CN1163273A - Process for producing rubber - Google Patents
Process for producing rubber Download PDFInfo
- Publication number
- CN1163273A CN1163273A CN 97101286 CN97101286A CN1163273A CN 1163273 A CN1163273 A CN 1163273A CN 97101286 CN97101286 CN 97101286 CN 97101286 A CN97101286 A CN 97101286A CN 1163273 A CN1163273 A CN 1163273A
- Authority
- CN
- China
- Prior art keywords
- rubber
- latex
- acid
- dispersion liquid
- ethylhexyl
- 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.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C1/00—Treatment of rubber latex
- C08C1/14—Coagulation
- C08C1/15—Coagulation characterised by the coagulants used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C1/00—Treatment of rubber latex
- C08C1/02—Chemical or physical treatment of rubber latex before or during concentration
- C08C1/065—Increasing the size of dispersed rubber particles
- C08C1/07—Increasing the size of dispersed rubber particles characterised by the agglomerating agents used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention provides a method for producing rubber by using latex. The method includes: adding acid into latex on rubber tree (trefoil rubber tree) collection point to accelerate latex solidification. Typical acid is formic which is preferably added into latex as a part of dispersible liquid which further includes four di(2-ethylhexyl) thiuram dissuified and/or tetramethyl thiuram dissuified and ZnO and Kcl. The product prepared in such a manner can be processed like traditional rubber production, the performance thereof is better than the rubber prepared by traditional method. It can be stored for several weeks before processing and offensive smell will not generates in further processing procedure.
Description
The present invention relates to a kind ofly produce improving one's methods of rubber, especially relate to a kind of method that comprises that the latex to collection place of rubber (Hevea) tree solidifies by latex.
Extract latex by so-called rubber tapping method from rubber tree traditionally.For this reason, can be by bark cutting technique (cut the banded bark of trunk so that impel latex to flow out (tapping rubber continuously)) by being same as above-mentioned cutting cutting thin layer bark, or promptly by this technology bark is made one or more perforation by the bark cutting technique and impel latex to flow out to realize rubber tapping.The latex that flows out tree is collected in (both is connected on the trunk) in the cup or in the laminated bag usually.Rubber tapping can repeat regular interval to be carried out, general at every turn tap rubber from same rubber tree every other day.
Latex is by solidifying formation rubber.Traditionally, take the latex of collection away, and in factory, carry out the solid step of acid cure subsequently from rubber tree.
Remaining untreated rubber wherein keeps in the tree in the collection cups or in the laminated bag or if the latex of taking away and storing suffers to solidify automatically formation " cup lump " after several days, this cup lump has the outward appearance that becomes the black micelle.Only cup lump just produces very strong taste beastly after several days, and this produces owing to bacterium causes the degraded of albumen egg.On the contrary, the solid latex of acid cure has the outward appearance of white micelle, does not send any taste of surveying.Latex that acid cure is solid and cup lump are all handled with hevea particle method then usually, and this method is in the nineteen sixty exploitation and be widely adopted (British Patent No. 1075234) from then on.Hevea particle method comprises presses solid latex of crape acid cure or cup lump to cause blob of viscose fragmentary.Dried material is packed the piece material that generates then, and according to color and foreign matter content deciding grade and level.The rubber that Malaysia produces is according to the various rank classifications of the Malaysian rubber (SMR) of standard.The SMRL (latex solution) that is produced by the solid latex of acid cure has extra best best.Produce SMR10 and SMR20 by cup lump, numeral refers to foreign matter content.The rubber of SMR10 and SMR20 level is used to make the goods such as doughnut.
