CN1015896B - Method for utilizing lignin as reinforcing agent of rubber - Google Patents
Method for utilizing lignin as reinforcing agent of rubberInfo
- Publication number
- CN1015896B CN1015896B CN 89109494 CN89109494A CN1015896B CN 1015896 B CN1015896 B CN 1015896B CN 89109494 CN89109494 CN 89109494 CN 89109494 A CN89109494 A CN 89109494A CN 1015896 B CN1015896 B CN 1015896B
- Authority
- CN
- China
- Prior art keywords
- rubber
- xylogen
- parts
- lignin
- formaldehyde resin
- 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.)
- Expired
Links
Abstract
The present invention relates to a method for using lignin as a rubber reinforcing agent, which belongs to the technical field of the application of lignin to rubber industry. The present invention adopts the key scheme that formaldehyde is added in concentrated papermaking waste liquid, and then, lignin formaldehyde resin is prepared; sulfur, zinc oxide, stearic acid, a vulcanizing agent, a vulcanization promoting agent, a vulcanization activating agent and rubber are proportionally added and sulfurized at certain temperature. By using the method, the rubber is filled with a large amount of lignin without the need of adding softeners; thus, a larger amount of rubber is saved, and the vulcanized rubber with excellent properties can be obtained; and simultaneously, no flying dust is generated in the process of sulfurization to pollute the environment, papermaking waste liquid is changed into valuable materials, and the method has the advantages of large social benefit and economic benefit.
Description
The present invention is with the method for xylogen formaldehyde resin as the paracril strengthening agent, belongs to the technical field that xylogen is used in rubber industry.
Xylogen extensively is present in the various spermatophytes, generally extracts from sulphate process paper-making pulping waste liquid.The applied research of xylogen in rubber industry starts from nineteen twenty-five, but still do not use as strengthening agent in rubber so far owing to following reason makes xylogen: the force of cohesion of first xylogen own is big, be difficult in rubber, disperse, simultaneously, the xylogen that molecular weight is lower and other the non-lignin component in the papermaking wastewater also hinder xylogen to disperse in rubber, and dispersiveness is filler can play strengthening action in rubber a important factor; Its two be xylogen in vulcanization of rubber process with sulfur reaction, generate excessive hydrogen sulfide and postpone the sulfuration.In addition, when xylogen and compounding rubber, generate loose key with rubber again, these keys can shield the point that participates in vulcanization reaction on some rubber molecular chains again, and make horizontal key density low, and make that the rubber product tensile modulus is low, tension set is big, and do not meet actual use.
Purpose of the present invention is exactly in order to overcome above-mentioned shortcoming, makes xylogen obtain utilizing as rubber reinforcing filler initiatively.This can reduce the pollution of paper mill to environment on the one hand, and the waste wood element in the waste liquid is utilized, and obtains bigger society and economic benefit.
Content of the present invention be solve xylogen in rubber dispersion and vulcanize two problems, and used xylogen need not through purifying, other compositions in the papermaking wastewater needn't be removed, but formaldehyde is directly added in the concentrating spent liquor, make the xylogen formaldehyde resin.But prior art all is must earlier xylogen be purified or is precipitated out earlier to add alkali dissolution again, reacts then, precipitate, wash, drying, sneak into rubber again.Main points of the present invention are to add sulphur, zinc oxide, stearic acid and vulcanizing agent, vulcanization activator, vulcanization accelerator (as TMTD, tetramethyl-thiazolyl phenyl disulfide etc.) in mixing process, mixing under 80～170 ℃ of temperature, rubber wood timber quality formaldehyde resin rubber unvulcanizate is vulcanized in the dynamic condition lower section.Because the effect of high temperature and power chemistry, xylogen formaldehyde resin and rubber all have bigger activity, therefore, with this understanding, rubber forms incomplete space reticulated structure, makes between xylogen formaldehyde resin and the rubber, and all produces certain reaction between the xylogen formaldehyde resin.But owing to do not form complete space reticulated structure, xylogen itself has been the xylogen formaldehyde resin simultaneously, has thermoplasticity, therefore, still keep goodish flowability, be unlikely hindering later forming