CN103232559B - Method for improving various technical indexes of skim rubber to meet requirements of standard Chinese rubber No. 10 - Google Patents
Method for improving various technical indexes of skim rubber to meet requirements of standard Chinese rubber No. 10 Download PDFInfo
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- CN103232559B CN103232559B CN201310111954.5A CN201310111954A CN103232559B CN 103232559 B CN103232559 B CN 103232559B CN 201310111954 A CN201310111954 A CN 201310111954A CN 103232559 B CN103232559 B CN 103232559B
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Abstract
The invention discloses a method for improving various technical indexes of skim rubber to meet the requirements of standard Chinese rubber No. 10 (SCR-10). The method includes: first using protease to treat skim latex, adding a surfactant to conduct surface replacement, adding sodium pyrosulfite to resist oxidation, then performing solidification, curing, tabletting and granulation, then putting wet gel in a sodium hydroxide solution, an oxalic acid solution and a calcium carbonate solution to soak respectively, and finally carrying out drying so as to obtain the skim rubber with various technical indexes meeting the requirements of SCR-10. The method effectively improves the skim rubber value, and has the characteristics of simple operation and low cost, thus completely having the prospects of industrialized popularization and application.
Description
[technical field]
The present invention relates to natural rubber Primary processing technology field, particularly a kind of all technical improving skim rubber reaches the method that standard rubbers No. 10 glue require.
[background technology]
To be fresh natural rubber latex prepare by centrifugal concentrating byproduct-skim latex that concentrated natural latex obtains to skim rubber prepares.Use skim rubber prepared by skim latex, rubber hydrocarbon content is 75-80%, and protein content is 8-15%, and acetone molten thing content is that 5-10% and the inorganic salt content such as copper, manganese are higher.And the standard rubbers using fresh latex to prepare, ordinary rubber hydrocarbon content is about 95%, and the molten thing content of acetone is about 3%, and protein content is about 2%.Relative to standard rubbers, skim rubber quality, performance, class are all very low, contrast with SCR-5, SCR-10 in standard GB/T/T8081-2008/ISO2000:2003 " caouttchouc technically classified rubber (TSR) specification directive/guide ", the plasticity initial value (P of skim rubber can be found
0), plasticity retention(percentage) (PRI) is lower, nitrogen content, ash grade higher, therefore, cause cheap.
In view of the present situation of skim rubber, there is the research for improving glue gel resin indices and performance for a long time always.The people such as Chen Guixiong (tropical crops journal, 30 (2): 211-214,2009) by nm-class montmorillonite filled skim rubber, improve P0, PRI and the mechanical property of skim rubber, but other all technicals do not improve, and the mechanical property of mineral filler raising rubber is a kind of method of routine.
Therefore, be necessary to provide a kind of performance that both effectively can improve skim rubber, make its all technical be up to state standards the requirement of the SCR-10 in GB/T8081-2008/ISO2000:2003 " caouttchouc technically classified rubber (TSR) specification directive/guide " simultaneously, easy and simple to handle again, method with low cost.
[summary of the invention]
A kind of the object of the present invention is to provide all technical improving skim rubber to reach method that standard rubbers No. 10 glue require (SCR-10).
Specifically, the present invention uses the protein in Sumizyme MP enzymolysis skim latex, anion surfactant (sodium lauryl sulphate) assists protease hydrolyzed and isolated protein, water-fast protein is processed into water-soluble small protein (or polypeptide, amino acid), the obtained skim latex processed; In the skim latex processed, add Sodium Pyrosulfite keep the color and luster of dry glue and improve its oxidation-resistance, the obtained skim latex again processed; Then by skim latex use 6% sulphuric acid soln solidify, slaking, compressing tablet, granulation, obtain skim rubber wet gel particle; Again wet gel particle is placed in respectively sodium hydroxide, oxalic acid and calcium carbonate soln solution to soak, finally dry, obtain all technical and to be up to state standards the skim rubber that SCR-10 in GB/T8081-2008/ISO2000:2003 " caouttchouc technically classified rubber (TSR) specification directive/guide " requires.
