CN101070413A - Regenerating method for waster and old polystrene and regenerated product mode thereby - Google Patents
Regenerating method for waster and old polystrene and regenerated product mode thereby Download PDFInfo
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- CN101070413A CN101070413A CNA2007101123704A CN200710112370A CN101070413A CN 101070413 A CN101070413 A CN 101070413A CN A2007101123704 A CNA2007101123704 A CN A2007101123704A CN 200710112370 A CN200710112370 A CN 200710112370A CN 101070413 A CN101070413 A CN 101070413A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/10—Greenhouse gas [GHG] capture, material saving, heat recovery or other energy efficient measures, e.g. motor control, characterised by manufacturing processes, e.g. for rolling metal or metal working
Abstract
The present invention relates to a recycling method of blending toughening modified waste polystyrene and the recycling product made by using this method. According to the method of the present invention, 65-80wt% polystyrene with the melt index of 10-25g/10min, 10-20wt% elastomer, 5-10wt% polyethylene with the melt index of 0.05-6g/10min and 5wt% compatibilizer are mixed together, and melted and blended on twin screw extruder under the temperature of 150-210deg.C, to acquire toughening-modified-polystyrene recycling material. The prepared recycling material can replace high impact polystyrene to be used to produce the components of up-and-mid grade household appliances such like computers and air conditioner, while solving the environmental pollution problems, and finding a new way to make use of waste polystyrene.
Description
Technical field
The present invention relates to a kind of to the renovation process of waste and old polystyrol (PS) blending toughening modification and the reconstituted product that utilizes this method to make.
Background technology
That polystyrene (PS) has is transparent, good moldability, good rigidly, easy dyeing, agent of low hygroscopicity and advantage such as cheap, is used widely in industries such as packing, electronics, building, vehicle appliance, instrument, daily necessities and toys.Yet the waste and old product of polystyrene (PS) are difficult to degraded, cause polystyrene (PS) and polystyrene foamed waste materials such as (EPS) to increase day by day.
The problem that mechanics physical and mechanical propertiess such as polystyrene (PS) product that polystyrene (PS) and polystyrene foamed (EPS) reclaimed materials are made exists that particle matter is crisp, resistance to impact shock, tensile strength and elongation descend significantly, and the rubber plastic blend technology be grow up nearly decades improve one of effective, the most most economical method of plastics performance, utilize the rubber plastic blend technology that the waste and old polystyrol (PS) of recovery is developed to the high-performance direction, thereby improve the added value of reconstituted product greatly.
In " Huang Farong, Chen Tao, Shen Xuening, the recycle of macromolecular material, Chemical Industry Press, 2002 " thus in recorded and narrated a kind of method that blending and modifyings such as waste and old polystyrol and rubber or fiber is improved the reconstituted product performance.When waste and old polystyrol and styrene-butadiene rubber(SBR) carry out mechanical blending; the consumption of styrene-butadiene rubber(SBR) generally is controlled at about 10%-15%; this moment, the resistance to impact shock of reconstituted product can improve more than two times; yet if will further improve the toughness of twice-laid stuff; need to surpass the styrene-butadiene rubber(SBR) of volume fraction 25%, the over-all properties of reconstituted product such as tensile strength descends simultaneously.
Be by adding in this external " Zhengping Fang; Zhenghong Guo; Linlin Zha; Toughening ofPolystyrenewith Ethylene-Propylene-Diene Terpolymer (EPDM) Compatibilizedby Styrene-Butadiene-Styrene Block Copolymer (SBS); Macromol.Mater.Eng.2004; 289:743-748 " as styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene-butylene-styrene segmented copolymer expanding materials such as (SEBS) improves the consistency of waste and old polystyrol and rubber, thereby improve the shock strength of reconstituted product, but that the tensile strength of reconstituted product descends still is more.
At present, the reconstituted product that obtains of above-mentioned toughening modifying waste and old polystyrol method can only be used to make low-end products such as wrapping material, articles for daily use.
Summary of the invention
The object of the invention is by utilizing elastomerics and a small amount of polyethylene coordination plasticizing polystyrene, and utilize expanding material to improve the interface performance of matrix and disperse phase, thereby obtain the toughening modifying polystyrene reconstituted product that can replace high-impact polystyrene fully and be mainly used in high-end casing of domestic electrical equipment such as scheduler, air-conditioning, refrigerator, colour TV.
To achieve these goals, the invention provides the method for following a kind of blending toughening modified waste old polystyrene: with the melting index of 65～80wt% is that the melting index of elastomerics, the 5～10wt% of polystyrene, the 10～20wt% of 10～25g/10min is that the expanding material of 0.05～6g/10min polyethylene and 5wt% mixes, thus again on the twin screw extruder under 150～210 ℃ temperature melt blending obtain toughening modifying polystyrene twice-laid stuff.
