CN103642184A - Dynamically vulcanized polylactic acid plastic/rubber thermoplastic elastomer and preparation method thereof - Google Patents
Dynamically vulcanized polylactic acid plastic/rubber thermoplastic elastomer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a dynamically vulcanized polylactic acid plastic/rubber thermoplastic elastomer and a preparation method thereof. The raw materials include, by weight: 20-90 parts of polylactic acid, 10-80 parts of rubber, 0.1-1 part of an antioxidant, 1-10 parts of an interface modifier, 0.1-4.8 parts of a cross-linking agent, and 0.1-4.2 parts of an assistant cross-linking agent. The preparation method comprises: under 150-190DEG C, mixing the polylactic acid, the antioxidant, the rubber and the interface modifier evenly, adding the cross-linking agent and the assistant cross-linking agent under high-speed shearing to conduct dynamic vulcanization on the rubber, thus obtaining the dynamically vulcanized polylactic acid plastic/rubber thermoplastic elastomer. The obtained polylactic acid plastic/rubber thermoplastic elastomer has the characteristics of high mechanical strength, excellent impact performance, reprocessability and the like, and can be widely used in the fields of medical treatment, automobile industry, agricultural production, packaging, clothing, electronic information industry, chemical industry, new energy and environmental protection, etc.
Description
Technical field
The present invention relates to a kind of thermoplastic elastic material, particularly relate to a kind of dynamic vulcanization polylactic acid plastic/rubber thermoplastic elastic body and preparation method thereof.
Background technology
The invention of petroleum-based plastics of 20th century is called as greatest invention, and petroleum-based plastics goods greatly facilitate the people's daily life, but these products waste after using is difficult to biological degradation, to the earth, has caused serious white pollution; Meanwhile, oil is Nonrenewable resources, overexploitation and use, and oneself makes petroleum resources close on exhaustion.Today, energy problem, environmental problem receive people's concern day by day.Searching can replace reproducible, the biodegradable environmentally friendly macromolecular material of petroleum-based plastics to cause various countries Materials science worker's very big interest.
Poly(lactic acid) (PLA) is a kind of thermoplasticity aliphatic polyester of linearity, the complete biodegradable polymer that the lactic acid being obtained as straw or fermented grain by renewable plant resources makes through chemosynthesis.Degraded product carbonic acid gas and water can return to the nature circle, rejoin in the photosynthesis process of plant, thereby make tellurian carbon cycle maintain balance.Broken away from the dependence to petroleum resources.Poly(lactic acid) has superior physicals, and intensity, rigidity is high, transparency good, has good biocompatibility, easily processing, and the poly(lactic acid) of different molecular weight is applicable to various complete processings such as blowing, thermoplastic, wire drawings, and the use range of product is wide.But poly(lactic acid) toughness, flexibility is poor, has notch sensitivity, and the notched Izod impact strength of PLA is only 2.0～3.0kJ/m
2, elongation at break be 2 ?10%, limited its application, in order to expand the Application Areas of PLA, need carry out modification to improve its toughness, flexibility to it.
It is initiator that Chinese invention patent CN102276965B adopts superoxide, natural rubber plasticizing polylactic acid.Wherein, poly(lactic acid) be 70 ?95 parts, natural rubber be 5 ?30 parts, superoxide be 0.2 ?1 part.But there is following problem in this patent: 1, amount of peroxide is unreasonable, be calculated in mass percent, it is 3.3% that superoxide accounts for rubber phase mass percent minimum, the highlyest closely reach 20%, from embodiment 1 to embodiment 4 superoxide, account for rubber rubber mass percent and be respectively 4%, 5%, 4%, 3.3%, excessive superoxide can cause poly(lactic acid) degraded, finally affects the performance of product; 2, vulcanization system is too simple, and take dicumyl peroxide as vulcanizing agent, and vulcanized article has peculiar smell, affects the application of product.Chinese invention patent application CN101864156A adopts n-methylolacrylamide and acrylate copolymer toughened polydactyl acid, poly(lactic acid) elongation at break, shock strength are improved, but n-methylolacrylamide and acrylate copolymer complicated process of preparation, the shortcomings such as poor reproducibility.
