CN102010531A - Modified-surface activated waste vulcanizate powder - Google Patents
Modified-surface activated waste vulcanizate powder Download PDFInfo
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- CN102010531A CN102010531A CN 201010547175 CN201010547175A CN102010531A CN 102010531 A CN102010531 A CN 102010531A CN 201010547175 CN201010547175 CN 201010547175 CN 201010547175 A CN201010547175 A CN 201010547175A CN 102010531 A CN102010531 A CN 102010531A
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Abstract
The invention discloses modified-surface activated waste vulcanizate powder, which comprises: uniformly mixing 100 weight parts of waste rubber powder (40 to 80 mesh) and 0.8 to 2 weight parts of ethanol solution of modifier; and adding 2 to 10 weigh parts of molten chlorinated paraffin, fully stirring at 50 to 70 DEG C till the mixture is uniform, and standing the mixture for 24 hours. The modifier is prepared by mixing a polytetrafluoroethylene oligomer, a sulfonamide rubber vulcanization accelerator, a dicarboximide rubber scorch retarder and an organic acid. The modifier is coated on the surface of the waste rubber powder for restoring the viscosity of the waste rubber powder and improving the compatibility of the waste rubber powder with a mixed rubber, and the doped amount of the waste rubber powder can be improved to 30 percent.
Description
One, technical field
The present invention relates to a kind of waste amine sulfide powder, particularly a kind of high-quality waste amine sulfide powder, specifically a kind of activation waste amine sulfide powder of surface modification treatment.
Two, background technology
Waste old belongs to thermoset copolymer material, is difficult to degraded under field conditions (factors), if abandon in the face of land or be embedded in the underground more than ten years also imputrescibility is rotten.The accumulation land occupation of waste old, contaminate environment is not only damaged residents ' health, and fire hazardous, and people claim that it is " black pollution ".Therefore, although waste old proportion in the solid waste total amount is less, be one of subject matter of solid waste processing.It is a kind of renewable resources that waste old has been handled well, and handling bad then is to the deleterious rubbish of environment for human survival.
It is a physical mechanical process that the waste old processing powder is broken into rubber powder.Producing the technical process of rubber powder simplifies, the operations such as High Temperature High Pressure desulfurization, washing, kneading and refining in the desulfurization regeneration glue production technique have been saved, and complicated component, the color depth that must add, irritating smell, mineral oil softener that contaminative is bigger are arranged, and multiple auxiliary agents such as regeneration activator, tackifier and oxidation inhibitor, not only eliminated of the pollution of the waste water,waste gas and industrial residue of desulfurization, washing, also saved investment and reduced production cost environment.The rough and careless estimation of a tree name is produced rubber powder than the desulfurization regeneration glue energy-conservation about 40% of producing equal quality.Therefore the waste old processing powder is broken into rubber powder, is best suited for one of mode of energy-saving and emission-reduction, recycle, so high-quality rubber powder output both domestic and external increases year by year.
Studies show that the rubber powder particle diameter is more little, specific surface area is big more, and interface compatibility is good more, and easier and new rubber unvulcanizate or other materials combine, and the product properties after it is mixed is also good more.Yet, the difficulty of processing of fine glue powder is big, need repeatedly broken or under the cryogenic freezing condition fragmentation just can reach requirement, so that production cost significantly improves, in addition, because rubber powder granule only contains shielding molecular linkage not crosslinked when originally vulcanizing on a small quantity, surfactivity is less, and the product properties that its doping level surpasses more than 20% declines to a great extent.
Three, summary of the invention
The present invention aims to provide a kind of activation waste amine sulfide powder through surface modification treatment improving its doping level, and technical problem to be solved is suitable properties-correcting agent and the corresponding method of modifying of selecting with vulcanized rubber powder generation chemisorption.
Thinking of the present invention is to select suitable properties-correcting agent, adopt corresponding surface modifying method, make properties-correcting agent in colloid surface generation chemisorption, to improve the surfactivity of rubber powder granule, improve the consistency and the dispersed homogeneous degree of rubber powder and new sizing material, thereby under the prerequisite that guarantees the goods physicals, improve the ratio of mixing of rubber powder.
This activation waste amine sulfide powder comprises each component of following weight part:
100 parts of waste amine sulfide powders
Properties-correcting agent 0.8-2 part
Tenderizer 2-10 part,
Described properties-correcting agent has following altered contents and weight ratio thereof:
Tetrafluoroethylene oligopolymer: sulphenamide compounds: dicarboximide compounds: organic acid=1: 0.5-0.8: 0.5-0.8: 0.1-0.3.
Preferably:
100 parts of waste amine sulfide powders
Properties-correcting agent 1-1.5 part
Tenderizer 5-8 part,
Altered contents and weight ratio thereof are in the properties-correcting agent:
Tetrafluoroethylene oligopolymer: sulphenamide compounds: dicarboximide compounds: organic acid=1: 0.6-0.75: 0.6-0.75: 0.15-0.25.
