CN103642184B - Dynamic vulcanization polylactic acid plastic/rubber thermoplastic elastomer and preparation method thereof - Google Patents
Dynamic vulcanization polylactic acid plastic/rubber thermoplastic elastomer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses dynamic vulcanization polylactic acid plastic/rubber thermoplastic elastomer and preparation method thereof.According to the mass fraction, its raw material includes following components: polylactic acid 20～90 parts, rubber 10～80 parts, antioxidant 0.1～1 part, interface modifier 1～10 parts, cross-linking agent 0.1～4.8 parts, assistant crosslinking agent 0.1～4.2 parts；During preparation, at a temperature of 150～190 DEG C, by polylactic acid, antioxidant, rubber and interface modifier mix homogeneously, under high speed shear, add cross-linking agent, with assistant crosslinking agent, rubber is carried out dynamic vulcanization mutually, obtain polylactic acid plastic/rubber thermoplastic elastomer prepared by dynamic vulcanization.The polylactic acid plastic/rubber thermoplastic elastomer mechanical strength of gained of the present invention is high; there is the features such as the impact property of excellence, repeatable processing, can be widely used for the fields such as medical treatment, auto industry, agricultural production, packaging, clothing, information electronic industries, chemical industry, new forms of energy and environmental conservation.
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
Elastomer and preparation method thereof.
Background technology
The invention of petroleum-based plastics of 20th century is referred to as greatest invention, and petroleum-based plastics goods greatly facilitate the people's
Daily life, but the garbage after these products use is difficult to biodegradation, causes serious white pollution to the earth；Meanwhile,
Oil is non-renewable resources, exhaustive exploitation and use, and oneself makes petroleum resources close on exhaustion.Today, energy problem, environment are asked
Topic is increasingly subject to the concern of people.Searching can replace the environmentally friendly macromolecule reproducible, biodegradable of petroleum-based plastics
Material has caused the great interest of various countries material science worker.
Polylactic acid (PLA) is a kind of linear thermoplastic aliphatic's polyester, by renewable plant resources such as straw or corn
The lactic acid that fermentation obtains is chemically synthesized prepared complete biodegradable macromolecule.Catabolite carbon dioxide and water can return
Nature, rejoins in the photosynthesis of plant, so that tellurian Carbon cycle maintains balance.Break away from stone
The dependence of oil resource.Polylactic acid has superior physical property, and intensity, rigidity are high, transparency is good, have good biofacies
Capacitive, easily processing, the polylactic acid of different molecular weight is applicable to the various different processing technique such as blowing, thermoplastic, wire drawing, produces
The range of product is wide.But polylactic acid toughness, flexibility is poor, has notch sensitivity, and the notch impact strength of PLA is only
2.0～3.0kJ/m2, elongation at break is 2 10%, limits its application, in order to expand the application of PLA, and need to be to it
It is modified improving its toughness, flexibility.
Chinese invention patent CN102276965B uses peroxide to be initiator, natural rubber plasticizing polylactic acid.Wherein, poly-
Lactic acid is 70 95 parts, and natural rubber is 5 30 parts, and peroxide is 0.2 1 parts.But this patent there is problems in that 1,
Amount of peroxide is unreasonable, is calculated in mass percent, and peroxide accounts for rubber phase mass percent minimum 3.3%, the highest
Closely reach 20%, account for rubber rubber mass percent from embodiment 1 to embodiment 4 peroxide and be respectively 4%, 5%, 4%, 3.3%,
The peroxide of excess can cause polylactic acid to degrade, and finally affects the performance of product；2, vulcanizing system is excessively simple, and with mistake
Oxidation diisopropylbenzene (DIPB) is vulcanizing agent, and vulcanized article has abnormal flavour, affects the application of product.Chinese invention patent application CN
101864156A employing n-methylolacrylamide and acrylate copolymer toughened polydactyl acid, polylactic acid elongation at break,
The shortcomings such as impact strength has an improvement, but n-methylolacrylamide and acrylate copolymer complicated process of preparation, poor reproducibility.