Summary of the invention
The object of the invention is to the defect for prior art and product existence, a kind of dynamic vulcanization polylactic acid plastic/natural rubber thermoplastic elastomer and preparation method thereof is provided, it is high that this thermoplastic elastomer has physical strength, excellent impact property, can repeat the excellent features such as processing.
The present invention is achieved through the following technical solutions:
A kind of dynamic vulcanization polylactic acid plastic/rubber thermoplastic elastic body: according to the mass fraction, its raw material comprises following component:
Described poly(lactic acid) for poly-L ?lactic acid, poly-D ?one or more of lactic acid and poly-dl-lactide;
Described oxidation inhibitor is one or more in irgasfos 168, antioxidant 1076, antioxidant 1010, antioxidant 2246, oxidation inhibitor 1098, oxidation inhibitor B102, oxidation inhibitor B900 and anti-oxidant DLTP;
Described interface modifier is one or more in glycidyl methacrylate, epoxy natural rubber, zinc methacrylate, magnesinm methacrylate and maleic anhydride;
Described linking agent is one or more in resin system vulcanizing agent, sulphur system vulcanizing agent and peroxide vulcanizing agent;
Described additional crosslinker is one or both the mixture in epoxidization phenolic resin, isocyanic ester, trivinyl isocyanuric acid ester, three propenyl cyanurates.
For further realizing the object of the invention, preferably, described resin system vulcanizing agent is comprised of resin and first kind activator, the consumption of resin is 3%～6% of rubber quality, the consumption of first kind activator is 0.5%～1.5% of rubber quality, described resin be SP ?1045, SZ ?2045,2402 and SP ?in 1055 one or more; Described first kind activator be in tin protochloride, iron protochloride and iron(ic) chloride one or more.
Described sulphur system vulcanizing agent is comprised of sulphur, Equations of The Second Kind activator and promotor, and the consumption of sulphur is rubber quality 1%～3.5%, and the consumption of Equations of The Second Kind activator is rubber quality 0.5%～3%, and the consumption of promotor is rubber quality 0.5%～1.5%; Described Equations of The Second Kind activator is zinc oxide and/or stearic acid; Described promotor is one or more in CZ, DM, TMTD and DZ.
Described peroxide vulcanizing agent is superoxide, and the consumption of superoxide is rubber quality 0.5%～2.5%; Described superoxide be the benzoyl peroxide formic acid tertiary butyl, benzoyl peroxide, 2,4 ?dichlorobenzoperoxide, dicumyl peroxide, di-t-butyl peroxide, bis-?one or more in (tert-butyl hydroperoxide sec.-propyl) benzene and dibenzoyl peroxide.
Described rubber is one or more in three leaf tree rubber, Chinese gutta percha and Guayule rubbers.
The raw material of described dynamic vulcanization polylactic acid plastic/rubber thermoplastic elastic body also comprises packing material; Described packing material is organic filler material or inorganic filling material; Described organic filler material is one or more in starch, maleic anhydride graft starch, xylogen, sisal fibers, nano micro crystal cellulose, bamboo fibers; Described inorganic filling material is one or more in silicon-dioxide, calcium carbonate, mica, talcum, clay, titanium oxide and carbon black; In mass fraction, the add-on of organic or inorganic packing material is 5～50 parts.
The preparation method of described dynamic vulcanization polylactic acid plastic/rubber thermoplastic elastic body: at the temperature of 150～190 ℃, poly(lactic acid), oxidation inhibitor, rubber and interface modifier are mixed, under high speed shear, add linking agent and additional crosslinker to carry out dynamic vulcanization to rubber phase, obtain polylactic acid plastic/rubber thermoplastic elastic body prepared by dynamic vulcanization.
The another kind of preparation method of described dynamic vulcanization polylactic acid plastic/rubber thermoplastic elastic body: be first to join in rubber and mix by packing material, at the temperature of 150～190 ℃, join in poly(lactic acid), oxidation inhibitor and interface modifier and mix, under high speed shear, add linking agent and additional crosslinker to carry out dynamic vulcanization to rubber phase; Or at the temperature of 150～190 ℃, after being mixed with natural rubber, poly(lactic acid) adds packing material, and add oxidation inhibitor and interface modifier to mix, under high speed shear, add linking agent and additional crosslinker to carry out dynamic vulcanization to rubber phase, obtain polylactic acid plastic/rubber thermoplastic elastic body prepared by dynamic vulcanization.
