CN102464768B - Preparation of high-strength nitrile butadiene rubber - Google Patents

Preparation of high-strength nitrile butadiene rubber Download PDF

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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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molecular weight
weight regulator
parts
initiator
preparation
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CN102464768A (en
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潘广勤
李彤霞
范永将
高卫光
李冬红
张守汉
齐永新
李红春
赵继忠
任彩霞
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China Petroleum and Natural Gas Co Ltd
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Abstract

The invention relates to a preparation method of high-strength nitrile butadiene rubber. Batch emulsion polymerization is adopted and butadiene and acrylonitrile are used as polymerization monomers. The preparation method comprises the following steps: adding soft water, emulsifier, initiator, triethanolamine, sodium hydroxide and molecular weight regulator, wherein the molecular weight regulator is added in three batches; and when the reaction conversion rate is up to 70-75%, adding terminator and antiager, degassing, agglomerating, washing and drying to obtain the high-strength nitrile butadiene rubber, wherein the emulsifier is a compound system of isproportionated potassium rosinate, potassium oleate soap and naphthalene sulfonated formaldehyde condensate sodium salt, the initiator is persulfate, and the molecular weight regulator is selected from molecular weight regulator D. The nitrile butadiene rubber has the Mooney viscosity of MS (1+4) 100 DEG C 40-65, the tensile strength not smaller than 27MPa and the break elongation not smaller than 400% and can meet the application requirements in the fields such as automobiles, aviation and aerospace, sealing gaskets and the like.

Description

A kind of preparation of high strength paracril
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
Figure BSA00000351805000041
Table 2
Figure BSA00000351805000051

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.
CN 201010550321 2010-11-18 2010-11-18 Preparation of high-strength nitrile butadiene rubber Active CN102464768B (en)

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Publication number Priority date Publication date Assignee Title
CN103421146B (en) * 2012-05-15 2016-03-09 中国石油天然气股份有限公司 A kind of 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 A kind of emulsion polymerization prepares paracril method
WO2015147052A1 (en) * 2014-03-27 2015-10-01 日本ゼオン株式会社 Nitrile group-containing copolymer rubber, crosslinkable rubber composition and crosslinked rubber product
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
CN114380948A (en) * 2020-10-21 2022-04-22 中国石油天然气股份有限公司 Nitrile rubber and preparation method and application thereof
CN114380949A (en) * 2020-10-21 2022-04-22 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

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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

Patent Citations (2)

* Cited by examiner, † Cited by third party
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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