an open mill.
Description
Technical Field
The invention relates to a preparation method of a butadiene styrene rubber softener, in particular to a low-molecular-weight butadiene styrene rubber softener with a flame-retardant function.
Background
The flame retardant method in the rubber field mainly comprises two methods of adding a flame retardant and blending with flame retardant rubber. The flame retardant is added with inorganic flame retardant and organic flame retardant, the inorganic flame retardant generally has cooling and blocking effects, and common varieties comprise aluminum hydroxide, magnesium hydroxide, boron series substances, molybdenum series substances and the like; the organic flame retardant is mainly bromine, chlorine or phosphorus-containing organic compounds, and bromine flame retardant can release hydrogen bromide during combustion to play a role in blocking oxygen. It was proposed by Zhi et al in "flame retardant rubber shallow analysis" (world rubber industry, vol. 31, No. 4, p.39) to add 15 parts of Sb to SBR2O3And 30 parts of chlorinated paraffin or 5 parts of Sb2O320 parts of chlorinated paraffin and 25 parts of Al (OH)3And the rubber material with better flame retardance can be obtained. Liang et al, in "flame retardant for rubber and flame retardant" (Special rubber products, vol.23, No. 3, page 25), proposed to mix bromine-containing phosphate, aromatic bromide, Sb2O3And 4 flame retardants of ammonium chloride are used together and added into SBR to obtain a sizing material with good flame retardant effect. Using 5-10 parts of dialkyl phenyl phosphate and 10-15 parts of Sb2O3And 3-10 parts of iodine are added into the SBR to obtain the sizing material with good flame retardant effect. The flame-retardant rubber is mainly a rubber species containing halogen, such as chloroprene rubber, polyvinyl chloride, epichlorohydrin rubber, chlorosulfonated polyethylene and the like.
The inorganic flame retardant has the defects of large useful amount and high cost, even if the factors are not considered, the additional flame retardant is not easy to realize in the production process of rubber, the self-agglomeration of the inorganic powder is serious, and the mixing of the inorganic powder and the rubber needs high energy, so that the repeated kneading and mixing for a long time on an open mill or an internal mixer are generally required. In the open milling or banburying process, a certain amount of softener is generally required to be added. Generally, the low molecular weight substances can provide a certain flexibility to the rubber compound, and can increase the plasticity, fluidity and adhesiveness of the rubber compound so as to facilitate the technological operations such as compression, molding and the like. And the dispersion of the powdery compounding agent is facilitated, the mixing temperature is reduced, and the processability of the rubber is improved.
The softener most used in rubber processing is a petroleum softener, and CN201410018005.7 provides a wet-skid resistant rubber softener and a preparation process, wherein the softener comprises the following raw materials in parts by weight: naphthenic oil: 70-90 parts of alkene mixed resin: 10-30 parts of aluminum trichloride: 0.1 to 1.0 portion. The anti-wet-skid rubber softener has the advantages of various performances of environment-friendly aromatic oil and environment-friendly naphthenic oil, and has good anti-wet-skid performance, lower rolling resistance and good wear resistance. CN201110345185.6 discloses a rubber softener and a preparation method thereof, which comprises the following raw materials in parts by weight: 10-30% of asphalt and 90-70% of naphthenic oil; the asphalt modified rubber softener is nontoxic and lower than European Union safety standards, fills up the blank of domestic production, and greatly saves the cost of domestic tire production enterprises. The softening agents reported in the patent are actually physical plasticizers, mainly comprising aromatic oil, paraffin oil, naphthenic oil, heavy oil, paraffin, vaseline, asphalt, petroleum resin and the like, and have only filling softening effect on rubber, have no flame retardant effect and are easy to separate out during the use of the product.
Disclosure of Invention
The invention aims to provide a preparation method of a flame-retardant softener for styrene butadiene rubber, which is characterized in that the flame-retardant softener is added into styrene butadiene rubber, so that the Mooney of base rubber is reduced by 0.2-2.0 units/part, and the oxygen index of the styrene butadiene rubber is improved by 0.1-1.0%/part.