Specific embodiments of the present invention are as follows:
(1), by proteolytic enzyme be dissolved in deionized water, then join in skim latex, and then add anion surfactant, 40 DEG C of stirred in water bath 24h, the obtained skim latex processed;
(2), by Sodium Pyrosulfite be dissolved in deionized water, join in the latex that (1) prepare, the obtained skim latex again processed;
(3) latex coagulation that (2) prepare by the sulphuric acid soln, with 6%, slaking, compressing tablet, granulation, obtain skim rubber wet gel particle;
(4) the skim rubber wet gel particle, by (3) obtained, is first placed in sodium hydroxide solution and soaks 24h; Take out wet gel particle, then the oxalic acid solution be placed in soaks 24h; Take out wet gel particle again, then be placed in calcium carbonate soln and soak 24h; Finally adopt the temperature of 110-120 DEG C to be dried by micelle, obtain the skim rubber that all technical standard rubbers No. 10 glue (SCR-10) be up to state standards in GB/T8081-2008/ISO2000:2003 " caouttchouc technically classified rubber (TSR) specification directive/guide " require.
One raising skim rubber all technical of the present invention reaches the method that standard rubbers No. 10 glue (SCR-10) require, described skim rubber adopts to prepare the by product after concentrated natural latex by fresh natural rubber latex is centrifugal---skim latex processing preparation.
One raising skim rubber all technical of the present invention reaches the method that standard rubbers No. 10 glue (SCR-10) require, described proteolytic enzyme is the Sumizyme MP of active 500,000 u/g, its consumption is add 2g-5g in per kilogram skim latex, and is made into the solution that concentration is 5%.
One raising skim rubber all technical of the present invention reaches the method that standard rubbers No. 10 glue (SCR-10) require, described anion surfactant is sodium lauryl sulphate, its consumption is add 1g-5g in per kilogram skim latex, and is made into the solution that concentration is 1%.
One raising skim rubber all technical of the present invention reaches the method that standard rubbers No. 10 glue (SCR-10) require, the consumption of described Sodium Pyrosulfite is add 0.5g-2g in per kilogram skim latex, and is made into the solution that concentration is 0.5%.
One of the present invention improves skim rubber all technical and reaches the method that standard rubbers No. 10 glue (SCR-10) require, it is the calcium carbonate soln of the sodium hydroxide solution of 5%-10%, the oxalic acid solution of 1%-3% and 0.5%-3% respectively that described wet gel soaks what adopt.
One raising skim rubber all technical of the present invention reaches the method that standard rubbers No. 10 glue (SCR-10) require, described wet gel bake out temperature is 110-120 DEG C.
Therefore, one raising skim rubber all technical of the present invention reaches the method that standard rubbers No. 10 glue (SCR-10) require, preferably adopts following embodiment:
(1) Sumizyme MP being, 500,000 u/g by 2g-5g activity is dissolved in deionized water, be made into the solution that concentration is 5%, then join in 1000g skim latex, and then add 1g-5g sodium lauryl sulphate, add and be fashionablely made into the sodium dodecyl sulfate solution that concentration is 1%, 40 DEG C of stirred in water bath 24h, the obtained skim latex processed;
(2), by 0.5g-2g Sodium Pyrosulfite be dissolved in deionized water, be made into the solution that concentration is 0.5%, join in (1) obtained latex, stir 2h, the obtained skim latex again processed;
(3) sulphuric acid soln, with 6%, by latex coagulation obtained to (2), slaking, compressing tablet, granulation, obtains skim rubber wet gel particle;
(4) it is that the sodium hydroxide solution of 5%-10% soaks 24h that the skim rubber wet gel particle, (3) obtained first is placed in concentration; Take out wet gel particle, then to be placed in concentration be that the oxalic acid solution of 1%-3% soaks 24h; Take out wet gel particle again, then to be placed in concentration be that the calcium carbonate soln of 0.5%-3% soaks 24h; Finally adopt the temperature of 110-120 DEG C to be dried by micelle, obtain the skim rubber that all technical reaches standard rubbers No. 10 glue requirements.
Key point of the present invention
Key problem in technology point of the present invention is:
1. the selection of proteolytic enzyme: because skim latex is the by product that concentrated natural latex is prepared in the centrifugal processing of fresh natural rubber latex, therefore nitrogen content is high, skim latex is in alkalescence.The present invention selects Sumizyme MP on the one hand for decomposing protein, becomes small-molecule substance soluble in water; Sumizyme MP is active high in alkaline environment on the other hand, and speed of response is fast.
2. the selection of tensio-active agent: kinds of surfactants is a lot, comprising: cats product, anion surfactant, nonionogenic tenside etc.The sodium lauryl sulphate that the present invention adopts is as anion surfactant, and this promoting agent had both been improved the effect of latex stability, can be accelerated again the hydrolysis of latex particle surface protein by metathesis.
