CN102391607B - Polylactic acid/styrene resin composition and preparation method thereof - Google Patents
Polylactic acid/styrene resin composition and preparation method thereof Download PDFInfo
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- CN102391607B CN102391607B CN 201110253827 CN201110253827A CN102391607B CN 102391607 B CN102391607 B CN 102391607B CN 201110253827 CN201110253827 CN 201110253827 CN 201110253827 A CN201110253827 A CN 201110253827A CN 102391607 B CN102391607 B CN 102391607B
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Abstract
The invention relates to a polylactic acid/styrene resin composition and a preparation method thereof. The composition comprises the following raw materials in part by weight: 5 to 90 parts of polylactic acid resin, 10 to 95 parts of styrene resin, 1 to 30 parts of heat-resistant modifier, 1 to 60 parts of toughening master batch, 0.5 to 5 parts of crystallizing promoter, 0.1 to 0.8 parts of antioxidant, and 0.1 to 2 parts of lubricating agent. The method comprises the following steps of: drying the raw materials at the temperature of 60 DEG C in a drying oven for 5 to 8 hours, premixing by using a high-speed mixing machine, melting and extruding by using a double-screw extruder, cooling and pelleting to obtain a product. Compared with the prior art, the product is environment-friendly and has high impact resistance and heat resistance and can be used for manufacturing plastic products with requirements on high heat resistance and impact resistance.
Description
Technical field
The present invention relates to a kind of resin combination and preparation method thereof, especially relate to a kind of polylactic acid/styrene resin composition and preparation method thereof.
Background technology
Requirement due to environmental protection, aspect materials used in auto manufacturing and electronic communication equipment, the poly(lactic acid) (PLA) that derives from the plants such as corn, sugarcane, Ipomoea batatas has been subject to great attention, and it under certain condition can complete biodegradable, is a kind of very friendly environment-friendly materials.Biodegradable resin poly(lactic acid) (PLA) has intensity height and the high characteristics of rigidity, and easily machine-shaping is applicable to the kinds of processes condition.But the shock resistance of PLA is poor, be a kind of hard and crisp material at normal temperatures, and its heat resisting temperature is lower.Can not use separately in the occasion that toughness reguirements is high, must carry out toughening modifying to PLA.
Method for toughening commonly used has: (1) modification by copolymerization: introduce another kind of molecular chain on the PLA molecular chain, the regularity of PLA molecular chain is descended, reduce its crystal property, reduce Tg, thereby improve toughness; (2) blending and modifying " blend such as the polymkeric substance of PLA and elastomerics, good toughness, filler or softening agent, blending and modifying can effectively improve the toughness of PLA; (3) by the method for processing forming modification: improve the mechanical propertys such as shock strength by complete processings such as stretch orientations; Wherein blending and modifying is high because of toughening efficiency, and more easily implements, and is a kind of both economical method of modifying.
ABS is the multiphase structure of vinyl cyanide, vinylbenzene, butadiene terpolymer, its form is two-phase system, and one is external phase SAN mutually, and another is the PB of graft SAN mutually, have good shock-resistance and processing fluidity, success is done toughner in the material of PC, PA, PBT.Be a kind of feasible method in conjunction with both advantages with poly(lactic acid) and ABS blend, yet between these two kinds of polymkeric substance, relatively poor consistency can cause their blend to occur significantly being separated, thus the mechanical property of decrease blend.
Therefore, from industrial practical application, be necessary blend that provides poly(lactic acid) a kind of economy, that have improved mechanical property and ABS and preparation method thereof.
Summary of the invention
Purpose of the present invention is exactly in order to overcome that being separated appears in blend that in prior art, PLA and ABS cause because consistency is relatively poor, and defective provides a kind of polylactic acid/styrene resin composition with good thermotolerance, shock resistance and mechanical property and preparation method thereof so that mechanical property declines to a great extent etc.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of polylactic acid/styrene resin composition comprises following component and parts by weight:
Polylactic resin 5～90
Phenylethylene resin series 10～95
Heat-proof modifier 1～30
Plasticizing mother particle 1～60
Crystallization promoter 0.5～5
Oxidation inhibitor 0.1～0.8
Lubricant 0.1～2.
