CN102464768B - Preparation of high-strength nitrile rubber - Google Patents
Preparation of high-strength nitrile rubber Download PDFInfo
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- CN102464768B CN102464768B CN 201010550321 CN201010550321A CN102464768B CN 102464768 B CN102464768 B CN 102464768B CN 201010550321 CN201010550321 CN 201010550321 CN 201010550321 A CN201010550321 A CN 201010550321A CN 102464768 B CN102464768 B CN 102464768B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 229920000459 Nitrile rubber Polymers 0.000 title abstract description 12
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000344 soap Substances 0.000 claims abstract description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 15
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 14
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 12
- -1 compound sodium salt Chemical class 0.000 claims abstract description 11
- 239000003999 initiator Substances 0.000 claims abstract description 11
- 208000012839 conversion disease Diseases 0.000 claims abstract description 10
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 5
- 239000008234 soft water Substances 0.000 claims abstract description 5
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract 2
- 229920013649 Paracril Polymers 0.000 claims description 19
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 16
- 229940072033 potash Drugs 0.000 claims description 16
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 16
- 235000015320 potassium carbonate Nutrition 0.000 claims description 16
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 8
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 8
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 8
- 239000005642 Oleic acid Substances 0.000 claims description 8
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 8
- ZRIHAIZYIMGOAB-UHFFFAOYSA-N butabarbital Chemical group CCC(C)C1(CC)C(=O)NC(=O)NC1=O ZRIHAIZYIMGOAB-UHFFFAOYSA-N 0.000 claims description 8
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 8
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 8
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 7
- 239000007859 condensation product Substances 0.000 claims description 7
- 159000000000 sodium salts Chemical class 0.000 claims description 5
- 229960004418 trolamine Drugs 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 239000004160 Ammonium persulphate Substances 0.000 claims description 2
- 239000004159 Potassium persulphate Substances 0.000 claims description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 2
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- 239000012991 xanthate Substances 0.000 claims description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract description 5
- 238000007872 degassing Methods 0.000 abstract description 3
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 abstract description 2
- QHOWYOKUKZPTPL-KVVVOXFISA-N (z)-octadec-9-enoic acid;potassium Chemical compound [K].CCCCCCCC\C=C/CCCCCCCC(O)=O QHOWYOKUKZPTPL-KVVVOXFISA-N 0.000 abstract 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract 1
- 230000015271 coagulation Effects 0.000 abstract 1
- 238000005345 coagulation Methods 0.000 abstract 1
- 239000002131 composite material Substances 0.000 abstract 1
- 238000009833 condensation Methods 0.000 abstract 1
- 230000005494 condensation Effects 0.000 abstract 1
- 229910052700 potassium Inorganic materials 0.000 abstract 1
- 239000011591 potassium Substances 0.000 abstract 1
- 238000007789 sealing Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000004945 emulsification Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229920013647 Krynac Polymers 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
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- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a preparation method of high-strength nitrile rubber, which adopts intermittent emulsion polymerization, wherein the polymerization monomers comprise butadiene and acrylonitrile, soft water, an emulsifier, an initiator, triethanolamine, sodium hydroxide and a molecular weight regulator are added, the molecular weight regulator is added in three batches in equal amount, when the reaction conversion rate reaches 70-75%, a terminator and an anti-aging agent are added, and the high-strength nitrile rubber is prepared after degassing, coagulation, washing and drying; the emulsifier is a composite system of disproportionated rosin acid potassium soap, oleic acid potassium soap and naphthalene sulfonic acid formaldehyde condensation compound sodium salt, and the initiator is persulfate; the molecular weight regulator is D; the nitrile rubber has Mooney viscosity MS(1+4) 100℃40-65, the tensile strength is more than or equal to 27MPa, the elongation at break is more than or equal to 400%, and the application requirements in the fields of automobiles, aerospace, sealing gaskets and the like can be met.
Description
Technical field:
The present invention relates to adopt the emulsification system of ternary built and the preparation method that thermal polymerization process prepares a kind of high strength paracril, especially for the preparation method of the high strength paracril in fields such as automobile, aerospace, seal washer.