3. the selection of antioxidant: the present invention selects Sodium Pyrosulfite as antioxidant, object is the antioxidant property improving skim rubber.
4. the selection of peptizer: skim latex ammonia is containing higher, and drc is low, and the sulphuric acid soln of choice for use 6% of the present invention solidifies.
5. the selection of soaking solution: the selection of soaking solution of the present invention mainly in order to reduce protein in skim latex and ash content, does not affect all technical of skim rubber simultaneously.Sodium hydroxide solution is used to soak wet gel, with peptizer (sulfuric acid) simultaneously; Use in oxalic acid and sodium hydroxide solution, finally adopt in a small amount of calcium carbonate soln and oxalic acid.
Effect of the present invention
The present invention by proteolytic enzyme and antioxidant process skim latex, obtained indices and performance is that obviously promote, high-quality skim rubber.According to the testing method test of defined in standard GB/T/T8081-2008/ISO2000:2003 " caouttchouc technically classified rubber (TSR) specification directive/guide ", find the nitrogen content of skim rubber after treatment, ash content obviously reduces; Plasticity initial value (P0), plasticity retention(percentage) (PRI) significantly improve; Mechanical property also has obvious lifting in addition, refers to the test result of the sample of table 1 and embodiment acquisition, has widened skim rubber range of application;
The present invention improves the value of skim rubber effectively, easy and simple to handle, and favorable reproducibility is with low cost, possesses the prospect of industrial application completely.
[subordinate list explanation]
Table 1 is the contrast of the indices of the technical requirements of No. 10 glue (SCR-10) in skim rubber, standard GB/T/T8081-2008/ISO2000:2003 " caouttchouc technically classified rubber (TSR) specification directive/guide " and the skim rubber after process.Can be clear that from table, adopt all technical of the skim rubber after process of the present invention to fully meet the requirement of No. 10 glue (SCR-10) in standard GB/T/T8081-2008/ISO2000:2003 " caouttchouc technically classified rubber (TSR) specification directive/guide ".
[embodiment]
Embodiment one:
1. the Sumizyme MP being 500,000 u/g by 3g activity is dissolved in deionized water, be made into the solution that concentration is 5%, then join in 1000g skim latex, and then add 5g sodium lauryl sulphate, add and be fashionablely made into the sodium dodecyl sulfate solution that concentration is 1%, be placed in water-bath, constant temperature 40 DEG C, mechanical stirring 24h, the obtained skim latex processed;
2. 0.5g Sodium Pyrosulfite is dissolved in deionized water, is mixed with the solution that concentration is 0.5%, add in the skim latex (1) prepared, mechanical stirring 2h, the obtained skim latex again processed;
3. (2) skim latex of preparing is stirred on limit, and limit slowly adds the sulphuric acid soln of 6%, skim latex is solidified, slaking 2 days, compressing tablet, granulation, makes skim rubber wet gel particle.
4. (3) skim rubber wet gel particle is first placed in concentration be 5% NaOH solution soak 24h; Take out wet gel particle, then be placed in concentration be 1% oxalic acid solution soak 24h; Take out wet gel particle again, then be placed in concentration be 0.5% calcium carbonate soln soak 24h; Finally adopt the temperature of 120 DEG C to be dried by micelle, obtain 56.9g skim rubber.
The clear rubber sample of glue after process, after tested, indices is as follows respectively:
Embodiment two:
1. the Sumizyme MP being 500,000 u/g by 2g activity is dissolved in deionized water, be made into the solution that concentration is 5%, then join in 1000g skim latex, and then add 3g sodium lauryl sulphate, add and be fashionablely made into the sodium dodecyl sulfate solution that concentration is 1%, be placed in water-bath, constant temperature 40 DEG C, mechanical stirring 24h, the obtained skim latex processed;
2. 2g Sodium Pyrosulfite is dissolved in deionized water, is mixed with the solution that concentration is 0.5%, add in the skim latex (1) prepared, mechanical stirring 2h, the obtained skim latex again processed;
3. skim latex prepared by (2) is stirred on limit, and limit slowly adds the sulphuric acid soln of 6%, is solidified by skim latex, slaking 2 days, compressing tablet, granulation, makes skim rubber wet gel particle.