Described polylactic resin is one or more the mixing in PLLA (PLLA), poly-dextrolactic acid (PDLA), poly-racemic lactic acid (PDLLA), described polylactic resin weight-average molecular weight is 70000～500000g/mol, preferred 100000～200000g/mol.
Described phenylethylene resin series is one or more the mixing in acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene-acrylic ester copolymer (ASA), MBS (MBS), vinyl cyanide-terpolymer EP rubber-styrol copolymer (AES), acrylonitrile-chlorianted polyethylene-styrene terpolymer (ACS).
Described heat-proof modifier is the multiple copolymer of multipolymer, N-phenylmaleimide and the maleic anhydride of styrene-maleic anhydride copolymer, alpha-methyl styrene-acrylonitrile copolymer, N-phenylmaleimide class and cinnamic terpolymer or N-phenylmaleimide and maleic anhydride, alpha-methyl styrene, vinyl cyanide, preferable weight-average molecular weight is 80000～200000g/mol, and second-order transition temperature is 160～200 ℃.
Described plasticizing mother particle is the self-control master batch, and the component that described self-control master batch comprises and the parts by weight of each component are: polylactic resin 20～80, acrylonitrile-butadiene-styrene copolymer (ABS) 10～60, compatilizer 10～50.
described compatilizer is selected from polypropylene grafted maleic anhydride, styrene-maleic anhydride copolymer (SMA), acrylonitrile-styrene-glycidyl methacrylate copolymer (SAG), the acrylonitrile-butadiene-styrene (ABS) grafted maleic anhydride, the acrylonitrile-styrene grafted maleic anhydride, acrylonitrile-styrene grafting methacrylic acid, the functionalization derivative of ethylene-methyl acrylate copolymer graft glycidyl methacrylate or oxazoline functional group is (as ethylene-methyl methacrylate methyl terpolymer (EMA), ethylene-methyl methacrylate butyl ester multipolymer, propylene-ethyl propylene acid butyl ester multipolymer, the different monooctyl ester multipolymer of ethylene-methyl methacrylate, ethylene-methyl methacrylate methyl esters-GMA multipolymer, ethylene-methyl methacrylate methyl esters-MAH multipolymer, ethylene-methyl methacrylate butyl ester-MA multipolymer etc.) a kind of in.
Described crystallization promoter is one or more the mixing in talcum powder, silicon-dioxide, nano imvite, metal phosphate, erucicamide, hard esteramides, oleylamide, the hard esteramides of ethylenebis, ethylenebisoleoamide, phthalic diamide.
Described oxidation inhibitor is phosphite ester kind antioxidant or Hinered phenols antioxidant, comprises commercially available irgasfos 168, antioxidant 1010, antioxidant 1076 or oxidation inhibitor 245.
Described lubricant comprises one or more the mixing in pentaerythritol stearate, polyethylene wax, ethylene bis stearamide, stearate, dimethylsilane.
A kind of preparation method who prepares above-mentioned polylactic acid/styrene resin composition of the present invention, the method comprises the following steps:
(1) prepare raw material according to following component and weight part content:
Polylactic resin 5～90
Phenylethylene resin series 10～95
Heat-proof modifier 1～30
Plasticizing mother particle 1～60
Crystallization promoter 0.5～5
Oxidation inhibitor 0.1～0.8
Lubricant 0.1～2;
(2) above raw material dry 5～8h in 60 ℃ of baking ovens, then be placed in super mixer premix 3～10min, obtains Preblend;
(3) twin screw extruder is passed through in Preblend, controlling temperature is 180～220 ℃, and screw speed is that 200～600rpm melt extrudes, and then through cooling granulation, namely obtains a kind of polylactic acid/styrene resin composition.
Compared with prior art, beneficial effect of the present invention is: from industrial practical application, blend of poly(lactic acid) a kind of economy, that have improved mechanical property and ABS and preparation method thereof is provided, and the polylactic acid/styrene resin composition that the present invention makes has good thermotolerance, shock resistance and mechanical property.
Embodiment
Embodiment of the present invention illustrate in greater detail with reference to following embodiment.Yet embodiment is in order to illustrate in greater detail, to limit the scope of the invention and be not interpreted as.
