CN101735579A - High-performance recovered PET/ABS alloy - Google Patents
High-performance recovered PET/ABS alloy Download PDFInfo
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Abstract
The invention discloses a high-performance recycled PET/ABS alloy. The alloy comprises the following components in percentage by weight: 30 to 80 percent of recycled PET, 10 to 50 percent of ABS, 1 to 10 percent of reinforcing agent, 2 to 15 percent of compatilizer, 0.5 to 5 percent of flexibilizer, 0.5 to 3 percent of polyhydroxy chemical coupling agent, and 0.1 to 1 percent of antioxidant. The alloy can improve a recycled PET system by using reasonable matching of additives, effects of the polyhydroxy chemical coupling agent, and excellent physical mechanic properties of an ABS system. Therefore, the recycled PET /ABS alloy has the advantages of high compatibility, high tensile strength, high mobility, good machinability and the like, is particularly suitable for producing complicated components and parts and large plates, has a simple process, is suitable for mass production of medium-sized and small enterprises, and has obvious economic benefit and social benefit.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of high-performance, reclaim the PET/ABS alloy cheaply.
Technical background
Polyethylene terephthalate (PET) is a class crystal type polyester, has good organic solvent-resistant, chemical proofing, self-lubricating property and moulding processability etc., is widely used in fiber, food packaging bottle, sheet material, plastic-steel band or the like.Meanwhile, waste PET is also constantly increasing with the speed in every year 12%.Whenever extrude once owing to reclaim PET, limiting viscosity (IV) value about 0.07dL/g that all can descend, in the long run, its degraded is comparatively serious, causes the limitation of regenerative PET Application Areas.To reclaim PET and make alloy material, can effectively slow down palliating degradation degree, and make PET have higher use value and wider Application Areas.
ABS plastic is an acrylonitrile-butadiene-styrene copolymer, has better comprehensive performance, high impulse strength, chemical stability and good electrical properties etc.Use the ABS modified PET, can significantly improve the shock strength of PET, reduce its brittle-ductile transition temperature, and give full play to the tensile strength of PET excellence, reach the performance complement after both blend.The interpolation of ABS can also make PET technology in melt-processed of recovery smooth and easy (phenomenon of trickling not occurring), and the mechanical property of alloy and mechanical property are greatly improved.
But because PET and ABS alloy are the materials that typically is separated, it is very difficult that only the mode by the physical mechanical blend obtains the alloy of excellent performance.
Chinese invention patent CN101508818A discloses a kind of ABS/PET Alloy And Preparation Method.Its composition is (%) by weight ratio: ABS 21-72%; PET 14-60%; Compatilizer 3-10%; Oxidation inhibitor 0.4-0.6%; Toughner 5-15%; Lubricant 0.3-1%.This invention is fused together ABS system and PET system well by selecting appropriate compatilizer and toughener for use, and the material that produces has dimensional stabilizing, high strength, high-modulus, high workability.It combines the advantage of ABS and PET, has improved thermotolerance, impact, processibility of anti-PET etc.This preparation method for plastics comprises following processing step: at first raw material is mixed according to the above ratio, enter then in the plastics extruder, temperature is controlled at 230～260 ℃, carries out granulation again, obtains the ABS/PET alloy.
Yet also have the following disadvantages in this technology: used expanding material is most to be maleic anhydride grafts, because the acid catalysis effect, the transesterification reaction of PET is exacerbated in the course of processing, makes that the PET molecular weight acutely descends in the alloy, and the every performance of alloy all will descend thereupon; In addition, used PET is a virgin material, and its processing temperature is 260 ~ 290 ℃, and under this temperature, ABS has begun to decompose, and alloy processing controllable temperature interval is very narrow, and not only operational difficulty, and quality product difficulty is secure.
Summary of the invention
The objective of the invention is to problem, provide a kind of and be applicable to industrialized mass production, have excellent tensile strength, shock strength and high workability, the high-performance recovered PET/ABS alloy of high chemical stability at the prior art existence.