In addition, elastomerics of the present invention is preferably selected from polyolefin elastomer POE, ethylene-propylene rubber(EPR) EPDM, styrene-butadiene rubber(SBR), cis-1,4-polybutadiene rubber, natural rubber or their mixture.Wherein polyolefin elastomer POE is meant that U.S. DuPont DOW chemical company adopts the POE of constrained geometry catalyst technology and relevant INSITE process exploitation.
In addition, polyethylene of the present invention is preferably selected from high density polyethylene(HDPE), medium-density polyethylene, new LDPE (film grade), linear low density polyethylene, recovery high density polyethylene(HDPE) or their mixture.
In addition, expanding material of the present invention is preferably selected from styrene-butadiene-styrene block copolymer (SBS), styrene-butadiene copolymer (SB), styrene-grafted ethylene copolymer (PS-g-PE), polystyrene-poly ethylene copolymer (PS-PE), styrene-isoprene-phenylethene thermoplastic elastomer or their mixture.
In addition, the present invention is preferably at polystyrene, elastomerics, polyethylene, adding oxidation inhibitor when expanding material mixes.
In addition, the percent by weight mark of the preferred oxidation inhibitor of the present invention is 0.001wt%.
In addition, the preferred oxidation inhibitor of the present invention is antioxidant 1010,136,1076,300 or 264.
To achieve these goals, the present invention also provides the reconstituted product that utilizes aforesaid method to obtain.
Because plastics and elastomeric blend often make the tensile strength of material descend greatly, material can not obtain good comprehensive performances, we use elastomerics and polyethylene coordination plasticizing waste and old polystyrol, control the melting index and the poly melting index of polystyrene simultaneously, the shock strength of twice-laid stuff, tensile strength all improve a lot, so this method can make toughness reinforcing enhanced modified waste old polystyrene twice-laid stuff, solved the twice-laid stuff problem that tensile strength descends when shock strength improves.The mechanical property of the twice-laid stuff of the modified waste old polystyrene that makes in this way improves greatly, and shock strength is more than 8～11 times of former waste and old polystyrol, and tensile strength improved 15%～40%, sees Table 1.
The mechanical property of waste and old PS of table 1 and modified system of the present invention relatively
| Material | Molten refer to (g/10min) of PE | Molten refer to (g/10min) of PS | Izod breach hit intensity (KJ/m 2) | Tensile strength (MPa) |
| Waste and |
0 | 15～25 | 0.97～1.02 | 18.14～20.32 |
| PS/ elastomerics/PE/ expanding material | 0.05～6 | 15～25 | 8.12～11.5 | 23.12～25.55 |
In addition, because the present invention has introduced polyethylene in toughened system, the elastomerics consumption is reduced, and the present invention also can use the waste and old high density polyethylene(HDPE) of melting index between 0.05～6g/10min, thereby can reduce the cost of the modified waste old polystyrene material that obtains.
Method provided by the invention is simple, technology controlling and process is easy, the notched Izod impact strength of the twice-laid stuff of the toughening modifying waste and old polystyrol of preparation and tensile strength are all far above former waste and old polystyrol, thereby can reclaim better and utilize waste and old polystyrol with increment, the modified polystyrene twice-laid stuff that makes can substitute high-impact polystyrene and be used for household electrical appliance parts such as scheduler, air-conditioning, refrigerator, colour TV, provides new way and new approaches for solving white pollution.
Description of drawings
Fig. 1 is the DSC curve of PS/POE/SBS/PE (75/15/5/5) system and pure PE, and wherein the melting index of PS is 20g/10min; The melting index of PE is 20g/10min.
Fig. 2 is the DSC curve of PS/POE/SBS/PE (75/15/5/5) system and pure PE, and wherein the melting index of PS is 20g/10min; The melting index of PE is 0.058g/10min.
Fig. 3 is the sem photograph of PS/EPDM/PE/PS-PE system.