4. the skim rubber wet gel particle (3) made first be placed in concentration be 10% NaOH solution soak 24h; Take out wet gel particle, then be placed in concentration be 3% oxalic acid solution soak 24h; Take out wet gel particle again, then be placed in concentration be 2% calcium carbonate soln soak 24h; Finally adopt the temperature of 110 DEG C to be dried by micelle, obtain 51.0g skim rubber.
Skim rubber sample after process, after tested, indices is as follows respectively:
Embodiment three:
1. the Sumizyme MP being 500,000 u/g by 5g activity is dissolved in deionized water, be made into the solution that concentration is 5%, then join in 1000g skim latex, and then add 1g sodium lauryl sulphate, add and be fashionablely made into the sodium dodecyl sulfate solution that concentration is 1%, be placed in water-bath, constant temperature 40 DEG C, mechanical stirring 24h, the obtained skim latex processed;
2. 1g Sodium Pyrosulfite is dissolved in deionized water, is mixed with the solution that concentration is 0.5%, add in the skim latex (1) prepared, mechanical stirring 2h, the obtained skim latex again processed
3. skim latex prepared by (2) is stirred on limit, and limit slowly adds the sulphuric acid soln of 6%, is solidified by skim latex, slaking 2 days, compressing tablet, granulation, makes skim rubber wet gel particle.
4. the skim rubber wet gel particle (3) made be placed in concentration be 8% NaOH solution soak 24h; Take out wet gel particle, then be placed in concentration be 2% oxalic acid solution soak 24h; Take out wet gel particle again, then be placed in concentration be 3% calcium carbonate soln soak 24h; Finally adopt the temperature of 120 DEG C to be dried by micelle, obtain 54.4g skim rubber.
Skim rubber sample after process, after tested, indices is as follows respectively:
The all technical of the skim rubber after table 1. skim rubber, SCR-10, process
Claims (1)
1. all technical improving skim rubber reaches the method that standard rubbers No. 10 glue require, it is characterized in that the method contains following steps:
(1), by proteolytic enzyme be dissolved in deionized water, then join in skim latex, and then add anion surfactant, 40 DEG C of stirred in water bath 24h, the obtained skim latex processed; Described proteolytic enzyme is the Sumizyme MP of active 500,000 u/g, and its consumption is add 2g-5g in per kilogram skim latex, and is made into the solution that concentration is 5%; Described anion surfactant is sodium lauryl sulphate, and its consumption is add 1g-5g in per kilogram skim latex, and is made into the solution that concentration is 1%;
(2), by Sodium Pyrosulfite be dissolved in deionized water, join in the skim latex that (1) prepare, the obtained skim latex again processed; The consumption of described Sodium Pyrosulfite is add 0.5g-2g in per kilogram skim latex, and is made into the solution that concentration is 0.5%;
(3) skim latex that (2) prepare solidifies by the sulphuric acid soln, with 6%, slaking, compressing tablet, granulation, obtain skim rubber wet gel particle;
(4) the skim rubber wet gel particle, by (3) obtained, is first placed in sodium hydroxide solution and soaks 24h; Take out wet gel particle, then be placed in oxalic acid solution and soak 24h; Take out wet gel particle again, then be placed in calcium carbonate soln and soak 24h; Finally adopt the temperature of 110-120 DEG C to be dried by micelle, obtain the skim rubber that all technical reaches standard rubbers No. 10 glue requirements; It is the calcium carbonate soln of the sodium hydroxide solution of 5%-10%, the oxalic acid solution of 1%-3% and 0.5%-3% respectively that described wet gel soaks what adopt.
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| CN103772532B (en) * | 2014-02-10 | 2015-05-27 | 海南天然橡胶产业集团股份有限公司 | Method for processing skim rubber |
| CN110922509B (en) * | 2019-12-04 | 2022-02-15 | 河南崤函生物科技有限公司 | Deproteinized rubber and preparation method thereof |
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| BR8806231A (en) * | 1988-11-23 | 1990-07-24 | Massakazu Outa | PROCESS FOR SKIMMING LATEX |
| JP2001122907A (en) * | 1999-10-22 | 2001-05-08 | Sumitomo Rubber Ind Ltd | Method for producing skim rubber |
| JP2005015585A (en) * | 2003-06-25 | 2005-01-20 | Nitto Denko Corp | Manufacturing process for deproteinized skim rubber, pressure-sensitive adhesive composition and pressure-sensitive adhesive tape or sheet |
| CN102268106B (en) * | 2011-08-26 | 2013-05-01 | 中国热带农业科学院农产品加工研究所 | Preparation method of high-purity natural rubber |
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