Described sulphenamide compounds is a thiofide, is selected from N-oxygen diethylene-2-[4-morpholinodithio sulphenamide, N tert butyl benzothiazole 2 sulfenamide or N cyclohexyl 2 benzothiazole sulfenamide.
Described dicarboximide compounds is a rubber anti-chark agent, is selected from N-cyclohexylthiophthalimide or N-morpholine sulfo-phthalic imidine etc.
Described organic acid is selected from oleic acid, citric acid or oxalic acid etc.
Described tenderizer is selected from liquid chlorinated paraffin.
This activation waste amine sulfide powder is preparation like this:
Add the heavy properties-correcting agent of 0.8-2 part in 100 parts of the waste amine sulfide powders (40-80 order), for helping the dispersion of properties-correcting agent, make its dissolving in advance with an amount of dehydrated alcohol, concentration is advisable with 10-30% (weight).Earlier properties-correcting agent is mixed in mixing tank with rubber powder, add the heavy clorafin (liquid state) of 2-10 part then, stir, whipping process carries out under 50-70 ℃.Placed about 24 hours after the discharging, make properties-correcting agent fully permeate vulcanized rubber powder, can finish the surface modification treatment of waste amine sulfide powder.
Experiment shows that the surface that this properties-correcting agent is coated on shoddy can recover its adhesion properties, improves its consistency of rubber unvulcanizate with it, reduces in the sulfidation because of the influence of vulcanizing agent migration to product performance, and its incorporation can bring up to 30%.
This method of modifying carries out at normal temperatures and pressures, and energy consumption is low, and technology is simple, and equipment requirements is not high, suitability for industrialized, thus open up a new approach for the recycle of renewable resource.
Four, embodiment
4.1 rubber powder modified
Below by embodiment technology of the present invention is further specified:
Example 1 useless butadiene-acrylonitrile rubber (NBR) rubber powder modified is handled
Get 100 parts of weights of butadiene-acrylonitrile rubber rubber powder that scrap stock grind in the 40 order Rubber processings, add 0.4 part of weight of properties-correcting agent tetrafluoroethylene oligopolymer, 0.3 part of weight of N cyclohexyl 2 benzothiazole sulfenamide, 0.3 part of weight of N-cyclohexylthiophthalimide, 0.2 part of weight of oleic acid, add 5 parts of weights of tenderizer clorafin again, atmospheric pressure at room high-speed stirring 7 minutes was placed 24 hours to such an extent that useless butadiene-acrylonitrile rubber rubber powder is handled in modification after the discharging.
Example 2 useless second third glue (EPDM) rubber powder modifieds are handled
Get 100 parts of weights of the second third glue rubber powder that scrap stock grind in the 60 order Rubber processings, add 0.5 part of weight of properties-correcting agent tetrafluoroethylene oligopolymer, N-oxygen diethylene-0.3 part of weight of 2-[4-morpholinodithio sulphenamide, 0.3 part of weight of N-cyclohexylthiophthalimide, 0.1 part of weight of citric acid, add 7 parts of weights of tenderizer clorafin again, atmospheric pressure at room high-speed stirring 10 minutes was placed 24 hours to such an extent that the useless second third glue rubber powder is handled in modification after the discharging.
Example 3 useless natural gum (NR) rubber powder modifieds are handled
Get 100 parts of weights of natural gum rubber powder that scrap stock grind in the 80 order Rubber processings, add 0.5 part of weight of properties-correcting agent tetrafluoroethylene oligopolymer, N-oxygen diethylene-0.3 part of weight of 2-[4-morpholinodithio sulphenamide, 0.3 part of weight of N-morpholine sulfo-phthalic imidine, 0.1 part of weight of oxalic acid, add 7 parts of weights of tenderizer clorafin again, atmospheric pressure at room high-speed stirring 10 minutes was placed 24 hours to such an extent that the useless second third glue rubber powder is handled in modification after the discharging.
4.2 modified glue powder performance evaluation
Performance for three kinds of modified glue powders in the example is tested according to following method: answer in 100 parts of heavy phases to add 20,30 parts of heavy modified glue powders and 20 parts of unmodified rubber powders of weight in the rubber unvulcanizate respectively, by compressing tablet sulfuration behind two roller mill thorough mixing, measure tensile strength and elongation according to GB/T528-1998.Test result sees the following form:
Table 1. adds the N7307 cross-linked rubber prototype test result of the active vulcanized rubber powder of useless NBR
*N7307 is enterprise's numbering of butadiene-acrylonitrile rubber rubber unvulcanizate
Table 2. adds the E6203K sulfuration prototype test result of the active vulcanized rubber powder of useless EPDM
*E6203K is enterprise's numbering of ethylene-propylene diene copolymer rubber unvulcanizate
Table 3. adds the R7626 sulfuration prototype test result of the active vulcanized rubber powder of useless NR
*R7626 is enterprise's numbering of natural gum rubber unvulcanizate
Be doped to behind the rubber powder modified in the corresponding rubber unvulcanizate, as can be seen from Table 1, for the useless NBR vulcanized rubber powder of 40 purposes, because of its particle diameter is bigger, specific surface area is less, and the osmotic effect of properties-correcting agent is undesirable, and the product properties of this rubber powder that causes mixing descends apparent in view; By table 2 and 3 as can be seen, along with diminishing of rubber powder particle diameter, the consistency of rubber powder and rubber unvulcanizate is better after the modification, and the tensile strength of rubber item, tensile yield and 100% tensile modulus change all less, and modification is better than unmodified rubber powder performance.Under the situation that does not influence the rubber item performance, the active waste amine sulfide powder for preparing by doping the present invention can effectively reduce production cost.
