CN102311528A - Waste rubber powder/polyolefin blending material and preparation method thereof - Google Patents
Waste rubber powder/polyolefin blending material and preparation method thereof Download PDFInfo
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- CN102311528A CN102311528A CN201110184175A CN201110184175A CN102311528A CN 102311528 A CN102311528 A CN 102311528A CN 201110184175 A CN201110184175 A CN 201110184175A CN 201110184175 A CN201110184175 A CN 201110184175A CN 102311528 A CN102311528 A CN 102311528A
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- rubber powder
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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
The invention discloses a method for preparing a waste rubber powder/polyolefin blending material. The method comprises the following steps: in parts by weight, carrying out surface desulfurization and plasticizing reaction on 10-100 parts of rubber powder and 1-10 parts of modifying agent in a mixing mill, wherein the reaction time is 5-30 minutes; then, controlling the temperature at 100-200 DEG C; mixing with 20-100 parts of polyolefin resin for 5-20 minutes; and then, adding 1-20 parts of grafting monomer and 1-5 parts of initiator to mix for 5-20 minutes so as to obtain the required blending material. In the method disclosed by the invention, through carrying out grafting blending modification on the waste rubber powder and polyolefin resin which are subjected to surface modification, the interfacial property between the waste rubber powder and the polyolefin resin is effectively improved, and a new way for recycling waste polymer materials is also provided.
Description
Technical field
The present invention relates to the recycling field of spent high molecular material, specifically is a kind of waste rubber powder/polyolefin blend material and preparation method thereof.
Background technology
Along with the fast development of polymer industry, the usage quantity of spent high molecular material is increasing, reclaims and comprehensive utilization is the trend that the recycling economy development pattern of core has become world development with waste and old resource.The technology of recycle of exploiting natural resources energetically will exert far reaching influence to the growth and the environment sustainable development of national economy.At present, the YO of world's waste old is above 2,000 ten thousand tons.Because the cross-linked network that rubber item forms in the course of processing makes it be difficult to reprocessing, becomes black pollution easily, environment is caused have a strong impact on, recycling rubber has caused that people pay attention to widely.The recycling of waste old has several different methods, as cushioning material, sound-proof material, processes shoddy, rubber powder etc. as directly.Process rubber powder to waste old and use, not only method is simple, less energy consumption, cost are low, and has higher economic value.Generally, rubber powder can add in rubber or the plastics, is applied to road pavement, waterproof roll, plastic toughening and preparation thermoplastic elastomer etc.Chinese scholars is to the existing many reports of the applied research of rubber powder, but the interface that mostly is to improve rubber powder and rubber or plastics is to improve the intensity of intermingling material.At present there is following several method to improve both consistencies usually: to increase the contact area with matrix through rubber powder desulfurization modification; Add compatilizer or rubber powder is coated; Strengthen interface compatibility through dynamic vulcanization.The two kinds of methods in front all are to improve the performance of intermingling material through physical bond; Thereby improved performance is limited, and adding compatilizer or coating can only be directed against a kind of matrix; Must use another kind of compatilizer instead or use other material coating instead other matrix resin, therefore preparation comparatively bothers.A kind of method in back is a Chemical bond, thereby is two keys and matrix generation chemical reaction raising consistency through vulcanized rubber powder.But the two keys of vulcanized rubber powder are less, and all be in a fixed position can not free movement, thereby crosslinked limited with matrix resin, and performance improves not obvious.
Summary of the invention
The object of the invention is the deficiency to prior art; A kind of waste rubber powder/polyolefin blend material and preparation method thereof is provided; Waste rubber powder and polyolefin resin that the present invention at first will pass through surface-treated carry out the graft-blending modification; Improve the interface performance between waste rubber powder and the polyolefin resin effectively, also a kind of new way is provided simultaneously for reclaiming spent high molecular material.
Realize that the technical scheme that the object of the invention adopted is:
A kind of waste rubber powder/polyolefin blend preparation methods comprises the steps: that each component counts by weight, in mixing roll; 10 ~ 100 parts of rubber powders and 1～10 part of properties-correcting agent are carried out surface devulcanization plasticizing reaction, and the reaction times is 5 ~ 30 minutes, and controlled temperature is 100 ℃～200 ℃ then; Again with mixing 5 ~ 20 minutes of 20～100 parts of polyolefin resines; And then adding 1～20 part of grafted monomer and 1～5 part of initiator is mixing, mixing time is 5 ~ 20 minutes, can obtain required intermingling material.
The particle diameter of said rubber powder is 10～200 orders.
Said polyolefin resin is any one in ethylene-octene copolymer, polyolefin elastomer, high density polyethylene(HDPE), new LDPE (film grade), Vestolen PP 7052 or the ethylene-vinyl acetate copolymer.
