CN1454936A - High-boiling alcohol lignin rubber modified additive preparing method - Google Patents
High-boiling alcohol lignin rubber modified additive preparing method Download PDFInfo
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- CN1454936A CN1454936A CN 03113395 CN03113395A CN1454936A CN 1454936 A CN1454936 A CN 1454936A CN 03113395 CN03113395 CN 03113395 CN 03113395 A CN03113395 A CN 03113395A CN 1454936 A CN1454936 A CN 1454936A
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Abstract
The present invention discloses a preparation method of high-boiling alcohol lignin rubber modification additive, including the following steps: (1) plasticating rubber for a period of time, adding sulfur or other vulcanizing agent, metal oxide and stearic acid adjuvant, etc. and mixing them; and (2). respectively adding high-boiling alcohol lignin and its derivative and carbon black, more plasticating them for a period of time, adding promotor and ageing-resisting agent, after plastication, curing for 24 hr. at room temp. and the vulcanizing under the proper condition. The high-boiling alcohol lignin is obtained by extracting wood slice, bamboo and straw and adopting high-boiling alcohol solvent method.
Description
Technical field:
The present invention is a kind of preparation method of high-boiling alcohol lignin modified rubber additive, belongs to the rubber industry class, the present invention relates to utilize high-boiling alcohol lignin and hbs lignin derivative thereof technology and the prescription as the modified rubber auxiliary agent.
Background technology:
As everyone knows, in rubber industry, had traditionally and use the precedent of sulfonated lignin as rubber modifier, but sulfonated lignin are to extract to obtain from traditional papermaking " black liquor ", not only foreign matter content is very high, and great structural modification takes place in the natural lignin in the plant material after the boiling of alkali and sulphite, and the modified rubber effect is a greater impact.
By retrieval as can be known: the sulfonated lignin that utilize papermaking " black liquor " extraction are by modification, be used for the existing report of modified rubber, as M.G.KUMARAN et al, " Utilization ofLi gninsin Rubber Compounding ", Journal of Applied PolymersScience, Vol.22,1885-1893 (1978), M.G.KUMARAN et al, " Effect ofaccelerator system and addition of lignin on the networkstructure of natural rubber vulcanizate ", Polymer, Vol.19,461-463 (1978), but it is that raw material is done rubber modifier that these researchs all adopt traditional papermaking process to make sulfonated lignin, natural lignin's lignin structure in alkali and sulphite digestion process is subjected to destroying largely, and ash oontent is higher, is a greater impact as the effect of modified rubber additive.The report that all high-boiling alcohol lignin and derivative thereof is not used for both at home and abroad the modified rubber auxiliary agent before this.
Summary of the invention:
The preparation method who the purpose of this invention is to provide a kind of high-boiling alcohol lignin modified rubber additive.
For achieving the above object, the preparation method's of high-boiling alcohol lignin modified rubber additive step is: plasticated rubber after for some time (1), add sulphur or other vulcanizing agents, metal oxide, auxiliary agents such as stearic acid are mixing, and (2) add the derivative of high-boiling alcohol lignin and high-boiling alcohol lignin, carbon black more respectively, reclaiming by plastification adds promotor and anti-aging agent after for some time, the postcure in 24 hours of slaking at room temperature behind the glued bundle of refining.
The present invention adopts the novel wooden element---and high-boiling alcohol lignin and derivative thereof are as the modified rubber auxiliary agent, and its characteristics are described as follows:
1. the high-boiling alcohol lignin of invention employing under certain temperature, pressure condition, makes lignin dissolution among high boiling alcoholic solvent, makes it separate with Mierocrystalline cellulose.Outside desolventizing, the preparation process of high-boiling alcohol lignin do not add other chemical agents, the high-boiling alcohol lignin purity height that obtains, and ash oontent is than low tens times of traditional sulfonated lignin.
2. because high-boiling alcohol lignin is that the high boiling solvent (hbs) method makes, it has kept the chemically reactive of natural lignin preferably.With the high-boiling alcohol lignin is raw material, under certain conditions, can make the aldehydes of high-boiling alcohol lignin, phenols, or halide derivative, also can form graft product or form mixture, can provide the high-boiling alcohol lignin additive of adequate types according to needs to different rubber item modifications with other monomers with other macromolecule emulsion cosedimentations.
3. high-boiling alcohol lignin and derivative thereof can improve the tensile strength and the tensile yield of rubber item as the modified rubber auxiliary agent, increase the flexibility of rubber, than traditional sulfonated lignin better modified effect are arranged.High-boiling alcohol lignin and derivative thereof are network-like superpolymer, after they and rubber are plasticated together and form inierpeneirating network structure between the rubber, have therefore improved the tensile strength and the tensile yield of rubber item, increase the flexibility of rubber.High-boiling alcohol lignin and derivative thereof keep more multi-active base group than traditional sulfonated lignin, thereby better modified effect is arranged.
