CN102417699A - Plastic alloy material composition, plastic alloy material and injection molding part - Google Patents
Plastic alloy material composition, plastic alloy material and injection molding part Download PDFInfo
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- CN102417699A CN102417699A CN2010102956007A CN201010295600A CN102417699A CN 102417699 A CN102417699 A CN 102417699A CN 2010102956007 A CN2010102956007 A CN 2010102956007A CN 201010295600 A CN201010295600 A CN 201010295600A CN 102417699 A CN102417699 A CN 102417699A
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Abstract
The invention discloses a plastic alloy material composition, a plastic alloy material prepared from the composition and an injection molding part prepared by carrying out injection molding on the plastic alloy material. The composition comprises polylactic acid, polycarbonate, acrylonitrile-styrene-butadiene terpolymer and compatilizer, wherein the compatilizer is maleic anhydride grafted acrylonitrile-butadiene-styrene terpolymer and/or maleic anhydride grafted polybutadiene-ethylene-butene terpolymer; and the terminal of the polybutadiene-ethylene-butene terpolymer is polystyrene. The plastic alloy material prepared from the composition has favorable plasticity; and the injection molding part prepared from the composition has good appearance, and can be directly used as surfaces of some electronic products.
Description
[technical field]
The material that the present invention relates to a kind of plastic alloy material compsn and prepared by said composition, particularly a kind of POLYACTIC ACID/Vestolen PP 7052/acrylonitrile-styrene-butadienecopolymer plastic alloy material compsn reach by the plastic alloy material of said composition, reach the moulding that is obtained by this plastic alloy material injection moulding.
[background technology]
POLYACTIC ACID (PLA) is a kind ofly to derive from monomer lactic acid in the plant materials and the synthetic aliphatic polyester; More and more receive the attention of science and industry member because it has fully biodegradable and regenerative nature, be considered to one of the most rising macromolecular material.
PLA has some self-defects; For example the toughness deficiency is more crisp behind the forming materials, shock resistance is poor, poor heat resistance; Heat-drawn wire has only 50～70 degree etc.; These drawbacks limit it in the application in engineering plastics field, present most companies are still with being applied to wrapping material and field of medicaments aspect after its modification.
The blended complex of a kind of PLA and thermoplastic resin is disclosed in the prior art; Described thermoplastic resin Vestolen PP 7052/acrylonitrile-styrene-divinyl polyblend (being the PC/ABS polyblend) and PLA blended complex; Wherein, PLA is 30wt%-40wt%, and described compatilizer is methyl/ethyl/propyl group/butyl-methacrylic ester.This plastic alloy material can be brought into play the advantage of POLYACTIC ACID and PC/ABS polyblend, yet the plasticity of this material is relatively poor, and the outward appearance of the moulding that injection moulding obtains is relatively poor relatively, and there is current mark on the surface, can't directly not have the surface of the electronic product of spraying as some.
[summary of the invention]
For the plasticity that overcomes existing P LA/PC/ABS plastic alloy material relatively poor; The relatively poor problem of moulding outward appearance that adopts this polyblend injection moulding to obtain; The invention provides a kind of plastic alloy material compsn; The plasticity of the plastic alloy material that makes through said composition is better, adopts the outward appearance of moulding of said composition preparation better, can be directly as the surface of some electronic products.
The invention discloses a kind of plastic alloy material compsn; Said composition comprises POLYACTIC ACID, polycarbonate, acrylonitrile-styrene-butadienecopolymer, compatilizer; Said compatilizer is the acrylonitrile-butadiene-styrene terpolymer of maleic anhydride graft and/or the polyhutadiene-ethene of maleic anhydride graft-butene terpolymers; Wherein, the end-blocking of said polyhutadiene-ethene-butene terpolymers is a PS.
End-blocking is that the polyhutadiene-ethene-butene terpolymers of PS is the known commercially available a kind of polymkeric substance of those skilled in the art, i.e. SEBS.
The present invention also provides a kind of plastic alloy material, through with each composition of plastic alloy material compsn through super-dry, mix after, heating and melting is extruded and is obtained in twin screw extruder again, said compsn is above-mentioned compsn.
The present invention also provides a kind of moulding, and said moulding is that above-mentioned plastic alloy material obtains through the injection moulding machine injection moulding.
