CN1876689A - Method for synthesizing butadiene styrene rubber polymerized from plant fatty acid latex and plant fatty acid - Google Patents
Method for synthesizing butadiene styrene rubber polymerized from plant fatty acid latex and plant fatty acid Download PDFInfo
- Publication number
- CN1876689A CN1876689A CN 200510043775 CN200510043775A CN1876689A CN 1876689 A CN1876689 A CN 1876689A CN 200510043775 CN200510043775 CN 200510043775 CN 200510043775 A CN200510043775 A CN 200510043775A CN 1876689 A CN1876689 A CN 1876689A
- Authority
- CN
- China
- Prior art keywords
- cooh
- fatty acid
- acid
- plant fatty
- vegetable fatty
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention relates the combined distribution of plant fatty acid. The distribution of plant fatty acid has good adjustment, chain length is concentrated, and the linolic acid, which contains conjugate double bonds, is removed. The plant fatty acid is used as abundant, cheap, and stable butadiene styrene rubber emulsifying agent. The invention has the advantages of low cost, fast reaction rate, good emulsion stability, long production facility run duration and stable butadiene styrene rubber quality.
Description
Technical field
The invention belongs to the China Synthetic Rubber Industry field, relate to the SBR emulsion polymeric emulsifiers.
Background technology
Fatty acid soaps (FAD) is traditional SBR emulsion polymeric emulsifiers, the cycle of operation and the styrene-butadiene rubber(SBR) quality of the good bad influence butylbenzene of its quality polymerization rate, equipment.It not only has emulsifying capacity preferably, can adjust rate of polymerization effectively by regulating its proportioning, and can remain in the rubber after the cohesion, improves the performance of styrene-butadiene rubber(SBR).Except stearic acid, also be mixed with a large amount of cool acid, palmitinic acid, oleic acid, linolic acid and other C in the general tallow fatty acid
20H
40-XO
2And C
22H
44-XO
2Acid.The lower fatty acid soap is applicable to the low temperature letex polymerization, and senior saturated fatty acid (stearic acid and Palmiticacid) has effect preferably for the letex polymerization under the comparatively high temps.Unsaturated composition in the lipid acid is very big to polyreaction influence, can significantly reduce polymerization rate, but unsaturated composition can not be very little, otherwise the solvability of lipid acid is bad, should keep the olefin(e) acid of some amount.Linoleic acid plus linolenic acid (CH=CH-CH=CH-) plays inhibition, can postpone polymerization and the plasticity of SBR is increased because of containing conjugated double bond.The preparation tallow fatty acid need be slaughtered a large amount of oxen and sheep, because abundant, cheap and easy to get having obtained in the SBR emulsion polymerization in its source used widely.But recent years, domestic SBR of emulsion polymerization output increase and makeup were increasing to the demand of Tallow Inedible Grade, and tallow fatty acid more and more can not satisfy the needs in market; And tallow fatty acid is owing to the place of production, asynchronism(-nization), and it is bigger that product is formed variation, the quality instability; The carbon chain lengths of tallow fatty acid has the trend of reduction in recent years, and the bad stability of styrene-butadiene latex causes the device kiss-coating situation of styrene-butadiene rubber(SBR) comparatively serious.The composition complexity of tallow fatty acid it is generally acknowledged that to obtain the lipid acid of close component from other channel very difficult, and vegetable fatty acid is to be got by vegetables oil, and raw material sources are abundant, and price is lower, and quality product can guarantee uniform and stable for a long time.In recent years, along with continuous advancement in technology, the technology that the lipid acid of different carbon chain lengths is isolated in the vegetables oil hydrolysis reaches its maturity, the lipid acid that makes fusion go out to meet the styrene-butadiene rubber(SBR) use becomes possibility, and the lipid acid of preparation is formed stable, and can be with the linoleic removal of its inhibition in the tallow fatty acid, make vegetable fatty acid become source abundant, form stable styrene-butadiene rubber(SBR) emulsifying agent.
