CN102311528B - 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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- CN102311528B CN102311528B CN2011101841759A CN201110184175A CN102311528B CN 102311528 B CN102311528 B CN 102311528B CN 2011101841759 A CN2011101841759 A CN 2011101841759A CN 201110184175 A CN201110184175 A CN 201110184175A CN 102311528 B CN102311528 B CN 102311528B
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- rubber powder
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- polyolefin
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Links
- 238000002156 mixing Methods 0.000 title claims abstract description 39
- 229920001971 elastomer Polymers 0.000 title claims abstract description 35
- 239000005060 rubber Substances 0.000 title claims abstract description 35
- 239000000843 powder Substances 0.000 title claims abstract description 34
- 239000000463 material Substances 0.000 title claims abstract description 30
- 239000002699 waste material Substances 0.000 title claims abstract description 20
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 8
- 238000002360 preparation method Methods 0.000 title claims description 11
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 19
- 239000003999 initiator Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 230000035484 reaction time Effects 0.000 claims abstract description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 5
- 229920001903 high density polyethylene Polymers 0.000 claims description 5
- 239000004700 high-density polyethylene Substances 0.000 claims description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 4
- 229920006124 polyolefin elastomer Polymers 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical class COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 3
- 235000003599 food sweetener Nutrition 0.000 claims description 3
- 229920001684 low density polyethylene Polymers 0.000 claims description 3
- 239000004702 low-density polyethylene Substances 0.000 claims description 3
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 claims description 3
- 229940067157 phenylhydrazine Drugs 0.000 claims description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 3
- 239000003765 sweetening agent Substances 0.000 claims description 3
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- -1 polypropylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229960001124 trientine Drugs 0.000 claims description 2
- 230000004048 modification Effects 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 4
- 238000006477 desulfuration reaction Methods 0.000 abstract description 3
- 230000023556 desulfurization Effects 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 description 5
- 239000004636 vulcanized rubber Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000012969 di-tertiary-butyl peroxide Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Graft Or Block Polymers (AREA)
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 a kind of waste rubber powder/polyolefin blending material and preparation method thereof.
Background technology
Along with the fast development of Polymeric Industry, the usage quantity of spent high molecular material is increasing, reclaims and fully utilize the trend that has become world development as the Circular Economy of core take waste and old resource.The technology of Devoting Major Efforts To Developing resource circulation utilization will exert far reaching influence to growth and the environment sustainable development of national economy.At present, the annual production 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 easily black pollution, 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, makes reclaimed rubber, rubber powder etc. as directly.Waste old is made rubber powder use, not only method is simple, less energy consumption, cost are low, and has higher economic worth.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 has many reports to the applied research of rubber powder, but mostly is to improve the interface of rubber powder and rubber or plastics to improve the intensity of intermingling material.At present usually there is following several method to improve both consistencies: to increase contact area with matrix by rubber powder desulfurization modification; Add compatilizer or rubber powder is coated; Strengthen interface compatibility by dynamic vulcanization.The two kinds of methods in front all are to improve the performance of intermingling material by physical bond, thereby improved performance is limited, and adding compatilizer or coat can only be for a kind of matrix, must use another kind of compatilizer instead or use other material coating instead other matrix resin, therefore preparation comparatively bothers.Rear a kind of method is Chemical bond, thereby is two keys and matrix generation chemical reaction raising consistency by 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 for the deficiencies in the prior art, a kind of waste rubber powder/polyolefin blending material and preparation method thereof is provided, the present invention at first will carry out the graft-blending modification through waste rubber powder and the polyolefin resin of surface modification, effectively improve the interface performance between waste rubber powder and the polyolefin resin, also provide a kind of new way for reclaiming spent high molecular material simultaneously.
Realize that the technical scheme that the object of the invention adopts is:
A kind of preparation method of waste rubber powder/polyolefin blending material, comprise 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 the surface devulcanization plastication, and the reaction times is 5 ~ 30 minutes, then controls 100 ℃～200 ℃ of temperature, 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 described rubber powder is 10～200 orders.
Described polyolefin resin is any one in ethylene-octene copolymer, polyolefin elastomer, high density polyethylene(HDPE), Low Density Polyethylene, polypropylene or the ethylene-vinyl acetate copolymer.
Described properties-correcting agent be in phenylhydrazine, thiazole, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, mercaptan, disulphide or the sweetening agent any one.
Described grafted monomer be vinylbenzene, maleic anhydride, glycidyl methacrylate, acrylic or methacrylic acid methyl esters any one or more than one.
Described initiator is any one in dibenzoyl peroxide, dicumyl peroxide or the ditertiary butyl peroxide.
