CN101885788A - Method for preparing hydrogenated nitrile-butadiene rubber with low Mooney viscosity - Google Patents
Method for preparing hydrogenated nitrile-butadiene rubber with low Mooney viscosity Download PDFInfo
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- CN101885788A CN101885788A CN 201010225039 CN201010225039A CN101885788A CN 101885788 A CN101885788 A CN 101885788A CN 201010225039 CN201010225039 CN 201010225039 CN 201010225039 A CN201010225039 A CN 201010225039A CN 101885788 A CN101885788 A CN 101885788A
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Abstract
The invention relates to a method for preparing a hydrogenated nitrile-butadiene rubber (NBR), which can regulate and control the Mooney viscosity. The method comprises the following steps of: plasticating and thin-passing NBR for certain times by using a two-roll mill; dissolving the NBR in an organic solvent; and performing hydrogenation with stirring and heating under certain hydrogen pressure and in the presence of a certain catalyst. The method is characterized by reducing the Mooney viscosity of the NBR by controlling the plasticating and thin-passing times of the NBR, thereby reducing, regulating and controlling the Mooney viscosity of the hydrogenated NBR, and improving the processing performance of the NBR.
Description
Technical field
The present invention relates to a kind of preparation method who reduces and regulate and control the hydrogenated nitrile-butadiene rubber Mooney viscosity, particularly to divinyl and the resulting paracril of acrylonitrile compolymer, reduce Mooney viscosity by the method for plasticating, then unsaturated carbon-to-carbon double bond on its molecular chain is carried out the solution selective hydrogenation, thereby reduce and regulate and control the mooney viscosity of HNBR.
Background technology
Hydrogenated nitrile-butadiene rubber (hereinafter to be referred as HNBR) generally adopts the solution hydrogenation of NBR to obtain.Have excellent oil-proofness, chemical proofing and weathering resistance, be mainly used in the sealing-ring, oil resistant pipeline of automobile, steamer, space industry etc.
The hydrogenation of NBR all has play-by-play in a lot of documents.Mohammadi and G.L.Rempel be at Macromolecules, and 1987,20, a kind of selective hydrogenation to carbon-carbon double bond among the NBR has been described among the 2362N.A., mainly be to select Wilkinson ' s catalyzer RhCl (PPh for use
3)
3To the hydrogenation of NBR, and characterized the molecular structure of HNBR after the hydrogenation by spectroscopic analysis.McManus and G.L.Rempel are at Rev.Macromol.Chem.Phys., 1995, C35 (2), the catalyst system of having described several different systems among the 239-285N.T. carries out hydrogenation to NBR, SBR etc., and catalyst system therefor comprises Rh, Ru, Pd and Ir ligand compound objects system.According to the literature, the mooney viscosity that can make usually of the HNBR that employing homogeneous phase solution hydrogenation method obtains raises, and causes processing difficulties.Patent WO-A-02/100941 in 2007 and WO-A-02/100905 report can prepare a kind of HNBR of low mooney viscosity by the combination of using replacement(metathesis)reaction and hydrogenation, its mooney viscosity, 100 ℃ of ML (1+4), in 2～50 scopes, Mw is in 30000～250000 scopes, and dispersiveness is then less than 3.0.Hu Haihua etc. adopt the way of adding liquid acrylonitrile butadiene rubber and free radical scavenger in the reaction system of NBR, are 180 * 10 at the using rhodium complex catalysts consumption
-6, hydrogenation pressure is that 7MPa, temperature are hydrogenation 10h under 80 ℃ the condition, obtained degree of hydrogenation and be 90%, mooney viscosity is 70～90, HNBR.The hydrogenation technology of US4581417 patent disclosure, selecting mooney viscosity for use is 29 NBR, and the fine content of propylene is 34.9%, and 100～145 ℃ of hydrogenation temperatures, catalyzer are RhCl (PPh
3)
3, consumption is 0.05～0.6%, the triphenylphosphine consumption is 2%.Obtain the increase with catalyst levels, the mooney viscosity of HNBR significantly increases.