Summary of the invention
The technical problem that will solve of the present invention provides a kind of method of vegetable fatty acid letex polymerization synthesizing butadiene styrene rubber, can reduce the production cost of styrene-butadiene rubber(SBR), improve polymerization rate, help the long-term operation of production unit and stablizing of styrene-butadiene rubber(SBR) quality; Another object of the present invention provides the vegetable fatty acid that is fit to the letex polymerization synthesizing butadiene styrene rubber.
The method of vegetable fatty acid letex polymerization synthesizing butadiene styrene rubber of the present invention is characterized in that the emulsifier for emulsion polymerization fatty acid soaps is obtained by the vegetable fatty acid saponification, adopts chromatogram analysis method, and the quality compositing range of described vegetable fatty acid is:
C
14H
30COOH (palmitinic acid is called for short C14:0): 0-5.0%;
C
16H
34COOH (Palmiticacid is called for short C16:0): 10-60%;
C
18H
38COOH (stearic acid is called for short C18:0): 2-60%;
C
18H
36COOH (oleic acid is called for short C18:1): 10-70%;
C
18H
34COOH (linolic acid is called for short C18:2): 0-6.0%;
Saturated acid: 30-80%;
C
18H
36COOH/C
18H
38COOH(C18:1/C18:0) 0.5-15；
C
18H
36COOH/C
16H
34COOH(C18:1/C16:0) 0.5-3；
C
18H
36COOH/C
14H
30COOH(C18:1/C14:0) 0-35；
C
18H
36COOH/ saturated acid (C18:1/ saturated acid) 30-80%.
The preferred quality compositing range of above-mentioned vegetable fatty acid is:
Vegetable fatty acid sodium hydroxide saponification, saponification liquor become transparent after, regulate PH and promptly substitute the emulsifier component that the tallow fatty acid soap is used for synthesizing butadiene styrene rubber to criterion of acceptability.Adopt the vegetable fatty acid soap not change the production technique of letex polymerization synthesizing butadiene styrene rubber.Other auxiliary agents such as the qualified sodium soap soap lye of configuration and nilox resin acid potash soap liquid are configured to the qualified soap lye that mixes, these processes and the used tallow fatty acid layoutprocedure consistent (comprising the saponification of vegetable fatty acid) of styrene-butadiene rubber(SBR) production according to a certain percentage.Mix in the standard production process adding polymeric kettle according to SBR of emulsion polymerization such as soap, water, divinyl, vinylbenzene, molecular weight regulator, reductive agent, be cooled to 5 ℃, add initiator, polyreaction begins.When polyreaction reaches predetermined transformation efficiency, add terminator, stop polyreaction.These are prior art technology.
The production of the natural acid of China is raw material with plam oil, Oleum Gossypii semen, cottonseed oil foot, rapeseed oil mainly, South East Asia is raw material with plam oil, Oleum Cocois, palm-kernel oil, American-European, Japanese except that utilizing natural fats and oils, also from Yatall MA, separate ready denier oil acid.The composition of vegetable fatty acid and tallow fatty acid have bigger difference, the middle-and-high-ranking fatty acid content height of tallow fatty acid, stearic acid, Palmiticacid, oleic acid proportion are higher, and the poly-composition of resistance such as linolic acid is less, forms the production of the suitable low temperature SBR of emulsion polymerization of structure; The lower aliphatic acid content is higher in the vegetable fatty acid, the poly-linoleic content of composition of resistance generally accounts for more than 30% of total amount, have only through after separation or the shortening, behind the linolic acid and part lower fatty acid of the removal overwhelming majority, just can be used for the production of styrene-butadiene rubber(SBR).In recent years, along with the domestic big production equipment of several covers of having introduced, throughput, technical capacity have increased significantly, and the composition after lipid acid is refining can reach the level of styrene-butadiene rubber(SBR) production with emulsifying agent.