Described 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 connect the functional group that can participate in reaction, further increased the reactive behavior with polyolefin resin.Then in mixing process, add grafted monomer and initiator, so that 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 of excellent mechanical performances/polyolefin resin intermingling material.
Embodiment
Below in conjunction with specific embodiment the present invention is done further concrete detailed description the in detail, but embodiments of the present invention are not limited to this, 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 tetraethylene pentamine 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 again grafted monomer glycidyl methacrylate 10g, vinylbenzene 10g, initiator DCP 1.5g, slice after mixing 8 minutes, namely obtain having the shoddy of excellent mechanical performances/polyolefin resin intermingling material, test with the batten that this material makes, its tensile strength is 9.43 MPa, tear strength can reach 63.0MPa, elongation at break is 337.4%, and 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 again grafted monomer maleic anhydride 5g, vinylbenzene 5g, initiator DCP 1g, slice after mixing 10 minutes namely obtains having the shoddy of excellent mechanical performances/polyolefin resin intermingling material.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, then in beginning to pratise machine, descend and the mixing 8min of 50g high density polyethylene in 180 ℃ on two rollers, add again grafted monomer glycidyl methacrylate 4g, vinylbenzene 4g, initiator DCP 0.6g, slice after mixing 10 minutes namely obtains having the shoddy of excellent mechanical performances/polyolefin resin intermingling material.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 again grafted monomer maleic anhydride 4g, vinylformic acid 4g, initiator B PO 0.8g, slice after mixing 15 minutes namely obtains having the shoddy of excellent mechanical performances/polyolefin resin intermingling material.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, then under 140 ℃, in two rollers are begun to pratise machine with 100g used vinyl-mixing 5min of vinyl acetate copolymer EVA, add again grafted monomer maleic anhydride 9g, methyl methacrylate 8g, initiator DTBP 1.5g, slice after mixing 15 minutes, namely obtain having the shoddy of excellent mechanical performances/polyolefin resin intermingling material, its tensile strength is 11.5 MPa, tear strength reaches 59.5MPa, elongation at break is 301.5%, and Shao A hardness is 85.
Above-described embodiment is the better embodiment of the present invention; but embodiments of the present invention are 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 (5)
1. the preparation method of a waste rubber powder/polyolefin blending material, it is characterized in that, comprise 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 the surface devulcanization plastication, reaction times is 5～30 minutes, then control 100 ℃～200 ℃ of temperature, again with mixing 5～20 minutes of 20～100 parts of polyolefin resines, and then add 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 wherein said rubber powder is 10～200 orders; Described properties-correcting agent be in phenylhydrazine, thiazole, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, mercaptan, disulphide or the sweetening agent any one; Described grafted monomer be vinylbenzene, maleic anhydride, glycidyl methacrylate, acrylic or methacrylic acid methyl esters any one or more than one.
2. preparation method according to claim 1 is characterized in that, described polyolefin resin is any one in ethylene-octene copolymer, polyolefin elastomer, high density polyethylene(HDPE), Low Density Polyethylene, polypropylene or the ethylene-vinyl acetate copolymer.
3. preparation method according to claim 2 is characterized in that, described initiator is any one in dibenzoyl peroxide, dicumyl peroxide or the ditertiary butyl peroxide.
4. preparation method according to claim 3 is characterized in that, described mixing roll is mill, Banbury mixer or forcing machine.
5. a waste rubber powder/polyolefin blending material is characterized in that, is prepared from by the described method of claim 1 to 4 any one.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101841759A CN102311528B (en) | 2011-07-04 | 2011-07-04 | Waste rubber powder/polyolefin blending material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101841759A CN102311528B (en) | 2011-07-04 | 2011-07-04 | Waste rubber powder/polyolefin blending material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
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| CN102311528A CN102311528A (en) | 2012-01-11 |
| CN102311528B true CN102311528B (en) | 2013-02-13 |
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| CN2011101841759A Expired - Fee Related CN102311528B (en) | 2011-07-04 | 2011-07-04 | Waste rubber powder/polyolefin blending material and preparation method thereof |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105254936B (en) * | 2015-11-05 | 2017-07-21 | 徐州工业职业技术学院 | A kind of rubber powder base dynamic vulcanization thermoplastic elastomer waterproof roll materials 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 |
| CN108045043B (en) * | 2017-12-04 | 2021-01-26 | 北京东方雨虹防水技术股份有限公司 | Polymer waterproof board and preparation method thereof |
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- 2011-07-04 CN CN2011101841759A patent/CN102311528B/en not_active Expired - Fee Related
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| CN102311528A (en) | 2012-01-11 |
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