SMR10 and SMR20 level rubber have all found to have good market, particularly at US and European.As last pointed, these other rubber of level of being given birth to by the cup lump that solidifies automatically can generation make us very offending smell in several days.In addition, these other rubber of level also produce a kind of offensive odour in the course of processing subsequently at it.This just hinders its use in some countries.Particularly, exsiccant cup lump material produces unpleasant taste, and this point is that environment is unacceptable, scrubber need be installed to absorb 90% smell on production line.In addition, be the latex-based material such as these countries of Japan because of it, so prefer with RSS level rubber (one-level smoked sheet).For RSS produces, collect open-air latex, and in factory, in container, use formic acid to carry out with after coagulation.Then coagulum is crumpled into sheet rubber, and with sheet rubber at the smoke-box inner drying.
Therefore need a kind of improving one's methods by latex production rubber.Especially, this method avoids the rubber item produced to produce taste beastly in the course of processing subsequently at mixing state and/or its.The described a kind of method that provides is provided in the present invention.
According to the invention provides a kind of method of producing rubber by latex, this method comprises acid is added in the latex at rubber tree bleeding point place to cause latex coagulation.The present invention also provides the coagulum that is produced by this method, and the rubber by the finished product form of using described method production also is provided in addition.
Here it is, and adding acid makes latex coagulation.Preferably use formic acid.The amount that needs to add acid is at least 0.6% (weight) based on wet open-air weight of latex, and more preferably amount is for about 4%.The amount that adds latex acid influences latex coagulation speed, exists favourable promotion to solidify in general in a large number.
Preferably the part as dispersion liquid is added to acid in the latex, and this dispersion liquid also comprises one or more following components: four pairs of (2-ethylhexyl) thiuram disulphide also have following formula
This compound is easily buied, and for example by Japan, the Ouchi ShinkoChemical Industrial company limited in Tokyo is that TOT-N sells with the trade mark.It is called a kind of new promotor, is used in dry rubber substance and the latex mixing to overcome the problem of volatilization nitrosamine.Zinc oxide (ZnO) Repone K (KCl)
Tetramethyl-thiuram disulfide (TMTD) is the known latex enriched material that is used for protecting; in the compounding rubber operation also is a kind of high-speed vulcanization promotor; be often used as second promotor; remove beyond four pairs of curing (2-ethylhexyl) thiuram; or replace four pairs of (2-ethylhexyl) thiurams of curing, also can there be TMTD.TMTD easily buys and is for example sold by the Bayer of Germany and Britain ICI.It will be appreciated that ZnO and KCl component also can be replenished or replaced by similar substance, this similar material has same effect, and for example NaCl can be used to replace KCl or uses with KCl.
Be applicable to that the typical dispersion in the inventive method comprises at least 0.6% formic acid, four pairs of (2-ethylhexyl) thiurams of at least 0.0125% curing and/or at least 0.0125% tetramethyl-thiuram disulfide, and 0.0125%ZnO and at least 0.01% KCl at least, all percentage ratios are the weight percentage of benchmark based on the wet open-air weight of latex of handling all.
When acid was solidified latex, other component of believing aforesaid dispersion liquid was used for preventing or delays proteinic decomposition, and proteinic decomposition takes place by bacteriological action and follows above-mentioned offensive odour.
Method feature of the present invention is to carry out solidifying of latex by the latex of panama rubber tree bleeding point.It is in the tree the cup or in the laminated bag that latex generally is collected in, and realizes coagulation step of the present invention in the described container by acid is simply splashed into the most usually.Yet, should understand that solid step is actual can take latex from cup or in the laminated bag away before finishing in acid cure.Essential characteristic is just to solidify from rubber tree collection latex the time or in very short time subsequently to take place.
Preferably acid is added in the latex a part as the above-mentioned type dispersion liquid.The most common dispersion liquid is splashed in the latex as a kind of preformed mixture.Yet one or more other components that it will be appreciated that acid and dispersion liquid splash into separately in the latex and also both can simultaneously or splash into successively fast.
When taking the solid micelle of acid cure away, inject the underground fertilizer effect of playing with remaining glue is clear.The coagulum that uses method of the present invention to obtain is white and can stores at least three weeks.At bleeding point on the rubber tree or after transporting to storage at, do not produce taste beastly or show other sign of degraded.The glue coagulum can be processed and carries out favourable comparison according to its performance as usually producing rubber.In addition, have found that the rubber of producing by method of the present invention does not produce taste beastly in its course of processing subsequently.