With respect to prior art, tool of the present invention has the following advantages:
1) dynamic vulcanization polylactic acid plastic/rubber thermoplastic elastic body that the present invention obtains is with polylactic acid plastic; the excellent properties of vegetable rubber; there is physical strength high; excellent impact property, the features such as processing can be repeated, the fields such as medical treatment, automotive industry, agriculture production, packing, clothes, information electronic industry, chemical industry, new forms of energy and environment protection can be widely used in.
2) interface modifier that the present invention adopts at least contains a function key, and in dynamic vulcanization process, peroxide cross-linking agent decomposes and produces free radical and cause natural rubber and occur crosslinked time, also can cause interface modifier and participate in radical polymerization.Interface modifier and polylactic acid plastic external phase have good consistency, so the two-phase interface of rubber phase and polylactic acid plastic forms transition layer, strengthen consistency and the interfacial adhesion of rubber phase and plastics phase.Interface modifier add and dynamic vulcanization technology has improved uncompatibility intrinsic between polylactic acid plastic and natural rubber, compare with polylactic acid plastic natural rubber, polylactic acid plastic/natural rubber thermoplastic elastomer prepared by the present invention has good consistency and product performance.
3) thermoplastic elastomer of the present invention can repeat processing use, and can use general method for processing forming, and shaping and processing device carries out forming process, contour machining equipment is conventional, power consumption of polymer processing is low, and complete processing is simple, can be shaped to according to application target the goods of arbitrary shape.
4) the present invention adopts dynamic vulcanization to prepare thermoplastic elastomer, under shearing action, adds linking agent and additional crosslinker to vulcanize on the spot natural rubber, makes material have better mechanical property.
5) the invention provides a kind of preparation simply, high tenacity with practical value, polylactic acid plastic/the rubber thermoplastic elastic body of flexibility, CN102276965B compares with Chinese invention patent, linking agent is resin system vulcanizing agent, sulphur system vulcanizing agent, peroxide vulcanizing agent or compound system vulcanizing agent, when vulcanization system is superoxide, in massfraction, superoxide account for rubber phase mass percent be 0.5 ?2.5%, poor for rubber and poly(lactic acid) consistency, during modification, add interface modifier to obtain good mechanical property, rubber is three leaf tree rubber, Chinese gutta percha, one or more in Guayule rubber, three leaf tree rubber, Chinese gutta percha, Guayule rubber all derives from plant, the milk of rubber tree secretion, through solidifying, the Hookean body of processing and making, the renewable natural resource with superior over-all properties.Especially have good elasticity, elastic extension can reach 1000%.The present invention suits development trend and the requirement of green, low-carbon (LC), environmental protection.
Accompanying drawing explanation
Fig. 1 is the stress-strain(ed) curve of comparative example 1, comparative example 2, embodiment 7.
Fig. 2 is the scanning electron microscope diagram sheet of embodiment 7 thermoplastic elastomer brittle failure faces.
Fig. 3 is the scanning electron microscope diagram sheet of comparative example 2 brittle failure faces.
Fig. 4 is the scanning electron microscope diagram sheets of embodiment 7 thermoplastic elastomers after chloroform etching.
Embodiment
For understanding better the present invention, below in conjunction with drawings and Examples, the present invention will be further described, but it should be noted that, embodiment does not form the restriction to the claimed scope of the present invention.In embodiment and comparative example, poly(lactic acid) is all dried 6 hours before use in 70 degree loft drier.
Embodiment 1
Choosing poly(lactic acid) is matrix resin (Zhejiang Hisun Biomaterials Co., Ltd, poly-dl-lactide (PDLLA)), and natural rubber is general basis rubber (three leaves tree rubber Malaysia 1#, Guangzhou rubber industry institute).First in mill, natural rubber (20g) is plasticated.By poly(lactic acid) (180g), it is 160 ℃ that antioxidant 1010 (0.4g) joins temperature, in the Haake torque rheometer of rotor speed 60r/min, after 5min, add natural rubber, interface modifier glycidyl methacrylate (6g), mix add after 3min linking agent Er ?(tert-butyl hydroperoxide sec.-propyl) benzene (0.2g) and additional crosslinker epoxidization phenolic resin (0.2g) carry out dynamic vulcanization, continuation blend 5min, discharging.With crusher, sample being broken for to tiny uniform particle, is then standard batten with single screw injection molding machine injection molding.The injection temperature of single screw injection molding machine is: 165 ℃ of feeding sections, and 170 ℃ of compression sections, 170 ℃ of homogenizing zones, 175 ℃ of machine head port mould parts, screw speed is 90r/min.