process, and xylogen formaldehyde resin and rubber compatibility are increased, become a macromolecular material composite monolithic.The inventive method is as follows: papermaking wastewater is concentrated into concentration more than 30%, mole ratio in content of lignin in the concentrated solution and formaldehyde is 1: the ratio of (0.02～0.2) adds formaldehyde, under 80～100 ℃ temperature, reacted 1～3 hour, promptly add concentration and be 5% sulfuric acid, its pH value is reduced to about 1～4, park filtered again in 20～24 hours, wash, drying, make the xylogen formaldehyde resin; Then by weight per 100 parts of paracrils of part (down with) and (50～200 parts) xylogen formaldehyde resin mixing evenly after, again by per 100 parts of paracrils add following weight than part vulcanizing agent, vulcanization accelerator, vulcanization activator:
Sulphur (S): 1.0～2.5 parts
Blue mother of autumn or thiazoles vulcanization accelerator: 0.01～1.0 part
Zinc oxide (ZnO): 2.0～5.0 parts
Stearic acid: 0.5～1.5 part
Carry out mixing evenly after, continuing mixing slice during to the rubber surface little rough under 80～170 ℃ of temperature again.Change over to then and continue on the opening rubber mixing machine to add to advance:
Thiazoles vulcanization accelerator: 0.01～0.40 part
Sulfenamide vulcanization accelerator: 0.50～1.50 part
Stearic acid: 0.5 part
Aniline type antioxidant: 1.0 parts
Sulphur (S): 0.02～1.0 part
Carry out mixing even slice, and then under 150 ℃ of temperature, vulcanize, just can obtain the cross-linked rubber of following advantageous property: tensile strength is 24.0(MPa), 100% tensile modulus is 5.6(MPa), 300% tensile modulus is 18.0(MPa), tension set 12.0%, elongation rate of tensile failure be 300%, hardness is 75(Shao Er A).
This original invention has following advantage and effect: (1) can make xylogen obtain practical application in rubber, the mechanical property of cross-linked rubber will be above the reinforcement level of high abrasion furnace black, under suitable loading level, can reach the effect of intermediate super abrasion furnace (carbon) black, make xylogen become rubber reinforcing filler; (2) in the prior art,, just be difficult to processing, and will add the tenderizer that costs an arm and a leg and be harmful to ageing property if (weight ratio part, down together) is filled when surpassing 50 parts of carbon blacks in per 100 parts of rubber.But the present invention can fill xylogen in a large number, can be filled into 200 parts of xylogen in 100 parts of rubber, still need not add tenderizer, and can obtain the cross-linked rubber of fine mechanical property.And since the light specific gravity of xylogen (specific gravity of black is 1.89, xylogen proportion is 1.33～1.45), by filling 100 parts in xylogen, the volume of filling xylogen is equivalent to (2 * 1.89/1.3)=2.9 times of sooty, when making the cross-linked rubber product, can save a large amount of rubber; (3) environmental pollution that does not have the such dust from flying of carbon black to cause in the course of processing in sulfuration, and safeguarded that directly the vulcaizer's is healthy; (4) reduced the pollution of paper mill effluent, particularly eliminated the salinization that waste water causes soil property, and the waste water in paper mill has been turned bane into boon, very big economic benefit and social benefit have been arranged environment.
The inventor has done long term studies and test to the method that makes the xylogen formaldehyde resin become the paracril strengthening agent, and a lot of successful embodiment are arranged.One of embodiment is as follows: by the above-mentioned inventive method of stating, at first papermaking wastewater is concentrated, and makes the xylogen formaldehyde resin, then by per 100 parts of paracrils (weight ratio part, down with) add 150 parts of xylogen formaldehyde resins mixing evenly after, add again:
Sulphur (S): 1.4 parts
Tetramethyl-thiazolyl phenyl disulfide (TT): 0.3 part
Zinc oxide (ZnO): 5 parts
Stearic acid: 1 part
Mixing evenly after, under 150 ℃ of temperature, continue mixingly to change on the opening rubber mixing machine to rubber surface little rough slice, continue to add:
Tetramethyl-thiazolyl phenyl disulfide (T.T): 0.2 part
N cyclohexyl 2 benzothiazole sulfenamide: 0.8 part
Stearic acid: 0.5 part
N-cyclohexyl-N-diphenyl-para-phenylene diamine: 1 part
Sulphur (S): 0.6 part
Mixing even back slice, the character of sulfuration gained cross-linked rubber is as follows under 150 ℃ of temperature: tensile strength is 23.3(MPa), 100% tensile modulus is 10.8(MPa), be permanently deformed to 16%, elongation rate of tensile failure is 280%, hardness is 90(Shao Er A).