In traditional SMR factory, need two production lines alone, i.e. processing SMRL rubber (i.e. the latex level rubber that obtains by latex, this latex has carried out gelling in factory handles admittedly) and another treatment S MR10 and SMR20 (promptly by the short rubber that solidifies cup lump production automatically).But use the latex that solidifies that produces by method of the present invention only to need a single standard production line and use the following step:
According to overall efficiency and cost savings, only needing in the factory, a single standard (the single processing) production line is conspicuous and has caused the applicant to get the single Malaysian rubber (or SUMAR) of handling of generation product standard.The advantage of the inventive method comprises as follows: * the present invention can produce the rubber (promptly have foreign matter content and be lower than 0.02%) of latex level.* production of the present invention presents the rubber of good rerum natura and can further process with traditional method.* rubber item does not produce offensive odour, can not produce in several weeks even store in further first being processed yet.Can not produce offensive odour in the course of processing subsequently at it yet.This method does not produce any pollution in addition.Therefore it is useful can being considered to environment.* present method is effective, can save the labor cost in rubber tree plantation and the Rubber processing factory.Therefore it has very strong cost competitiveness.* present method can be applicable to anyly need conventional rubber or more in the final rubber item of specialty elastomer.Suitable chemical simply is included in the dispersion liquid, dispersion liquid is splashed in the latex at rubber tree bleeding point place.For example obtain light-colour rubber by the disulphide that adds sodium; By adding the rubber of hydroxyl neutral sulfatase (HNS) generation stable viscosity; And prepare Deproteinated natural rubber by adding suitable enzymes.
The present invention is described further by the following example.
Embodiment
Use method of the present invention to carry out following technological assessment by the rubber that the solid latex of acid cure forms
The performance of untreated rubber
Table 1 is listed the characteristic and the performance of the various rank Standard Malasian rubber of being stipulated at present by Malaysia (SMR) that just needing.
The result that the required specification that the rubber sample that table 2 expression is produced by method of the present invention (being called " new rubber ") his-and-hers watches 1 are listed obtains when estimating.By the SMRL that commercial sources obtains, SMR10, the sample of SMR20 and RSS3 is tested under the same conditions in order to compare purpose.New as can be seen rubber has low impurity content level very even good than SMRL, and has high PO value.Yet the PRI value is lower than SMRL, but will get well and can be comparable with SMR10 and SMR 20 than RSS3.
The performance of unloaded vulcanizate
SMRL, SMR20, the sample of RSS3 and the product (being called " novel material ") that obtains with method of the present invention estimate and the result that will obtain is illustrated in the table 3.The rubber (for example SMR10 and SMR20) that the well-known rubber that is solidified (for example SMRL) latex more solid than acid cure of no use that is produced by traditional method obtains has slower curing time.People know that also if rubber is suitably washed, curing time can improve, and are illustrated as the curing time that the sample by table 3RSS3 obtains.Yet find out that in surprise and advantageously novel material has curing time faster.Even it also is like this admittedly that its manufacturing comprises acid cure.The most of rerum naturas of other that list in the table 3 keep being similar to by these performances that rubber presented of previously known simultaneously, find out also that novel material presents better to tear, and stretch and the compression set characteristic.
The mixing of carbon black rubber unvulcanizate research in Brabender
Three kinds of new rubber that rubber promptly uses the present invention to obtain, the mixing behavior of the sample of SMR20 and RSS3 use the carbon black sizing material to estimate (natural rubber of promptly making filler with carbon black) in the Brabender mixing roll.Obtain following result
Total mixing energy
New rubber (166)＞RSS3 (163)＞SMR20 (159) Nm-minute
Outlet temperature
New rubber (126 ℃)＞RSS3 (121 ℃)＞SMR20 (121 ℃)
Final torque
New rubber (23.7Nm) 〉=RSS3 (23.4Nm)＞SMR20 (21.3Nm)
These results show that new rubber has higher total mixing energy, higher outlet temperature and higher final moment of torsion, and should also be noted that difference only is limited (margmal).