The technical scheme that realizes the object of the invention is as follows:
A kind of high-performance recovered PET/ABS alloy, its composition is as follows by weight percentage:
Reclaim polyethylene terephthalate (PET) 30% ~ 80%
Acrylonitrile-butadiene-styrene copolymer ABS 10% ~ 50%
Toughener 1% ~ 10%
Compatilizer 2% ~ 15%
Toughner 0.5% ~ 5%
Poly-hydroxy chemistry coupling agent 0.5% ~ 3%
Antioxidant 0.1% ~ 1%.
High-performance recovered PET provided by the invention/ABS alloy is by said ratio that feed composition elder generation dry mixed is good, drops in the twin screw extruder routinely processing condition then and carries out the melt blending extruding pelletization and get final product.
Recovery polyethylene terephthalate (PET) material used in the above material is for reclaiming mineral water bottle gained water white transparency flaky material after letter sorting, fragmentation, cleaning, flotation, drying, reclaiming PET purity is 99.6%, wherein still contain minute quantity PVC label paper, but alloy material of the present invention is not constituted influence.Repeatedly measure through differential scanning heat instrument, the melt temperature scope that reclaims polyethylene terephthalate (PET) section is 249 ℃ ~ 253 ℃, and dimension card heat-drawn wire is 211 ℃ ~ 216 ℃.
Further, described toughener is one or more the composition in AS resin, polymethylmethacrylate, glass fibre, basalt fibre, organo montmorillonite, gas phase nano silicon-dioxide, the nano-calcium carbonate.
Further, it is characterized in that described compatilizer is one or more the composition among ABS-g-MAH, AS-g-MAH, SBS-g-MAH, SEBS-g-MAH, PE-g-MAH, PP-g-MAH, PS-g-PMMA, the EPDM-g-MAH.
Further, described toughner is one or more the composition in ethylene-propylene rubber(EPR), polybutadiene rubber, isoprene-isobutylene rubber, paracril, styrene-butadiene rubber(SBR), styrene butadiene thermoplasticelastomer, hydrogenated styrene-butadiene thermoplastic elastomerics, methyl methacrylate-butadiene-styrene terpolymer, chlorinatedpolyethylene, ethylene-vinyl acetate copolymer, the nano fumed silica.
Further, described poly-hydroxy chemistry coupling agent is an ethylene glycol, 1, ammediol, glycerine, tetramethylolmethane, 1,4-butyleneglycol, 1,5 pentanediol, 1,6-hexylene glycol, 1,7-heptanediol, 1,8-ethohexadiol, 1, the composition of one or more in 9-nonanediol, decamethylene-glycol, single stearic acid glycerine lipoprotein, polyoxyethylene glycol, the polypropylene glycol.
Further, described oxidation inhibitor is four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester.
Compared with the prior art the present invention has the following advantages:
Since in high-performance recovered PET provided by the invention/ABS alloy PET and ABS belong to the incompatible system of thermodynamics, thereby the material that carries out simple melt blending gained not only can cause two-phase interface coarse, and can make degradation.Once there was the scholar to utilize acid anhydride-grafted thing to improve its consistency to improve its performance, but carboxyl (existence meeting COOH) and PET long-chain generation transesterification reaction, cause the fracture in various degree of PET long-chain, the minimizing and the molecular weight distribution of molecular weight further broaden, the capital reduces shock strength, also can't offset the influence that causes because of transesterification reaction although add different types of toughner.
The present invention reconnects the PET chain that disconnects by adding poly-hydroxy chemistry coupling agent, makes the alloy main chain that in various degree growth be arranged, and its effect is excellent in common chain propagation agent on the basis that keeps highly compatible.The above poly-hydroxy chemistry coupling agent of interpolation binary can produce lightly crosslinked simultaneously with many PET chain generation esterifications, its shock strength is promoted greatly.And the consumption of poly-hydroxy chemistry coupling agent is few, and is little to the burden of cost, helps preparing meeting company interest demand, good toughness, intensity height, good fluidity, high-performance recovered PET/ABS alloy that cost is low.
2. because the processing temperature of virgin material PET is 260-290 ℃, but ABS decomposes violently being higher than under 240 ℃ the temperature, and the plastics glossiness descends, and mechanical property and mechanical property all have obvious decline.If the processing temperature of yielding to ABS can cause the PET plasticizing not enough; If the processing temperature of yielding to PET, ABS decomposes violent, causes degradation.