The preparation of vegetable fatty acid is that vegetables oil is hydrolyzed into pure and mild lipid acid under acidic conditions, lipid acid obtains corps acid through the light component of rectifying cut-out, and corps acid is allocated (mixing) by specified carbon type distribution (quality compositing range) and a spot of lower fatty acid and formed.
Because saturated fatty acid content is lower in the Vegetable oil lipoprotein, can carry out appropriate hydrogenation earlier to Vegetable oil lipoprotein,, reduced the linoleic content of inhibition to improve the content of saturated fatty acid.
The Vegetable oil lipoprotein hydrolysis is the first step of producing vegetable fatty acid, plant and working condition according to different oil, greasy method for hydrolysis mainly contains saponification acid hydrolyzation, normal pressure catalyst hydrolysis method, grease and adds enzyme hydrolysis method, low pressure (catalyst or do not have catalyst) batch hydrolysis, " high pressure list tower ", " middle pressure double tower " and do not have catalyst hydrolysis method etc. continuously.Make intermediates such as croude fatty acids and glycerine after the Vegetable oil lipoprotein hydrolysis, croude fatty acids separates the required lipid acid of preparation styrene-butadiene rubber(SBR) again.The separation method of lipid acid mainly contains freezing squeezing partition method, organic solvent partition method, tensio-active agent partition method, rectifying separation method, urea bag and partition method etc., after separating, obtain corps acid, modulate the vegetable fatty acid that is used for styrene-butadiene rubber(SBR) production usefulness more as required again.
Advantage of the present invention:
The carbon type distribution controllability of vegetable fatty acid is stronger, and the carbon chain lengths of lipid acid is comparatively concentrated, and polymerization has the poly-composition of the resistances such as linolic acid that contain conjugated double bond of inhibition to reject to styrene-butadiene rubber(SBR).That vegetable fatty acid becomes source is abundant, cheap, form stable styrene-butadiene rubber(SBR) emulsifying agent.The fatty acid soaps that obtains with vegetable fatty acid substitutes the tallow fatty acid soap and makes the composition of emulsifying agent and prepare styrene-butadiene rubber(SBR), and production cost is low, and polymerization production process is easy to control, polymerization rate is fast, latex stability is good, and the production unit cycle of operation is long, the styrene-butadiene rubber(SBR) steady quality.
Embodiment
Further specify the present invention with comparative example in conjunction with the embodiments, but do not limit the scope of the invention.
The carbon type of vegetation fat acid product distributes and sees embodiment 1-4.
The by-product oil soap stock hydrolysis of different industrial refining oils obtains acidifying oil, and the processing parameter of hydrolysis: temperature 160-190 ℃, pressure 0.7-1.2MPa, time 5-9 hour, amount of water was the heavy 25%-35% of acidifying oil.About percent hydrolysis 95%, different lipid acid are formed result such as following table after the hydrolysis:
Table 1 acidifying fatty acid oil is formed
| Form title | The behenic acid carburetion | Rape oil acidifying oil | The cotton oil acid carburetion | The Zoomeric acid carburetion |
| C14:0 C16:0 C18:0 C18:1 C18:2 | 0.00 10.25 3.53 25.63 60.52 | 0.00 6.83 2.14 60.38 30.65 | 0.89 17.56 3.08 25.97 52.05 | 1.35 42.10 4.63 41.34 10.58 |
Above-mentioned each lipid acid is at working pressure 10mmHg, service temperature: column bottom temperature 240-260 ℃, in the time of cat head 170-190 ℃, mainly isolate palmitinic acid (C16:0), and according to the difference of palmitic acid content in the raw material, can first rectifying go out the palmitinic acid of part; In the time of cat head 220-230 ℃, oleic acid and linoleic acid content reduce in the overhead distillate, and the lipid acid of low carbon chain obviously reduces in the tower bottoms.
Table 2 is formed for the carbon type of the overhead distillate (having removed a spot of low carbon chain component) of Zoomeric acid carburetion.The carbon type composition of tower bottoms sees Table 3.Tower bottoms with the overhead distillate fusion, can obtain embodiment 2, embodiment 3, embodiment 4 simultaneously through suitable hydrogenation.