Summary of the invention
The object of the present invention is to provide a kind of method that reduces and regulate and control the hydrogenated nitrile-butadiene rubber Mooney viscosity, pretreatment process by thin-pass that paracril is plasticated, reduce and regulate and control the mooney viscosity of NBR, reduce and regulate and control the mooney viscosity of HNBR then by method of hydrotreating, thereby obtain to have the HNBR product of excellent machinability.
For achieving the above object, method of the present invention is, the thin-pass of at first the two roller mills of paracril process being plasticated 10～140 times, be dissolved in xylene solvent then, be configured to concentration and be 2～7% NBR glue, add 0.01～5% (calculating) free radical scavenger, Na-1010, anti-aging agent 246 or anti-aging agent TD with dry glue quality, in 20～100 ℃ of temperature ranges, stirred 1～8 hour.Then, add catalyzer, consumption is 0.1～1.0% for dry glue quality per-cent, and control pressure is at 1～5MPa, and temperature is 100～160 ℃, hydrogenation reaction 2～8 hours.Test the mooney viscosity of resulting hydrogenated nitrile-butadiene rubber and compare with relevant hydrogenated nitrile-butadiene rubber.
Do not limit paracril (NBR), the styrene-butadiene rubber(SBR) thin-passes of plasticating such as (SBR) among the present invention, the thin-pass number of times is also unqualified, and thin-pass number of times scope is 10～140 times.
Not limiting Na-1010, anti-aging agent 246 or anti-aging agent TD among the present invention is free radical scavenger, and its consumption is also unqualified, and amount ranges is 0.1～5.0%
Do not limit the preparation method of paracril (NBR), liquid acrylonitrile butadiene rubber (LNBR), styrene-butadiene rubber(SBR) (SBR) among the present invention.NBR can be a random copolymers, also can be alternating copolymer, and wherein the fine content of propylene is 20～50%, and optimum content is 32～45%.
Catalyzer used in the present invention does not limit especially yet, can adopt general chemigum hydrogenation catalyzer and add-on, as can also can being heterogeneous hydrogenation catalyst systems such as load P d, Pt for homogeneous phase solution hydrogenation catalyst system such as rhodium (Rh), ruthenium (Ru), palladium (Pd) and Ru-Rh.Be preferably RhX (PPh
3)
3, wherein X is Cl, Br, I, is preferably Cl; Optimum catalyst is RhCl (PPh
3)
3, consumption 0.1～1.0% (calculating with dry glue quality) is preferably 0.3～0.6%, and the triphenylphosphine consumption is 1.8～3.6% (calculating with dry glue quality).
The present invention reduces the method for HNBR Mooney viscosity, and its advantage is:
1. the HNBR that obtains according to preparation method of the present invention has low relatively mooney viscosity, and Mooney viscosity can be controlled by the thin-pass number of times of paracril.
2. use two rod mills that NBR is plasticated among the present invention, do not influence the solution hydrogenation effect of NBR, and compare with NBR without over-mastication, mooney viscosity reduces, and has improved the processing characteristics of HNBR.
3. the present invention can be used for the hydrogenation of the NBR of fine content of different propylene and different mooney viscosities.
4. catalyzer used in the present invention is the homogeneous catalysis solution hydrogenation system that triphenylphosphine closes the halogenation rhodium, has higher hydrogenation activity.
Description of drawings
The GPC spectrogram that is respectively the resulting hydrogenated nitrile-butadiene rubber of paracril of the present invention (embodiment 3) illustrated in figures 1 and 2 and
1H NMR spectrogram.
Fig. 3 and the GPC spectrogram that is respectively the resulting hydrogenated nitrile-butadiene rubber of paracril (comparison example 1) shown in Figure 4 and
1H NMR spectrogram.
Embodiment
Detail has been listed among the following embodiment.Following embodiment is used to further specify the present invention, rather than is used for limiting the scope of the invention.Except as otherwise noted, used per-cent all is based on weight.
Reduce the step of hydrogenated nitrile-butadiene rubber mooney viscosity method:
Paracril through two roller mill thin-passes 10～500 times, is made into concentration and is 1～10% NBR glue then, add 0.01～5% (ratio of dry glue quality) free radical scavenger, in 20～100 ℃ of temperature ranges, stirred 1～8 hour.Add catalyzer RhCl (PPh
3)
3, under 60～160 ℃ of temperature of reaction and 1～5MPa pressure condition, hydrogenation 2～8 hours is cooled to room temperature, Virahol cohesion, drying.With bromine iodine assay degree of hydrogenation,, adopt GB-T1232.1-2000 standard test mooney viscosity, GB/T528-1998 standard test mechanical property with the infrared and structure nmr analysis product.