The recovery polyethylene terephthalate (PET) that high-performance recovered PET provided by the invention/ABS alloy is utilized, its processing temperature is 210-240 ℃, make ABS keep high performance while and PET to form the higher alloy of performance, need not to add any plasticizer, therefore preparation cost reduces, and more meets enterprise's production requirement.
3. high-performance recovered PET provided by the present invention/ABS alloy, its tensile strength, shock strength are all suitable with pure ABS, can substitute ABS fully and be widely used in industry, social benefit and remarkable in economical benefits such as household electrical appliance, electric product, electronics, office equipment, building materials.
4. preparation technology is simple for high-performance recovered PET provided by the invention/ABS alloy material, do not relate to material modification technology or any preceding blend, back blending technology, only need in proportion the exsiccant raw material to be mixed, the crowded machine of input twin screw technology extruding pelletization routinely gets final product, and need not to add any organic solvent, improve production security to a certain extent, compliance with environmental protection requirements more, the input of production unit is little, and general middle-size and small-size manufacturing enterprise all can produce, popularization is strong, meets the production economic requirement.
5. the present invention is the alloy material main body to reclaim polyethylene terephthalate (PET), with acrylonitrile-butadiene-styrene copolymer ABS is modified matrix, on the original excellent tensile strength of PET, the tensile strength of alloy further strengthens, and also has both the physical and mechanical property of the every excellence of ABS.
6. high-performance recovered PET provided by the invention/ABS alloy has been inherited the high workability of PET, is suitable for being injection molded into big, the baroque component of volume.
Description of drawings
Fig. 1 is for reclaiming the electron micrograph that PET and ABS simple blend alloy impact section;
Fig. 2 is the electron micrograph that embodiment 1 high-performance recovered PET/ABS alloy impacts section.
Embodiment
Provide embodiment below so that the present invention is carried out concrete description; be necessary to be pointed out that at this following examples only are used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, content still belongs to protection scope of the present invention to some nonessential improvement and the adjustment that the present invention makes to the person skilled in the art in this field according to the present invention.
In the present invention, take by weighing dry good recovery polyethylene terephthalate (PET) sheet stock and acrylonitrile-butadiene-styrene copolymer (ABS) and various auxiliary agent by weight ratio.The starting material that weigh up are put in the super mixer to do mixed 5 minutes, dropping in the twin screw extruder routinely again, the expressing technique extruding pelletization gets final product.
Embodiment 1
Take by weighing dry good recovery PET sheet stock 80.0% by weight ratio, ABS resin 10.1%, AS resin 1.0%, AS-g-MAH 3.0%, polybutadiene rubber 5.0%, ethylene glycol 0.5%, antioxidant four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester (antioxidant 1010) 0.4%.The material that mixes is joined in the twin screw extruder, and through melt blending, extruding pelletization becomes alloy material.Wherein, processing temperature is 190 ~ 235 ℃, and the residence time is 2 ~ 3min, and melt pressure is more than 12MPa.
Fig. 2 is the electron micrograph that embodiment 1 high-performance recovered PET/ABS alloy impacts section
Big from the visible high-performance recovered PET provided by the invention of Fig. 2/ABS alloy section performance waviness, be tangible ductile rupture pattern, and alloy morphology is continuous, do not have obvious macroface and separate; And alloy section shown in Figure 1 is smooth, is obvious feature of brittle, and alloy substrate has tangible layering.PET and ABS have consistency preferably in this explanation recovery PET/ABS alloy provided by the present invention, and the toughness of material is better.
Embodiment 2
Take by weighing dry good recovery PET sheet stock 69.8% by weight ratio, ABS resin 10.8%, polymethylmethacrylate 5.8%, PS-g-PMMA 5.1%, methyl methacrylate-butadiene-styrene terpolymer 4.5%, 1,10-decanediol 3.0%, antioxidant 1010 1.0%.The material that mixes is joined in the twin screw extruder, and through melt blending, extruding pelletization becomes alloy material.Wherein, processing temperature is 190 ~ 235 ℃, and the residence time is 2 ~ 3min, and melt pressure is more than 12MPa.