The performance of carbon black cross-linked rubber (50pphr HAF)
The rubber (claiming new rubber) and the sample of rubber SMR20 and RSS3 that use method of the present invention to obtain are estimated, and the result who obtains lists in table 4 and the table 5.The result show new rubber can with as traditional rubber material same procedure process, and have some advantageous feature.
Table 1
Wherein Po is initial plasticity
| ?????SMRL | ?????SMR10 | ?????SMR20 | |
| Impurity, %max ash, %max N 2，％max ?Po，min ?PRI，min ?Mv | ?????0.02 ?????0.5 ?????0.6 ?????35 ?????60 ?????- | ?????0.08 ?????0.75 ?????0.6 ?????30 ?????40 ?????- | ??????0.16 ??????1.00 ??????0.6 ??????30 ??????40 ??????- |
PRI is a plasticity retention index
Mv is a mooney viscosity table 2
| ??RSS3 | New rubber | ???SMRL | ????SMR10 | ???SMR20 | |
| Impurity, % ash, % N 2，％ ?Po ?PRI ?Mv | ????- ????- ????- ????48 ????84 ????85 | ????0.002 ????0.28 ????0.30 ????52 ????67 ????85 | ????0.004 ????0.19 ????0.33 ????44 ????81 ????85 | ????0.023 ????0.29 ????0.30 ????45 ????65 ????85 | ????0.05 ????0.32 ????0.27 ????47 ????69 ????85 |
Table 3
Wherein TS is a tensile strength
| ??SMRL | Novel material | ??SMR20 | ???RSS3 | |
| Time of scorch t5@120 ℃ (minute) curing temperature, ℃ time of scorch t2 (minute) curing time, (minute) TS, MPa EB, % M100, MPa M300, @23 ℃ of MPa Dunlop Dan Xing, % Trouser tears, N/mm IRHD compression set, 22h/70 ℃, % | ??61 ??160 ??5.5 ??9.1 ??24.4 ??730 ??0.9 ??1.9 ??88 ??5.9 ??41 ??35.6 | ????45 ????160 ????3.5 ????7 ????25.5 ????710 ????0.9 ????2.0 ????84 ????8.0 ????42 ????24.8 | ??50 ??160 ??4.4 ??8 ??22.8 ??680 ??0.9 ??2.0 ??91 ??6.6 ??43 ??28.1 | ????55 ????160 ????5.0 ????8 ????24.7 ????700 ????1.0 ????2.3 ????89 ????7.3 ????43 ????28.7 |
EB is an extension at break
IRHD is an intemational rubber hardness degree(IRHD) sclerometer Durometer table 4
| New rubber | ??SMR20 | ????RSS3 | |
| Time of scorch ts@120 ℃ curing temperature, ℃ time of scorch t2, (minute) curing time, t90, (minute) | ????14 ????160 ????2.2 ????4.1 | ????16 ????160 ????2.2 ????4.2 | ????17 ????160 ????2.3 ????4.2 |
Table 5
| Rerum natura | New rubber | ???SMR20 | ???RSS3 |
| TS, MPa EB, % M100, MPa M300, MPa compression set, 22h@70 ℃ of Din abrasion, ARI Akron abrasion, % loss/1000 goes back to elasticity, %@23 ℃ of Trouser tears, N/mm gives birth to 100 ℃ of temperature temperature @120 mins of heat (0.025 "/24 1b); a ℃ IRHD DeMattia subdues the C level; the anti-scarfing of kilocycle increases aging 7 days/70 ℃ TS of property 2-4mm kilocycle 4-8mm kilocycle 8-12mm kilocycle; MPa EB, % M100 M300 IRHD | ????26.8 ????540 ????2.4 ????10.8 ????32.6 ????103 ????75.5 ????62 ????15.6 ????29.4 ????64 ????70 ????6 ????9 ????15.1 ????25.4 ????500 ????2.9 ????12.5 ????70 | ????27.6 ????550 ????2.4 ????10.9 ????32.9 ????110 ????69.7 ????68 ????16.7 ????26.4 ????26.4 ????83 ????4 ????4.5 ????8.8 ????26.8 ????490 ????2.9 ????13.1 ????69 | ????26.1 ????510 ????2.7 ????11.9 ????33.9 ????94 ????65.9 ????65 ????11.2 ????34.0 ????34.0 ????53 ????6 ????12.8 ????30.9 ????26.3 ????470 ????3.6 ????14.7 ????71 |
Claims (9)
1 one kinds of methods of producing rubber by latex, this method comprise acid are added in the latex at rubber tree bleeding point place so that make latex coagulation.