The present invention is described in detail below in conjunction with specific embodiment.
The raw material sources that embodiments of the invention 1～13 use are as follows:
Polylactic resin uses the PLA3251D(of U.S. NATURE WORKS company hereinafter to be referred as PLLA)
Phenylethylene resin series uses the synthetic acrylonitrile-butadiene-styrene copolymer (body ABS) of substance law of Gaoqiao Petrochemical Company
Heat-proof modifier uses commercially available N-phenylmaleimide and maleic anhydride and cinnamic terpolymer (hereinafter to be referred as MSNI), and its weight-average molecular weight is 100000g/mol, and second-order transition temperature is 180 ℃.
Crystallization promoter uses 5000 commercially available purpose talcum powder (hereinafter to be referred as Talc);
Compatilizer use Shanghai day rise fine chemistry industry acrylonitrile-styrene-glycidyl methacrylate copolymer (hereinafter to be referred as SAG), the styrene-maleic anhydride copolymer (hereinafter to be referred as SMA) of Gaoqiao Petrochemical Company, commercially available ethylene-methyl methacrylate methyl terpolymer EMA);
Plasticizing mother particle a is homemade master batch, and its component and weight part content are as follows: PLLA:80, and ABS:10, SAG:10, irgasfos 168 (being phosphite ester kind antioxidant): 0.2, antioxidant 1010 (being Hinered phenols antioxidant): 0.2.
Plasticizing mother particle b is homemade master batch, and its component and weight part content are as follows: PLLA:50, and ABS:35, SMA:30, irgasfos 168: 0.2, antioxidant 1010: 0.2.
Plasticizing mother particle c is homemade master batch, and its component and weight part content are as follows: PLLA:20, and ABS:60, EMA:50, irgasfos 168: 0.2, antioxidant 1010: 0.2.
Other components: phosphite ester kind antioxidant 168, Hinered phenols antioxidant 1010, vapour bar elite.
Lubricant: ethylene bis stearamide (EBS): HONEYWELL.
Above-mentioned raw materials uses after dry 5～8h in 60 ℃ of baking ovens.
Embodiment 1～9
In each embodiment, the concrete component of using sees Table 1; Component and consumption that in form, each embodiment is corresponding are joined discharging after stirring 10min in high-speed mixer, then extruding pelletization in the twin screw extruder that be 36 in length-to-diameter ratio, diameter is 35mm, the barrel zone temperature of forcing machine is 200 ℃, and screw speed is 500rpm.
Table 1
Comparative Examples 1～3
In each Comparative Examples, the concrete component of using sees Table 2;
The component that each Comparative Examples in form is corresponding and consumption join discharging after stirring 10min in high-speed mixer, then extruding pelletization in the twin screw extruder that be 36 in length-to-diameter ratio, diameter is 35mm, the barrel zone temperature of forcing machine is 200 ℃, and screw speed is 500rpm.
Table 2
Simultaneous test
Above-described embodiment 1～9 and Comparative Examples 1～3 are carried out tensile strength, modulus in flexure, shock strength and heat-resisting simultaneous test, and concrete grammar is:
Carry out tension test according to ASTM D638, test condition is 50mm/min;
Carry out pliability test according to ASTM D790, test condition is 3mm/min;
Carry out the notched Izod impact strength test according to ASTM D256, batten thickness is 3.2mm, and probe temperature is 23 ℃.
Carry out the heat-drawn wire test according to ASTM D648, test condition is 0.45MPa, unit:
Test result sees the following form 3.
Table 3
As can be seen from Table 3, embodiment 1,2,3 is from Comparative Examples 1,2,3 difference: the heat-proof modifier that has increased different amounts; Find out from above table: after having added heat-proof modifier, heat-drawn wire improves obviously.
Embodiment 4,5,6,7 and Comparative Examples 1,2,3 difference be: added the self-control plasticizing mother particle; Find out from above table: embodiment 4,5,6,7 is than Comparative Examples 1,2,3, and property indices all has a distinct increment, and is wherein obvious with the lifting of notched Izod impact strength index; Wherein best with the property indices that has added the embodiment 5 that makes plasticizing mother particle a 50kg by oneself.