Table 2 overhead distillate stratographic analysis result
| Form title | Quality is formed |
| C14:0 C16:0 C18:0 C18:1 C18:2 saturated acid C18:1/ C18:0 C18:1/ C16:0 C18:1/ C14:0 C18:1/ saturated acid % | 0 58.7 2.2 30 5.8 60.90 13.64 0.51 0 49.26 |
Table 3 tower bottoms stratographic analysis result
| Form title | Quality is formed |
| C14:0 C16:0 C18:0 C18:1 C18:2 | 0 34.54 0 52.87 12.59 |
Embodiment 1:
Vegetable fatty acid stratographic analysis result 1 is that the carbon type of the overhead distillate of table 2 Zoomeric acid carburetion is formed.
Embodiment 2
Table 4 vegetable fatty acid stratographic analysis result 2
| Form title | Embodiment 2 |
| C14:0 C16:0 C18:0 C18:1 C18:2 saturated acid C18:1/ C18:0 C18:1/ C16:0 C18:1/ C14:0 C18:1/ saturated acid % | 0.94 48.0 14.76 31.5 0.8 63.7 2.13 0.66 33.51 49.45 |
Embodiment 3
Table 5 vegetable fatty acid stratographic analysis result 3
| Form title | Embodiment 3 |
| C14:0 C16:0 C18:0 C18:1 C18:2 saturated acid C18:1/ C18:0 C18:1/ C16:0 C18:1/ C14:0 C18:1/ saturated acid % | 2.95 37.33 23.74 32.66 0.24 64.02 1.38 0.87 11.07 51.02 |
Embodiment 4
Table 6 lipid acid stratographic analysis result 4
| Form title | Embodiment 4 |
| C14:0 C16:0 C18:0 C18:1 C18:2 saturated acid C18:1/ C18:0 C18:1/ C16:0 C18:1/ C14:0 C18:1/ saturated acid % | 3.58 26.27 28.02 38.25 0.07 57.87 1.46 1.37 10.40 66.09 |
Comparative example
Table 7 tallow fatty acid stratographic analysis result
| Form title | Comparative example |
| C14:0 C16:0 C18:0 C18:1 C18:2 saturated acid C18:1/ C18:0 C18:1/ C16:0 C18:1/ C14:0 C18:1/ saturated acid % | 3.04 25.54 23.27 34.91 0.45 60.00 1.50 1.37 11.48 58.18 |
By above four embodiment and comparative example as can be seen, the carbon type profile adjustment of vegetable fatty acid is comparatively flexible, can prepare the vegetable fatty acid that different carbon types distribute neatly by regulating rectification temperature, the a small amount of lower fatty acid of suitable again allotment, the carbon type that can reach tallow fatty acid fully distributes, and can remove the linolic acid that plays inhibition of the overwhelming majority, the production that helps styrene-butadiene rubber(SBR) is stable.
Below be the effect of vegetable fatty acid in styrene-butadiene rubber(SBR) is produced:
After the vegetable fatty acid saponification, prescription and process according to the standard emulsion styren-butadiene rubber are applied in the styrene-butadiene rubber(SBR), and carry out controlled trial with tallow fatty acid, and vegetable fatty acid sees Table 8 to the situation that influences of polyreaction, the styrene-butadiene rubber(SBR) of preparation is measured its physical and mechanical properties, the results are shown in Table 9.