Background technology:
Paracril is because of oil resistant, benzene resistance energy, resistance toheat and physical and mechanical properties excellence, become the reference rounds gonosome of oil resisting rubber goods, be widely used in fields such as automobile, aerospace, oil production, petrochemical complex, weaving, electric wire, printing and food product pack.For many years, the research of paracril is constantly synthesized in countries in the world, and the mechanism of domestic research paracril polyreaction is few, and the invention disclosed patent is few, the article comparatively small amt of delivering, and be confined to technology controlling and process or simple formulation adjustment more.How external paracril polyreaction is emulsifying agent with alkyl aryl sulphonic acid alkaline metal salt, fatty acid alkali metal salt class, RA rosin acid and mixing soap thereof, NBR product as German Bayer company's employing biological degradation emulsifying agent manufacturer's product Krynac XN by name, the aralkyl sulfonated bodies that replaces nonbiodegradability with the biological degradation compound is made emulsifying agent, dissolved organic concentration is significantly reduced, it is about 90% to discharge COD value minimizing in the waste water, and does not need to increase new installation; Japan bright dipping petroleum chemistry company limited has developed a kind of NBR letex polymerization dispersant with high efficiency, is made up of toxilic acid (acid anhydride) and styrene sulfonate, uses this dispersion agent, can improve the dispersiveness of monomer and the stability of NBR; Russian then adopt sodium alkylether sulphate, the Sodium dodecylbenzene sulfonate of polyoxyethylene modification, the mixture of sodium olefin sulfonate to prepare NBR as compound emulsifying agent; Japan JSR company adopts nonionic surface active agent such as polyethylene oxide alkyl ethers, polyoxyethylene fatty acid esters, polyoxyethylene sorbose fatty ester, ethylene oxide/propylene oxide segmented copolymer to make emulsifying agent.The Study on polymerization technology aspect, a kind of bound acrylonitrile content has been invented up to 50% NBR continuous emulsion polymerization technique by Holland Stamicarbon B.V. company, polymeric kettle is at least 2, be preferably 5, with whole vinyl cyanide, the part divinyl, water, emulsifying agent, auxiliary agents such as initiator add in the 1st reactor together continuously, react under 10 ℃, first still polymerisation conversion is controlled 24%, respectively at 40%, 56%, in the 2nd~5 polymeric kettle, add divinyl respectively continuously under 72% and 82% transformation efficiency, stop, the degassing, cohesion, can obtain bound acrylonitrile content after washing and the drying is 47.2%, mooney viscosity is 48, tensile strength is 15.6MPa, elongation is that 385%, 300% stress at definite elongation is 12.1MPa and environment resistant good high nitrile NBR product.But the technology that this patent provides adopts the synthetic paracril of nilox resin acid potash soap and oleic acid potash soap compound emulsion system and Re Fa emulsion polymerization technique, 100 ℃ 40~65 of its mooney viscosity MS (1+4), tensile strength 〉=27MPa and tensile yield 〉=400%.
Summary of the invention:
The objective of the invention is to adopt ternary built emulsification system and Re Fa emulsion polymerization technique to prepare the method for the paracril of a kind of high strength (paracril of tensile strength 〉=27Mpa and tensile yield 〉=400%).
