The purpose of this invention is to provide that a kind of technology is simple and direct under normal temperature and pressure conditions, save energy, pollution-free and product physicals and the good waste or used vulcanized rubber renovation process of processing characteristics.
Implementation method of the present invention is as follows:
Raw material is the micelle (4 order) of the cross-linked rubber of natural gum or synthetical glue or both mixtures, substantially not fibre-bearing and metallic impurity.
Above-mentioned micelle 100 weight parts; add in the mixing reactor; the agitator that starts in the mixing reactor stirs (the agitator stirring velocity can be 900-1000 rev/min); (the blade high speed rotating of agitator makes micelle be subjected to shearing force in reactor in the mixing reactor to make it give birth to the heat intensification; the effect of multiple power such as frictional force and surging force; its temperature was raised to the temperature range of the initial stage adding assistant of reaction requirement in 10-15 minute) when the micelle temperature is raised to 80-100 ℃ in the mixing reactor; under continuous agitation condition; add 7-10 weight part activator LR-104 and 0.5-1 weight part catalyzer LA-78 successively; the catalytic activation reaction of carrying out micelle fracture sulfur cross-linking point is after 2-3 minute; add 3-5 weight part properties-correcting agent LB-43 again; continue to stir and carry out activation modification reaction 5-7 minute, promptly finish micelle activation modification response procedures.
Micelle activation modification temperature of reaction is controlled at less than 80 ℃, greater than (temperature of reaction control can realize by feeding water coolant to reactor jacket) in 140 ℃ the scope.The activation modification reaction times was controlled at 7-10 minute.
After the reaction of micelle activation modification is finished; the reacted micelle of activation modification is entered (can feed water coolant toward the water cooler chuck cools off) in the watercooler; the agitator that starts watercooler stirs (the agitator stirring velocity can be 100-150 rev/min) cool to room temperature, makes activation modification micelle termination reaction.The activation modification micelle of cool to room temperature is discharged water cooler, (can select roll spacing is 0.1-0.3mm to deliver to opening rubber mixing machine, the roller temperature is 45 ± 5 ℃, the roller speed ratio is 1: 1.12) on, add nucleophilic reagent LP-7 mixing together 7-10 minute in the activation modification micelle of 100 weight parts than the ratio of the nucleophilic reagent LP-7 of 3-5 weight part, promptly make regenerated rubber.
The optimal activation modified-reaction temperature of micelle in mixing tank is 100-120 ℃.If temperature of reaction is lower than 80 ℃, activator, the properties-correcting agent molten phenomenon of part caking less then easily takes place, make the activation modification reaction not exclusively, influence the regenerated rubber physicals; If temperature of reaction surpasses 140 ℃, then strong chain-breaking reaction takes place in process, and the regenerated rubber physicals is descended significantly.
Regenerated rubber physicals evaluation prescription of the present invention and physical and chemical performance are as follows:
1, regenerated rubber physicals of the present invention is identified prescription:
Regenerated rubber of the present invention: 100; Sulphur: 1.5; Zinc oxide: 2.0; Accelerant CZ: 0.3; Add up to: 103.8 (more than be weight part).
Make mixed sheet by above-mentioned prescription,, on vulcanizing press, vulcanized 7-10 minute, obtain regenerated rubber vulcanizating glue physical performance such as table 1 at 142 ℃ and be not less than under the condition of 20kg/cm pressure.
2, regenerated rubber physics of the present invention and chemical property are as table-1.
The present invention makes used additives molecular structure and the trade mark as follows:
1, activator LR-104 (trade mark LR-104), its composition are that curing aromatic hydrocarbon acid amides and many sulfuration aromatic hydrocarbon acid amides (containing little fat family disulphide) and thinner---oil system and pine tar are the general tenderizer of rubber.Molecular structural formula is as follows:
Annotate: n in the molecular structural formula 〉=3;
2, catalyzer LA-78 (trade mark LA-78), have and with the rubber covulcanization and to have the side group ring compound of response capacity, its molecule has the molecule that can effectively the disperse desulfurization regeneration activator LR-104 long-chain fat family amine structure to each sulfuration micelle, and has sulfone class functional group.The sulfur cross-linking point that has the sulfuration micelle has unique avidity and penetrating force and very strong solvency power.Its molecular structure signal formula adds down:
Annotate: in the molecular structural formula, n≤6 carbon atom, x≤3;
This catalyzer can make micelle when activating and regenerating reacts, and impels the activator molecule to be evenly dispersed on each micelle, can make the activator molecule partly be penetrated into micelle inside simultaneously and activate desulphurization reaction, has played the effect of quickening priming reaction.