Embodiment 3
Take by weighing dry good recovery PET sheet stock 60.3% by weight ratio, ABS resin 16.2%, glass fibre 3.6%, SEBS-g-MAH 12.1%, chlorinatedpolyethylene 4.3%, polyoxyethylene glycol 2.7%, antioxidant 1010 0.8%.The material that mixes is joined in the twin screw extruder, and through melt blending, extruding pelletization becomes alloy material.Wherein, processing temperature is 190 ~ 235 ℃, and the residence time is 2 ~ 3min, and melt pressure is more than 12MPa.
Embodiment 4
Take by weighing dry good recovery PET sheet stock 51.7% by weight ratio, ABS resin 28.4%, organo montmorillonite 6.8%, SBS-g-MAH 11.3%, styrene butadiene thermoplasticelastomer 0.6%, single stearic acid glycerine lipoprotein 0.5%, antioxidant 1010 0.7%.The material that mixes is joined in the twin screw extruder, and through melt blending, extruding pelletization becomes alloy material.Wherein, processing temperature is 190 ~ 235 ℃, and the residence time is 2 ~ 3min, and melt pressure is more than 12MPa.
Take by weighing dry good recovery PET sheet stock 40.8% by weight ratio, ABS resin 33.6%, gas phase nano silicon-dioxide 8.6%, EPDM-g-MAH 14.9%, paracril 1.4%, glycerine 0.6%, antioxidant 1010 0.1%.The material that mixes is joined in the twin screw extruder, and through melt blending, extruding pelletization becomes alloy material.Wherein, processing temperature is 190 ~ 235 ℃, and the residence time is 2 ~ 3min, and melt pressure is more than 12MPa.
Embodiment 6
Take by weighing dry good recovery PET sheet stock 31.5% by weight ratio, ABS resin 48.1%, basalt fibre 5.4%, PP-g-MAH 9.9%, nano fumed silica 2.9%, polypropylene glycol 1.6%, antioxidant 1010 0.6%.The material that mixes is joined in the twin screw extruder, and through melt blending, extruding pelletization becomes alloy material.Wherein, processing temperature is 190 ~ 235 ℃, and the residence time is 2 ~ 3min, and melt pressure is more than 12MPa.
Embodiment 7
Take by weighing dry good recovery PET sheet stock 55.5% by weight ratio, ABS resin 30.2%, nano-calcium carbonate 5.4%, PE-g-MAH5.1%, ethylene-propylene rubber(EPR) 2.3%, 1,5 pentanediols 1.0%, antioxidant 1010 0.5%.The material that mixes is joined in the twin screw extruder, and through melt blending, extruding pelletization becomes alloy material.Wherein, processing temperature is 190 ~ 235 ℃, and the residence time is 2 ~ 3min, and melt pressure is more than 12MPa.
Embodiment 8
Take by weighing dry good recovery PET sheet stock 65.7% by weight ratio, ABS resin 23.2%, glass fibre 6.1%, EPDM-g-MAH 2.0%, ethylene-vinyl acetate copolymer 1.8%, 1,8-ethohexadiol 0.9%, antioxidant 1010 0.3%.The material that mixes is joined in the twin screw extruder, and through melt blending, extruding pelletization becomes alloy material.Wherein, processing temperature is 190 ~ 235 ℃, and the residence time is 2 ~ 3min, melt pressure
Embodiment 9
Take by weighing dry good recovery PET sheet stock 49.7% by weight ratio, ABS resin 38.2%, AS resin 2.4%, glass fibre 3.1%, PP-g-MAH 2.6%, ethylene-vinyl acetate copolymer 2.1%, 1,7-heptanediol 0.5%, polyoxyethylene glycol 0.9%, antioxidant 1010 0.5%.The material that mixes is joined in the twin screw extruder, and through melt blending, extruding pelletization becomes alloy material.Wherein, processing temperature is 190 ~ 235 ℃, and the residence time is 2 ~ 3min, and melt pressure is more than 12MPa.