4. high-boiling alcohol lignin and derivative thereof the addition in rubber item can be according to the needs and the decision of hbs lignin derivative type characteristic of modified rubber, generally can be between 20%-400%, its result had both improved the performance of rubber item, can reduce production costs again, improve competitiveness of product.
High-boiling alcohol lignin is to adopt the high boiling solvent (hbs) method from wood chip, extraction obtains in bamboo and the vegetation stalk, hbs lignin derivative is by high-boiling alcohol lignin and aldehydes, phenols, halogenide or with other monomer-grafted formation, hbs lignin derivative also comprises with the macromolecule emulsion sedimentation handles the high-boiling alcohol lignin mixture that obtains.Add high-boiling alcohol lignin or hbs lignin derivative to can improve rubber item in the rubber greatly tensile strength and tensile yield with other rubber ingredients, increase the flexibility of rubber, better modified effect is arranged than traditional sulfonated lignin.High-boiling alcohol lignin does not add alkali or sulphite in preparation process, just Mierocrystalline cellulose and lignin separation, has kept the performance of natural lignin preferably, and better result of use is arranged in modified rubber.
Specific embodiments of the invention:
Adopting novel material high-boiling alcohol lignin and derivative thereof is the modified rubber auxiliary agent, improves the performance of rubber item.The high-boiling alcohol lignin that the raw material of hbs lignin derivative makes for the high boiling solvent (hbs) method, utilize the active group and the aldehydes of high-boiling alcohol lignin, phenols, halogenation or with other monomer-grafted formation derivatives, hbs lignin derivative also comprises the mixture of handling the high-boiling alcohol lignin obtain with the macromolecule emulsion sedimentation.
The described high-boiling alcohol lignin of step 2 be by the high boiling solvent (hbs) method from timber, extract in the farm crop raw materials such as bamboo and vegetation straw and to obtain, high boiling solvent (hbs) method technology only uses high boiling alcohols to be solvent at digestion process, does not add alkali or sulphite.So it is low that high-boiling alcohol lignin has an ash oontent, characteristics such as chemically reactive height.Plasticating equipment of the present invention comprises rubber, the mill of plastics, Banbury mixer, forcing machine equipment.
Embodiment:
The preparation of hbs lignin derivative: take by weighing the 100.0g high-boiling alcohol lignin, dissolve with ω (sodium hydroxide)=10% aqueous sodium hydroxide solution 40g, thin up is to 1000ml, add in the there-necked flask, be heated to 95 ℃, slowly drip 0.3mol or 0.6mol formaldehyde respectively, isothermal reaction 2h, reaction finishes that the aqueous sulfuric acid 98g that the back adds ω (sulfuric acid)=5% makes the xylogen precipitation, filters, make behind the dry 12h in the washing, 60 ℃ of baking ovens and contain the few HBS xylogen I of formaldehyde amount and contain the many HBS xylogen II modified resin of formaldehyde amount.Calcium lignin sulphonate is also adopted the method processing same with HBS xylogen I resin, make the lignosulfonic acid salt resin.
With NBR rubber (roller temperature 40-50 ℃) the 6min after vulcanization sulphur of in 8# mill (Kobe Kikai Co., Ltd.'s product), plasticating, add zinc oxide and stearic acid after refining 4min again, add carbon black and lignin derivative behind the mixing 5min in batches, add promotor and anti-aging agent behind the reclaiming by plastification 20min, the 15-20min that plasticates, 50-55min altogether plasticates.After slaking 24h is restrainted at room temperature in the refining gluing, implement sulfuration (LH-2 type vulcanizer, Niri Shoji K. K. produces) again, 160 ℃ * 12min of cure conditions.Rubber print after the sulfuration is carried out performance test.The basic recipe NBR0# of sample is NBR rubber 500.0g, zinc oxide 25.0g, sulphur 10.0g, stearic acid 7.5g, altax 7.5g, TM monex TD3.0g; NBR1# adds carbon black 200.0g in addition; NBR2# adds the 100.0g carbon black in addition, 100.0gHBS lignin derivative I; NBR3# adds 200.0gHBS lignin derivative I in addition; NBR4# adds carbon black 100.0g in addition, HBS lignin derivative II100.0g; NBR5# adds carbon black 100.0g in addition, lignosulfonic acid salt derivative 100.0g.
Hbs lignin derivative is to the modified effect of NBR-26 rubber: be the effect of investigation hbs lignin derivative as the modified rubber auxiliary agent, high-boiling alcohol lignin and calcium lignin sulphonate modified resin are added in the NBR rubber by proportioning, and the print performance that makes after the sulfuration is as shown in table 1.