Embodiment 2
Choosing poly(lactic acid) is matrix resin (Zhejiang Hisun Biomaterials Co., Ltd, poly-dl-lactide (PDLLA)), and natural rubber is general basis rubber (three leaves tree rubber Malaysia 1#, Guangzhou rubber industry institute).First in mill, natural rubber (40g) is plasticated.By poly(lactic acid) (160g), it is 190 ℃ that irgasfos 168 (2g) joins temperature, in the Haake torque rheometer of rotor speed 60r/min, after 5min, add natural rubber, interface modifier epoxidation natural gum (10g), after mixing 3min, add linking agent di-t-butyl peroxide (0.6g) and additional crosslinker isocyanic ester (8.4g) to carry out dynamic vulcanization, continue blend 5min, discharging.With crusher, sample being broken for to tiny uniform particle, is then standard batten with single screw injection molding machine injection molding.The injection temperature of single screw injection molding machine is: 165 ℃ of feeding sections, and 170 ℃ of compression sections, 170 ℃ of homogenizing zones, 175 ℃ of machine head port mould parts, screw speed is 90r/min.
Embodiment 3
Choosing poly(lactic acid) is matrix resin (Zhejiang Hisun Biomaterials Co., Ltd, poly-dl-lactide (PDLLA)), and natural rubber is general basis rubber (three leaves tree rubber Malaysia 1#, Guangzhou rubber industry institute).First in mill, natural rubber (60g) is plasticated.By poly(lactic acid) (140g), it is 170 ℃ that antioxidant 1076 (1.5g) joins temperature, in the Haake torque rheometer of rotor speed 60r/min, after 5min, add rubber unvulcanizate, interface modifier zinc methacrylate (6g), after mixing 3min, add linking agent dicumyl peroxide (0.9g) and additional crosslinker three propenyl cyanurates (1.1g) to carry out dynamic vulcanization, continue blend 5min, discharging.With crusher, sample being broken for to tiny uniform particle, is then standard batten with single screw injection molding machine injection molding.The injection temperature of single screw injection molding machine is: 165 ℃ of feeding sections, and 170 ℃ of compression sections, 170 ℃ of homogenizing zones, 175 ℃ of machine head port mould parts, screw speed is 90r/min.
Embodiment 4
Choosing poly(lactic acid) is matrix resin (Zhejiang Hisun Biomaterials Co., Ltd, poly-dl-lactide (PDLLA)), and natural rubber is general basis rubber (three leaves tree rubber Malaysia 1#, Guangzhou rubber industry institute).First in mill, natural rubber (60g) is plasticated.By poly(lactic acid) (140g), it is 170 ℃ that anti-oxidant DLTP (0.2g) joins temperature, in the Haake torque rheometer of rotor speed 60r/min, after 5min, add rubber unvulcanizate, interface modifier glycidyl methacrylate (6g), after mixing 3min, add resin 2402(3g), tin protochloride (0.6g) and additional crosslinker epoxidization phenolic resin (1.1g) carry out dynamic vulcanization, continuation blend 5min, discharging.With crusher, sample being broken for to tiny uniform particle, is then standard batten with single screw injection molding machine injection molding.The injection temperature of single screw injection molding machine is: 165 ℃ of feeding sections, and 170 ℃ of compression sections, 170 ℃ of homogenizing zones, 175 ℃ of machine head port mould parts, screw speed is 90r/min.