Embodiment
Because polyethylene and polystyrene are inconsistent, when polystyrene is more close with poly viscosity ratio, especially polystyrene and poly viscosity ratio leveled off to 1 o'clock, poly Tc descends greatly in the mixed system, drop to 82 ℃ for 117.342 ℃ from the Tc of pure PE, see Fig. 1.This explanation polyethylene is dispersed into small droplets easily in the polystyrene matrix, small droplets does not contain or contain effective heterogeneous nucleation agent seldom, and polyethylene can only heterogeneous nucleation crystallization even homogeneous nucleation crystallization under higher condensate depression, the fractional crystallisation behavior occurred; And at this moment the dispersed phase size of polyethylene in the polystyrene matrix is too small, not only do not have the effect that stops the crazing cracking and stop crazing, also can become focal point of stress and induce the initiation crazing, the impact strength decreased that causes material has only 3.7KJ/m as the notched Izod impact strength that Fig. 1 mixed system gained material records
2But when polystyrene and poly viscosity differed big, the Tc of the Tc of PE and pure PE was compared almost constantly in the mixed system, sees Fig. 2.This explanation polyethylene is difficult for disperseing in the polystyrene matrix, and the particle diameter of polyethylene dispersion phase is bigger, and the heterogeneous nucleation agent that comprises is more, and polyethylene heterogeneous nucleation crystallization under lower condensate depression easily is so can keep higher Tc; And at this moment the dispersed phase size of polyethylene in the polystyrene matrix is bigger, can stop the cracking of crazing and play the effect that stops crazing, thereby improve the shock strength of material, and the notched Izod impact strength that records as Fig. 2 mixed system gained material can reach 9.3KJ/m
2In addition, the viscosity that can reflect polymkeric substance according to melt index indirectly, and its viscosity and their melting index (MFI) are the characteristics of inverse relation, the present invention also defines the melting index of waste and old polystyrol in the above technical solution that provides should be at 15～25g/10min, poly melting index should be at 0.05～6g/10min, control their viscosity indirectly by limiting polystyrene and poly melting index so on the one hand, on the other hand owing to having increased polystyrene and poly melting index have enlarged them than (MFIPS/MFIPE 〉=2.5) viscosity ratio, thereby reached the purpose that stops the fractional crystallisation behavior of a small amount of polyethylene in the polystyrene matrix, the dispersed phase size of polyethylene in the polystyrene matrix increased, brought into play its effect that stops the cracking of crazing and stop crazing, so the notched Izod impact strength of the toughening modifying waste and old polystyrol material of the present invention by limiting viscosity ratio that polystyrene and poly melting index are controlled both and poly fractional crystallisation behavior preparation and tensile strength see Table 2 all far above former waste and old polystyrol.
The different molten fingers of table 2 control PS with PE than the time material mechanical property
| Material | PS/POE/PE/SBS | |||
| Form proportioning (wt%) | 72/18/5/5 | |||
| The |
20 | 20 | 20 | 20 |
| The PE melting index | 0.058 | 1.1 | 5.5 | 20 |
| Shock strength | 9.29 | 8.36 | 8.52 | 3.69 |
| (KJ/m 2) | ||||
| Tensile strength (Mpa) | 24.08 | 24.20 | 25.55 | 23.519 |
Because after the present invention has added the less polyethylene of melting index, the waste and old polystyrol bigger with melting index, the quaternary system of elastomerics and expanding material has formed the polydispersion form, see Fig. 3, wherein A is the medium and small POE particle that does not come off, B is the hole of the medium and small POE particle that comes off, the big PE particle of C for not coming off, D is the hole of the bigger PE particle that comes off, so existing medium and small rubber grain that helps causing and stopping little crazing among the figure, the bigger PE particle of the crackle that helps stopping crazing again and develop into by crazing, thereby can stop the crazing cracking effectively and stop crazing, improve the resistance to impact shock of material greatly, the material modified notched Izod impact strength that the present invention is obtained can reach 11.5KJ/m
2, not only high about 11 times than the notched Izod impact strength of polystyrene virgin material, even the notched Izod impact strength that also surpasses the special high-impact polystyrene for preparing sees Table 31 times more.
Typical HIPS of table 3 and PS mechanical property are relatively
| Mechanical property | PS | HIPS |
| Tensile strength (MPa) | 54 | 21 |
| Izod notched Izod impact strength (KJ/m 2) | 1.0 | 4.5 |
This shows data from document: Ostromislensky II.US Pat.1,613,673.
The present invention is described further below in conjunction with the embodiment of the invention; be necessary to be pointed out that at this following examples only are used for the present invention is further detailed; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment to the present invention according to the invention described above content.
The used umber of each component is weight part in following examples.
In addition, Izod notched Izod impact strength that what deserves to be explained is product of the present invention is according to the GB/T1834-1996 test, and tensile strength is then tested according to GB/T 1040-92 standard.