Claims (6)
1. the activation waste amine sulfide powder of a surface modification is characterized in that: each component that comprises following weight part
100 parts of waste amine sulfide powders
Properties-correcting agent 0.8-2 part
Tenderizer 2-10 part,
Described properties-correcting agent has following altered contents and weight ratio thereof:
Tetrafluoroethylene oligopolymer: sulphenamide compounds: dicarboximide compounds: organic acid=1: 0.5-0.8: 0.5-0.8: 0.1-0.3.
2. activation waste amine sulfide powder according to claim 1 is characterized in that:
100 parts of waste amine sulfide powders
Properties-correcting agent 1-1.5 part
Tenderizer 5-8 part,
Altered contents and weight ratio thereof are in the properties-correcting agent:
Tetrafluoroethylene oligopolymer: sulphenamide compounds: dicarboximide compounds: organic acid=1: 0.6-0.75: 0.6-0.75: 0.15-0.25.
3. activation waste amine sulfide powder according to claim 1 and 2 is characterized in that: described sulphenamide compounds is selected from N-oxygen diethylene-2-[4-morpholinodithio sulphenamide, N tert butyl benzothiazole 2 sulfenamide or N cyclohexyl 2 benzothiazole sulfenamide.
4. activation waste amine sulfide powder according to claim 1 and 2 is characterized in that: described dicarboximide compounds is selected from N-cyclohexylthiophthalimide or N-morpholine sulfo-phthalic imidine.
5. activation waste amine sulfide powder according to claim 1 and 2 is characterized in that: described organic acid is selected from oleic acid, citric acid or oxalic acid.
6. activation waste amine sulfide powder according to claim 1 and 2 is characterized in that: described tenderizer is selected from liquid chlorinated paraffin.
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| CN 201010547175 CN102010531A (en) | 2010-11-17 | 2010-11-17 | Modified-surface activated waste vulcanizate powder |
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| CN 201010547175 CN102010531A (en) | 2010-11-17 | 2010-11-17 | Modified-surface activated waste vulcanizate powder |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391589A (en) * | 2011-07-04 | 2012-03-28 | 四川大学 | Preparation method of surface halogenation modified vulcanized rubber powder/polyvinyl chloride blended compound |
| CN112334322A (en) * | 2018-06-21 | 2021-02-05 | 米其林集团总公司 | Rubber composition comprising specific rubber powder |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1087099A (en) * | 1992-11-17 | 1994-05-25 | 中国科学院大连化学物理研究所 | A kind of properties-correcting agent and treatment process that is used for waste amine sulfide powder |
| CN101696285A (en) * | 2009-09-30 | 2010-04-21 | 徐州工业职业技术学院 | New method for activating and recycling tyre waste rubber powder |
| CN101747527A (en) * | 2008-12-16 | 2010-06-23 | 安徽中鼎密封件股份有限公司 | High-activity vulcanized rubber powder and preparation method thereof |
-
2010
- 2010-11-17 CN CN 201010547175 patent/CN102010531A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1087099A (en) * | 1992-11-17 | 1994-05-25 | 中国科学院大连化学物理研究所 | A kind of properties-correcting agent and treatment process that is used for waste amine sulfide powder |
| CN101747527A (en) * | 2008-12-16 | 2010-06-23 | 安徽中鼎密封件股份有限公司 | High-activity vulcanized rubber powder and preparation method thereof |
| CN101696285A (en) * | 2009-09-30 | 2010-04-21 | 徐州工业职业技术学院 | New method for activating and recycling tyre waste rubber powder |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391589A (en) * | 2011-07-04 | 2012-03-28 | 四川大学 | Preparation method of surface halogenation modified vulcanized rubber powder/polyvinyl chloride blended compound |
| CN112334322A (en) * | 2018-06-21 | 2021-02-05 | 米其林集团总公司 | Rubber composition comprising specific rubber powder |
| CN112334322B (en) * | 2018-06-21 | 2022-11-04 | 米其林集团总公司 | Rubber composition comprising specific rubber powder |
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Application publication date: 20110413 |