Table 8 vegetable fatty acid polymerization results
| Project | Comparative example | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Polymerization reaction time (h) | 9.5 | 9.0 | 9.25 | 9.75 | 10.25 |
| Mechanical stability/% | 2.89 | 2.74 | 2.43 | 2.14 | 2.04 |
| Gel content/g | 0.107 | 0.072 | 0.097 | 0.035 | 0.052 |
Table 9 rubber physical mechanical property
| Project | Comparative example | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| ML1+4100 ℃ of rubber Mooney | 55 | 54 | 54 | 53 | 51 | |
| ML1+4100 ℃ of rubber unvulcanizate Mooney | 67 | 68 | 67 | 66.0 | 67.0 | |
| 300% stress at definite elongation (Mpa) | 25′ | 11.8 | 12.3 | 12.1 | 12.5 | 12.6 |
| 35′ | 14.0 | 14.1 | 14.3 | 14.2 | 14.3 | |
| 50′ | 16.0 | 16.2 | 16.4 | 16.5 | 16.7 | |
| Tensile strength MPa 35 ' | 23.7 | 23.9 | 23.8 | 24.8 | 25.0 | |
| Tensile yield %35 ' | 498 | 502 | 509 | 518 | 507 | |
Vegetable fatty acid linoleic acid content among embodiment 1, the embodiment 2 is higher, the lower aliphatic acid content is lower, polymerization rate is slower slightly than comparative example, and the mechanical stability of latex and gel content and tallow fatty acid are more or less the same, and the physicals of rubber is also close with tallow fatty acid; Vegetable fatty acid linoleic acid content among embodiment 3, the embodiment 4 obviously reduces, the carbon type distributes close with tallow fatty acid, polymerization rate obviously improves, and the mechanical stability and the gel content of latex are better than tallow fatty acid, and the physicals of rubber is better than tallow fatty acid.
Claims (4)
1, a kind of method of vegetable fatty acid letex polymerization synthesizing butadiene styrene rubber is characterized in that the emulsifier for emulsion polymerization fatty acid soaps is obtained by the vegetable fatty acid saponification, and the quality compositing range of described vegetable fatty acid is:
C
14H
30COOH： 0-5.0％；
C
16H
34COOH： 10-60％；
C
18H
38COOH： 2-60％；
C
18H
36COOH： 10-70％；
C
18H
34COOH： 0-6.0％；
Saturated acid: 30-80%;
C
18H
36COOH/C
18H
38COOH 0.5-15；
C
18H
36COOH/C
16H
34COOH 0.5-3；
C
18H
36COOH/C
14H
30COOH 0-35；
C
18H
36COOH/ saturated acid 30-80%.
2, method according to claim 1 is characterized in that the quality compositing range of vegetable fatty acid is:
C
14H
30COOH： 3-4％；
C
16H
34COOH： 20-30％；
C
18H
38COOH： 20-30％；
C
18H
36COOH： 30-40％；
C
18H
34COOH： 0-5.0％；
Saturated acid: 55-70%;
C
18H
36COOH/C
18H
38COOH 1.2-1.8；
C
18H
36COOH/C
16H
34COOH 1.2-1.8；
C
18H
36COOH/C
14H
30COOH 8-15；
C
18H
36COOH/ saturated acid 50-60%.
3, the vegetable fatty acid of the described letex polymerization synthesizing butadiene styrene rubber of a kind of claim 1 is characterized in that the quality compositing range of vegetable fatty acid is:
C
14H
30COOH： 0-5.0％；
C
16H
34COOH： 10-60％；
C
18H
38COOH： 2-60％；
C
18H
36COOH： 10-70％；
C
18H
34COOH： 0-6.0％；
Saturated acid: 30-80%;
C
18H
36COOH/C
18H
38COOH 0.5-15；
C
18H
36COOH/C
16H
34COOH 0.5-3；
C
18H
36COOH/C
14H
30COOH 0-35；
C
18H
36COOH/ saturated acid 30-80%.