Said properties-correcting agent be in phenylhydrazine, thiazole, diethylenetriamine, triethylene tetramine, TEPA, mercaptan, disulphide or the sweetening agent any one.
Said grafted monomer be vinylbenzene, maleic anhydride, SY-Monomer G, acrylic or methacrylic acid methyl esters any one or more than one.
Said initiator is any one in BPO, Di Cumyl Peroxide 99 or the ditertiary butyl peroxide.
Said mixing roll is mill, Banbury mixer or forcing machine.
Compared with prior art; The present invention has following advantage and beneficial effect: the rubber powder modified agent that the present invention adopts can make vulcanized rubber powder desulfurization plasticizing; Improved the linear lag of vulcanized rubber powder; Thereby increased the reactive behavior between rubber powder and the polyolefin resin, and connected the functional group that can participate in reaction, further increased reactive behavior with polyolefin resin.In mixing process, add grafted monomer and initiator then; Make rubber powder and polyolefin resin generation graft reaction; Polyolefin resin is grafted on the rubber powder, and between has been set up strong interface, thereby obtains having the waste rubber powder/polyolefin resin intermingling material of excellent mechanical performances.
Embodiment
Below in conjunction with specific embodiment the present invention is done further concrete detailed description the in detail, but embodiment of the present invention is not limited thereto, the processing parameter for not indicating especially can carry out with reference to routine techniques.
Embodiment 1
With 80 order waste rubber powder 40g and 2g TEPA in mill, carrying out mixing 10min under the room temperature, then under 160 ℃, in two rollers are begun to pratise machine with the mixing 5min of 100g polyolefin elastomer TPO; Add grafted monomer SY-Monomer G 10g, vinylbenzene 10g, initiator DCP 1.5g again, slice after mixing 8 minutes promptly obtains having the shoddy/polyolefin resin intermingling material of excellent mechanical performances; Batten with this material makes is tested; Its tensile strength is 9.43 MPa, and tear strength can reach 63.0MPa, and elongation at break is 337.4%; Shao A hardness is 83, and material has good thermoplasticity.
Embodiment 2
With 100 order shoddy 60g and 3gDe-link sweetening agent in Banbury mixer, carrying out mixing 8min under the room temperature; Then under 170 ℃; In internal mixer with the mixing 6min of 80g polyolefin elastomer TPE; Add grafted monomer maleic anhydride 5g, vinylbenzene 5g, initiator DCP 1g again, slice after mixing 10 minutes promptly obtains having the shoddy/polyolefin resin intermingling material of excellent mechanical performances.Its tensile strength is 13.3 MPa, and tear strength can reach 58.8MPa, and elongation at break is 404.3%, and Shao A hardness is 88, and material has good thermoplasticity.
Embodiment 3
With 60 order shoddy 70g and 4g thiazole under the room temperature in mill mixing 10min;, descend and the mixing 8min of 50g high density polyethylene on two rollers in beginning to pratise machine then in 180 ℃; Add grafted monomer SY-Monomer G 4g, vinylbenzene 4g, initiator DCP 0.6g again; Slice after mixing 10 minutes promptly obtains having the shoddy/polyolefin resin intermingling material of excellent mechanical performances.Its tensile strength is 18.3MPa, and tear strength can reach 106.4MPa, and elongation at break is 287.4%, and Shao A hardness is 95, and material has good thermoplasticity.
Embodiment 4
With 80 order shoddy 50g and 3g disulphide in Banbury mixer, carrying out mixing 8min under the room temperature; Then under 150 ℃; In internal mixer with the mixing 10min of the waste and old low density polyethylene of 60g; Add grafted monomer maleic anhydride 4g, vinylformic acid 4g, initiator B PO 0.8g again, slice after mixing 15 minutes promptly obtains having the shoddy/polyolefin resin intermingling material of excellent mechanical performances.Its tensile strength is 12.3 MPa, and tear strength can reach 60.8MPa, and elongation at break is 284.2%, and Shao A hardness is 95, and material has good thermoplasticity.
Embodiment 5
With 80 order shoddy 40g and 2g phenylhydrazine in mill, carrying out mixing 8min under the room temperature; Under 140 ℃,, two rollers, add grafted monomer maleic anhydride 9g, TEB 3K 8g, initiator DTBP 1.5g again in beginning to pratise machine then with 100g used vinyl-mixing 5min of vinyl acetate copolymer EVA; Slice after mixing 15 minutes; Promptly obtain having the shoddy/polyolefin resin intermingling material of excellent mechanical performances, its tensile strength is 11.5 MPa, and tear strength reaches 59.5MPa; Elongation at break is 301.5%, and Shao A hardness is 85.