3, properties-correcting agent LB-43 (trade mark LB-43), molecular structure is a ring-type, and has conjugated double bond and have the carboxyl of response capacity and the side group of hydroxyl.Its molecular structure signal formula is as follows:
Annotate: in the molecular structural formula, n≤3, R is a 5-8 carbon atom alkyl.
This properties-correcting agent can resolve into new free radical in micro acid medium, this free radical is the receptor that micelle activation desulfurization generates radical, can guarantee that the molecular weight of final activation modification product is all even not too low.
4, nucleophilic reagent LP-7 (trade mark LP-7) has the polynuclear compound of resol type structure, and molecular structure signal formula is as follows:
Annotate: in the molecular structural formula, R is a 5-8 carbon atom.
This nucleophilic reagent prevents airborne oxygen and rubber combined with radical, prevents that rubbery chip from generating, and prevents that the regenerated rubber molecular weight from reducing and keeping the homogeneity of molecular weight.This nucleophilic reagent and rubber combined with radical increase the regenerated rubber molecular weight, improve its physicals.
Above-mentioned four kinds of auxiliary agents are produced by the Guangzhou Inst. of Regenerated Resource Utilization, are the commercially available prod.
Advantage of the present invention:
1, the present invention is except the mixing reactor that adopts self design, also can adopt general-purpose equipment such as the powder blenders (a little change to use) of traditional oil process (disc type method) reclaimed rubber factory or General Purpose Rubber products factory or plastics factory and opening rubber mixing machine, need not specific installation, technical process is simple, the less investment of founding the factory, easily suitability for industrialized production.
2, the scrap rubber granularity of the present invention's use is big, is-4 orders; The micelle activation modification is reflected at lesser temps (100-120 ℃) scope and finishes in the short period of time (7-10 minute); its product does not need intense mechanical post-treatment (refining); thereby the production of regenerated rubber of the present invention to have energy consumption low; with short production cycle; the production efficiency height; production cost is low, the advantage of environmentally safe.
3, the present invention has same desulfurization regeneration effect to specialty elastomer cross-linked rubber (butyronitrile, neoprene, butyl, second third gradegrade C cross-linked rubber).
4, the regenerated rubber of manufacturing of the present invention has good physical and mechanical properties.Tire class regenerated rubber revulcanization of the present invention glue, it pulls apart powerful at 13-18Mpa, and tensile yield is at 320-400%, thereby regenerated rubber of the present invention can be applied to go in tire manufacturing and other any rubber items again.
Embodiment 1-example 4
Use the micelle granularity to be 4-8 purpose truck tyre, passenger vehicle tyre, the micelle of polishing when mixing tire and tyre rebuilding, (processing parameter of selection is prepared regenerated rubber and is carried out the physicals test by aforementioned regenerated rubber physicals authentication method shown in table-2, its result lists in table-2 by the invention process method.
Table-2 micelles (4-8 order) activation modification prescriptions (weight part) and performance
Embodiment 5
Use useless butyronitrile vulcanized rubber grain (4-8 order): 100 weight parts, activator LR-104:10 weight part, other auxiliary agent umbers and processing condition are all undertaken by the invention process method regulation, make the butadiene-acrylonitrile rubber regenerated rubber.The butyronitrile regenerated rubber cooperates by following sulfurizing formula.
Butyronitrile regenerated rubber: 100; Sulphur: 1.0; Zinc oxide: 4.0; Magnesium oxide: 4.0; Altax: 1.0; Amount to: 110.0 (more than be weight part).
Cooperate by above prescription, make cross-linked rubber, it pulls apart powerful at 13-14Mpa, and tensile yield is 350-400%.