Summary of the invention
Present invention aims to prior art and the defect of product existence, it is provided that a kind of dynamic vulcanization polylactic acid plastic/sky
So rubber thermoplastic elastic body and preparation method thereof, this thermoplastic elastomers has mechanical strength high, 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 elastomer: according to the mass fraction, its raw material includes following components:
Described polylactic acid is one or more of poly-L lactic acid, poly-D lactic acid and poly-dl-lactide；
Described antioxidant is irgasfos 168, antioxidant 1076, antioxidant 1010, antioxidant 2246, antioxidant 1098, resists
One or more in oxygen agent B102, antioxidant B900 and anti-oxidant DLTP；
Described interface modifier is glycidyl methacrylate, epoxy natural rubber, zinc methacrylate, metering system
One or more in acid magnesium and maleic anhydride；
Described cross-linking agent is one or more in resin system vulcanizing agent, sulfur system vulcanizing agent and peroxide vulcanizing agent；
Described assistant crosslinking agent is epoxidization phenolic resin, isocyanates, trivinyl isocyanuric acid ester, three acrylic cyanurates
In one or both mixture.
For realizing the object of the invention further, it is preferable that described resin system vulcanizing agent is made up of resin and first kind activator,
The consumption of resin is the 3%～6% of rubber quality, and the consumption of first kind activator is the 0.5%～1.5% of rubber quality, described tree
Fat is SP 1045, in SZ 2045,2402 and SP 1055 one or more；Described first kind activator is stannous chloride, chlorine
Change one or more in ferrous iron and iron chloride.
Described sulfur system vulcanizing agent is made up of sulfur, Equations of The Second Kind activator and accelerator, and the consumption of sulfur is rubber quality
1%～3.5%, the consumption of Equations of The Second Kind activator is the 0.5%～3% of rubber quality, the consumption of accelerator be rubber quality 0.5%～
1.5%；Described Equations of The Second Kind activator is zinc oxide and/or stearic acid；Described accelerator is in CZ, DM, TMTD and DZ
One or more.
Described peroxide vulcanizing agent is peroxide, and the consumption of peroxide is the 0.5%～2.5% of rubber quality；Described mistake
Oxide be the perbenzoic acid tert-butyl group, benzoyl peroxide, 2,4 dichlorobenzoperoxides, cumyl peroxide,
One or more in di-t-butyl peroxide, two (t-butylperoxyisopropyl) benzene and dibenzoyl peroxide.
Described rubber is one or more in SANYE tree rubber, gutta percha and Guayule rubber.
The raw material of described dynamic vulcanization polylactic acid plastic/rubber thermoplastic elastomer also includes packing material；Described packing material is
Organic filler material or inorganic filling material；Described organic filler material is starch, maleic anhydride graft starch, lignin, sword
One or more in flaxen fiber, nano micro crystal cellulose, bamboo fibre；Described inorganic filling material be silicon dioxide, calcium carbonate,
One or more in Muscovitum, Talcum, clay, titanium oxide and white carbon black；In terms of mass fraction, organic or inorganic packing material
Addition is 5～50 parts.
The preparation method of described dynamic vulcanization polylactic acid plastic/rubber thermoplastic elastomer: at a temperature of 150～190 DEG C, will
Polylactic acid, antioxidant, rubber and interface modifier mix homogeneously, add cross-linking agent and assistant crosslinking agent to rubber under high speed shear
Carry out dynamic vulcanization mutually, obtain polylactic acid plastic/rubber thermoplastic elastomer prepared by dynamic vulcanization.
The another kind of preparation method of described dynamic vulcanization polylactic acid plastic/rubber thermoplastic elastomer: be first to add by packing material
Enter in rubber mix homogeneously, at a temperature of 150～190 DEG C, join in polylactic acid, antioxidant and interface modifier and mix
Uniformly, under high speed shear, add cross-linking agent and assistant crosslinking agent and rubber is carried out mutually dynamic vulcanization；Or at 150～190 DEG C
At a temperature of, add packing material after being mixed homogeneously with natural rubber by polylactic acid, and add antioxidant and interface modifier mixing all
Even, under high speed shear, add cross-linking agent, with assistant crosslinking agent, rubber is carried out dynamic vulcanization mutually, obtain poly-breast prepared by dynamic vulcanization
Acid plastics/rubber thermoplastic elastic body.
Relative to prior art, present invention have the advantage that
1) the dynamic vulcanization polylactic acid plastic/rubber thermoplastic elastomer that the present invention obtains is with polylactic acid plastic, vegetable rubber
Excellent properties, there is mechanical strength high, the feature such as excellent impact property, repeatable processing, can be widely used for medical treatment, vapour
The fields such as turner industry, agricultural production, packaging, clothing, information electronic industries, chemical industry, new forms of energy and environmental conservation.