Contriver of the present invention finds through a large amount of tests; General compatilizer methyl/ethyl/propyl group/butyl-methacrylic ester also is not suitable for the PLA/PC/ABS system; It is compatible preferably that PLA and PC/ABS polyblend are formed; Contriver of the present invention adopts SEBS-g-MAH or ABS-g-MAH; Make PLA and PC/ABS can improve the interface compatibility of PLA and PC through the maleic anhydride in compatilizer part, SEBS in the compatilizer or ABS partly then have good consistency with ABS, and it is the PLA-PC-ABS three-phase system at center with the compatilizer that the adding of said compatilizer has formed.Through the effect of compatibiliser, strengthened the combination between PLA, PC, the ABS component, when keeping mechanical strength, the toughness of plastic alloy material is significantly improved, shown in embodiments of the invention and Comparative Examples 1.Simultaneously, because of plastic alloy material of the present invention contains this degradable biomaterial of PLA, the characteristics that plastic alloy material that therefore prepares and moulding have green low-carbon.
[embodiment]
The invention discloses a kind of plastic alloy material compsn; Said composition comprises POLYACTIC ACID, polycarbonate, acrylonitrile-styrene-butadienecopolymer, compatilizer; Said compatilizer is the acrylonitrile-butadiene-styrene terpolymer of maleic anhydride graft and/or the polyhutadiene-ethene of maleic anhydride graft-butene terpolymers; Wherein, the end-blocking of said polyhutadiene-ethene-butene terpolymers is a PS.
In said composition, POLYACTIC ACID is that 25～65wt%, polycarbonate are that 20～50wt%, acrylonitrile-styrene-butadienecopolymer are that 10～30wt%, compatilizer are 5～15wt%.
Said PLA be known in those skilled in the art be the polyester material of raw material production with lactic acid, have good biodegradable performance, mechanical property and physicals preferably, and can be compatible with other material.The viscosity-average molecular weight of said POLYACTIC ACID is 50,000-500,000, and fusing point is 150-200 ℃.Being preferably viscosity-average molecular weight is 70,000-300,000, and fusing point is 160-200 ℃.Said POLYACTIC ACID can be commercially available, the POLYACTIC ACID produced of U.S. natureworks company for example, and the trade mark is 3051D, and injection moulding rank, viscosity-average molecular weight are 180,000, and fusing point is 200 ℃.
Said PC or ABS are conventionally known to one of skill in the art; ABS can be processed by vinyl cyanide, Succinic Acid, three kinds of monomer copolymerizations of vinylbenzene, and the preparation method of PC or ABS is that those skilled in the art is known, also can be purchased; Among the present invention, said PC or ABS weight-average molecular weight are 50,000-150,000.
Said compatibiliser SEBS-g-MAH or ABS-g-MAH are commercially available.For example the SEBS-g-MAH of the company that the rises production of company or Shanghai day rises in U.S. section; The ABS-g-MAH that the light company of Ningbo ability produces.
Preferably polycarbonate and acrylonitrile-styrene-butadienecopolymer exist with polycarbonate/acrylonitrile-styrene-butadiene copolymer polyblend form; PC and ABS have consistency preferably through modification; Tightr with the three-phase system interfacing of PLA blend formation again; Described PC/ABS polyblend is commercially available, the PC/ABS Cycoloy Resin C1200HF that produces of Sabic company for example, the PC/ABS Bayblend T45 that Bayer company produces.
Preferably, also contain toughner and oxidation inhibitor in the said compsn.
In said composition, said toughner is 0.5～10wt%, and said oxidation inhibitor is 0.1～0.5wt%.
Said toughner is one or more in MBS (MBS), silicon-vinyl resin, the TEB 3K-ethyl propenoate-butyl acrylate copolymer (ACR); Said oxidation inhibitor is butylated hydroxy anisole, butylated hydroxytoluene, tertiarybutylhydroquinone, phosphorous acid benzene two isodecyl esters, pentaerythritol bis-phosphite, [3-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, tricresyl phosphite (2; The 4-di-tert-butyl-phenyl) ester, [β-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid] in ten caprylates, four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester one or several.Said toughner and oxidation inhibitor all can be commercially available, for example the toughner silicon-vinyl resin s-2001 of the Li Yang of Mitsubishi company production.
According to plastic alloy material compsn provided by the invention; In order to make the plastic alloy material compsn have various needed performances; Under preferable case, said plastic alloy material compsn also contains one or more among lubricant, modified fillers therefor, photostabilizer, the look mother.
In said composition, said lubricant is 0～2wt%, and said modified fillers therefor is that 0～10wt%, said photostabilizer are 0～0.5wt%, the look female 0.1-0.5wt% of being.