For realizing the purpose of this invention, the technology of employing is: adopting divinyl and vinyl cyanide is polymerization single polymerization monomer, and emulsification system adopts nilox resin acid potash soap, oleic acid potash soap and the compound use of naphthalene sulfonic acidformaldehyde condensation product sodium salt.Initiator system adopts the persulfuric acid salt, as Potassium Persulphate or ammonium persulphate water soluble starter, free alkali 0.01~0.1% in the aqueous phase system, molecular weight regulator can be selected molecular weight regulator fourth (connecting the di-isopropyl xanthate) for use, adopt the intermittent feeding mode of in batches adding molecular weight regulator, synthesize butadiene-acrylonitrile cement, add terminator and anti-aging agent, and will make a kind of high-intensity paracril after its process degassing, cohesion, washing and the drying.Specifically:
Set of monomers becomes that (add-on in divinyl and vinyl cyanide is 100 weight parts, as follows) 275 parts of soft water, 50~60 parts of divinyl, 40~50 parts of vinyl cyanide, emulsifying agent is nilox resin acid potash soap, oleic acid potash soap and naphthalene sulfonic acidformaldehyde condensation product sodium salt compound system, the emulsifying agent consumption is 2.5~6.5 parts, and nilox resin acid potash soap and oleic acid potash soap weight ratio are (3~8): 1, and naphthalene sulfonic acidformaldehyde condensation product sodium salt weight is 0.2~0.5 part; 0.01~0.1 part in sodium hydroxide; 0.2~1.0 part of initiator; 0.1 part trolamine; Adopt monomer, the disposable adding of initiator, three times equivalent adds molecular weight regulator, the intermittent type letex polymerization, and polymerization temperature is 25~30 ℃.
In a word, adopting nilox resin acid potash soap, oleic acid potash soap and naphthalene sulfonic acidformaldehyde condensation product sodium salt ternary built emulsification system and Re Fa emulsion polymerization technique is technical essential of the present invention.
Technological process:
Polymeric kettle vacuumizes the back and drops into soft water, emulsifying agent, sodium hydroxide, part and whole monomer, trolamine, after being warmed up to 30 ℃, add initiator, when reaction conversion ratio reaches 35~40%, add for the second time molecular weight regulator, when reaction conversion ratio reaches 50~55%, add molecular weight regulator for the third time, when reaction conversion ratio reaches 70~75%, discharging after cooling to 20-25 ℃, add terminator and anti-aging agent, and outgas, condense, make a kind of high-intensity paracril after washing and the drying.
The paracril that uses the present invention to produce has higher draw tensile strength and tensile yield, can satisfy the application requiring in fields such as automobile, aerospace, seal washer.
The conventional testing method of the testing method of rubber: the SH/T1154-92 standard is adopted in the total solid substance test; Mooney viscosity MS
(1+4) 100 ℃The GB/T1232.1-2000 standard is adopted in test; The GB/T528-1998 standard is adopted in the tensile strength test; The GB/T528-1998 standard is adopted in the tensile yield test; The SH/T1157-1997 standard is adopted in the bound acrylonitrile test.
Invention effect: adopt technology of the present invention can produce mooney viscosity MS
(1+4) 100 ℃40~65, the paracril of tensile strength 〉=27Mpa and tensile yield 〉=400%; The paracril that uses the present invention to produce satisfies the application requiring in fields such as automobile, aerospace, seal washer; In addition, when utilizing this patent to carry out rubber cement synthetic, polymerization process is steady, and energy consumption is lower.
Embodiment:
Embodiment 1:
The 10L polymeric kettle vacuumizes, nitrogen replacement, vacuum tightness reaches-0.1Mpa, drop into 275 parts of soft water, 55 parts of divinyl, 45 parts of vinyl cyanide successively, emulsifying agent (wherein 1.75 parts of nilox resins acid potash soap, 1.75 parts of oleic acid potash soaps, naphthalene sulfonic acidformaldehyde condensation product sodium salt are 0.5 part), 0.03 part in sodium hydroxide, 0.1 part of trolamine, 0.15 part of molecular weight regulator fourth.Begin then to heat up, when temperature of reaction reaches 30 ℃, add 0.3 part of initiator potassium persulfate.When reaction conversion ratio reaches 35~40%, secondary adds the molecular weight regulator fourth, when reaction conversion ratio reaches 50~55%, add the molecular weight regulator fourth three times, when reaction conversion ratio reaches 70~75%, discharging after cooling to 20-25 ℃ adds terminator and anti-aging agent, and outgases, condenses, makes a kind of high-intensity paracril after washing and the drying.