2) interface modifier that the present invention uses at least contains a function key, during dynamic vulcanization, peroxide cross-linking agent
While decomposition generation free radical causes natural rubber to crosslink, it is also possible to cause interface modifier to participate in radical polymerization
In.Interface modifier and polylactic acid plastic continuous phase have the good compatibility, then rubber phase and two phase boundaries of polylactic acid plastic
Face then forms transition zone, strengthens rubber phase and the compatibility of plastics phase and interfacial adhesion.The addition of interface modifier and dynamic sulfur
Change technology improves incompatibility intrinsic between polylactic acid plastic and natural rubber, compared with polylactic acid plastic natural rubber, this
Polylactic acid plastic/natural rubber the thermoplastic elastomers of invention preparation has the preferable compatibility and properties of product.
3) the repeatable processing of the thermoplastic elastomer (TPE) of the present invention uses, and can use general method for processing forming, molding
Processing unit (plant) is shaped processing, and contour machining equipment is commonly used, and power consumption of polymer processing is low, and processing technique is simple, can be according to using mesh
The goods being shaped to arbitrary shape.
4) present invention uses dynamic vulcanization to prepare thermoplastic elastomer (TPE), under shear action, adds cross-linking agent and assistant crosslinking agent pair
Natural rubber is carried out in situ sulfuration, makes material have more preferable mechanical performance.
5) present invention provides a kind of and prepares high tenacity simple, with practical value, the polylactic acid plastic/rubber thermoplastic of flexibility
Elastomer, compared with Chinese invention patent CN102276965B, cross-linking agent be resin system vulcanizing agent, sulfur system vulcanizing agent,
Peroxide vulcanizing agent or compound system vulcanizing agent, when vulcanizing system is peroxide, in terms of mass fraction, peroxide accounts for rubber
Glue phase mass percent is 0.5 2.5%, for rubber and polylactic acid poor compatibility, adds interface modifier to obtain relatively time modified
Good mechanical property, rubber is one or more in SANYE tree rubber, gutta percha, Guayule rubber, SANYE tree rubber, Du
Secondary rubber, Guayule rubber all derive from plant, the milk of rubber tree secretion, the elastic solid (Hookean body) prepared through solidification, processing, tool
There are the renewable natural resources of superior combination property.Especially having good elasticity, elastic extension is up to 1000%.This
Bright suit green, low-carbon (LC), the development trend of environmental protection and requirement.
Accompanying drawing explanation
Fig. 1 is comparative example 1, comparative example 2, the stress-strain diagram of embodiment 7.
Fig. 2 is the scanning electron microscope diagram sheet in embodiment 7 thermoplastic elastomer (TPE) brittle failure face.
Fig. 3 is the scanning electron microscope diagram sheet in comparative example 2 brittle failure face.
Fig. 4 is embodiment 7 thermoplastic elastomer (TPE) scanning electron microscope diagram sheet after chloroform etches.
Detailed description of the invention
For being more fully understood that the present invention, the present invention will be further described with embodiment below in conjunction with the accompanying drawings, but needs explanation
It is that embodiment is not intended that the restriction to claimed scope.Embodiment the most all exists with polylactic acid in comparative example
70 degree of drying baker are dried 6 hours.
Embodiment 1
Choosing polylactic acid is matrix resin (Zhejiang Hisun Biomaterials Co., Ltd, poly-dl-lactide (PDLLA)), sky
So rubber is general basis rubber (SANYE tree rubber Malaysia 1#, Guangzhou rubber industry institute).First in mill
Upper natural rubber (20g) is plasticated.By polylactic acid (180g), it is 160 DEG C that antioxidant 1010 (0.4g) joins temperature, turns
In the Haake torque rheometer of rotor speed 60r/min, adding natural rubber after 5min, interface modifier Glycidyl methacrylate is sweet
Grease (6g), adds cross-linking agent two (t-butylperoxyisopropyl) benzene (0.2g) and assistant crosslinking agent epoxy after mixing 3min
Change phenolic resin (0.2g) and carry out dynamic vulcanization, continue 5min, discharging are blended.It is fine uniform with disintegrating machine by sample broke
Granule, be then injection molded into standard batten with single screw injection molding machine.The injection temperature of single screw injection molding machine is: feeding section
165 DEG C, 170 DEG C, compression section, homogenizing zone 170 DEG C, machine head port mould part 175 DEG C, screw speed is 90r/min.