According to plastic alloy material compsn provided by the invention; Adopt lubricant can improve the interface compatibility of polycarbonate and polylactic acid molecule; Improve the slickness on plastic alloy material compsn surface, and the friction that reduces mixture and preparation equipment in the preparation process is to wearing and tearing that this equipment caused.Said lubricant is for well known to a person skilled in the art various lubricants, and the example of this lubricant comprises ethylene bis stearic amide, ethylene bis stearic amide grafts, silicone, metallic soap salt and wax.
According to plastic alloy material compsn provided by the invention, said modified fillers therefor well known to a person skilled in the art various weighting agents, is generally the inorganic mineral weighting agent, for example one or more in active talcum powder, wollastonite and the mica.
According to plastic alloy material compsn provided by the invention; Adopt photostabilizer can improve polypropylene composite material to the especially ultraviolet stability of light; Said photostabilizer is for well known to a person skilled in the art various photostabilizers, and the example of this photostabilizer comprises dihydroxy benaophenonel photostabilizer and hydroxyl azimidobenzene photostabilizer.Said look female is for the known material that can be used for reconciling the plastic alloy material color of those skilled in the art, and is commercially available.
The present invention also provides a kind of plastic alloy material, through with each composition of plastic alloy material compsn through super-dry, mix after, heating and melting is extruded and is obtained in twin screw extruder again, said compsn is above-mentioned compsn.
The present invention also provides a kind of moulding, and said moulding is that above-mentioned plastic alloy material obtains through the injection moulding machine injection moulding.
Be the water cut in the control plastic alloy material composition material,, be generally in the vacuum drying oven so earlier the plastic alloy material composition material is carried out drying under the preferable case, at 0.05-0.1MPa, 75-110 ℃ of following dry 1-6h.
In order better to improve the heat-resisting and mechanical property of material; Before general said material was extruded in forcing machine, through the low speed mixer thorough mixing, method of mixing was for to join composition material in the low speed mixer; Under 40-60 ℃; The every mixing of low speed stopped 30s in 1 minute, and circulation 4-8 time makes to mix.
Said extrusion method is in twin screw extruder; In length-to-diameter ratio is 20-40, and rate of feeding 35～55r/min, screw speed are 160-220r/min; Each zone temperatures is respectively shown in the following table 1; The vacuum tightness of each section is to mix under the condition of 0.02-0.06MPa, extrudes then, obtains extruding product.Said vacuum tightness is psia.Said twin screw extruder can be this area twin screw extruder commonly used, like the twin screw extruder of Nanjing New Time Co. production.
Table 1
Can add the look mother in 6 districts compsn is mixed colours, quality accounts for 0.1% of total mass.The lines of extruding are through the recirculated water cooling tie rod, the dicing machine pelletizing.
Said tie rod, pelletizing and injection moulding process are this area method commonly used; As will extrude product through tank cooling carrying out tie rod; With dicing machine (machinery ltd of Zhangjagang City the United Nations General Assembly; Model is QLJ-1) under rotating speed 350r/min, carry out pelletizing, after the oven dry of the micelle after cutting, carry out injection moulding with injection moulding machine.
Select SUMITOMO CHEMICAL SE180DU injection moulding machine for use, carry out the electronic product casing injection moulding by following parameter: 240～255 ℃ of injection temperatures, 50～75 ℃ of mould temperature penetrate pressure 1550～1700kg/cm
2, back pressure 40～50kg/cm
2, pressurize 1000～1300kg/cm
2, cooling time 25～40s.
Through embodiment the present invention is further described below.
Embodiment 1
Present embodiment is used to explain plastic alloy material compsn provided by the invention and plastic alloy material.
1, raw materials mix, mixing
With the POLYACTIC ACID (POLYACTIC ACID that U.S. natureworks company produces; The trade mark is 3051D; Injection moulding rank, viscosity-average molecular weight are 180,000, and fusing point is 200 ℃), polycarbonate (the PC Lexan ResinEXL1414T of Sabic company), acrylonitrile-styrene-butadienecopolymer (ABS of the ABS PA-747 of Taiwan Qi Mei company) put into vacuum drying oven; At 0.1MPa, 90 ℃ of following dry 4h.