Embodiment 8 is with the difference of Comparative Examples 1,2,3 on component: added heat-proof modifier and self-control plasticizing mother particle; Can find out from above table: with component recently like embodiment 4,5,6,7 compare, when the property indices of embodiment 8 keeps promoting, the heat-drawn wire index is further promoted.
Embodiment 9 is with the difference of Comparative Examples 1,2,3 on component: added heat-proof modifier, self-control master batch and crystallization promoter; Like nearest with component, the difference of embodiment 8 on component is for having added crystallization promoter; Can find out from above table: property indices is all better, compares modulus in flexure and heat-drawn wire with embodiment 8 and all promotes to some extent.
Comprehensive above-mentioned comparative analysis is as can be known: embodiment 9 property indices are all more satisfactory, that is to say that the poly(lactic acid)/composition of styrene resin that contains PLA resin, ABS resin, heat-proof modifier, plasticizing mother particle, crystallization promoter, oxidation inhibitor, lubricant component has good thermotolerance, shock resistance, stretch-resistance and resistance to bending.
Embodiment 10
With PLLA resin 5kg, ABS resin 95kg, heat-proof modifier MSNI10kg, plasticizing mother particle a 1kg, crystallization promoter 5kg, 0.8kg oxidation inhibitor (comprises antioxidant 1010 and irgasfos 168, both weight ratios are 1:1), Lubricate EBS 0.1kg joins discharging after premix 10min in high-speed mixer, extruding pelletization in the twin screw extruder that then be 36 in length-to-diameter ratio, diameter is 35mm, the barrel zone temperature of forcing machine is 200 ℃, and screw speed is 500rpm.
Embodiment 11
With PLLA resin 90kg, ABS resin 10kg, heat-proof modifier MSNI20kg, plasticizing mother particle a10kg, crystallization promoter 1kg, 0.1kg oxidation inhibitor (comprises antioxidant 1010 and irgasfos 168, both weight ratios are 1:1), Lubricate EBS 1kg joins discharging after premix 7min in high-speed mixer, extruding pelletization in the twin screw extruder that then be 36 in length-to-diameter ratio, diameter is 35mm, the barrel zone temperature of forcing machine is 220 ℃, and screw speed is 200rpm.
Embodiment 12
With PLLA resin 30kg, ABS resin 70kg, heat-proof modifier MSNI30kg, plasticizing mother particle a 20kg, crystallization promoter 2kg, 0.6kg oxidation inhibitor (comprising that antioxidant 1010 and irgasfos 168 weight ratio are 1:1), Lubricate EBS 2kg joins discharging after stirring premix 3min in high-speed mixer, then extruding pelletization in the twin screw extruder that be 36 in length-to-diameter ratio, diameter is 35mm, the barrel zone temperature of forcing machine is 180 ℃, screw speed is 600rpm.
Embodiment 13
With PLLA resin 75kg, ABS resin 25kg, heat-proof modifier MSNI1kg, plasticizing mother particle a60kg, crystallization promoter 0.5kg, 0.3kg oxidation inhibitor (comprising that antioxidant 1010 and irgasfos 168 weight ratio are 1:1), Lubricate EBS 1.5kg joins discharging after stirring premix 5min in high-speed mixer, then extruding pelletization in the twin screw extruder that be 36 in length-to-diameter ratio, diameter is 35mm, the barrel zone temperature of forcing machine is 210 ℃, screw speed is 300rpm.
Embodiment 14～21
With polylactic resin, phenylethylene resin series, heat-proof modifier, plasticizing mother particle, crystallization promoter, oxidation inhibitor, lubricant joins discharging after stirring premix 8min in high-speed mixer, then extruding pelletization in the twin screw extruder that be 36 in length-to-diameter ratio, diameter is 35mm, the barrel zone temperature of forcing machine is 200 ℃, screw speed is 400rpm.Component and the weight part of embodiment 14～21 correspondences are as shown in table 4; The composition that plasticizing mother particle in table 4 is corresponding and weight part content are as shown in table 5.
Above-described embodiment 10～13 and embodiment 14～21 have good thermotolerance, shock resistance, stretch-resistance and resistance to bending all with embodiment 9.