Getting NBR 1052M43 acrylonitrile content is 33%, and 200g transfers to 0.1mm to the roll spacing of two rod mills, under the normal temperature condition, and the thin-pass of plasticating 15 times.Being dissolved in xylene solvent, to be configured to concentration be 7% NBR glue, adds 0.01% free radical scavenger Na-1010 in solution, 50 ℃, and reaction 4h.Add catalyzer RhCl (PPh
3)
3, consumption is 0.4% of a dried glue, 145 ℃ of controlled temperature, pressure 2.5MPa, reaction times 6h.The results are shown in Table 1
Comparative Examples 1
Getting NBR 1052M43 acrylonitrile content is 33%, 200g, and being dissolved in xylene solvent, to be configured to concentration be 7% NBR glue, adds catalyzer RhCl (PPh
3)
3, consumption is 0.42% of a dried glue, 145 ℃ of controlled temperature, pressure 2.5MPa, reaction times 6h.The results are shown in Table 1
The thin-pass number of times of plasticating among the embodiment 1 is changed into 40 times, and other are with embodiment 1.The results are shown in Table 1
The thin-pass number of times of plasticating among the embodiment 1 is changed into 55 times, and other are with embodiment 1.The results are shown in Table 1
The thin-pass number of times of plasticating among the embodiment 1 is changed into 90 times, and other are with embodiment 1.The results are shown in Table 1
The thin-pass number of times of plasticating among the embodiment 1 is changed into 140 times, and other are with embodiment 1.The results are shown in Table 1
Table 1. influence of thin-pass number of times of plasticating to the HNBR mooney viscosity
Getting NBR 1052M43 acrylonitrile content is 33%, 200g, and thin-pass 55 times, being dissolved in xylene solvent, to be configured to concentration be 7% NBR glue, adds free radical scavenger Na-10100.01%, 50 ℃, reaction 4h.Hydroconversion condition is to add catalyzer in the NBR glue, and consumption is 0.42% of a dried glue, and triphenylphosphine, consumption are 2.4% of dried glue, 145 ℃ of controlled temperature, pressure 2.5MPa, reaction 6h.Degree of hydrogenation 88%, mooney viscosity 81.57.The results are shown in Table 2
Comparative Examples 6
Getting NBR 1052M43 acrylonitrile content is 33%, 200g, and thin-pass 55 times, being dissolved in xylene solvent, to be configured to concentration be 7% NBR glue, adds catalyzer RhCl (PPh
3)
3, consumption is 0.42% of a dried glue, 145 ℃ of controlled temperature, and pressure 2.5MPa,, reaction 6h.Obtain degree of hydrogenation 97.31%, mooney viscosity 67.80.The results are shown in Table 2
Free radical scavenger was to the influence of hydrogenation after table 2 thin-pass was plasticated
Embodiment 7
It is 40% that NBR among the embodiment 1 is changed into acrylonitrile content, and the thin-pass of plasticating number of times changes into 55 times, and other are with embodiment 1.The results are shown in Table 3
The NBR hydrogenation situation contrast of the different acrylonitrile contents of table 3
Embodiment 8
Thin-pass number of times in the example 1 is changed 55 times into catalyzer RhCl (PPh
3)
3Consumption change 0.2 of dry glue quality into, other are with example 1.The results are shown in Table 4
Embodiment 9
Thin-pass number of times in the example 1 is changed 55 times into catalyzer RhCl (PPh
3)
3Consumption change 0.4 of dry glue quality into, other are with example 1.The results are shown in Table 4
Thin-pass number of times in the example 1 is changed 55 times into catalyzer RhCl (PPh
3)
3Consumption change 0.6 of dry glue quality into, other are with example 1.The results are shown in Table 4
Table 4 different catalysts RhCl (PPh
3)
3The NBR hydrogenation situation contrast of consumption
Embodiment 11
Thin-pass number of times in the example 1 is changed into 55 times, and free radical scavenger changes anti-aging agent 246 into, and other are with example 1.The results are shown in Table 5