POLYACTIC ACID, polycarbonate, acrylonitrile-styrene-butadienecopolymer and various additive after according to the weight percent raw material shown in the table 2 above-mentioned drying being dewatered mixes 5min down in 60 ℃ in low speed mixer, make to mix.The material that mixes places twin screw extruder, is 20 in length-to-diameter ratio, and screw speed is 200r/min, and each zone temperatures is as shown in table 1, and the vacuum tightness of each section is to mix under the condition of 0.05MPa, extrudes product then.
2, tie rod, pelletizing, injection moulding
To extrude product through tank cooling carrying out tie rod, (machinery ltd of Zhangjagang City the United Nations General Assembly, model is QLJ-1) carries out pelletizing under rotating speed 350r/min with dicing machine, after the oven dry of the micelle after cutting, carries out injection moulding with injection moulding machine.Obtain plastic alloy material A1.
3, injection moulding
Place the injection moulding machine injection moulding to obtain 100 moulding sample A11 of the present invention plastic alloy material A1.The injecting condition of injection moulding machine is: injection temperature T1 is 245 ℃, and T2 is 255 ℃, and T3 is 255 ℃, and T4 is 250 ℃, and 70 ℃ of die temperatures penetrate pressure 1600kg/cm
2, back pressure 48kg/cm
2, pressurize 1200kg/cm
2, cooling time 35s.
Embodiment 2
Present embodiment is used to explain plastic alloy material compsn disclosed by the invention and this plastic alloy material.Be that with the difference of embodiment 1 raw material in the compsn of employing is different with embodiment 1, and is specifically as shown in table 2.Obtain plastic alloy material A2.Obtain 100 moulding sample A12 of the present invention.
Embodiment 3
Present embodiment is used to explain plastic alloy material compsn disclosed by the invention and this plastic alloy material.
Be that with the difference of embodiment 1 raw material in the compsn of employing is different with embodiment 1, and is specifically as shown in table 2.Obtain plastic alloy material A3.Obtain 100 moulding sample A13 of the present invention.
Embodiment 4
Present embodiment is used to explain plastic alloy material compsn disclosed by the invention and this plastic alloy material.
Be that with the difference of embodiment 1 raw material in the compsn of employing is different with embodiment 1, and is specifically as shown in table 2.Obtain plastic alloy material A4.Obtain 100 moulding sample A14 of the present invention.
Comparative Examples 1
This Comparative Examples is used to explain plastic alloy material compsn of the prior art and this plastic alloy material.
Be that with the difference of embodiment 1 raw material in the compsn of employing is different with embodiment 1, and is specifically as shown in table 2.Obtain plastic alloy material D1.Obtain 100 moulding sample D11 of the present invention.
The plastic alloy material performance test
Adopt ASTM (U.S.'s test and materials association) standard that the above-mentioned plastic alloy material that makes is carried out following test;
1, tensile strength and elongation at break
Adopt ASTM D638 method to measure the tensile strength and the elongation at break of material;
2, flexural strength and modulus in flexure
Adopt ASTM D790 method to measure the flexural strength and the modulus in flexure of material;
3, notched Izod impact strength
Adopt ASTM D256 method to measure the notched Izod impact strength of material;
4, heat-drawn wire
Adopt ASTM D648 method to measure the heat-drawn wire of material;
Moulding A11-A14 and the test of D11 appearance:
Adopt visual method, whether the electronic product casing of inspection injection moulding exists following defective: current mark, weld mark.
Table 2
As shown in table 3 below to plastic alloy material performance test and moulding test result:
Table 3
Test result from table 3 can be found out; The plastic alloy material A1-A4 moulding D1 corresponding with Comparative Examples that embodiments of the invention are corresponding compares; The physical strength of the material that the present invention prepares is compared with D1; Basically similar, the toughness of plastic alloy material is that notched Izod impact strength then is significantly improved; In addition, the plastic alloy material for preparing of the present invention can satisfy the requirement of ordinary electronic product to the mechanical property and the resistance toheat of plastic material.
Simultaneously, the moulding A11-A14 moulding D11 corresponding with Comparative Examples that embodiments of the invention are corresponding compares, and the outward appearance of the moulding that makes through compsn of the present invention is better, can be directly as the surface of some electronic products, the effect that realization exempts to spray; And Comparative Examples D11 surperficial visual has the current mark defective, shows between compsn not form good compatible effect, still needs surface treatment further, like applying coating etc.