Choosing poly(lactic acid) is matrix resin (Zhejiang Hisun Biomaterials Co., Ltd, poly-dl-lactide (PDLLA)), and natural rubber is general basis rubber (three leaves tree rubber Malaysia 1#, Guangzhou rubber industry institute).First in mill, natural rubber (60g) is plasticated.By poly(lactic acid) (140g), it is 170 ℃ that antioxidant 1010 (1g) joins temperature, in the Haake torque rheometer of rotor speed 60r/min, after 5min, add rubber unvulcanizate, interface modifier glycidyl methacrylate (6g), adds sulphur (1.5g), zinc oxide (1.2g), stearic acid (0.6g), CZ(0.3g after mixing 3min) DM(0.2g), additional crosslinker epoxidization phenolic resin (1.1g) carries out dynamic vulcanization, continue blend 5min, discharging.With crusher, sample being broken for to tiny uniform particle, is then standard batten with single screw injection molding machine injection molding.The injection temperature of single screw injection molding machine is: 165 ℃ of feeding sections, and 170 ℃ of compression sections, 170 ℃ of homogenizing zones, 175 ℃ of machine head port mould parts, screw speed is 90r/min.
Embodiment 6
Choosing poly(lactic acid) is matrix resin (Zhejiang Hisun Biomaterials Co., Ltd, poly-dl-lactide (PDLLA)), and natural rubber is general basis rubber (three leaves tree rubber Malaysia 1#, Guangzhou rubber industry institute).First the mixing even rubber unvulcanizate that becomes of natural rubber (60g) and filler starch (10g) in mill.By poly(lactic acid) (140g), it is 170 ℃ that antioxidant 1010 (2g) joins temperature, in the Haake torque rheometer of rotor speed 60r/min, after 5min, add rubber unvulcanizate, interface modifier glycidyl methacrylate (6g), after mixing 3min, add sulphur (0.7g), zinc oxide (0.6g), stearic acid (0.3g), CZ(0.15g) DM(0.1g), resin 2402(2.5g), tin protochloride (0.1g), additional crosslinker trivinyl isocyanuric acid ester (1.1g) carries out dynamic vulcanization, continue blend 5min, discharging.With crusher, sample being broken for to tiny uniform particle, is then standard batten with single screw injection molding machine injection molding.The injection temperature of single screw injection molding machine is: 165 ℃ of feeding sections, and 170 ℃ of compression sections, 170 ℃ of homogenizing zones, 175 ℃ of machine head port mould parts, screw speed is 90r/min.
Embodiment 7
Choosing poly(lactic acid) is matrix resin (Zhejiang Hisun Biomaterials Co., Ltd, poly-dl-lactide (PDLLA)), and natural rubber is general basis rubber (three leaves tree rubber Malaysia 1#, Guangzhou rubber industry institute).First in mill, natural rubber (80g) is plasticated.By poly(lactic acid) (120g), it is 150 ℃ that antioxidant 1010 (0.8g) joins temperature, in the Haake torque rheometer of rotor speed 60r/min, after 5min, add natural rubber, interface modifier glycidyl methacrylate (10g), mix add after 3min vulcanizing agent Er ?(tert-butyl hydroperoxide sec.-propyl) benzene (1.2g) and additional crosslinker epoxidization phenolic resin (0.8g) carry out dynamic vulcanization, continuation blend 5min, discharging.With crusher, sample being broken for to tiny uniform particle, is then standard batten with single screw injection molding machine injection molding.The injection temperature of single screw injection molding machine is: 165 ℃ of feeding sections, and 170 ℃ of compression sections, 170 ℃ of homogenizing zones, 175 ℃ of machine head port mould parts, screw speed is 90r/min.
Embodiment 8
Choosing poly(lactic acid) is matrix resin (Zhejiang Hisun Biomaterials Co., Ltd, poly-dl-lactide (PDLLA)), and natural rubber is general basis rubber (three leaves tree rubber Malaysia 1#, Guangzhou rubber industry institute).First in mill, natural rubber (100g) is plasticated.By poly(lactic acid) (100g), it is 170 ℃ that antioxidant 1010 (1g) joins temperature, in the Haake torque rheometer of rotor speed 60r/min, after 5min, add natural rubber, filler clay (60g), interface modifier glycidyl methacrylate (7g), mix add after 3min vulcanizing agent Er ?(tert-butyl hydroperoxide sec.-propyl) benzene (1.2g) and additional crosslinker epoxidization phenolic resin (1g) carry out dynamic vulcanization, continue blend 5min, discharging.Melting in 150 ℃ of mills, hot-forming on vulcanizing press, the about 1mm of thickness of sample, is cut into standard batten.