Embodiment 2
Choosing polylactic acid is matrix resin (Zhejiang Hisun Biomaterials Co., Ltd, poly-dl-lactide (PDLLA)), sky
So rubber is general basis rubber (SANYE tree rubber Malaysia 1#, Guangzhou rubber industry institute).First in mill
Upper natural rubber (40g) is plasticated.By polylactic acid (160g), it is 190 DEG C that irgasfos 168 (2g) joins temperature, rotor
In the Haake torque rheometer of rotating speed 60r/min, addition natural rubber after 5min, interface modifier epoxidation natural gum (10g),
Add cross-linking agent di-t-butyl peroxide (0.6g) after mixing 3min and assistant crosslinking agent isocyanates (8.4g) carry out dynamic vulcanization,
Continue 5min, discharging are blended.It is the granule of fine uniform with disintegrating machine by sample broke, then with single screw injection molding machine injection
It is shaped to standard batten.The injection temperature of single screw injection molding machine is: feeding section 165 DEG C, 170 DEG C, compression section, homogenizing zone 170
DEG C, machine head port mould part 175 DEG C, screw speed is 90r/min.
Embodiment 3
Choosing polylactic acid is matrix resin (Zhejiang Hisun Biomaterials Co., Ltd, poly-dl-lactide (PDLLA)), sky
So rubber is general basis rubber (SANYE tree rubber Malaysia 1#, Guangzhou rubber industry institute).First in mill
Upper natural rubber (60g) is plasticated.By polylactic acid (140g), it is 170 DEG C that antioxidant 1076 (1.5g) joins temperature, turns
In the Haake torque rheometer of rotor speed 60r/min, addition elastomeric compound after 5min, interface modifier zinc methacrylate (6g),
Add cross-linking agent cumyl peroxide (0.9g) after mixing 3min and assistant crosslinking agent three acrylic cyanurate (1.1g) is carried out
Dynamic vulcanization, continues 5min, discharging are blended.It is the granule of fine uniform with disintegrating machine by sample broke, then with single screw rod
Injection machine is injection molded into standard batten.The injection temperature of single screw injection molding machine is: feeding section 165 DEG C, 170 DEG C, compression section,
Homogenizing zone 170 DEG C, machine head port mould part 175 DEG C, screw speed is 90r/min.
Embodiment 4
Choosing polylactic acid is matrix resin (Zhejiang Hisun Biomaterials Co., Ltd, poly-dl-lactide (PDLLA)), sky
So rubber is general basis rubber (SANYE tree rubber Malaysia 1#, Guangzhou rubber industry institute).First in mill
Upper natural rubber (60g) is plasticated.By polylactic acid (140g), it is 170 DEG C that anti-oxidant DLTP (0.2g) joins temperature, turns
In the Haake torque rheometer of rotor speed 60r/min, after 5min, add elastomeric compound, interface modifier methyl propenoic acid glycidyl
Ester (6g), adds resin 2402(3g after mixing 3min), stannous chloride (0.6g) and assistant crosslinking agent epoxidization phenolic resin
(1.1g) carry out dynamic vulcanization, continue 5min, discharging are blended.It is the granule of fine uniform with disintegrating machine by sample broke, so
It is injection molded into standard batten afterwards with single screw injection molding machine.The injection temperature of single screw injection molding machine is: feeding section 165 DEG C, compression
Section 170 DEG C, homogenizing zone 170 DEG C, machine head port mould part 175 DEG C, screw speed is 90r/min.
Embodiment 5
Choosing polylactic acid is matrix resin (Zhejiang Hisun Biomaterials Co., Ltd, poly-dl-lactide (PDLLA)), sky
So rubber is general basis rubber (SANYE tree rubber Malaysia 1#, Guangzhou rubber industry institute).First in mill
Upper natural rubber (60g) is plasticated.By polylactic acid (140g), it is 170 DEG C that antioxidant 1010 (1g) joins temperature, rotor
In the Haake torque rheometer of rotating speed 60r/min, after 5min, add elastomeric compound, interface modifier glycidyl methacrylate
(6g), after mixing 3min, sulfur (1.5g), zinc oxide (1.2g), stearic acid (0.6g), CZ(0.3g are added) DM(0.2g),
Assistant crosslinking agent epoxidization phenolic resin (1.1g) carries out dynamic vulcanization, continues 5min, discharging are blended.With disintegrating machine, sample is broken
The broken granule for fine uniform, is then injection molded into standard batten with single screw injection molding machine.The injection temperature of single screw injection molding machine
For: feeding section 165 DEG C, 170 DEG C, compression section, homogenizing zone 170 DEG C, machine head port mould part 175 DEG C, screw speed is 90r/min.