Claims (11)
1. plastic alloy material compsn; It is characterized in that; Said composition comprises POLYACTIC ACID, polycarbonate, acrylonitrile-styrene-butadienecopolymer, compatilizer; Said compatilizer is the acrylonitrile-butadiene-styrene terpolymer of maleic anhydride graft and/or the polyhutadiene-ethene of maleic anhydride graft-butene terpolymers, and wherein, the end-blocking of said polyhutadiene-ethene-butene terpolymers is a PS.
2. compsn according to claim 1 is characterized in that: in said composition, POLYACTIC ACID is that 25～65wt%, polycarbonate are that 20～50wt%, acrylonitrile-styrene-butadienecopolymer are that 10～30wt%, compatilizer are 5～15wt%.
3. compsn according to claim 1 is characterized in that: said compatilizer is maleic anhydride grafted acrylonitrile-butadiene-styrene terpolymer and the polyhutadiene-ethene of maleic anhydride graft-butene terpolymers.
4. compsn according to claim 1 is characterized in that: in the said compsn, polycarbonate and acrylonitrile-styrene-butadienecopolymer exist with polycarbonate/acrylonitrile-styrene-butadiene copolymer polyblend form.
5. compsn according to claim 1 is characterized in that: also contain toughner and oxidation inhibitor.
6. compsn according to claim 5; It is characterized in that: said toughner is TEB 3K/butadiene/styrene copolymers, silicon-vinyl resin, TEB 3K-ethyl propenoate-butyl acrylate copolymer; Said oxidation inhibitor is butylated hydroxy anisole, butylated hydroxytoluene, tertiarybutylhydroquinone, phosphorous acid benzene two isodecyl esters, pentaerythritol bis-phosphite, [3-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, tricresyl phosphite (2; The 4-di-tert-butyl-phenyl) ester, [β-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid] in ten caprylates, four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester one or several.
7. according to claim 5 or 6 described compsns, it is characterized in that: in said composition, said toughner is 0.5～10wt%, and said oxidation inhibitor is 0.1～0.5wt%.
8. compsn according to claim 5 is characterized in that: also contain among lubricant, weighting agent, photostabilizer, the look mother one or more.
9. compsn according to claim 8 is characterized in that: in said composition, said lubricant is 0～2wt%, and said weighting agent is that 0～10wt%, said photostabilizer are 0～0.5wt%, the look female 0.1-0.5wt% of being.
10. plastic alloy material, through with each composition of plastic alloy material compsn through super-dry, mix after, heating and melting is extruded and is obtained in twin screw extruder again, it is characterized in that: said compsn is the described compsn of claim 1-7.
11. being the described plastic alloy material of claim 10, a moulding, said moulding obtain through the injection moulding machine injection moulding.
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| CN102863760A (en) * | 2012-09-20 | 2013-01-09 | 常熟市永祥机电有限公司 | Polycarbonate alloy material filled with talcum powder |
| CN102911492A (en) * | 2012-11-21 | 2013-02-06 | 张向南 | Excellent-performance plastic alloy |
| CN103408906A (en) * | 2013-08-20 | 2013-11-27 | 杭州师范大学 | High-plant high-performance polylactic acid alloy material |
| CN104364319A (en) * | 2012-06-13 | 2015-02-18 | 松下知识产权经营株式会社 | Poly(lactic acid) resin composition, method for producing molded article, molded article, and holder for electronic device |
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| CN104364319A (en) * | 2012-06-13 | 2015-02-18 | 松下知识产权经营株式会社 | Poly(lactic acid) resin composition, method for producing molded article, molded article, and holder for electronic device |
| CN102863760A (en) * | 2012-09-20 | 2013-01-09 | 常熟市永祥机电有限公司 | Polycarbonate alloy material filled with talcum powder |
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| CN105647138A (en) * | 2014-11-30 | 2016-06-08 | 黑龙江鑫达企业集团有限公司 | Method for preparing high-toughness ABS/PLA based alloy |
| CN105713360A (en) * | 2014-12-05 | 2016-06-29 | 黑龙江鑫达企业集团有限公司 | Preparation method of high-toughness polycarbonate/polylactic acid based alloy |
| CN106700388A (en) * | 2015-11-15 | 2017-05-24 | 合肥杰事杰新材料股份有限公司 | Scratch-resistant and low-temperature impact resistant ABS/TPU alloy material and preparation method thereof |
| CN106543670A (en) * | 2016-12-08 | 2017-03-29 | 四川长虹电器股份有限公司 | Exempt from sprayed biological base PLA/PC composites and preparation method thereof |
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Application publication date: 20120418 |