Embodiment 9
Choosing poly(lactic acid) is matrix resin (Zhejiang Hisun Biomaterials Co., Ltd, poly-dl-lactide (PDLLA)), and natural rubber is general basis rubber (three leaves tree rubber Malaysia 1#, Guangzhou rubber industry institute).First in mill, natural rubber (120g) is plasticated.By poly(lactic acid) (80g), it is 180 ℃ that antioxidant 1010 (1.5g) joins temperature, in the Haake torque rheometer of rotor speed 60r/min, after 5min, add natural rubber, filler-silicon dioxide (100g), interface modifier maleic anhydride (19g), mix add after 3min vulcanizing agent Er ?(tert-butyl hydroperoxide sec.-propyl) benzene (1.7g) and additional crosslinker epoxidization phenolic resin (1.1g) carry out dynamic vulcanization, continue blend 5min, discharging.Melting in 150 ℃ of mills, hot-forming on vulcanizing press, the about 1mm of thickness of sample, is cut into standard batten.
Embodiment 10
Choosing poly(lactic acid) is matrix resin (Zhejiang Hisun Biomaterials Co., Ltd, poly-dl-lactide (PDLLA)), and natural rubber is general basis rubber (three leaves tree rubber Malaysia 1#, Guangzhou rubber industry institute).First in mill, natural rubber (140g) is plasticated.By poly(lactic acid) (60g), it is 170 ℃ that oxidation inhibitor (1g) joins temperature, in the Haake torque rheometer of rotor speed 60r/min, after 5min, add natural rubber, interface modifier methacrylic zinc (9g), mix add after 3min vulcanizing agent Er ?(tert-butyl hydroperoxide sec.-propyl) benzene (1.7g) and additional crosslinker epoxidization phenolic resin (1.1g) carry out dynamic vulcanization, continuation blend 5min, discharging.Melting in 150 ℃ of mills, hot-forming on vulcanizing press, the about 1mm of thickness of sample, is cut into standard batten.
Embodiment 11
Choosing poly(lactic acid) is matrix resin (Zhejiang Hisun Biomaterials Co., Ltd, poly-dl-lactide (PDLLA)), and natural rubber is general basis rubber (three leaves tree rubber Malaysia 1#, Guangzhou rubber industry institute).First in mill, natural rubber (160g) is plasticated.By poly(lactic acid) (40g), it is 190 ℃ that antioxidant 1010 (1.6g) joins temperature, in the Haake torque rheometer of rotor speed 60r/min, after 5min, add natural rubber, interface modifier glycidyl methacrylate (20g), mix add after 3min vulcanizing agent Er ?(tert-butyl hydroperoxide sec.-propyl) benzene (2.5g) and additional crosslinker epoxidization phenolic resin (1.5g) carry out dynamic vulcanization, continuation blend 5min, discharging.Melting in 150 ℃ of mills, hot-forming on vulcanizing press, the about 1mm of thickness of sample, is cut into standard batten.
Comparative example 1
Choosing poly(lactic acid) is matrix resin (Zhejiang Hisun Biomaterials Co., Ltd, poly-dl-lactide (PDLLA)), by poly(lactic acid) (230g), it is 170 ℃ that antioxidant 1010 (0.46g) joins temperature, blend 5min in the Haake torque rheometer of rotor speed 60r/min, discharging.With crusher, sample being broken for to tiny uniform particle, is then standard batten with single screw injection molding machine injection molding.The injection temperature of single screw injection molding machine is: 165 ℃ of feeding sections, and 170 ℃ of compression sections, 170 ℃ of homogenizing zones, 175 ℃ of machine head port mould parts, screw speed is 90r/min.
Comparative example 2(Chinese patent CN102276965B embodiment 2)
Choosing poly(lactic acid) is matrix resin (Zhejiang Hisun Biomaterials Co., Ltd, poly-dl-lactide (PDLLA)), and natural rubber is general basis rubber (three leaves tree rubber Malaysia 1#, Guangzhou rubber industry institute).First in mill, natural rubber (20g) is plasticated.By poly(lactic acid) (180g), it is 160 ℃ that natural rubber joins temperature, in the Haake torque rheometer of rotor speed 70r/min, adds dicumyl peroxide (1g) after 4min, continues blend 6min, discharging.With crusher, sample being broken for to tiny uniform particle, is then standard batten with single screw injection molding machine injection molding.The injection temperature of single screw injection molding machine is: 165 ℃ of feeding sections, and 170 ℃ of compression sections, 170 ℃ of homogenizing zones, 175 ℃ of machine head port mould parts, screw speed is 90r/min.