The foregoing description is a preferred implementation of the present invention; But embodiment of the present invention is not restricted to the described embodiments; Other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; All should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (8)
1. waste rubber powder/polyolefin blend preparation methods is characterized in that, comprises the steps: that each component counts by weight; In mixing roll; 10 ~ 100 parts of rubber powders and 1～10 part of properties-correcting agent are carried out surface devulcanization plasticizing reaction, and the reaction times is 5 ~ 30 minutes, and controlled temperature is 100 ℃～200 ℃ then; Again with mixing 5 ~ 20 minutes of 20～100 parts of polyolefin resines; And then adding 1～20 part of grafted monomer and 1～5 part of initiator is mixing, mixing time is 5 ~ 20 minutes, can obtain required intermingling material.
2. preparation method according to claim 1 is characterized in that, the particle diameter of said rubber powder is 10～200 orders.
3. preparation method according to claim 1 and 2; It is characterized in that said polyolefin resin is any one in ethylene-octene copolymer, polyolefin elastomer, high density polyethylene(HDPE), new LDPE (film grade), Vestolen PP 7052 or the ethylene-vinyl acetate copolymer.
4. preparation method according to claim 3 is characterized in that, said properties-correcting agent be in phenylhydrazine, thiazole, diethylenetriamine, triethylene tetramine, TEPA, mercaptan, disulphide or the sweetening agent any one.
5. preparation method according to claim 4 is characterized in that, said grafted monomer be vinylbenzene, maleic anhydride, SY-Monomer G, acrylic or methacrylic acid methyl esters any one or more than one.
6. preparation method according to claim 5 is characterized in that, said initiator is any one in BPO, Di Cumyl Peroxide 99 or the ditertiary butyl peroxide.
7. preparation method according to claim 6 is characterized in that, said mixing roll is mill, Banbury mixer or forcing machine.
8. waste rubber powder/polyolefin blend material is characterized in that, is prepared from any said method of claim 1 to 7.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2011101841759A CN102311528B (en) | 2011-07-04 | 2011-07-04 | Waste rubber powder/polyolefin blending material and preparation method thereof |
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| CN2011101841759A CN102311528B (en) | 2011-07-04 | 2011-07-04 | Waste rubber powder/polyolefin blending material and preparation method thereof |
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| CN102311528B CN102311528B (en) | 2013-02-13 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702592A (en) * | 2012-05-03 | 2012-10-03 | 湖北工业大学 | High-performance regenerated rubber and preparation method thereof |
| CN104292401A (en) * | 2014-09-30 | 2015-01-21 | 苏州博利迈新材料科技有限公司 | Wood fiber-reinforced polypropylene composite material and preparation method thereof |
| CN105254936A (en) * | 2015-11-05 | 2016-01-20 | 徐州工业职业技术学院 | Rubber powder based material used for dynamically vulcanized thermoplastic elastomer (TPE) waterproof roll and preparation method thereof |
| CN106633264A (en) * | 2016-12-27 | 2017-05-10 | 中国葛洲坝集团绿园科技有限公司 | Elastic alloy and preparation method therefor |
| CN107236188A (en) * | 2017-06-26 | 2017-10-10 | 湖北大学 | A kind of modified waste rubber powder and pp intermingling materials and preparation method thereof |
| CN108045043A (en) * | 2017-12-04 | 2018-05-18 | 北京东方雨虹防水技术股份有限公司 | Macromolecule splash guard and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102702592A (en) * | 2012-05-03 | 2012-10-03 | 湖北工业大学 | High-performance regenerated rubber and preparation method thereof |
| CN102702592B (en) * | 2012-05-03 | 2014-08-20 | 湖北工业大学 | High-performance regenerated rubber and preparation method thereof |
| CN104292401A (en) * | 2014-09-30 | 2015-01-21 | 苏州博利迈新材料科技有限公司 | Wood fiber-reinforced polypropylene composite material and preparation method thereof |
| CN105254936A (en) * | 2015-11-05 | 2016-01-20 | 徐州工业职业技术学院 | Rubber powder based material used for dynamically vulcanized thermoplastic elastomer (TPE) waterproof roll and preparation method thereof |
| CN106633264A (en) * | 2016-12-27 | 2017-05-10 | 中国葛洲坝集团绿园科技有限公司 | Elastic alloy and preparation method therefor |
| CN107236188A (en) * | 2017-06-26 | 2017-10-10 | 湖北大学 | A kind of modified waste rubber powder and pp intermingling materials and preparation method thereof |
| CN108045043A (en) * | 2017-12-04 | 2018-05-18 | 北京东方雨虹防水技术股份有限公司 | Macromolecule splash guard and preparation method thereof |
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| CN102311528B (en) | 2013-02-13 |
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