For those skilled in the art, after knowing the instruction that aforementioned description provides, can expect many modifications of the present invention and other embodiments.Therefore, be to be understood that the specific embodiment that the present invention should not be confined to disclose, these modifications and other embodiments are included in appended claim scope.Although used in the text specific term, they only are used with general and descriptive meaning and are not used in the purpose of restriction, and scope of the present invention is defined by the claims.
The component of table 4: embodiment 14～21 and consumption
Table 5: the composition of plasticizing mother particle d～k and weight part content
Claims (8)
1. a polylactic acid/styrene resin composition, is characterized in that, the component that said composition comprises and the parts by weight of each component are:
Described plasticizing mother particle is the self-control master batch, and the component that described self-control master batch comprises and the parts by weight of each component are: polylactic resin 20～80, acrylonitrile-butadiene-styrene copolymer 10～60, compatilizer 10～50;
Described compatilizer is a kind of in the functionalization derivative of polypropylene grafted maleic anhydride, styrene-grafted maleic anhydride, acrylonitrile-styrene-glycidyl methacrylate copolymer, acrylonitrile-butadiene-styrene (ABS) grafted maleic anhydride, acrylonitrile-styrene grafted maleic anhydride, acrylonitrile-styrene grafting methacrylic acid, ethylene-methyl acrylate copolymer graft glycidyl methacrylate or oxazoline functional group.
2. polylactic acid/styrene resin composition according to claim 1, it is characterized in that, described polylactic resin is one or more the mixing in PLLA, poly-dextrolactic acid, poly-racemic lactic acid, and described polylactic resin weight-average molecular weight is 70000～500000g/mol.
3. polylactic acid/styrene resin composition according to claim 1, it is characterized in that, described phenylethylene resin series is one or more the mixing in acrylonitrile-butadiene-styrene copolymer, acrylonitrile-styrene-acrylic ester copolymer, MBS, vinyl cyanide-terpolymer EP rubber-styrol copolymer, acrylonitrile-chlorianted polyethylene-styrene terpolymer.
4. polylactic acid/styrene resin composition according to claim 1, it is characterized in that, described heat-proof modifier is the multiple copolymer of multipolymer, N-phenylmaleimide and the maleic anhydride of styrene-maleic anhydride copolymer, alpha-methyl styrene-acrylonitrile copolymer, N-phenylmaleimide class and cinnamic terpolymer or N-phenylmaleimide and maleic anhydride, alpha-methyl styrene, vinyl cyanide, described heat-proof modifier weight-average molecular weight is 80000～200000g/mol, and second-order transition temperature is 160～200 ℃.
5. polylactic acid/styrene resin composition according to claim 1, it is characterized in that, described crystallization promoter is one or more the mixing in talcum powder, silicon-dioxide, nano imvite, metal phosphate, erucicamide, hard esteramides, oleylamide, the hard esteramides of ethylenebis, ethylenebisoleoamide, phthalic diamide.
6. polylactic acid/styrene resin composition according to claim 1, is characterized in that, described oxidation inhibitor is phosphite ester kind antioxidant or Hinered phenols antioxidant.
7. polylactic acid/styrene resin composition according to claim 1, is characterized in that, described lubricant is one or more the mixing in pentaerythritol stearate, polyethylene wax, ethylene bis stearamide, stearate, dimethylsilane.
8. a method for preparing the described polylactic acid/styrene resin composition of claim 1, is characterized in that, comprises the following steps:
(1) prepare raw material according to described component and weight part content;
(2) with the dry 5～8h in 60 ℃ of baking ovens of the raw material in step (1), then be placed in high-speed mixer premix 3～10min, obtain Preblend;
(3) Preblend that step (2) is obtained is by twin screw extruder, and controlling temperature is 180～220 ℃, and screw speed is that 200～600rpm melt extrudes, and then through cooling granulation, namely obtains a kind of polylactic acid/styrene resin composition.
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| CN111171493B (en) * | 2020-03-13 | 2022-12-23 | 浙江大学台州研究院 | Heat-resistant impact-resistant polystyrene/polylactic acid alloy and preparation method thereof |
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