Table 1NBR rubber print physical property measurement is title material test portion thickness/mm hot strength/TB MPa elongation at break/EB% hardness/° NBR0# 2.34 2.5 270 50NBR1# 2.43 21.4 290 73NBR2# 2.27 14.9 380 69NBR3# 2.41 14.8 440 68NBR4# 2.15 9.0 540 59NBR5# 2.23 10.3 330 68 as a result
High-boiling alcohol lignin modified resin has good effect to the tensile yield of improving rubber item as can be seen from Table 1.NBR rubber is not as adding the carbon black toughener, and tensile strength is very little, but only adds carbon black, and tensile yield is improved not obvious.Carbon black and high-boiling alcohol lignin modified resin are shared, and effect is better.Although the sooty addition is identical, the character of NBR2# and NBR4# has bigger difference, shows the effect that the modification degree that changes high-boiling alcohol lignin can also be regulated the NBR modified rubber.Compare with the sulfonated lignin that traditional papermaking obtains, the modified effect of high-boiling alcohol lignin is more remarkable, and this may be that high-boiling alcohol lignin is active high, and net high-polymer that generates after the modification and NBR rubber interpenetrate, and form inierpeneirating network structure institute extremely.In addition, in above-mentioned NBR rubber print was plasticated process, finding to add high-boiling alcohol lignin modified resin had plastification.The hardness that records from rubber sample, there is the hardness of the print that adds the lignin modification resin all little than only adding sooty hardness, especially NBR4# print particularly soft, the high-boiling alcohol lignin that suitable modification is described can also use as the softening agent of NBR rubber, and the softening agent of polymer often has better result of use in the design of macromolecular material.Also can when setting the prescription of NBR rubber item, suitably reduce the addition of softening agent, reach the purpose that reduces cost.
Claims (5)
1. the preparation method of high-boiling alcohol lignin modified rubber additive, it is characterized in that: step is: plasticated rubber after for some time (1), add sulphur or other vulcanizing agents, metal oxide, auxiliary agents such as stearic acid are mixing, and (2) add the derivative of high-boiling alcohol lignin and high-boiling alcohol lignin, carbon black more respectively, reclaiming by plastification adds promotor and anti-aging agent after for some time, the postcure in 24 hours of slaking at room temperature behind the glued bundle of refining.
2. the preparation method of high-boiling alcohol lignin modified rubber additive according to claim 1 is characterized in that: adopting novel material high-boiling alcohol lignin and derivative thereof is the modified rubber auxiliary agent.
3. the preparation method of high-boiling alcohol lignin modified rubber additive according to claim 1, it is characterized in that: the high-boiling alcohol lignin that the raw material of hbs lignin derivative makes for the high boiling solvent (hbs) method, utilize the active group and the aldehydes of high-boiling alcohol lignin, phenols, halogenation or with other monomer-grafted formation derivatives, hbs lignin derivative also comprises the mixture of handling the high-boiling alcohol lignin obtain with the macromolecule emulsion sedimentation.
4. the preparation method of high-boiling alcohol lignin modified rubber additive according to claim 1, it is characterized in that: the described high-boiling alcohol lignin of step 2 is from timber by the high boiling solvent (hbs) method, extraction obtains in bamboo and the vegetation straw farm crop raw material, high boiling solvent (hbs) method technology only uses high boiling alcohols to be solvent at digestion process, does not add alkali or sulphite.
5. the preparation method of high-boiling alcohol lignin modified rubber additive according to claim 1 is characterized in that: use the plasticating equipment of macromolecular material, comprise rubber, the mill of plastics, Banbury mixer, forcing machine equipment.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101649125B (en) * | 2009-09-15 | 2011-06-29 | 福州大学 | Lignin modified high molecular compatible additive and preparation method thereof |
| CN101314675B (en) * | 2008-05-06 | 2012-07-04 | 张仲伦 | Industry xylogen reinforced and filled coblended elastomer material, and preparation method thereof |
| CN105873970A (en) * | 2014-03-28 | 2016-08-17 | 住友电木株式会社 | Phenol-modified lignin resin, method for producing same, resin composition, rubber composition, and cured product |
-
2003
- 2003-05-03 CN CN 03113395 patent/CN1244638C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101314675B (en) * | 2008-05-06 | 2012-07-04 | 张仲伦 | Industry xylogen reinforced and filled coblended elastomer material, and preparation method thereof |
| CN101649125B (en) * | 2009-09-15 | 2011-06-29 | 福州大学 | Lignin modified high molecular compatible additive and preparation method thereof |
| CN105873970A (en) * | 2014-03-28 | 2016-08-17 | 住友电木株式会社 | Phenol-modified lignin resin, method for producing same, resin composition, rubber composition, and cured product |
| CN105873970B (en) * | 2014-03-28 | 2019-09-10 | 住友电木株式会社 | Phenol modified lignin resin resin and its manufacturing method and resin combination, rubber composition and solidfied material |
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| CN1244638C (en) | 2006-03-08 |
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