The preparation method of the flame-retardant softener for styrene butadiene rubber disclosed by the invention specifically comprises the following steps of: styrene butadiene rubber is dissolved in a solvent to prepare a solution with the concentration of 1% w-50% w, preferably 5% w-15% w, based on 100 parts by mass of rubber, 0.1-1.0 part, preferably 0.1-0.3 part, of olefin double decomposition catalyst and 1-50 parts, preferably 15-35 parts, of rubber flame retardant are added, air and water are isolated at the temperature of 15-50 ℃, preferably 20-25 ℃, the reaction is carried out for 0.5-5 hours, preferably 1-2 hours, and glue solution after the reaction is removed through the solvent, so that the styrene butadiene rubber flame retardant softener is obtained.
The solvent is preferably a solvent which does not contain alkene in the structure and can dissolve styrene butadiene rubber; selected from hexane, cyclohexane, toluene, ethylbenzene, etc.
The rubber flame retardant is an organic chloride monomer containing an alkene unsaturated substituent group, and the structural formula of the rubber flame retardant is as follows: RX; wherein: r-unsaturated olefin aliphatic chain segment containing 2-18 carbon atoms, which can be vinyl, propenyl, isopropenyl, isopentenyl, 3-pentenyl, 6-octenyl, trimethylvinyl, 1-heptenyl, methacryloxypropyl, methacryloxy, preferably vinyl; x is F, Cl, Br, or I, preferably Br;
the olefin metathesis catalyst of the invention is a ruthenium carbene complex catalyst, which can be (o-isopropoxybenzylidene) (tricyclohexylphosphine) ruthenium (II) dichloride
Dichloro [ o-isopropoxybenzylidene ] group][1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolinylidene]Ruthenium complex
And the like, preferably a metal carbene-based catalyst having an olefin metathesis function
The term "part" as used herein means a part by mass. The invention is based on the technical principle that:
as shown in the chemical reaction equation (1), the molecular weight of the styrene-butadiene rubber is reduced under the action of the olefin metathesis catalyst, and the halogen flame-retardant group is introduced into the side group; rubber combustion in the presence of oxygen is a very vigorous oxidation reaction, also a chain chemical reaction, which generates reactive HO-radicals when burned, and hydrocarbons and water when the HO-radicals encounter rubber molecules. Under aerobic conditions, the hydrocarbon can continue to decompose and generate HO-free radicals, thereby forming chain reactions and continuing the combustion. To prevent burning or to extinguish the rubber, it is necessary to block oxygen or to reduce the concentration of HO-radicals. The flame-retardant softener is heated to decompose and release halogen gas and hydrogen halide, and the halogen can play a certain role in blocking oxygen; the hydrogen halide can react with HO-free radicals to generate water and halogen ions, the halogen ions can react with hydrocarbons to generate hydrogen halide, and the hydrogen halide can further eliminate the HO-free radicals, thereby reducing the concentration of the HO-free radicals and slowing the combustion speed until the HO-free radicals are extinguished. Meanwhile, the softener is generated after the styrene butadiene rubber is degraded, has the same composition with the rubber base material, plays a role in softening in the rubber processing process, and is vulcanized and crosslinked with the base material in the later vulcanization process.
The Mn of the styrene butadiene rubber flame-retardant softener prepared by the method is 3000-100000, and the flame-retardant softener is added into styrene butadiene rubber as an auxiliary agent, so that the Mooney index of base rubber can be reduced by 0.2-2.0 units/part, and the oxygen index can be improved by 0.1-1.0%/part.