The performance of comparative example 1～2 and embodiment 1～11 is shown in Table 1.Elongation test according to GB/T1040 ?2006(comparative example 1～2 and embodiment 1～7), GB/T528 ?1998(implement 8～11) standard, Impact Test according to GB/T1843 ?2008 standards, tear test according to GB/T529 standard.
Table 1
| Title | Elongation at break (%) | Shock strength (kj/m 2） | Tear strength/MPa |
| Comparative example 1 | 13 | 2.75 | ? |
| Comparative example 2 | 16 | 3.63 | ? |
| Embodiment 1 | 24 | 5.85 | ? |
| Embodiment 2 | 39 | 7.25 | ? |
| Embodiment 3 | 61 | 17.75 | ? |
| Embodiment 4 | 73 | 18.10 | ? |
| |
67 | 17.93 | ? |
| Embodiment 6 | 81 | 18.50 | ? |
| Embodiment 7 | 210 | 58.25 | ? |
| Embodiment 8 | 91 | ? | 67.0 |
| Embodiment 9 | 96 | ? | 44.6 |
| Embodiment 10 | 103 | ? | 40.5 |
| Embodiment 11 | 110 | ? | 35.4 |
From can finding out of table 1, according to comparative example 2 and embodiment 1, add after interface modifier, the elongation at break of sample, shock strength have improved respectively 50%, 61.2%.Comparative example 3,4,5,6, and the performance difference of peroxide vulcanizing agent, resin system vulcanizing agent, sulphur system vulcanizing agent and compound system vulcanizing agent gained sample is little, and compound system vulcanizing agent slightly well.Compare with embodiment 7 with comparative example 1, the elongation at break of sample, shock strength have improved 16.2 times, 21.2 times.
Fig. 1 be comparative example 1, comparative example 2, embodiment 7 stress-strain(ed) curve (according to GB/T1040 ?2006 test).Elongation at break, the shock strength of polylactic acid plastic/rubber thermoplastic elastic body that as can be known from Fig. 1, prepared by employing present method obviously improve.
Comparison diagram 2, Fig. 3 draws (the Dutch PHILIPS Sirion200 of company type field emission scanning electron microscope, test condition: plating Au film, tube voltage 5.0kV), in embodiment 7 samples, the interface compatibility of poly(lactic acid) and rubber is better, and goods have good mechanical property.
(the Dutch PHILIPS Sirion200 of company type field emission scanning electron microscope, test condition: plating Au film, tube voltage 5.0kV) as can be seen from Figure 4, polylactic acid plastic phase and rubber phase form “ Hai ?extra large " structure.This is dispersed in plastics external phase and has the different of matter, this structure to make material have more excellent impact property with spheroidal particle from rubber phase.
The invention provides a kind of preparation simply, high tenacity with practical value, polylactic acid plastic/the rubber thermoplastic elastic body of flexibility, CN102276965B compares with Chinese invention patent, linking agent is resin system vulcanizing agent, sulphur system vulcanizing agent, peroxide vulcanizing agent or compound system vulcanizing agent, when vulcanization system is superoxide, in massfraction, superoxide account for rubber phase mass percent be 0.5 ?2.5%, poor for rubber and poly(lactic acid) consistency, during modification, add interface modifier to obtain good mechanical property, rubber is three leaf tree rubber, Chinese gutta percha, one or more in Guayule rubber, three leaf tree rubber, Chinese gutta percha, Guayule rubber all derives from plant, the milk of rubber tree secretion, through solidifying, the Hookean body of processing and making, the renewable natural resource with superior over-all properties.Especially have good elasticity, elastic extension can reach 1000%.The present invention suits development trend and the requirement of green, low-carbon (LC), environmental protection.