Embodiment 10
Take by weighing dry good recovery PET sheet stock 30.1% by weight ratio, ABS resin 50.0%, AS resin 5.3%, polymethylmethacrylate 4.7, AS-g-MAH 1.9%, PS-g-PMMA 2.7%, polybutadiene rubber 2.1%, ethylene-vinyl acetate copolymer 0.5%, tetramethylolmethane 0.9%, 1,9-nonanediol 1.2%, antioxidant 1010 0.6%.The material that mixes is joined in the twin screw extruder, and through melt blending, extruding pelletization becomes alloy material.Wherein, processing temperature is 190 ~ 235 ℃, and the residence time is 2 ~ 3min, and melt pressure is more than 12MPa.
Each embodiment The performance test results sees Table 1, and test condition is:
Tensile strength is tested by GB/T 1040 standards, specimen types is the I type, batten size (mm): 170 (length) x (20 ± 0.2) (end width) x (4 ± 0.2) (thickness), draw speed are 50mm/min, and testing tool is the high cryotronics universal testing machine of WSM-10KB computer control.Wherein, the testing tool of elongation at break is the digital extension measurement device of SCS-1000.
Flexural strength and modulus in flexure are tested by GB 9341/T standard, specimen types is the I type, batten size (mm): 80x (10 ± 0.2) x (4 ± 0.2), rate of bending are 20mm/min, and testing tool is the high cryotronics universal testing machine of WSM-10KB computer control.
Notched Izod impact strength is tested by GB/T 1043 standards, and specimen types is the I type, batten size (mm): 80x (10 ± 0.2) x (4 ± 0.2), and the breach type is a category-A, the breach residual thickness is 3.2mm.Testing tool is a JJ-20 memory type shock-testing machine.
Table 1 embodiment 1 ~ 10 prescription and material property
Claims (7)
1. high-performance recovered PET/ABS alloy is characterized in that its composition is as follows by weight percentage:
Reclaim PET 30% ~ 80%
ABS 10％~50％
Toughener 1% ~ 10%
Compatilizer 2% ~ 15%
Toughner 0.5% ~ 5%
Poly-hydroxy chemistry coupling agent 0.5% ~ 3%
Antioxidant 0.1% ~ 1%.
2. high-performance recovered PET as claimed in claim 1/ABS alloy is characterized in that, described recovery PET, and the melt temperature scope is 249 ℃ ~ 253 ℃, dimension card heat-drawn wire is 211 ℃ ~ 216 ℃.
3. high-performance recovered PET as claimed in claim 1/ABS alloy, it is characterized in that described toughener is one or more the composition in AS resin, polymethylmethacrylate, glass fibre, basalt fibre, organo montmorillonite, gas phase nano silicon-dioxide, the nano-calcium carbonate.
4. high-performance recovered PET as claimed in claim 1/ABS alloy, it is characterized in that described compatilizer is one or more the composition among ABS-g-MAH, AS-g-MAH, SBS-g-MAH, SEBS-g-MAH, PE-g-MAH, PP-g-MAH, PS-g-PMMA, the EPDM-g-MAH.
5. high-performance recovered PET as claimed in claim 1/ABS alloy, it is characterized in that described toughner is one or more the composition in ethylene-propylene rubber(EPR), polybutadiene rubber, isoprene-isobutylene rubber, paracril, styrene-butadiene rubber(SBR), styrene butadiene thermoplasticelastomer, hydrogenated styrene-butadiene thermoplastic elastomerics, methyl methacrylate-butadiene-styrene terpolymer, chlorinatedpolyethylene, ethylene-vinyl acetate copolymer, the nano fumed silica.
6. high-performance recovered PET as claimed in claim 1/ABS alloy, it is characterized in that, described poly-hydroxy chemistry coupling agent is an ethylene glycol, 1, ammediol, glycerine, tetramethylolmethane, 1,4-butyleneglycol, 1,5 pentanediols, 1,6-hexylene glycol, 1,7-heptanediol, 1,8-ethohexadiol, 1, the composition of one or more in 9-nonanediol, decamethylene-glycol, single stearic acid glycerine lipoprotein, polyoxyethylene glycol, the polypropylene glycol.
7. high-performance recovered PET as claimed in claim 1/ABS alloy is characterized in that, described oxidation inhibitor is four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester.
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Application publication date: 20100616 |