Detailed Description
The raw material auxiliaries required for the specific implementation of the invention are as follows:
(1) styrene butadiene rubber SBR1500, SBR1712, technical grade, langzhou petrochemical division;
(2) vinyl chloride, 1-dichloroethylene, vinyl bromide, trans-1, 2-dibromoethylene, reagent grade, carbofuran technologies ltd;
(3) olefin metathesis catalyst:
ruthenium carbene catalyst, 500 mg/bottle, purity more than or equal to 98% w, Bailingwei science and technology Limited;
(4) hexane, cyclohexane, toluene, ethylbenzene, technical grade, langzhou petrochemical division;
blending a softener with styrene butadiene rubber on an open mill, and testing the Mooney viscosity and the oxygen index of the raw rubber; the Mooney viscosity of the rubber is measured according to GB/T1232.1-2000, and the molecular weight of the rubber softener is measured by GPC. The oxygen index is tested according to GB 10707-89, the high oxygen index indicates that the material is not easy to burn, the low oxygen index indicates that the material is easy to burn, the oxygen index is less than 22 and belongs to flammable materials, the oxygen index is between 22 and 27 and belongs to the nonflammable materials, and the oxygen index is more than 27.
The flame-retardant softening agent disclosed by the invention has the following evaluation on flame-retardant and softening effects, and is prepared by adding 1-100 parts of the flame-retardant softening agent into 500g of rubber and uniformly mixing the mixture on an open mill to obtain a rubber product and testing related performances.
Example 1:
styrene butadiene rubber SBR1500 is dissolved in hexane solvent to prepare 1 percent solution, and olefin metathesis catalyst with the mass ratio of 0.1 part is added according to 100 parts of rubber
And 1 part of rubber flame retardant chloroethylene, isolating air and water at 15 ℃, reacting for 0.5 hour, and removing a glue solution after the reaction by using a solvent to obtain a flame-retardant softener product with Mn of 100000.
10 parts of the flame-retardant softener is added into styrene butadiene rubber SBR1500 on an open mill, and through tests, the Mooney viscosity is reduced from 52 to 50, and the oxygen index is increased from 18.7% to 23.9%.
Comparative example 1: without adding flame retardant
Compared with the example 1, the other conditions are the same, except that no flame retardant is added, specifically: styrene butadiene rubber SBR1500 is dissolved in hexane solvent to prepare 1 percent solution, and olefin metathesis catalyst with the mass ratio of 0.1 part is added
Air and water are isolated at 15 ℃, the reaction is carried out for 0.5 hour, and the glue solution after the reaction is removed by a solvent, thus obtaining the softener product with Mn of 100000.
10 parts of the softening agent is added into styrene butadiene rubber SBR1500 on an open mill, and the Mooney viscosity is reduced from 52 to 50 and the oxygen index is 18.7 percent without improvement through tests.
Example 2:
styrene butadiene rubber SBR1500 is dissolved in toluene solvent to prepare 10 percent solution, and olefin metathesis catalyst with the mass ratio of 1 part is added according to 100 parts of rubber
And 50 parts of rubber flame retardant 1, 1-dichloroethylene, isolating air and water at 50 ℃, reacting for 5 hours, and removing glue solution after reaction through a solvent to obtain a flame-retardant softener product with Mn of 3000.
10 parts of the softener is added into styrene butadiene rubber SBR1500 on an open mill, and the Mooney viscosity is reduced to 32 from 52 and the oxygen index is improved to 27.2 from 18.7 percent through tests.
Comparative example 2: without addition of olefin metathesis catalyst
Compared with example 2, the other conditions are the same, except that no olefin metathesis catalyst is added, specifically: styrene butadiene rubber SBR1500 is dissolved in a toluene solvent to prepare a 10% concentration solution, 50 parts by mass of rubber flame retardant 1, 1-dichloroethylene is added, air and water are isolated at 50 ℃, the reaction is carried out for 5 hours, and glue solution after the reaction is removed through the solvent, so that a flame-retardant softener product with Mn of 170000 is obtained.
10 parts of the softener is added into styrene butadiene rubber SBR1500 on an open mill, and the Mooney viscosity is 52 without reduction through testing, the oxygen index is increased from 18.7 percent to 20.4 percent, and white smoke generated by decomposing 1, 1-dichloroethylene exists during mixing.