Claims (8)
1. dynamic vulcanization polylactic acid plastic/rubber thermoplastic elastic body, is characterized in that: according to the mass fraction, its raw material comprises following component:
Described poly(lactic acid) for poly-L ?lactic acid, poly-D ?one or more of lactic acid and poly-dl-lactide;
Described oxidation inhibitor is one or more in irgasfos 168, antioxidant 1076, antioxidant 1010, antioxidant 2246, oxidation inhibitor 1098, oxidation inhibitor B102, oxidation inhibitor B900 and anti-oxidant DLTP;
Described interface modifier is one or more in glycidyl methacrylate, epoxy natural rubber, zinc methacrylate, magnesinm methacrylate and maleic anhydride;
Described linking agent is one or more in resin system vulcanizing agent, sulphur system vulcanizing agent and peroxide vulcanizing agent;
Described additional crosslinker is one or both the mixture in epoxidization phenolic resin, isocyanic ester, trivinyl isocyanuric acid ester, three propenyl cyanurates.
2. dynamic vulcanization polylactic acid plastic/rubber thermoplastic elastic body according to claim 1, it is characterized in that: described resin system vulcanizing agent is comprised of resin and first kind activator, the consumption of resin is 3%～6% of rubber quality, the consumption of first kind activator is 0.5%～1.5% of rubber quality, described resin be SP ?1045, SZ ?2045,2402 and SP ?in 1055 one or more; Described first kind activator be in tin protochloride, iron protochloride and iron(ic) chloride one or more.
3. dynamic vulcanization polylactic acid plastic/rubber thermoplastic elastic body according to claim 1, it is characterized in that: described sulphur system vulcanizing agent is comprised of sulphur, Equations of The Second Kind activator and promotor, the consumption of sulphur is 1%～3.5% of rubber quality, the consumption of Equations of The Second Kind activator is 0.5%～3% of rubber quality, and the consumption of promotor is rubber quality 0.5%～1.5%; Described Equations of The Second Kind activator is zinc oxide and/or stearic acid; Described promotor is one or more in CZ, DM, TMTD and DZ.
4. dynamic vulcanization polylactic acid plastic/rubber thermoplastic elastic body according to claim 1, is characterized in that: described peroxide vulcanizing agent is superoxide, and the consumption of superoxide is rubber quality 0.5%～2.5%; Described superoxide be the benzoyl peroxide formic acid tertiary butyl, benzoyl peroxide, 2,4 ?dichlorobenzoperoxide, dicumyl peroxide, di-t-butyl peroxide, bis-?one or more in (tert-butyl hydroperoxide sec.-propyl) benzene and dibenzoyl peroxide.
5. dynamic vulcanization polylactic acid plastic/rubber thermoplastic elastic body according to claim 1, is characterized in that: described rubber is one or more in three leaf tree rubber, Chinese gutta percha and Guayule rubbers.
6. dynamic vulcanization polylactic acid plastic/rubber thermoplastic elastic body according to claim 1, is characterized in that: the raw material of described dynamic vulcanization polylactic acid plastic/rubber thermoplastic elastic body also comprises packing material; Described packing material is organic filler material or inorganic filling material; Described organic filler material is one or more in starch, maleic anhydride graft starch, xylogen, sisal fibers, nano micro crystal cellulose, bamboo fibers; Described inorganic filling material is one or more in silicon-dioxide, calcium carbonate, mica, talcum, clay, titanium oxide and carbon black; In mass fraction, the add-on of organic or inorganic packing material is 5～50 parts.
Claim 1 ?the preparation method of dynamic vulcanization polylactic acid plastic/rubber thermoplastic elastic body described in 5 any one, it is characterized in that, at the temperature of 150～190 ℃, poly(lactic acid), oxidation inhibitor, rubber and interface modifier are mixed, under high speed shear, add linking agent and additional crosslinker to carry out dynamic vulcanization to rubber phase, obtain polylactic acid plastic/rubber thermoplastic elastic body prepared by dynamic vulcanization.
8. the preparation method of dynamic vulcanization polylactic acid plastic/rubber thermoplastic elastic body claimed in claim 6, it is characterized in that, by packing material, be first to join in rubber and mix, at the temperature of 150～190 ℃, join in poly(lactic acid), oxidation inhibitor and interface modifier and mix, under high speed shear, add linking agent and additional crosslinker to carry out dynamic vulcanization to rubber phase; Or at the temperature of 150～190 ℃, after being mixed with natural rubber, poly(lactic acid) adds packing material, and add oxidation inhibitor and interface modifier to mix, under high speed shear, add linking agent and additional crosslinker to carry out dynamic vulcanization to rubber phase, obtain polylactic acid plastic/rubber thermoplastic elastic body prepared by dynamic vulcanization.
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