Embodiment 6
Use the micelle (4-8 order) of waste butyl rubber cross-linked rubber: 100 weight parts, activator LR-104:5 weight part, other auxiliary agent umbers and processing condition are all undertaken by the invention process method.Made basic regenerated rubber, cooperated by following sulfurizing formula.
Butyl renewable rubber: 100; Sulphur: 2.0; Captax: 0.5; Promotor TT:1.0; Stearic acid: 0.5 part; Add up to: 104.0 (more than be weight part).
Cooperate by above-mentioned prescription, make revulcanization glue, it pulls apart powerful at 13-13.5Mpa, tensile yield 380-450%.
Embodiment 7
Use tire class micelle (4-8 order), activator LR-104, properties-correcting agent LB-43, nucleophilic reagent LP-7 carry out the variable test respectively, during one of them auxiliary agent variable, other auxiliary agents and implementing process method are all carried out (processing parameter of selection is shown in table-3,4,5) by the invention process method, make regenerated rubber.Cooperate by aforementioned regenerated rubber physicals evaluation, make the regenerated rubber sulfide film, carry out performance test.Its test result is listed in respectively in table-3,4,5.
Table-3 activator LR-104 variablees
Routine number of project | Example-1 | Example-2 | Example-3 | Example-4 | Example-5 |
4-8 order micelle weight part | ????100 | ????100 | ????100 | ????100 | ????100 |
Activator LR-104 weight part | ????5 | ????7 | ????8 | ????9 | ????10 |
Catalyzer LA-78 weight part | ????1 | ????1 | ????1 | ????1 | ????1 |
Properties-correcting agent LB-43 weight part | ????3 | ????3 | ????3 | ????3 | ????3 |
Activation modification temperature of reaction ℃ | ????100 | ????100 | ????100 | ????100 | ????100 |
In the activation modification reaction times, divide | ????7 | ????7 | ????7 | ????7 | ????7 |
Micelle weight part behind the activation modification | ????100 | ????100 | ????100 | ????100 | ????100 |
Nucleophilic reagent LP-7 weight part | ????3 | ????3 | ????3 | ????3 | ????3 |
Mill mixing time branch | ????8 | ????8 | ????8 | ????8 | ????8 |
142 ℃ * minute of cure conditions | ????10 | ????10 | ????10 | ????10 | ????10 |
Hardness (Shao Er A) degree | ????64 | ????65 | ????64 | ????64 | ????62 |
Pull apart powerful Mpa | ????14.0 | ????14.5 | ????14.8 | ????14.5 | ????14.0 |
Tensile yield % | ????360 | ????365 | ????356 | ????367 | ????361 |
Table-4 properties-correcting agent LB-43 variablees
Routine number of project | Example-1 | Example-2 | Example-3 | Example-4 | Example-5 |
4-8 order micelle, weight part | ????100 | ????100 | ????100 | ????100 | ????100 |
Activator LR-104 weight part | ????7 | ????7 | ????7 | ????7 | ????7 |
Catalyzer LA-78 weight part | ????1 | ????1 | ????1 | ????1 | ????1 |
Properties-correcting agent LB-43 weight part | ????2 | ????3 | ????4 | ????5 | ????6 |
Activation modification temperature of reaction ℃ | ????100 | ????100 | ????100 | ????100 | ????100 |
In the activation modification reaction times, divide | ????7 | ????7 | ????7 | ????7 | ????7 |
Micelle behind the activation modification | ????100 | ????100 | ????100 | ????100 | ????100 |
Nucleophilic reagent LP-7 weight part | ????3 | ????3 | ????3 | ????3 | ????3 |
Mill mixing time branch | ????8 | ????8 | ????8 | ????8 | ????8 |
142 ℃ * minute of cure conditions | ????10 | ????10 | ????10 | ????10 | ????10 |
Hardness (Shao Er A) degree | ????62 | ????65 | ????65 | ????64 | ????62 |
Pull apart powerful Mpa | ????13.7 | ????14.5 | ????14.3 | ????14.1 | ????14.1 |
Tensile yield % | ????378 | ????365 | ????361 | ????367 | ????361 |