Embodiment 6
Choosing polylactic acid is matrix resin (Zhejiang Hisun Biomaterials Co., Ltd, poly-dl-lactide (PDLLA)), sky
So rubber is general basis rubber (SANYE tree rubber Malaysia 1#, Guangzhou rubber industry institute).First in mill
Upper natural rubber (60g) mixing with filler starch (10g) uniform become elastomeric compound.By polylactic acid (140g), antioxidant 1010
(2g) joining temperature is 170 DEG C, in the Haake torque rheometer of rotor speed 60r/min, adds elastomeric compound after 5min,
Interface modifier glycidyl methacrylate (6g), mixing 3min after add sulfur (0.7g), zinc oxide (0.6g),
Stearic acid (0.3g), CZ(0.15g) DM(0.1g), resin 2402(2.5g), stannous chloride (0.1g), assistant crosslinking agent three
Vinyl isocyanuric acid ester (1.1g) carries out dynamic vulcanization, continues 5min, discharging are blended.It is thin with disintegrating machine by sample broke
Little uniform granule, is then injection molded into standard batten with single screw injection molding machine.The injection temperature of single screw injection molding machine is: add
Material section 165 DEG C, 170 DEG C, compression section, homogenizing zone 170 DEG C, machine head port mould part 175 DEG C, screw speed is 90r/min.
Embodiment 7
Choosing polylactic acid is matrix resin (Zhejiang Hisun Biomaterials Co., Ltd, poly-dl-lactide (PDLLA)), sky
So rubber is general basis rubber (SANYE tree rubber Malaysia 1#, Guangzhou rubber industry institute).First in mill
Upper natural rubber (80g) is plasticated.By polylactic acid (120g), it is 150 DEG C that antioxidant 1010 (0.8g) joins temperature, turns
In the Haake torque rheometer of rotor speed 60r/min, adding natural rubber after 5min, interface modifier Glycidyl methacrylate is sweet
Grease (10g), adds vulcanizing agent two (t-butylperoxyisopropyl) benzene (1.2g) and assistant crosslinking agent ring after mixing 3min
Oxidation phenolic resin (0.8g) carries out dynamic vulcanization, continues 5min, discharging are blended.It is tiny all with disintegrating machine by sample broke
Even granule, is then injection molded into standard batten with single screw injection molding machine.The injection temperature of single screw injection molding machine is: feeding section
165 DEG C, 170 DEG C, compression section, homogenizing zone 170 DEG C, machine head port mould part 175 DEG C, screw speed is 90r/min.
Embodiment 8
Choosing polylactic acid is matrix resin (Zhejiang Hisun Biomaterials Co., Ltd, poly-dl-lactide (PDLLA)), sky
So rubber is general basis rubber (SANYE tree rubber Malaysia 1#, Guangzhou rubber industry institute).First in mill
Upper natural rubber (100g) is plasticated.By polylactic acid (100g), it is 170 DEG C that antioxidant 1010 (1g) joins temperature, turns
In the Haake torque rheometer of rotor speed 60r/min, after 5min, add natural rubber, filler clay (60g), interface modifier
Glycidyl methacrylate (7g), adds vulcanizing agent two (t-butylperoxyisopropyl) benzene (1.2g) after mixing 3min
Carry out dynamic vulcanization with assistant crosslinking agent epoxidization phenolic resin (1g), continue 5min, discharging are blended.Melt in 150 DEG C of mills
Melt, hot-forming on vulcanizing press, thickness of sample about 1mm, it is cut into standard batten.
Embodiment 9
Choosing polylactic acid is matrix resin (Zhejiang Hisun Biomaterials Co., Ltd, poly-dl-lactide (PDLLA)),
Natural rubber is general basis rubber (SANYE tree rubber Malaysia 1#, Guangzhou rubber industry institute).First in mill
On machine, natural rubber (120g) is plasticated.By polylactic acid (80g), it is 180 DEG C 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), boundary
Face modifying agent maleic anhydride (19g), adds vulcanizing agent two (t-butylperoxyisopropyl) benzene (1.7g) after mixing 3min
Carry out dynamic vulcanization with assistant crosslinking agent epoxidization phenolic resin (1.1g), continue 5min, discharging are blended.In 150 DEG C of mills
Melted, hot-forming on vulcanizing press, thickness of sample about 1mm, it is cut into standard batten.