4, vegetable fatty acid according to claim 3 is characterized in that the quality compositing range of vegetable fatty acid is:
C
14H
30COOH： 3-4％；
C
16H
34COOH： 20-30％；
C
18H
38COOH： 20-30％；
C
18H
36COOH： 30-40％；
C
18H
34COOH： 0-5.0％；
Saturated acid: 55-70%;
C
18H
36COOH/C
18H
38COOH 1.2-1.8；
C
18H
36COOH/C
16H
34COOH 1.2-1.8；
C
18H
36COOH/C
14H
30COOH 8-15；
C
18H
36COOH/ saturated acid 50-60%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510043775 CN1876689A (en) | 2005-06-11 | 2005-06-11 | Method for synthesizing butadiene styrene rubber polymerized from plant fatty acid latex and plant fatty acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510043775 CN1876689A (en) | 2005-06-11 | 2005-06-11 | Method for synthesizing butadiene styrene rubber polymerized from plant fatty acid latex and plant fatty acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1876689A true CN1876689A (en) | 2006-12-13 |
Family
ID=37509266
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200510043775 Pending CN1876689A (en) | 2005-06-11 | 2005-06-11 | Method for synthesizing butadiene styrene rubber polymerized from plant fatty acid latex and plant fatty acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1876689A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101597383B (en) * | 2009-07-10 | 2011-11-30 | 淄博腾辉油脂化工有限公司 | Synthetic process of emulsifier special for rubber |
| CN108192739A (en) * | 2017-12-19 | 2018-06-22 | 如皋市傲东化工有限公司 | A kind of fatty acid formulation for surfactant production |
-
2005
- 2005-06-11 CN CN 200510043775 patent/CN1876689A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101597383B (en) * | 2009-07-10 | 2011-11-30 | 淄博腾辉油脂化工有限公司 | Synthetic process of emulsifier special for rubber |
| CN108192739A (en) * | 2017-12-19 | 2018-06-22 | 如皋市傲东化工有限公司 | A kind of fatty acid formulation for surfactant production |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1854277B (en) | Process for producing fat or oil | |
| EP0902082B1 (en) | Production of materials rich in conjugated isomers of long chain polyunsaturated fatty acid residues | |
| AU2005233615B2 (en) | Method of preparing fatty acid alkyl esters from waste or recycled fatty acid stock | |
| EP1894913A1 (en) | Production of esters of fatty acids and lower alcohols | |
| Wang et al. | Novel biodiesel production technology from soybean soapstock | |
| CN1133032A (en) | Method of producing fatty alcohols from vegetable oils by fractional distillation | |
| CN1071298C (en) | Unsaturated fatty substances with improved cold behaviour | |
| CN1105094C (en) | Unsaturated fats with improved low-temp behaviour | |
| CN1876689A (en) | Method for synthesizing butadiene styrene rubber polymerized from plant fatty acid latex and plant fatty acid | |
| EP1892232A1 (en) | Production of esters of fatty acids and lower alcohols | |
| CN1142033C (en) | Process for preparing floatation catcher of iron ore | |
| US7560579B2 (en) | Process for preparing purified fatty acids | |
| CN104086412A (en) | Process method for producing butyl oleate by using rape oil fatty acid | |
| CN1257253C (en) | Biological diesel fuel preparing method from natural grease | |
| US6409649B1 (en) | Method for commercial preparation of conjugated linoleic acid using recycled alkali transesterification catalyst | |
| ZA200601185B (en) | Process for preparing purified fatty acids | |
| DE102008008319B4 (en) | Treatment of salt and glycerine-containing residues | |
| CN1031070C (en) | Producing technology for fathy acid alkyl ester | |
| WO2021167338A3 (en) | Method for producing low-viscosity dimer acid | |
| CN1133878A (en) | Process for preparing semi-saturated fatty acid | |
| US5296576A (en) | Fatty oil ex Helianthus annuus for the production of emulsifiers for emulsion polymerization | |
| Beal et al. | Soybean soapstock utilization: Fatty acid adducts with ethylene and 1‐butene | |
| CN1048481C (en) | Technological process of preparing fatty acid with the side product from sebacid acid production | |
| CN1242113C (en) | Slivering and crude oil | |
| KR100808806B1 (en) | Enzymatic process for the isolation of fatty acid from high erucic acid rapeseed oils |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |