CN1127271A - Improvement in and relating to the receiving of naural and synthetic rubber - Google Patents
Improvement in and relating to the receiving of naural and synthetic rubber Download PDFInfo
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- CN1127271A CN1127271A CN95109174A CN95109174A CN1127271A CN 1127271 A CN1127271 A CN 1127271A CN 95109174 A CN95109174 A CN 95109174A CN 95109174 A CN95109174 A CN 95109174A CN 1127271 A CN1127271 A CN 1127271A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Abstract
A process of recycling used sulphur-cured elastomeric materials comprising masticating the said elastomeric materials at temperatures below 50 DEG C with a novel chemical mixture which is capable of initiating proton exchange in a controlled manner and thereby open up or delink the vulcanised network of the elastomeric materials. The novel chemical mixture is made from one or more compounds which are capable of performing rubber accelerator function and one or more activators capable of initiating proton exchange at temperatures below 70 DEG C and thereby open up or delink the vulcanised network of the sulphur-cured elastomeric material to provide sulphur-curable reclaimed elastomeric material.
Description
The present invention relates to rubber product, for example promote the tire that the vulcanization system sulfuration obtains from natural rubber or synthetic rubber or its mixture sulphur by routine, molding, the regeneration of products such as wrist-watch and belt is in order that make regeneration can be repeated to utilize as glue.
Industrial, the regenerated rubber that reuses old rubber product be for people known.The rubber of annual recycling is about 200,000 tons.Conventional rubber recycling method is to adopt high temperature and catalyzer, separates the rubber material that will reuse with steaming, and the result consumes big energy, and the regenerated rubber material is degraded significantly.Because the physical properties of regenerated rubber is poor, its purposes is restricted.Common regenerated rubber has the tensile strength that is not more than 5-6MPa, and the raw material natural rubber that contains same compound can provide 20MPa above tensile strength.In addition, the labour intensity of ordinary method is big, with regard to quality control and stdn, is difficult and trouble.
Common rubber process process comprises substantially with sulfurized rubber scraps and catalyst mix, separates in steaming to make mixture more than Temperature Treatment 4-6 more than 170 ℃ hour in the jar.The slabbing of then product being kneaded.The above-mentioned rubber product of a small amount of ratio is used as thinner as the secondary process auxiliary agent or with the virgin rubber compound.The rubber of the recycling that exists in mixture can have a negative impact to the physics and the kinetic property of whole vulcanized rubber.
Old tire and other rubber articles are becoming global environmental hazard.Therefore, a kind of gratifying recycling method of the clear and definite demand of people is to tackle growing environmental problem.Now, a large amount of old tires that exist on the earth are a kind of inflammable substance.Many effort and research had been done already to relax this environmental problem.Wherein report has: granular tire is used for the road surface; Above-mentioned chip is burnt with generate energy, or the like.
Knew having under the promotor situation already, vulkacit H and Resorcinol can cut off crosslinked in the vulcanized rubber, and this report comes from Czechoslovakian document (hereinafter being called " Czechoslovakian method ").But this method is uncontrollable, and the rubber of the recycling of generation is changed and degraded.Though this reaction mechanism describes in detail, it is believed that this method comprises the proton transfer reaction of certain form.
Therefore, still successfully made any real progress in this global making us of solution aspect the nerve-racking problem without any an ordinary method or research.
Thereby need a kind of reasonable price, can reuse the method for old rubber product effectively, this method can make the crosslinked of vulcanized network structure in the old rubber scraps open or open chain (delink), and trunk polymer is exceedingly degraded.Regenerated rubber can successfully keep former natural and elastomeric original physical and dynamics more, and the application of above-mentioned regenerated rubber in next step rubber manufacturing process is just extensive more.
We had developed a kind of method already, and this method preferably changes into the rubber material with the chip form with old rubber product basically, and this material has the character that the virgin rubber with similar compound is close.This method is fine and simple, does not promptly consume energy, and labour intensity is also little.
We have carried out research again to the Czechoslovakian method, have developed a kind of brand-new system that can cause the proton transfer reaction now, it is believed that this reaction is absolutely necessary.Yet our method does not adopt the hexamine of handling as hazardous chemicals, but is used in the pharmaceutical chemicals that uses in the conventional rubber manufacturing process.
Our exploitation mainly comprises adopts a kind of new chemical mixture, and this mixture can preferably be lower than under 50 ℃ in the mode of control 70 ℃ of following temperature, causes proton exchange, even the vulcanized network of rubber material is opened or open chain.
Therefore, the invention provides a kind of from the rubber material of free sulfur cure the method for regenerated rubber material, this method comprises and adopts one or more compounds that can have the rubber accelerator function and one or more to handle described vulcanized rubber material being lower than the activator that causes proton exchange under 70 ℃ of temperature, thereby the vulcanized network that makes the vulcanized rubber material is opened or open chain, so that vulcanizable regenerated rubber material to be provided.
In addition, the present invention also comprises open chain composition as herein described.
Our new chemical composition (hereinafter being called " open chain composition ") comprises one or more compounds that can have the rubber accelerator function and one or more activators.Usually the compound that is used as rubber accelerator must make the vulcanized network of vulcanized rubber material open or open chain, so that vulcanizable regenerated rubber material to be provided when using jointly with one or more activators that can cause proton exchange under being lower than 70 ℃ of temperature.
Preferably, the compound that can have the rubber accelerator function comprises the thiocarbamate zinc salt, for example ziram (hereinafter being called " ZDMC ") and 2-mercaptobenzothiazole (hereinafter being called " MBT ") or derivatives thereof, mol ratio is 1: 1-1: 12.Promotor is by using one or more activators, and preferably stearic acid and zinc oxide come activatory.Also sulphur can be joined in the mixture.
Preferred promotor ZDMC of above-mentioned conduct and MBT can replace with other promotor (the some of them activity is less).The example of replaced ZDMC that the following people of being know and MBT promotor, but be not whole.
ZDMC can replace with other zinc salt of dithiocarbamate by mole, ziram for example, zinc diethyldithiocarbamate (ZDEC), the dipropyl zinc dithiocarbamate, dibutyl sulfide is for carbaminate (ZBDC) or zinc dibenzyldithiocarbamate (ZBEC), perhaps use zinc dialkyl dithiophosphate, for example zinc dibutyldithiophosphate and replace with other compounds with rubber accelerator function.
Similarly, MBT can replace with other thiazole promotor by mole, benzothiazole based bisulfide (MBTS) for example, or 2-mercaptobenzothiazole zinc (ZMBT), perhaps use sulfinyl amine promotor, for example N-cyclohexyl-2-[4-morpholinodithio sulfinyl amine (CBS) or N-tertiary butyl 2-[4-morpholinodithio sulfinyl amine (TBBS), perhaps use thiuram accelerator, Thiuram disulphide (TETD) for example, tetramethyl thiuram disulfide (TMTD) or tetra-benzyl thiram disulphide (TBETD), perhaps use nitrogen base promotor, guanidine for example, N, N '-diphenylguanidine, dextrorotation o-tolyl guanidine and 4,4 '-dithiomorpholine or replace with other compounds with rubber accelerator function.
The derivative of MBT or MBT or other promotor and ZDMC or ZDMC derivative composition in molar ratio causes proton-exchange reaction, and the existence of stearic acid and zinc oxide promotes this reaction.It is found that a small amount of having of sulphur helps last sulfuration, but optional.The existence of glycol helps the dispersion of powder equally, and perhaps can activator mixture, but this is not absolutely necessary.
New chemical mixture, be open chain composition (" open chain composition " Delink herein) when with tire chip or other any sulfurized rubber scrapss, when preferably in opening rubber mixing machine, mixing in the ratio of 6 parts of open chain compositions of per 100 parts of rubber, can make the vulcanized network open chain effectively, and vulcanizable regenerated rubber product is provided, it can be used for mold pressing and sulfuration at any time.All mixing times are only used 7-10 minute, preferably, mixingly carry out being lower than under 70 ℃.In addition, open chain composition and tire chip mix in Intermix(machine) (intermix) earlier, and be mixing in opening rubber mixing machine then.
In addition, we have developed a kind of open chain method for compositions of handling more conveniently, promptly use the master batch method.With open chain composition elder generation and fresh or sulfurized rubber mix, the ratio of open chain composition and rubber is 90: 10-40: 60.The master batch mixture is in guaranteeing the open chain composition: the final ratio of rubber is that 6: 100 ratio is mixed with the sulfurized chip.Umber is parts by weight.
Now, with reference to following embodiment and Biao, by explanation, describe some embodiments of the present invention, character explanation the present invention of the compound of generation is actually effective means.
Embodiment 1
Press the given following material of mixed:
1. 2-sulfydryl thionaphthene (MBT) 20.0
2. ziram (ZDMC) 6.0
3. stearic acid 2.0
4. zinc oxide 2.0
5. sulphur 1.5
6. glycol ether 12.0
At first, powder is firmly stirred, mix fully, add glycol ether then, make whole open chain compositions become slick paste.
With 500g tire chip mixing 3 minutes, add 15 gram open chain compositions with 2 roll opening rubber mixing machines.Again after mixing 2 minutes, add 15 gram open chain compositions again.Last 2 minutes is mixing mixing under narrow roll gap condition.At this moment, compound can the compressing tablet discharging, and this compound can be used for 150 ℃ of sulfurations 15-30 minute down at any time.Employing derives from Malaysia and lists in the following table 1 with the character of the vulcanized rubber of the tire chip in Europe.
Table 1
The character of the vulcanized rubber that makes by 100% natural rubber tire chip
*V
RelBe to calculate with Mooney Rivlin formula:
| Numbering | The country of origin | Malaysia | Europe | ||
| Characteristic | ????1 | ????2 | ????3 | ????4 | |
| ?1. | Size (mm) | ??0.1-0.5 | ??0.1-0.5 | ?0.1-0.5 | ??＞1.0 |
| ?2. | Open chain composition (umbers of per hundred parts of chips) | ????6 | ????6 | ????6 | ????6 |
| ?3. | Sulfuration (℃) | ????143 | ????155 | ????143 | ????143 |
| ?4. | Mooney viscosity M t 100 | ????68 | ????68 | ????75 | ????120 |
| ?5. | Stress (Mpa) in 100% elongation | ????3 | ????3 | ????3.5 | ????5.5 |
| ?6. | Tensile strength (MPa) | ????12.1 | ????12.7 | ????14.5 | ????16 |
| ?7. | Elongation at break (%) | ????350 | ????350 | ????375 | ????400 |
| ?8. | Extension strain (%) | ????15 | ????15 | ????15 | ????12 |
| ?9. | The relative concentration of chain, V rel×10 4(mole/cm 3) * | ????1.1 | ????1.2 | ????1.2 | ????1.3 |
| ?10. | Snappiness component A * 10 of creep 3(MPa)(σ o＝0.8MPa) ** | ????0.5 | ????0.5 | ????0.4 | ????0.4 |
Wherein E is strain
λ is an extensibility
R is a gas law constant; With
T is a temperature
*Be calculated as follows creep:
D(σ，T)＝D
o(σ，T)+A(σ，T)Log
T+T/η(σ，T)
Wherein D is strain (%), D
oIt is initial strain (%) at T=1 minute;
A is the rate constant (1/MPa) of the creep of high elastic strain
η is viscosity (Pas)
Embodiment 2
Embodiment 1 described open chain composition is added in the granular substance of tire debris and old gloves the open chain composition: the ratio of vulcanized rubber fragment is 6: 100.By embodiment 1 described kneading and the open chain composition mixing process of carrying out.The opening rubber mixing machine temperature does not allow above 70 ℃.Total mixing time remained in 10 minutes.Below table 2 listed the character that obtains by tire and gloves chip.For purpose relatively, will from contain the general character that the two virgin rubber of (tire compound) and no filler (gum compound) obtains list in below the table 2.
Table 2
By chip Outer Tyre face and chip gloves gained
Character compares with the compound that adopts virgin rubber
| Material type | The tire chip | The chip gloves | Virgin rubber (tire compound) | Virgin rubber (gum compound) |
| Tensile strength (MPa) | 13 | ?14.5 | ????18-21 | ????21-23 |
| Elongation (%) | 300 | ?900 | ????350-500 | ????700-800 |
| Extension strain (%) | 10 | ?15 | ???????- | ???????- |
| The relative concentration V of chain rel×10 3(mole/cm 3) | 1.4 | ?0.6 | ???????- | ???????- |
Embodiment 3
In the present embodiment, with open chain composition (it is described to press embodiment 1) and virgin rubber, tire chip and gloves chip mix, and obtain containing the master batch of 90% open chain composition and 50% open chain composition.The master batch that will so produce is infiltrated respectively in tire chip and the gloves chip by embodiment 1 described mode then, just, under the master batch situation of 90% open chain composition, 100 parts of vulcanized rubber chips use 6.6 parts of master batchs, master batch for 50%, per 100 parts of chips use 12 parts of master batchs.Product characteristics is listed in the table 3.
Table 3
Adopt the character of open chain composition master batch gained
| The master batch type | Fresh NR: open chain composition 10: 90 | NR: open chain composition 50: 50 | Gloves: open chain composition 10: 90 | Gloves: open chain composition 50: 50 | ||||
| The vulcanized rubber chip | The Outer Tyre face | Gloves | The Outer Tyre face | Gloves | The Outer Tyre face | Gloves | The Outer Tyre face | Gloves |
| Tensile strength (MPa) | ????11.5 | ???17 | ????11 | ?10 | ????10 | ?13.5 | ????12 | ?10.5 |
| Elongation (%) | ????250 | ???860 | ????250 | ?610 | ????250 | ?780 | ????320 | ??600 |
| Extension strain (%) | ????5 | ???10 | ????6 | ?15 | ????10 | ?10 | ????6 | ??15 |
| The relative concentration V of chain rel×10 4(mole/cm 3) | ????1.3 | ???0.7 | ????1.3 | ?0.6 | ????1.2 | ?0.6 | ????1.3 | ??0.6 |
The foregoing description be explanation the inventive method provide by old natural rubber, synthetic rubber sulfide, and the versatility of the rubber compound of the recycling that obtains of natural and mixture synthetic rubber sulfide and effect.
The regenerated rubber compound product has gratifying physics and dynamics.Above-claimed cpd can be directly used in the article of mold pressing or use with fresh compound.In mold pressing and vulcanization process commonly used, the example of the above-mentioned article that employing regeneration synthetic rubber makes is tires, mat, underlayment, electric insulation layer, industrial tire, the old tire of tubing and renovation.
In addition, can replace natural rubber further to improve masterbatch process with styrene-butadiene rubber(SBR).During kneading, control comprehensive physics and dynamics that open chain composition mixing process, mixing process and temperature can further strengthen the final regeneration compound that is produced by tire and gloves waste material carefully.
The following example explanation replaces the certain situation of MBT with other promotor.
Embodiment 4
With the following material of given mixed:
1. benzothiazole based bisulfide (MBTS) 27.8
2. zinc diethyldithiocarbamate (ZDEC) 7.6
3. stearic acid 5.1
4. zinc oxide 2.5
It is described to press embodiment 1,10 parts of these open chain mixtures is joined in 100 parts of tire chips and 12.5 parts of raw material natural rubbers go.The relevant physical properties of mixture is listed in the following table 4.
Table 4
Adopt the character of the MBTs mixture of raw material natural rubber
| Modulus (MPa) during (5) 300% elongations of tensile strength (MPa) elongation at break | ????10.0 ????336 ????5.6 |
Embodiment 5
With the following material of given mixed:
1.N-cyclohexyl-2-[4-morpholinodithio sulfinyl amine (CBS) 43.9
2. zinc diethyldithiocarbamate (ZDEC) 7.6
3. stearic acid 5.1
4. zinc oxide 2.5
It is described to press embodiment 1, and 10 parts of these open chain mixtures are joined in 100 parts of tire chips and the 12.5 parts of raw material natural rubbers.The some relevant physical properties of this mixture is listed in the table 5.
Table 5
Adopt the character of the CBS mixture of raw material natural rubber
| The modulus (MPa) of tensile strength (MPa) elongation at break (%) under 300% elongation | ????11.1 ????369 ????7.9 |
Embodiment 6
With the following material of given mixed:
1.N-the tertiary butyl-2-[4-morpholinodithio sulfinyl amine (TBBs) 39.8
2. zinc diethyldithiocarbamate (ZDEC) 7.6
3. stearic acid 5.1
4. zinc oxide 2.5
It is described to press embodiment 1, and 10 parts of these open chain mixtures are joined in 10 parts of tire chips and the 12.5 parts of raw material natural rubbers.The some relevant physical properties of this mixture is listed in the table 6.
Table 6
Adopt the character of the TBBS mixture of raw material natural rubber and tire chip
| Modulus (MPa) during tensile strength (MPa) elongation at break (%) 300% elongation | ????12.0 ????353 ????9.3 |
To be described like this, but obvious, particular procedure as herein described can adopt many methods to change in the present invention.Such change should not be considered to depart from scope of the present invention.
Those skilled in the art recognize that above-mentioned new features can be brought lot of advantages.It should be noted that, except using stearic acid, can use methylacrylic acid, perhaps the alternatively.In addition, can also use propylene glycol, the suitable diol that dipropylene glycol or triethylene glycol and other available simple experiment are identified is to replace Diethylene Glycol.
It will be understood by those skilled in the art that the described compound in the scope of the invention also comprises common compounds, and the compound that can be used as promotor except above-mentioned compound with rubber accelerator function.
No matter whether they are included in the scope of following claim, these all are each aspects independently of the present invention, and for example, " paste " component of embodiment 1 can change by adding and subtracting 20%, preferably adds and subtracts 10%.Therefore the open chain composition can comprise (a) component, for example 4.8-7.2 part (weight) ZDMC and (b) component, for example 16-24 part (weight) MBT.The stearic acid and the zinc oxide that preferably, in the open chain composition, also can have 1.6-2.4 part (weight).In addition, also can there be 1.2-1.8 (weight) in sulphur, glycol, and for example can there be 9.6-14.4 part (weight) in Diethylene Glycol.
Should be noted that the present invention also comprises above-mentioned composition and those pastes or master batch.
Claims (19)
1. method from the rubber material regenerated rubber material of free sulfur cure, this method is included in to be lower than under 70 ℃ of temperature and can causes this vulcanized rubber material of Treatment with activating agent of proton exchange with one or more compounds with rubber accelerator function with one or more, thereby the network of sulfurized rubber material is opened or open chain, so that vulcanizable regenerated rubber material to be provided.
2. according to the process of claim 1 wherein that rubber accelerator is selected from one or more following a few class promotor:
(a) thiocarbamate zincum salts, ziram for example, zinc diethyldithiocarbamate, dipropyl zinc dithiocarbamate, zinc dibutyl dithiocarbamate, and zinc dibenzyldithiocarbamate;
(b) 2-mercaptobenzothiazole or derivatives thereof, for example mercaptobenzothiazole zinc and benzothiazole based bisulfide;
(c) sulfinylamines, for example N-cyclohexyl-2-[4-morpholinodithio sulfinyl amine and the N-tertiary butyl-2-[4-morpholinodithio sulfinyl amine;
(d) thiurams, Thiuram disulphide for example, tetramethyl thiuram disulfide and tetra-benzyl thiram disulphide;
(e) nitrogen base rubber accelerator, guanidine for example, N, N '-diphenylguanidine, di-o-tolyl guanidine and 4,4 '-dithiomorpholine;
(f) zinc dialkyl dithiophosphate, for example zinc dibutyldithiophosphate.
3. according to the method for claim 2, wherein the promotor component comprises each from following two class promoter compound:
(a) thiocarbamate zincum salts, ziram for example, zinc diethyldithiocarbamate, dipropyl zinc dithiocarbamate, zinc dibutyl dithiocarbamate, and zinc dibenzyldithiocarbamate;
(b) 2-mercaptobenzothiazole or derivatives thereof, for example mercaptobenzothiazole zinc and benzothiazole based bisulfide.
4. according to the method for claim 3, wherein the corresponding mol ratio of two class promotor is about 1: 1-1: 12.
5. according to the method for above-mentioned arbitrary claim, wherein proton exchange is to be lower than under 50 ℃ of temperature, to be initiated with control mode.
6. according to the method for any one aforesaid right requirement, wherein the activator component is stearic acid and zinc oxide.
7. wherein there is sulphur in the method that requires according to any one aforesaid right.
8. the method that requires according to any aforesaid right, be to add activator in promotor comprising the master batch of rubber accelerator and activator and old rubber mixtures of materials: the rubber material is about 40: 60-90: 10 ratio is used.
9. the method that requires according to aforesaid right, wherein promotor to add the mixture of activator and described rubber material be the blended that compares by per 100 parts of about 6 parts of described mixtures of rubber material.
10. according to the method for claim 9, wherein adopt the master batch of claim 8, and regulate master batch and rubber material's proportion, thereby make mixture: the rubber material's proportion is 6: 100.
11. according to the method that any aforesaid right requires, wherein adopt the old rubber material of free sulfur cure, and wherein the rubber material from natural rubber, synthetic rubber or its mixture.
12. according to the method for one of aforesaid right requirement, wherein sulfurized rubber material is shred.
13. method that the regenerated rubber that method produced that requires with any one aforesaid right comes article of manufacture, wherein the regenerated rubber material is by moulding, mold pressing and/or sulfuration are formed to rubber product, described goods are, tire for example, cushions, underlayment, electronic isolation part or insulation layer, industrial tire, tubing and renovation thing.
14. the vulcanized network that can make the vulcanized rubber material is opened or the composition of open chain, comprises one or more following promotor:
(a) thiocarbamate zincum salts, ziram for example, zinc diethyldithiocarbamate, dipropyl zinc dithiocarbamate, zinc dibutyl dithiocarbamate, and zinc dibenzyldithiocarbamate;
(b) 2-mercaptobenzothiazole or derivatives thereof, for example mercaptobenzothiazole zinc and benzothiazole based bisulfide;
(c) sulfinylamines, for example N-cyclohexyl-2-[4-morpholinodithio sulfinyl amine and the N-tertiary butyl-2-[4-morpholinodithio sulfinyl amine;
(d) thiurams, Thiuram disulphide for example, tetramethyl thiuram disulfide and tetra-benzyl thiram disulphide;
(e) nitrogen base rubber accelerator, guanidine for example, N, N '-diphenylguanidine, di-o-tolyl guanidine and 4,4 '-dithiomorpholine;
(f) zinc dialkyl dithiophosphate, for example zinc dibutyldithiophosphate.
15. according to the composition of claim 14, said composition comprises following two class promotor:
(a) thiocarbamate zincum salts, ziram for example, zinc diethyldithiocarbamate, dipropyl zinc dithiocarbamate, zinc dibutyl dithiocarbamate, and zinc dibenzyldithiocarbamate;
(b) 2-mercaptobenzothiazole or derivatives thereof, for example mercaptobenzothiazole zinc and benzothiazole based bisulfide.
16. according to the composition of claim 15, wherein the corresponding mol ratio of two promotor is about 1: 1-1: 12.
17. according to any one composition of claim 14-16, said composition comprises the activator that contains stearic acid and zinc oxide.
18. according to any one composition of claim 14-17, said composition also comprises sulphur.
19. according to the composition of claim 14-18, said composition is the mixture with the open chain composition component of master batch form and old vulcanized rubber material chip, the open chain composition is about 40 with the ratio of rubber material: 60-90: 10.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| MYPI9401654 | 1994-06-25 | ||
| MY9401654 | 1994-06-25 | ||
| EP95301399.2 | 1995-03-03 | ||
| EP19950301399 EP0690091B1 (en) | 1994-06-25 | 1995-03-03 | Improvements in and relating to the reclaiming of natural and synthetic rubbers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1127271A true CN1127271A (en) | 1996-07-24 |
| CN1086715C CN1086715C (en) | 2002-06-26 |
Family
ID=26140066
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95109174A Expired - Fee Related CN1086715C (en) | 1994-06-25 | 1995-06-26 | Improvement in and relating to the receiving of naural and synthetic rubber |
Country Status (13)
| Country | Link |
|---|---|
| JP (1) | JPH0841107A (en) |
| CN (1) | CN1086715C (en) |
| AU (1) | AU696872B2 (en) |
| BR (1) | BR9502937A (en) |
| CA (1) | CA2152641A1 (en) |
| CZ (1) | CZ166595A3 (en) |
| DK (1) | DK72095A (en) |
| EG (1) | EG20625A (en) |
| FI (1) | FI953036A (en) |
| HU (1) | HU214782B (en) |
| IL (1) | IL114297A0 (en) |
| NZ (1) | NZ272426A (en) |
| PL (1) | PL309273A1 (en) |
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| WO2006037278A1 (en) * | 2004-10-09 | 2006-04-13 | Min Duo Chen | A reclaiming method of waste elastomer |
| CN105949503A (en) * | 2016-05-27 | 2016-09-21 | 徐州工业职业技术学院 | Environment-friendly active hydrogenated acrylonitrile butadiene rubber vulcanized rubber powder and preparation method thereof |
| WO2023239994A1 (en) * | 2022-06-06 | 2023-12-14 | Exxonmobil Chemical Patents Inc. | Producing copolymers of elemental sulfur and comonomers recovered from post-consumer polymer stream |
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| CZ302953B6 (en) * | 1999-10-22 | 2012-01-25 | Ket Kunststoff- Und Elasttechnik Gmbh Liegau-Augustusbad | Method for producing a devulcanization product of comminuted rubber waste and process for preparing devulcanization mixture |
| CZ300227B6 (en) * | 2001-08-08 | 2009-03-25 | Ester, Spol. S R. O. | Waste rubber recycling process |
| JP2007154348A (en) * | 2005-12-02 | 2007-06-21 | Towa Corp:Kk | Glove and method for producing the same |
| LU91419B1 (en) * | 2006-07-13 | 2008-04-21 | Elastomer Technologies Ltd | Improvements in and relating to the recycling of natural and synthetic rubbers. |