Embodiment 1
Be that 18 parts in 72 parts of polystyrene, the styrene-butadiene rubber(SBR) of 20g/10min, 5 parts and 0.001 part antioxidant 1076 of 5 parts of new LDPE (film grade)s, SIS/SEBS that melting index is 5.5g/10min mix with melting index earlier, put into twin screw extruder then, be respectively 150 ℃, 170 ℃, 190 ℃, 210 ℃, 210 ℃, 200 ℃ following melt blendings in each district's temperature and obtain toughening modifying waste and old polystyrol material.The notched Izod impact strength that this material records is 9.27KJ/m
2, tensile strength is 24.13MPa.
Embodiment 2
Be that 20 parts of 68 parts of polystyrene, the natural rubbers of 23g/10min, 5 parts and 0.001 part antioxidant 1010 of 7 parts of medium-density polyethylenes, styrene-isoprene-phenylethene thermoplastic elastomer that melting index is 3.0g/10min mix with melting index earlier, put into twin screw extruder then, be respectively 150 ℃, 170 ℃, 190 ℃, 210 ℃, 210 ℃, 200 ℃ following melt blendings in each district's temperature and obtain toughening modifying waste and old polystyrol material.The notched Izod impact strength that this material records is 10.22KJ/m
2, tensile strength is 23.45MPa.
Embodiment 3
80 parts of polystyrene, polyolefin elastomer POE10 part, the melting index that with melting index is 15g/10min earlier is that 5 parts and 0.001 part antioxidant 1010 of 5 parts of high density polyethylene(HDPE)s, styrene-grafted ethylene copolymer of 0.058g/10min mixes, put into twin screw extruder then, be respectively 150 ℃, 170 ℃, 190 ℃, 210 ℃, 210 ℃, 200 ℃ following melt blendings in each district's temperature and obtain toughening modifying waste and old polystyrol material.The notched Izod impact strength that this material records is 8.12KJ/m
2, tensile strength is 25.55MPa.
Embodiment 4
Be that 15 parts in 75 parts of polystyrene, the ethylene-propylene rubber(EPR) of 18g/10min, 5 parts and 0.001 part antioxidant 300 of 5 parts of new LDPE (film grade)s, styrene-butadiene copolymer that melting index is 1.1g/10min mix with melting index earlier, put into twin screw extruder then, be respectively 150 ℃, 170 ℃, 190 ℃, 210 ℃, 210 ℃, 200 ℃ following melt blendings in each district's temperature and obtain toughening modifying waste and old polystyrol material.The notched Izod impact strength that this material records is 8.44KJ/m
2, tensile strength is 24.8MPa.
Embodiment 5
Be that 20 parts of 65 parts of polystyrene, the cis-1,4-polybutadiene rubbers of 25g/10min, 5 parts and 0.001 part oxidation inhibitor 136 of 10 parts of recovery high density polyethylene(HDPE)s, styrene-butadiene-styrene synthetic rubber that melting index is 0.2g/10min mix with melting index earlier, put into twin screw extruder then, be respectively 150 ℃, 170 ℃, 190 ℃, 210 ℃, 210 ℃, 200 ℃ following melt blendings in each district's temperature and obtain toughening modifying waste and old polystyrol material.The notched Izod impact strength that this material records is 11.5KJ/m
2, tensile strength is 23.12MPa.
Claims (8)
1, a kind of method of blending toughening modified waste old polystyrene: with the melting index of 65～80wt% is that the melting index of elastomerics, the 5～10wt% of polystyrene, the 10～20wt% of 10～25g/10min is that the expanding material of 0.05～6g/10min polyethylene and 5wt% mixes, thus again on the twin screw extruder under 150～210 ℃ temperature melt blending obtain toughening modifying polystyrene twice-laid stuff.
2, the process of claim 1 wherein that elastomerics is selected from polyolefin elastomer POE, ethylene-propylene rubber(EPR) EPDM, styrene-butadiene rubber(SBR), cis-1,4-polybutadiene rubber, natural rubber or their mixture.
3, the process of claim 1 wherein that polyethylene is selected from high density polyethylene(HDPE), medium-density polyethylene, new LDPE (film grade), linear low density polyethylene, recovery high density polyethylene(HDPE) or their mixture.
4, the process of claim 1 wherein that expanding material is selected from styrene-butadiene-styrene block copolymer, styrene-butadiene copolymer, styrene-grafted ethylene copolymer, polystyrene-poly ethylene copolymer, styrene-isoprene-phenylethene thermoplastic elastomer or their mixture.
5, the arbitrary method of claim 1-4 is wherein at polystyrene, elastomerics, polyethylene, adding oxidation inhibitor when expanding material mixes.
6, the method for claim 5, wherein the percent by weight mark of oxidation inhibitor is 0.001wt%.