2 according to the process of claim 1 wherein that acid comprises formic acid.
3 methods according to claim 2, wherein the formic acid add-on is about 4% (weight) of wet open-air weight of latex.
4 each methods according to aforementioned claim, wherein acid adds in the latex as the part of dispersion liquid, and described dispersion liquid also comprises four pairs of curing (2-ethylhexyl) thiuram and/or tetramethyl-thiuram disulfide.
5 methods according to claim 4, wherein dispersion liquid also comprises zinc oxide and Repone K.
6 methods according to claim 4 or 5, wherein dispersion liquid comprises at least 0.6% formic acid, four pairs of (2-ethylhexyl) thiurams of at least 0.0125% curing and/or at least 0.0125% tetramethyl-thiuram disulfide, at least 0.0125% zinc oxide, at least 0.01% Repone K, all percentage ratios are the weight percentage based on wet open-air weight of latex.
7 coagulums of producing by each method of claim 1 to 6.
The rubber of the 8 finished product forms of producing by each method of claim 1 to 6.
9 dispersion liquids that use according to each method of claim 4 to 6, this dispersion liquid comprises at least 0.6% formic acid, four pairs of (2-ethylhexyl) thiurams of at least 0.0125% curing and/or at least 0.0125% tetramethyl-thiuram disulfide, at least 0.0125% zinc oxide, at least 0.01% Repone K, all percentage ratios are based on the weight percentage of wet open-air weight of latex.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| MYPI9600470 | 1996-02-08 | ||
| MYPI9600470 | 1996-02-08 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1163273A true CN1163273A (en) | 1997-10-29 |
| CN1161385C CN1161385C (en) | 2004-08-11 |
Family
ID=19749732
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB971012865A Expired - Fee Related CN1161385C (en) | 1996-02-08 | 1997-02-07 | Process for producing rubber |
Country Status (4)
| Country | Link |
|---|---|
| CN (1) | CN1161385C (en) |
| BR (1) | BR9700934A (en) |
| ID (1) | ID15901A (en) |
| OA (1) | OA10599A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111295296A (en) * | 2017-11-23 | 2020-06-16 | 米其林集团总公司 | Natural rubber |
-
1997
- 1997-02-07 BR BR9700934A patent/BR9700934A/en not_active IP Right Cessation
- 1997-02-07 CN CNB971012865A patent/CN1161385C/en not_active Expired - Fee Related
- 1997-02-07 OA OA60965A patent/OA10599A/en unknown
- 1997-02-07 ID IDP970384A patent/ID15901A/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111295296A (en) * | 2017-11-23 | 2020-06-16 | 米其林集团总公司 | Natural rubber |
| US11345795B2 (en) | 2017-11-23 | 2022-05-31 | Compagnie Generale Des Etablissements Michelin | Natural rubber |
Also Published As
| Publication number | Publication date |
|---|---|
| BR9700934A (en) | 1998-12-08 |
| CN1161385C (en) | 2004-08-11 |
| ID15901A (en) | 1997-08-14 |
| OA10599A (en) | 2002-07-10 |
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| PB01 | Publication | ||
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| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
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| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20040811 Termination date: 20120207 |