Embodiment 10
Choosing polylactic acid is matrix resin (Zhejiang Hisun Biomaterials Co., Ltd, poly-dl-lactide (PDLLA)),
Natural rubber is general basis rubber (SANYE tree rubber Malaysia 1#, Guangzhou rubber industry institute).First in mill
On machine, natural rubber (140g) is plasticated.By polylactic acid (60g), it is 170 DEG C that antioxidant (1g) joins temperature, and rotor turns
In the Haake torque rheometer of speed 60r/min, add natural rubber, interface modifier metering system zinc (9g) after 5min, mix
Vulcanizing agent two (t-butylperoxyisopropyl) benzene (1.7g) and assistant crosslinking agent epoxidization phenolic resin (1.1g) is added after closing 3min
Carry out dynamic vulcanization, continue 5min, discharging are blended.Melt in 150 DEG C of mills, hot-forming on vulcanizing press, sample
Product thickness about 1mm, is cut into standard batten.
Embodiment 11
Choosing polylactic acid is matrix resin (Zhejiang Hisun Biomaterials Co., Ltd, poly-dl-lactide (PDLLA)), sky
So rubber is general basis rubber (SANYE tree rubber Malaysia 1#, Guangzhou rubber industry institute).First in mill
Upper natural rubber (160g) is plasticated.By polylactic acid (40g), it is 190 DEG C that antioxidant 1010 (1.6g) joins temperature, turns
In the Haake torque rheometer of rotor speed 60r/min, adding natural rubber after 5min, interface modifier Glycidyl methacrylate is sweet
Grease (20g), adds vulcanizing agent two (t-butylperoxyisopropyl) benzene (2.5g) and assistant crosslinking agent ring after mixing 3min
Oxidation phenolic resin (1.5g) carries out dynamic vulcanization, continues 5min, discharging are blended.Melt in 150 DEG C of mills, at flat board
On vulcanizer hot-forming, thickness of sample about 1mm, be cut into standard batten.
Comparative example 1
Choosing polylactic acid is matrix resin (Zhejiang Hisun Biomaterials Co., Ltd, poly-dl-lactide (PDLLA)), will
Polylactic acid (230g), it is 170 DEG C that antioxidant 1010 (0.46g) joins temperature, the Haake torque of rotor speed 60r/min
5min, discharging are blended in flow graph.It is the granule of fine uniform with disintegrating machine by sample broke, then with single screw injection molding machine
It is injection molded into standard batten.The injection temperature of single screw injection molding machine is: feeding section 165 DEG C, 170 DEG C, compression section, homogenizing zone
170 DEG C, machine head port mould part 175 DEG C, screw speed is 90r/min.
Comparative example 2(Chinese patent CN102276965B embodiment 2)
Choosing polylactic acid is matrix resin (Zhejiang Hisun Biomaterials Co., Ltd, poly-dl-lactide (PDLLA)), sky
So rubber is general basis rubber (SANYE tree rubber Malaysia 1#, Guangzhou rubber industry institute).First in mill
Upper natural rubber (20g) is plasticated.By polylactic acid (180g), it is 160 DEG C that natural rubber joins temperature, rotor speed 70r/min
Haake torque rheometer in, after 4min add cumyl peroxide (1g), continue be blended 6min, discharging.Use disintegrating machine
It is the granule of fine uniform by sample broke, is then injection molded into standard batten with single screw injection molding machine.Single screw injection molding machine
Injection temperature is: feeding section 165 DEG C, 170 DEG C, compression section, homogenizing zone 170 DEG C, machine head port mould part 175 DEG C, screw speed
For 90r/min.
Comparative example 1～2 and the performance of embodiment 1～11 be shown in Table 1.Extension test is according to GB/T1040 2006(comparative example
1～2 and embodiment 1～7), GB/T528 1998(implement 8～11) standard, shock-testing according to GB/T1843 2008 standard,
Tear test is according to GB/T529 standard.
Table 1
| Title | Elongation at break (%) | Impact strength (kj/m2) | Tearing 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 | |
| Embodiment 5 | 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 table 1 it can be seen that according to comparative example 2 and embodiment 1, after adding interface modifier, the elongation at break of sample,
Impact strength has been respectively increased 50%, 61.2%.Comparative example 3,4,5,6, peroxide vulcanizing agent, resin system sulfur
The performance difference of agent, sulfur system vulcanizing agent and compound system vulcanizing agent gained sample is little, and compound system vulcanizing agent is the best.