Table-5 nucleophilic reagent LP-7 variablees
Routine number of project | Example-1 | Example-2 | Example-3 | Example-4 | Example-5 |
4-8 order micelle weight part | ????100 | ????100 | ????100 | ????100 | ????100 |
Activator LR-104 weight part | ????7 | ????7 | ????7 | ????7 | ????7 |
Catalyzer LA-78 weight part | ????1 | ????1 | ????1 | ????1 | ????1 |
Properties-correcting agent LB-43 weight part | ????3 | ????3 | ????3 | ????3 | ????3 |
Activation modification temperature of reaction ℃ | ????100 | ????100 | ????100 | ????100 | ????100 |
In the activation modification reaction times, divide | ????7 | ????7 | ????7 | ????7 | ????7 |
Micelle weight part behind the activation modification | ????100 | ????100 | ????100 | ????100 | ????100 |
Nucleophilic reagent LP-7 weight part | ????2 | ????3 | ????4 | ????5 | ????6 |
Mill mixing time branch | ????8 | ????8 | ????8 | ????8 | ????8 |
142 ℃ * minute of cure conditions | ????10 | ????10 | ????10 | ????10 | ????10 |
Hardness (Shao Er A) degree | ????63 | ????65 | ????66 | ????65 | ????62 |
Pull apart powerful MPA | ????13.4 | ????14.5 | ????14.6 | ????14.4 | ????14.0 |
Tensile yield % | ????361 | ????365 | ????365 | ????362 | ????361 |
From table-3,4,5 data as can be known, activator LR-104 consumption is at the 7-10 weight part, and properties-correcting agent LB-43 consumption is at the 3-5 weight part, nucleophilic reagent LP-7 consumption at 3 weight parts for well.
Embodiment 8
Use tire class micelle (4-8 order), to the test that elects respectively of activation modification temperature of reaction and reaction times parameter.During one of them changes in process parameters, another processing parameter and implementing process method are all undertaken by the invention process method.The regenerated rubber that makes identifies that by aforesaid regenerated rubber physicals the regenerated rubber sulfuration sheet that cooperates and make carries out performance test, and it is surveyed the formula result and lists table-6 and table-7 respectively in.
Table-6 micelle activation modification temperature of reaction are selected test
Routine number of project | Example-1 | Example-2 | Example-3 | Example-4 | Example-5 | Example-6 |
4-8 order micelle weight part | ????100 | ????100 | ????100 | ????100 | ????100 | ????100 |
Activator LR-104 weight part | ????7 | ????7 | ????7 | ????7 | ????7 | ????7 |
Catalyzer LA-78 weight part | ????1 | ????1 | ????1 | ????1 | ????1 | ????1 |
Properties-correcting agent LH-43 weight part | ????3 | ????3 | ????3 | ????3 | ????3 | ????3 |
Activation modification temperature of reaction ℃ | ????70 | ????80 | ????100 | ????120 | ????140 | ????150 |
In the activation modification reaction times, divide | ????7 | ????7 | ????7 | ????7 | ????7 | ????7 |
Micelle weight part behind the activation modification | ????100 | ????100 | ????100 | ????100 | ????100 | ????100 |
Nucleophilic reagent LP-7 weight part | ????3 | ????3 | ????3 | ????3 | ????3 | ????3 |
Mill mixing time branch | ????8 | ????8 | ????8 | ????8 | ????8 | ????8 |
142 ℃ * minute of cure conditions | ????10 | ????10 | ????10 | ????10 | ????10 | ????10 |
Hardness (Shao Er A) degree | ????60 | ????62 | ????65 | ????64 | ????65 | ????65 |
Pull apart powerful Mpa | ????12.4 | ????13.7 | ????14.5 | ????14.4 | ????14.0 | ????14.1 |
Tensile yield % | ????361 | ????363 | ????365 | ????362 | ????362 | ????358 |
-7 micelle activation modification reaction times of table are selected test
Routine number of project | Example-1 | Example-2 | Example-3 | Example-4 | Example-5 | Example-6 |