Example 3:
styrene butadiene rubber SBR1712 base rubber is dissolved in cyclohexane solvent to prepare 25 percent solution, and olefin metathesis catalyst with the mass ratio of 0.4 part is added according to 100 parts by mass of rubber
And 25 parts of rubber flame retardant vinyl bromide, isolating air and water at 25 ℃, reacting for 2.5 hours, and removing glue solution after reaction through a solvent to obtain the flame-retardant softener product with Mn of 60000.
30 parts of the softening agent is added into styrene butadiene rubber SBR1712 on an open mill, and the Mooney viscosity is reduced to 90 from 120 and the oxygen index is increased to 23.8 from 18.7 percent through tests.
Comparative example 3: aromatic oil is used as softener
Compared with the example 3, the other conditions are the same, except that the aromatic oil is adopted as the softening agent, specifically: 30 parts of high aromatic oil is added into styrene butadiene rubber SBR1712 on an open mill, and tests show that the Mooney viscosity is reduced to 80 from 120, the oxygen index is reduced to 16.8 from 18.7 percent, and the high aromatic oil is more flammable.
Example 4:
styrene butadiene rubber SBR1712 base rubber is dissolved in a solvent to prepare a 50 percent solution, and olefin metathesis catalyst with the mass ratio of 0.5 part is added according to 100 parts by mass of rubber
And 1 part of rubber flame retardant vinyl bromide, isolating air and water at 15 ℃, reacting for 5 hours, and removing glue solution after reaction through a solvent to obtain the flame-retardant softener product with Mn of 40000.
30 parts of the softening agent is added into styrene butadiene rubber SBR1712 on an open mill, and the Mooney viscosity is reduced to 60 from 120 and the oxygen index is improved to 24.6 from 18.7 percent through tests.
Comparative example 4: the flame retardant is dibromoethane
Compared with example 4, the other conditions are the same, except that the flame retardant 1, 1-dibromoethane is adopted, specifically: styrene butadiene rubber SBR1712 base rubber is dissolved in a solvent to prepare a 50 percent solution, and 0.5 part of olefin metathesis catalyst is added in the mass ratio
And 1 part of rubber flame retardant 1, 1-dibromoethane, isolating air and water at 15 ℃, reacting for 5 hours, and removing glue solution after the reaction through a solvent to obtain the flame-retardant softener product with Mn of 40000.
30 parts of the softener is added into styrene butadiene rubber SBR1712 on an open mill, and tests show that the Mooney viscosity is reduced to 60 from 120, the oxygen index is increased to 19.4 from 18.7 percent, and the white smoke generated by decomposition of dibromoethane is generated during mixing.
Example 5:
styrene butadiene rubber SBR1500 is dissolved in hexane solvent to prepare 40 percent concentration solution, and olefin metathesis catalyst with the mass ratio of 0.18 part is added according to 100 parts by mass of rubber
And 12 parts of rubber flame retardant trans-1, 2-dibromoethene, wherein air and water are isolated at 35 ℃, the reaction is carried out for 4 hours, and glue solution after the reaction is removed by a solvent to obtain the flame-retardant softener product with Mn of 98000.
100 parts of the flame-retardant softener is added into styrene butadiene rubber SBR1500 on an open mill, and through tests, the Mooney viscosity is reduced from 52 to 48, and the oxygen index is increased from 18.7% to 29.3%.
Comparative example 5: direct post-processing addition of flame retardants
Compared with the example 5, the other conditions are the same, except that the flame retardant is added in the post-processing procedure, specifically: styrene butadiene rubber SBR1500 is dissolved in hexane solvent to prepare 40 percent solution, and olefin metathesis catalyst with the mass ratio of 0.18 part is added
Air and water are isolated at 35 ℃, the reaction is carried out for 4 hours, and the glue solution after the reaction is removed through a solvent, so that the softener product with Mn of 98000 is obtained.