Compared with comparative example 1 and embodiment 7, the elongation at break of sample, impact strength improve 16.2 times, 21.2 times.
Fig. 1 is the stress-strain diagram (testing according to GB/T1040 2006) of comparative example 1, comparative example 2, embodiment 7.From
Understanding in Fig. 1, the elongation at break of polylactic acid plastic/rubber thermoplastic elastomer, impact strength prepared by employing this method are bright
Aobvious raising.
Comparison diagram 2, Fig. 3 draw (Holland PHILIPS company Sirion200 type field emission scanning electron microscope, test condition:
Plating Au film, tube voltage 5.0kV), in embodiment 7 sample, polylactic acid is more preferable with the interface compatibility of rubber, and goods have well
Mechanical property.
(Holland's PHILIPS company Sirion200 type field emission scanning electron microscope, test condition: plating as can be seen from Figure 4
Au film, tube voltage 5.0kV), polylactic acid plastic phase and rubber form " Hai Hai " structure mutually.This with rubber with spheroidal particle
Being dispersed in the difference having matter in plastics continuous phase, this structure makes material have more excellent impact property.
The present invention provides a kind of and prepares high tenacity simple, with practical value, the polylactic acid plastic/rubber thermoplastic bullet of flexibility
Gonosome, compared with Chinese invention patent CN102276965B, cross-linking agent be resin system vulcanizing agent, sulfur system vulcanizing agent,
Peroxide vulcanizing agent or compound system vulcanizing agent, when vulcanizing system is peroxide, in terms of mass fraction, peroxide accounts for rubber
Glue phase mass percent is 0.5 2.5%, for rubber and polylactic acid poor compatibility, adds interface modifier to obtain relatively time modified
Good mechanical property, rubber is one or more in SANYE tree rubber, gutta percha, Guayule rubber, SANYE tree rubber, Du
Secondary rubber, Guayule rubber all derive from plant, the milk of rubber tree secretion, the elastic solid (Hookean body) prepared through solidification, processing, tool
There are the renewable natural resources of superior combination property.Especially having good elasticity, elastic extension is up to 1000%.This
Bright suit green, low-carbon (LC), the development trend of environmental protection and requirement.
Claims (8)
1. a dynamic vulcanization polylactic acid plastic/rubber thermoplastic elastomer, it is characterised in that: according to the mass fraction, it is former
Material includes following components:
Described polylactic acid is one or more of poly-L lactic acid, poly-D lactic acid and poly-dl-lactide；
Described antioxidant be irgasfos 168, antioxidant 1076, antioxidant 1010, antioxidant 2246, antioxidant 1098,
One or more in antioxidant B102, antioxidant B900 and anti-oxidant DLTP；
Described interface modifier is glycidyl methacrylate, epoxy natural rubber, zinc methacrylate, methyl-prop
One or more in olefin(e) acid magnesium and maleic anhydride；
Described cross-linking agent is one or more in resin system vulcanizing agent, sulfur system vulcanizing agent and peroxide vulcanizing agent；
Described assistant crosslinking agent is epoxidization phenolic resin, isocyanates, trivinyl isocyanuric acid ester, three acrylic cyanurate
One or both mixture in ester；
During preparation, at a temperature of 150～190 DEG C, by polylactic acid, antioxidant, rubber and interface modifier mix homogeneously,
Under high speed shear, add cross-linking agent, with assistant crosslinking agent, rubber is carried out dynamic vulcanization mutually, obtain polylactic acid prepared by dynamic vulcanization
Plastics/rubber thermoplastic elastic body.
Dynamic vulcanization polylactic acid plastic/rubber thermoplastic elastomer the most according to claim 1, it is characterised in that: institute
Stating resin system vulcanizing agent to be made up of resin and first kind activator, the consumption of resin is the 3%～6% of rubber quality, the first kind
The consumption of activator is the 0.5%～1.5% of rubber quality, and described resin is SP 1045, SZ 2045,2402 and SP 1055
In one or more；Described first kind activator is one or more in stannous chloride, ferrous chloride and iron chloride.