Embodiment 12
Thin-pass number of times in the example 1 is changed into 55 times, and free radical scavenger changes anti-aging agent TD into, and other are with example 1.The results are shown in Table 5
The NBR hydrogenation situation contrast of the different free radical scavengers of table 5
Embodiment 13
Get embodiment 1,2,3,4,5,6 resulting HNBR, carry out 170 ℃ * 60min and vulcanize, sulfurizing formula sees Table 6, carries out GB/T528-1998 standard test mechanical property.The results are shown in Table 7
Comparative Examples 13
Get comparison example 1 resulting HNBR, carry out 170 ℃ * 60min and vulcanize, sulfurizing formula sees Table V, carries out GB/T528-1998 standard test mechanical property.The results are shown in Table 7
The sulfurizing formula of table 6 embodiment 1 (c) and comparison example 1
The mechanical property of table 7 embodiment 3 and Comparative Examples 3 gained HNBR
Claims (7)
1. the preparation method of a hydrogenated nitrile-butadiene rubber with low Mooney viscosity, the thin-pass of at first the two roller mills of paracril process being plasticated 10～500 times, be dissolved in organic solvent, be made into the NBR glue of mass percent concentration 1-15%, add free radical scavenger in the NBR glue, free radical scavenger is amine or fragrant class, free radical scavenger be in the NBR glue dry glue quality 0.01～5%, 50 ℃, reacted 1～8 hour.At the hydrogen pressure of 1～5MPa, add catalyzer RhX (PPh then
3)
3, wherein X is Cl, Br, I, catalyzer RhX (PPh
3)
3Be in the NBR glue dry glue quality 0.1～1.0%, stir, carry out hydrogenation under 60～160 ℃ the condition.
2. method according to claim 1 is characterized in that the thin-pass number of times is 10-140 time.
3. method according to claim 1 is characterized in that the solvent of using in the NBR glue is a dimethylbenzene, chlorobenzene or methyl chloride.
4. method according to claim 1 is characterized in that NBR glue mass percent concentration is 2-7%.
5. method according to claim 1 also adds triphenylphosphine when it is characterized in that adding catalyzer, consumption is the dried glue 2.4% of dry glue quality in the NBR glue.
6. method according to claim 1 is characterized in that catalyzer Rh (PPh
3)
3Consumption be in the NBR glue dry glue quality 0.2～0.6%.
7. method according to claim 1 is characterized in that free radical scavenger is Na-1010, anti-aging agent 246 or anti-aging agent TD.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013056459A1 (en) * | 2011-10-21 | 2013-04-25 | Lanxess Deutschland Gmbh | Catalyst compositions and their use for hydrogenation of nitrile rubber |
| WO2013056463A1 (en) * | 2011-10-21 | 2013-04-25 | Lanxess Deutschland Gmbh | Catalyst compositions and their use for hydrogenation of nitrile rubber |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1865304A (en) * | 2005-05-20 | 2006-11-22 | 中国石油天然气股份有限公司 | Hydrogenation method of nitrile rubber |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1865304A (en) * | 2005-05-20 | 2006-11-22 | 中国石油天然气股份有限公司 | Hydrogenation method of nitrile rubber |
Non-Patent Citations (1)
| Title |
|---|
| 《实用橡胶工艺学》 20050630 杨清芝 《实用橡胶工艺学》 第326页第1行－第326页倒数第1行，以及第333页第1行－第334页倒数第1行 1-7 , 1 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013056459A1 (en) * | 2011-10-21 | 2013-04-25 | Lanxess Deutschland Gmbh | Catalyst compositions and their use for hydrogenation of nitrile rubber |
| WO2013056463A1 (en) * | 2011-10-21 | 2013-04-25 | Lanxess Deutschland Gmbh | Catalyst compositions and their use for hydrogenation of nitrile rubber |
| US9598506B2 (en) | 2011-10-21 | 2017-03-21 | Arlanxeo Deutschland Gmbh | Catalyst compositions and their use for hydrogenation of nitrile rubber |
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Application publication date: 20101117 |