100 parts of the softening agent is added into styrene butadiene rubber SBR1500 on an open mill, 12 parts of rubber flame retardant trans-1, 2-dibromoethene is added at the same time, the Mooney viscosity is reduced to 48 from 52 through testing, the oxygen index is improved to 19.9 from 18.7 percent, and white smoke decomposed by the trans-1, 2-dibromoethene exists during mixing.
Example 6:
styrene butadiene rubber SBR1500 is dissolved in cyclohexane solvent to prepare 20 percent solution, and olefin metathesis catalyst with the mass ratio of 0.9 part is added according to 100 parts by mass of rubber
And 38 parts of rubber flame retardant chloroethylene, isolating air and water at 28 ℃, reacting for 3.2 hours, and removing glue solution after reaction by using a solvent to obtain the flame-retardant softener product with Mn of 8000.
1 part of the flame-retardant softener is added into styrene butadiene rubber SBR1500 on an open mill, and through tests, the Mooney viscosity is reduced from 52 to 50, and the oxygen index is increased from 18.7% to 23.7%.
Comparative example 6: adding aromatic oil and fire retardant directly in post-processing
Compared with the example 6, the other conditions are the same, except that the aromatic oil is adopted as the softening agent, and the flame retardant is added, specifically: 1 part of high aromatic oil and 1 part of rubber flame retardant chloroethylene are added into styrene butadiene rubber SBR1500 on an open mill, and tests show that the Mooney viscosity and the oxygen index are not obviously changed, and white smoke generated by decomposing chloroethylene is generated during mixing.
Claims (10)
1. The preparation method of the flame-retardant softener is characterized by comprising the following steps: dissolving styrene butadiene rubber in a solvent to prepare a solution with the concentration of 1-50 w%, adding 0.1-1.0 part of olefin metathesis catalyst and 1-50 parts of rubber flame retardant based on 100 parts by mass of rubber, isolating air and water at 15-50 ℃, reacting for 0.5-5 hours, and removing the reacted glue solution through the solvent to obtain the styrene butadiene rubber flame-retardant softener; the structural formula of the rubber flame retardant is as follows: RX; wherein: r is an unsaturated olefin aliphatic chain segment containing 2-18 carbon atoms; x is F, Cl, Br, or I.
2. The method of preparing a flame-retardant softener according to claim 1, wherein styrene-butadiene rubber is dissolved in a solvent to prepare a solution having a concentration of 5 w% to 15 w%.
3. The process for producing the flame-retardant softener according to claim 1, wherein 0.1 to 0.3 part by mass of the olefin metathesis catalyst is added based on 100 parts by mass of the rubber.
4. The process for producing the flame-retardant softener according to claim 1, wherein 15 to 35 parts by mass of a rubber flame retardant is added based on 100 parts by mass of rubber.
5. The method of preparing a flame-retardant softener according to claim 1, wherein the solvent is a solvent capable of dissolving styrene-butadiene rubber without containing an olefin in its structure.
6. The method of preparing a flame retardant softener according to claim 1 or 5, wherein the solvent is hexane, cyclohexane, toluene or ethylbenzene.
7. The method of producing a flame-retardant softener according to claim 1, wherein R in the formula of the rubber flame retardant is selected from the group consisting of vinyl, propenyl, isopropenyl, isopentenyl, 3-pentenyl, 6-octenyl, trimethylvinyl, 1-heptenyl, methacryloxypropyl and methacryloxy.
8. The method for preparing a flame-retardant softener according to claim 1, wherein X is Br in the structural formula of the rubber flame retardant.
9. The method for producing the flame-retardant softener according to claim 1, wherein the olefin metathesis catalyst is a metal carbene-based catalyst having an olefin metathesis function.
10. The method of claim 1 wherein the olefin metathesis catalyst is selected from the group consisting of (o-isopropoxybenzylidene) ruthenium (II) (tricyclohexylphosphine) dichloride [ o-isopropoxybenzylidene ] dichloride][1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolinylidene]Ruthenium complex,
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