Dynamic vulcanization polylactic acid plastic/rubber thermoplastic elastomer the most according to claim 1, it is characterised in that: institute
State sulfur system vulcanizing agent to be made up of sulfur, Equations of The Second Kind activator and accelerator, the consumption of sulfur be rubber quality 1%～
3.5%, the consumption of Equations of The Second Kind activator is the 0.5%～3% of rubber quality, the consumption of accelerator be rubber quality 0.5%～
1.5%；Described Equations of The Second Kind activator is zinc oxide and/or stearic acid；Described accelerator is in CZ, DM, TMTD and DZ
One or more.
Dynamic vulcanization polylactic acid plastic/rubber thermoplastic elastomer the most according to claim 1, it is characterised in that: institute
Stating peroxide vulcanizing agent is peroxide, and the consumption of peroxide is the 0.5%～2.5% of rubber quality；Described peroxide
For the perbenzoic acid tert-butyl group, benzoyl peroxide, 2,4 dichlorobenzoperoxides, cumyl peroxide, peroxidating
One or more in di-t-butyl, two (t-butylperoxyisopropyl) benzene and dibenzoyl peroxide.
Dynamic vulcanization polylactic acid plastic/rubber thermoplastic elastomer the most according to claim 1, it is characterised in that: institute
Stating rubber is one or more in SANYE tree rubber, gutta percha and Guayule rubber.
Dynamic vulcanization polylactic acid plastic/rubber thermoplastic elastomer the most according to claim 1, it is characterised in that: institute
The raw material stating dynamic vulcanization polylactic acid plastic/rubber thermoplastic elastomer also includes packing material；Described packing material is organic filling out
Fill material or inorganic filling material；Described organic filler material is starch, maleic anhydride graft starch, lignin, Folium Agaves Sisalanae fibre
One or more in dimension, nano micro crystal cellulose, bamboo fibre；Described inorganic filling material be silicon dioxide, calcium carbonate,
One or more in Muscovitum, Talcum, clay, titanium oxide and white carbon black；In terms of mass fraction, organic or inorganic packing material
Addition be 5～50 parts.
7. the preparation method of the dynamic vulcanization polylactic acid plastic/rubber thermoplastic elastomer described in any one of claim 15,
It is characterized in that, at a temperature of 150～190 DEG C, by polylactic acid, antioxidant, rubber and interface modifier mix homogeneously,
Under high speed shear, add cross-linking agent, with assistant crosslinking agent, rubber is carried out dynamic vulcanization mutually, obtain polylactic acid prepared by dynamic vulcanization
Plastics/rubber thermoplastic elastic body.
8. the preparation method of the dynamic vulcanization polylactic acid plastic/rubber thermoplastic elastomer described in claim 6, its feature exists
In, it is to be charged first to mix homogeneously in rubber by packing material, at a temperature of 150～190 DEG C, joins polylactic acid, resist
Mix homogeneously in oxygen agent and interface modifier, adds cross-linking agent and assistant crosslinking agent under high speed shear and rubber carries out dynamic sulfur mutually
Change；Or at a temperature of 150～190 DEG C, add packing material after being mixed homogeneously with natural rubber by polylactic acid, and add
Enter antioxidant and interface modifier mix homogeneously, under high speed shear, add cross-linking agent with assistant crosslinking agent, rubber is carried out dynamically mutually
Sulfuration, obtains polylactic acid plastic/rubber thermoplastic elastomer prepared by dynamic vulcanization.
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| CN110435170B (en) * | 2019-08-12 | 2021-04-13 | 南京林业大学 | Modification method for improving shape memory performance of gutta percha |
| CN111423544A (en) * | 2020-05-23 | 2020-07-17 | 青岛科技大学 | High-toughness polylactic acid |
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| CN114058164B (en) * | 2021-04-09 | 2022-06-28 | 中国科学院兰州化学物理研究所 | Polylactic acid bio-based shape memory thermoplastic elastomer and preparation method and application thereof |
| CN113201211A (en) * | 2021-06-15 | 2021-08-03 | 安徽展业塑胶制品有限公司 | Composite dynamic cross-linked polylactic acid/natural rubber/starch elastomer and preparation method thereof |
| CN113265132A (en) * | 2021-06-15 | 2021-08-17 | 安徽展业塑胶制品有限公司 | Composite dynamic cross-linked PLA/PBS/NR/starch elastomer and preparation method thereof |
| CN117511152B (en) * | 2023-11-03 | 2024-07-02 | 江苏万航新材料有限公司 | Environment-friendly polylactic acid plastic and preparation method and application thereof |
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