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| CN113150416B (en) * | 2021-02-26 | 2022-08-26 | 三河市长城橡胶有限公司 | Shearing aid for processing waste rubber and method for obtaining high-molecular ecological rubber by using shearing aid |
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|---|---|---|---|---|
| US4101463A (en) * | 1975-02-04 | 1978-07-18 | Amerace Corporation | Molded composition and article molded therefrom |
| JPS6017202B2 (en) * | 1976-12-10 | 1985-05-01 | 株式会社ブリヂストン | Manufacturing method of sulfur vulcanized isomerized rubber |
| JPS541391A (en) * | 1977-06-07 | 1979-01-08 | Bridgestone Tire Co Ltd | Regeneration of waste rubber |
| US4110240A (en) * | 1977-07-29 | 1978-08-29 | Wyrough And Loser, Inc. | Coprecipitation process |
| DE3014717A1 (en) * | 1980-04-17 | 1981-10-22 | Bayer Ag, 5090 Leverkusen | VULCANIZATION SYSTEM, THIS CONTAINING RUBBER MIX, AND A METHOD FOR VULCANIZATION |
-
1995
- 1995-06-15 JP JP14902595A patent/JPH0841107A/en active Pending
- 1995-06-20 EG EG48595A patent/EG20625A/en active
- 1995-06-20 FI FI953036A patent/FI953036A/en unknown
- 1995-06-22 CZ CZ951665A patent/CZ166595A3/en unknown
- 1995-06-23 IL IL11429795A patent/IL114297A0/en unknown
- 1995-06-23 HU HU9501872A patent/HU214782B/en not_active IP Right Cessation
- 1995-06-23 PL PL30927395A patent/PL309273A1/en unknown
- 1995-06-23 NZ NZ272426A patent/NZ272426A/en unknown
- 1995-06-23 DK DK72095A patent/DK72095A/en not_active Application Discontinuation
- 1995-06-26 BR BR9502937A patent/BR9502937A/en not_active Application Discontinuation
- 1995-06-26 AU AU23270/95A patent/AU696872B2/en not_active Ceased
- 1995-06-26 CN CN95109174A patent/CN1086715C/en not_active Expired - Fee Related
- 1995-06-26 CA CA 2152641 patent/CA2152641A1/en not_active Abandoned
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1100084C (en) * | 2000-12-29 | 2003-01-29 | 李大年 | Waste rubber regenerating process and waste rubber regenerant |
| WO2006037278A1 (en) * | 2004-10-09 | 2006-04-13 | Min Duo Chen | A reclaiming method of waste elastomer |
| CN105949503A (en) * | 2016-05-27 | 2016-09-21 | 徐州工业职业技术学院 | Environment-friendly active hydrogenated acrylonitrile butadiene rubber vulcanized rubber powder and preparation method thereof |
| CN105949503B (en) * | 2016-05-27 | 2019-08-09 | 徐州工业职业技术学院 | A kind of environment-friendly type active hydrogenation butadiene-acrylonitrile-rubber vulcanized rubber powder and preparation method thereof |
| WO2023239994A1 (en) * | 2022-06-06 | 2023-12-14 | Exxonmobil Chemical Patents Inc. | Producing copolymers of elemental sulfur and comonomers recovered from post-consumer polymer stream |
Also Published As
| Publication number | Publication date |
|---|---|
| AU696872B2 (en) | 1998-09-17 |
| BR9502937A (en) | 1996-03-12 |
| MX9502610A (en) | 1998-07-31 |
| AU2327095A (en) | 1996-01-11 |
| EG20625A (en) | 1999-10-31 |
| CN1086715C (en) | 2002-06-26 |
| NZ272426A (en) | 1998-07-28 |
| IL114297A0 (en) | 1995-10-31 |
| CZ166595A3 (en) | 1996-01-17 |
| DK72095A (en) | 1995-12-26 |
| HU214782B (en) | 1998-05-28 |
| PL309273A1 (en) | 1995-12-27 |
| JPH0841107A (en) | 1996-02-13 |
| CA2152641A1 (en) | 1995-12-26 |
| HU9501872D0 (en) | 1995-08-28 |
| HUT73207A (en) | 1996-06-28 |
| FI953036A (en) | 1995-12-26 |
| FI953036A0 (en) | 1995-06-20 |
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