4-8 order micelle weight part | ????100 | ????100 | ????100 | ????100 | ????100 | ????100 |
Activator LR-104 weight part | ????7 | ????7 | ????7 | ????7 | ????7 | ????7 |
Catalyzer LA-78 weight part | ????1 | ????1 | ????1 | ????1 | ????1 | ????1 |
Properties-correcting agent LB-43 weight part | ????3 | ????3 | ????3 | ????3 | ????3 | ????3 |
Activation modification temperature of reaction ℃ | ????100 | ????100 | ????100 | ????100 | ????100 | ????100 |
In the activation modification reaction times, divide | ????6 | ????7 | ????8 | ????9 | ????10 | ????11 |
Micelle weight part behind the activation modification | ????100 | ????100 | ????100 | ????100 | ????100 | ????100 |
Nucleophilic reagent LP-7 weight part | ????3 | ????3 | ????3 | ????3 | ????3 | ????3 |
Mill mixing time branch | ????8 | ????8 | ????8 | ????8 | ????8 | ????8 |
142 ℃ * minute of cure conditions | ????10 | ????10 | ????10 | ????10 | ????10 | ????10 |
Hardness (Shao Er A) degree | ????60 | ????65 | ????64 | ????64 | ????63 | ????63 |
Pull apart powerful Mpa | ????13.1 | ????14.5 | ????14.0 | ????14.1 | ????14.0 | ????13.8 |
Tensile yield % | ????366 | ????365 | ????366 | ????365 | ????362 | ????361 |
By the table-6 with the table-7 data as can be known: micelle activation modification temperature of reaction optimum range is 100-120 ℃; The micelle activation modification reaction times was at 7-10 minute.
Regenerated rubber of the present invention is mixed simultaneous test in various rubbers:
1, regenerated rubber of the present invention, the activation modification rubber powder, commercially available reclaimed rubber is mixed simultaneous test and is seen Table-8 in natural gum.
Table-8 (unit: weight part, if do not indicate)
2, regenerated rubber of the present invention, activation modification rubber powder, commercially available reclaimed rubber are mixed simultaneous test and are seen Table-9 in butadiene-styrene rubber.
Table-9 (unit: weight part, if do not indicate)
3, regenerated rubber of the present invention is mixed test and is seen Table-10 in natural gum, cis-butadiene cement, butadiene-styrene rubber.
Table-10 (unit: weight part, if do not indicate)
Regenerated rubber of the present invention is mixed prescription and performance in tire tread glue:
1, regenerated rubber of the present invention in riding tire tread glue, mix the prescription with physicals as the table-11.
Table-11 (unit: weight part, if do not indicate)
Hardness (Shao Er A) degree | ????63 | ????67 | ????67 | ????67 | ????67 | ????67 | ????67 |
Pull apart powerful Mpa | ????23.5 | ????17.8 | ????17.6 | ????16.5 | ????15.6 | ????15.1 | ????14.8 |
Tensile yield % | ????626 | ????464 | ????488 | ????480 | ????500 | ????500 | ????500 |
300% fixed stretching strength MPa | ????8.9 | ????9.9 | ????9.7 | ????9.0 | ????8.9 | ????8.2 | ????7.9 |
Elasticity % | ????26 | ????27 | ????26 | ????25 | ????26 | ????27 | ????27 |
Tear powerful KN/m | ????83 | ????79 | ????68 | ????65 | ????67 | ????58 | ????57 |
Subdue ten thousand times/Type B | ????36.8 | ????33.7 | ????25.4 | ????18.3 | ????12.2 | ????8.5 | ????6.8 |
Akron abrasion cm/1.61km | ????0.26 | ????0.29 | ????0.27 | ????0.27 | ????0.28 | ????0.35 | ????0.37 |
After 100 ℃ * 24 hours thermal ageings | Warm air |
Pull apart powerful MPa | ????20.0 | ????15.4 | ????16.4 | ????15.6 | ????15.0 | ????14.4 | ????14.3 |
Tensile yield % | ????520 | ????380 | ????416 | ????380 | ????388 | ????380 | ????420 |
2, regenerated rubber of the present invention in load-carrying tire tread glue, mix the prescription with physicals as the table-12.
Table-12 (unit: weight part, if do not indicate)