Embodiment 2-5 and comparative example 1-3 (referring to table 1) table 1
Table 2
Claims (2)
1. the preparation method of a high strength paracril, tensile strength 〉=27Mpa and tensile yield 〉=400%; It is characterized in that: adopt the intermittent type letex polymerization, polymerization single polymerization monomer is divinyl and vinyl cyanide, and by weight, monomer divinyl and vinyl cyanide are 100 parts, wherein: 50~60 parts of divinyl, 40~50 parts of vinyl cyanide; Add 275 parts of soft water, 2.5~6.5 parts of emulsifying agents, 0.2~1.0 part of initiator, 0.1 part of trolamine, 0.01~0.1 part in sodium hydroxide, 0.45~0.6 part of molecular weight regulator, polymerization temperature are 25~30 ℃, with molecular weight regulator equivalent adding in three batches, when reaction conversion ratio reaches 35~40%, for the second time add molecular weight regulator, when reaction conversion ratio reaches 50~55%, add molecular weight regulator for the third time, when reaction conversion ratio reaches 70~75%, discharging after cooling to 20-25 ℃ adds terminator and anti-aging agent, and outgases, cohesion, make high-intensity paracril after washing and the drying;
Emulsifying agent is nilox resin acid potash soap, oleic acid potash soap and naphthalene sulfonic acidformaldehyde condensation product sodium salt compound system, and wherein nilox resin acid potash soap and oleic acid potash soap weight ratio are (3~8): 1, and naphthalene sulfonic acidformaldehyde condensation product sodium salt weight is 0.2~0.5 part;
Initiator is persulphate;
Molecular weight regulator is selected the molecular weight regulator fourth for use; Described molecular weight regulator fourth is for connecting the di-isopropyl xanthate.
2. the preparation method of high strength paracril according to claim 1, it is characterized in that: initiator is selected Potassium Persulphate or ammonium persulphate for use.
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Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
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CN103421146B (en) * | 2012-05-15 | 2016-03-09 | 中国石油天然气股份有限公司 | Preparation method of nitrile rubber with high acrylonitrile content |
CN103450399B (en) * | 2012-06-01 | 2016-04-06 | 中国石油天然气股份有限公司 | Method for preparing nitrile rubber by emulsion polymerization method |
US10280244B2 (en) * | 2014-03-27 | 2019-05-07 | Zeon Corporation | Nitrile group-containing copolymer rubber, cross-linkable rubber composition, and cross-linked rubber |
CN107178613A (en) * | 2017-05-09 | 2017-09-19 | 柳州市够旺贸易有限公司 | Rubber ring |
CN109306035A (en) * | 2018-09-27 | 2019-02-05 | 安徽龙川橡塑科技有限公司 | A kind of environmental protection flame retardant NBR material and preparation method thereof |
CN111019046A (en) * | 2018-10-09 | 2020-04-17 | 中国石油天然气股份有限公司 | Preparation method of nitrile rubber |
CN114380949B (en) * | 2020-10-21 | 2024-03-01 | 中国石油天然气股份有限公司 | Nitrile rubber and preparation method and application thereof |
CN114380948B (en) * | 2020-10-21 | 2024-03-01 | 中国石油天然气股份有限公司 | Nitrile rubber and preparation method and application thereof |
CN114456316B (en) * | 2020-11-07 | 2024-01-09 | 中国石油化工股份有限公司 | Method for improving emulsion polymerized styrene-butadiene rubber conversion rate |
CN113248804A (en) * | 2021-05-21 | 2021-08-13 | 山东东都汽车部件股份有限公司 | Low-temperature-resistant automobile sealing rubber strip and preparation method thereof |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1865306A (en) * | 2005-05-20 | 2006-11-22 | 中国石油天然气集团公司 | Low content nitrile cross-linked powdery acrylonitrile butadiene preparation method |
CN1978476A (en) * | 2005-12-05 | 2007-06-13 | 中国石油天然气集团公司 | Method for preparing liquid nitrile butadiene rubber |
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CN1978476A (en) * | 2005-12-05 | 2007-06-13 | 中国石油天然气集团公司 | Method for preparing liquid nitrile butadiene rubber |
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