Claims (1)
1, a kind of with the method for xylogen formaldehyde resin as the paracril strengthening agent, it is characterized in that: the concentrated papermaking wastewater that 1. concentration is reached more than 30% in the mole ratio of its content of lignin and formaldehyde is: 1: the ratio of (0.02～0.2) adds formaldehyde, react under 80～100 ℃ of temperature that promptly to add concentration in 1～3 hour be 5% sulfuric acid, its pH value is reduced to about 1～4, park filtered in 20～24 hours, wash, drying, make the xylogen formaldehyde resin; 2. () per 100 parts of paracrils are mixing evenly with (50～200 parts) xylogen formaldehyde resin down together by weight part, add the into vulcanizing agent of following weight ratio part by per 100 parts of paracrils again, vulcanization accelerator, vulcanization activator: 1.0～2.5 parts in sulphur, 0.01～1.0 part of thiuram or thiazoles vulcanization accelerator, 2.0～5.0 parts in zinc oxide, stearic acid carries out mixing even for 0.5～1.5 part, continuing mixing slice during to the rubber surface little rough under 80～170 ℃ of temperature again, change over to then and continue on the opening rubber mixing machine to add to advance: 0.01～0.40 part of thiazoles vulcanization accelerator, 0.5～1.5 part of sulfenamide vulcanization accelerator, 0.5 part of stearic acid, 1 part of aniline type antioxidant, 0.02～1.0 part in sulphur, mixing even slice, and then under 150 ℃ of temperature, vulcanize, obtain the cross-linked rubber of high dominator.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89109494 CN1015896B (en) | 1989-12-19 | 1989-12-19 | Method for utilizing lignin as reinforcing agent of rubber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89109494 CN1015896B (en) | 1989-12-19 | 1989-12-19 | Method for utilizing lignin as reinforcing agent of rubber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1044477A CN1044477A (en) | 1990-08-08 |
| CN1015896B true CN1015896B (en) | 1992-03-18 |
Family
ID=4858034
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89109494 Expired CN1015896B (en) | 1989-12-19 | 1989-12-19 | Method for utilizing lignin as reinforcing agent of rubber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1015896B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304507C (en) * | 2000-11-17 | 2007-03-14 | 华中农业大学 | Konjaku paint for both outer and inner walls and its production process |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003268678A (en) * | 2002-03-14 | 2003-09-25 | Nippon Sheet Glass Co Ltd | Glass fiber treating agent for rubber reinforcement, rubber reinforcing cord using the same and rubber product |
| CN101314675B (en) * | 2008-05-06 | 2012-07-04 | 张仲伦 | Industry xylogen reinforced and filled coblended elastomer material, and preparation method thereof |
| CN102173066B (en) * | 2011-01-22 | 2013-08-21 | 广州天河胶管制品有限公司 | Method for manufacturing steel wire hydraulic knitted rubber hose containing formaldehyde modified lignin |
| CN103387677B (en) * | 2013-07-19 | 2016-04-13 | 济南圣泉集团股份有限公司 | The preparation method of a kind of xylogen rubber ingredients and rubber for tire |
| CN103756060A (en) * | 2013-12-16 | 2014-04-30 | 华南理工大学 | Rubber composite material filled by cardanol modified lignin and preparation method thereof |
| CN109553801A (en) * | 2018-11-19 | 2019-04-02 | 青岛中科和源新材料有限公司 | A kind of preparation of zinc electroplating bath |
| CN116178976A (en) * | 2023-02-21 | 2023-05-30 | 上海昶法新材料有限公司 | Preparation method of modified lignin and application of modified lignin in natural rubber |
-
1989
- 1989-12-19 CN CN 89109494 patent/CN1015896B/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304507C (en) * | 2000-11-17 | 2007-03-14 | 华中农业大学 | Konjaku paint for both outer and inner walls and its production process |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1044477A (en) | 1990-08-08 |
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