7, claim 5 or 6 method, wherein oxidation inhibitor is antioxidant 1010,136,1076,300 or 264.
8, the reconstituted product of the arbitrary method acquisition of claim 1-7.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102585391A (en) * | 2011-01-18 | 2012-07-18 | 苏州汉扬精密电子有限公司 | Modification and recovery formula for defective material of high impact polystyrene |
| CN102702633A (en) * | 2011-12-30 | 2012-10-03 | 天津金发新材料有限公司 | In-situ fiber-forming toughened regenerated polystyrene material and preparation method |
| CN103665718A (en) * | 2013-12-10 | 2014-03-26 | 四川长虹格润再生资源有限责任公司 | Method for toughening high impact polystyrene by using waste thermoplastic elastomer |
| CN104927222A (en) * | 2015-07-07 | 2015-09-23 | 四川塑金科技有限公司 | Polystyrene pipe special material and preparation method thereof |
| CN105017670A (en) * | 2015-07-07 | 2015-11-04 | 四川塑金科技有限公司 | Moulding process for polystyrene tubular product |
| CN106700375A (en) * | 2016-12-18 | 2017-05-24 | 合肥会通新材料有限公司 | Special corrosion-resistant PS/PE (Poly Styrene/Poly Ethylene) alloy material and preparation method thereof |
| CN110066444A (en) * | 2019-04-29 | 2019-07-30 | 中南大学 | A kind of plastic cement track plates and its preparation process |
| CN113459618A (en) * | 2021-06-04 | 2021-10-01 | 苏州瑞赛科物流科技股份有限公司 | Antistatic lining material and preparation method thereof |
| CN113980401A (en) * | 2021-11-30 | 2022-01-28 | 上海金山锦湖日丽塑料有限公司 | EPS foam modification-based high impact polystyrene material and preparation method thereof |
| CN115058044A (en) * | 2022-07-14 | 2022-09-16 | 昆山恒光塑胶股份有限公司 | Antistatic HIPS material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102585391A (en) * | 2011-01-18 | 2012-07-18 | 苏州汉扬精密电子有限公司 | Modification and recovery formula for defective material of high impact polystyrene |
| CN102702633B (en) * | 2011-12-30 | 2014-07-23 | 天津金发新材料有限公司 | In-situ fiber-forming toughened regenerated polystyrene material and preparation method |
| CN102702633A (en) * | 2011-12-30 | 2012-10-03 | 天津金发新材料有限公司 | In-situ fiber-forming toughened regenerated polystyrene material and preparation method |
| CN103665718B (en) * | 2013-12-10 | 2016-03-23 | 四川长虹格润再生资源有限责任公司 | Utilize the method for waste and old thermoplastic elastomer toughening high-impact polystyrene |
| CN103665718A (en) * | 2013-12-10 | 2014-03-26 | 四川长虹格润再生资源有限责任公司 | Method for toughening high impact polystyrene by using waste thermoplastic elastomer |
| CN104927222A (en) * | 2015-07-07 | 2015-09-23 | 四川塑金科技有限公司 | Polystyrene pipe special material and preparation method thereof |
| CN105017670A (en) * | 2015-07-07 | 2015-11-04 | 四川塑金科技有限公司 | Moulding process for polystyrene tubular product |
| CN104927222B (en) * | 2015-07-07 | 2018-03-13 | 四川塑金科技有限公司 | A kind of polystyrene pipe PP Pipe Compound and preparation method thereof |
| CN105017670B (en) * | 2015-07-07 | 2018-04-20 | 四川塑金科技有限公司 | A kind of moulding process of polystyrene pipe |
| CN106700375A (en) * | 2016-12-18 | 2017-05-24 | 合肥会通新材料有限公司 | Special corrosion-resistant PS/PE (Poly Styrene/Poly Ethylene) alloy material and preparation method thereof |
| CN110066444A (en) * | 2019-04-29 | 2019-07-30 | 中南大学 | A kind of plastic cement track plates and its preparation process |
| CN113459618A (en) * | 2021-06-04 | 2021-10-01 | 苏州瑞赛科物流科技股份有限公司 | Antistatic lining material and preparation method thereof |
| US11807746B2 (en) | 2021-08-05 | 2023-11-07 | Industrial Technology Research Institute | Impact-resistant polystyrene resin |
| CN113980401A (en) * | 2021-11-30 | 2022-01-28 | 上海金山锦湖日丽塑料有限公司 | EPS foam modification-based high impact polystyrene material and preparation method thereof |
| CN115058044A (en) * | 2022-07-14 | 2022-09-16 | 昆山恒光塑胶股份有限公司 | Antistatic HIPS material and preparation method thereof |
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