CN109535673A - A kind of heat-proof impact-resistant high transparency lactic acid composite material and preparation method thereof - Google Patents
A kind of heat-proof impact-resistant high transparency lactic acid composite material and preparation method thereof Download PDFInfo
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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- C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2453/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
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- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
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- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
Abstract
The present invention relates to a kind of heat-proof impact-resistant high transparency lactic acid composite materials and preparation method thereof, composite material includes the component of following parts by weight: 100 parts of polylactic acid, 1-5 parts of toughener, 0.1-0.5 parts of chain extenders, 0.01-1 parts of crystallization nucleating agents, 0.01-0.05 parts of crystallization promoters, 0.1-3 parts of antistatic agents, the polylactic acid are multi-arm branched polylactic acid.Compared with conventional straight chain poly lactic acid resin, the polylactic acid probability that the long interchain of macromolecular can be intertwined in the molten state after branching is higher, and the intensity mutually wound is also bigger, toughener is used in conjunction with each other with chain extender simultaneously, considerably increase the toughness of polylactic acid, the synergistic effect of crystallization nucleating agent and crystallization promoter, make poly-lactic acid material while obtaining high temperature tolerance, also assure its transparency, bis- (beta-hydroxyethyl) coco amines are as antistatic agent, the antistatic property for substantially improving polylactic acid can be applicable to and take out on tableware.
Description
Technical field
The present invention relates to a kind of heat-proof impact-resistant high transparency lactic acid composite materials and preparation method thereof, belong to high molecular material
Technical field.
Background technique
In recent years, as online food and drink carryout service flourishes, carryout is bringing great convenience to people's life
While, following a large amount of packagings of taking out cause very big pollution to environment.Currently, plastics cutlery box, tableware main product
Main component be polypropylene, polypropylene has many advantages, such as that low in cost, production is easy, functional, but its non-degradable, existing
Have become one of the major pollutants for causing " white pollution ".In face of the environmental pollution to increasingly sharpen, need to find it is environmental-friendly,
The material of fully biodegradable removes substitution polypropylene.
Polylactic acid is a kind of thermoplastic resin from renewable plant resources such as corn, cassava, sugarcanes, and being can be complete
Biodegradable high molecular material, while polylactic acid also has the brilliant transparency, excellent processing forming, stable melt
Intensity can be processed to sheet material, then the products such as cutlery box, pallet, cup lid are made through plastic uptake, to be applied to take-away industry.
But polylactic acid, as a kind of linear type aliphatic polyester, material thermal resistance is insufficient, especially toughness is insufficient, rigidity is big, brittleness
Greatly, it easily cracks during machine-shaping, while crazing phenomenon occurs, so that can not stablize, continuous article of manufacture,
The above deficiency seriously constrains polylactic acid in the application of blister packaging arts.Therefore, it is necessary to change to polylactic resin
Property to improve its form insufficient problem.
In order to improve the heat resistance and toughness of polylactic acid article, while guaranteeing the high transparency of product, scientific research personnel is to changing
Property polylactic resin has carried out a large amount of R&D work, is exemplified below:
Document number is that the patent of CN101983986B discloses a kind of transparent polylactic resin and its preparation side with toughening
Method, this method are blended prilling process with toughener, plasticizer and antioxidant using polylactic acid and polylactic acid modified resin are made, mention
The high tension fracture elongation rate and impact strength of polylactic acid, maintains the transparency of polylactic acid, but its heat resistance is insufficient, also
It is far from satisfying the demand in packing articles field；
The patent that document number is CN104312121B discloses a kind of transparent polylactic acid film of high tenacity and preparation method thereof,
Toughener by using the network-like polyester polyols copolymer from synthesis as polylactic resin, along with the association of heat stabilizer
It helps, so that polylactic acid modified resin has good toughness, and the transparency is excellent, but its heat resistance does not get a promotion；
The patent that document number is CN105062024A discloses a kind of high transparency high-temperature resistant lactic acid composite material and its system
Preparation Method is blended by using polylactic acid, toughener, crystallization nucleating agent, stabilisers against hydrolysis, lubricant and is granulated, improves poly-
The transparency of lactic acid, temperature tolerance and hydrolytic stability, but its impact strength promoted and it is little, plastic-adsorption lunch box system can not be applied to
Product；
Document number discloses a kind of for blowing the polylactic resin of transparency and heat-proof bottle for the patent of CN106633727A
Composition realizes the height of product by using the elastic body toughening modifying agent of poly (l-lactic acid), inorganic filler and core-shell structure
Heat resistance can be applied suitable for the product of blowing technology, but the light transmittance of its modified polylactic acid material only has 80%,
And its impact resilience is not also embodied well.
Foregoing invention patent to polylactic resin in terms of the transparency, heat resistance, impact resilience all respectively carried out improve and
It improves, but combines the transparency, heat resistance, impact resilience without a modified polylactic resin, be far from satisfying packing timber
The requirement of material field based article needs research and prepares a kind of heat-proof impact-resistant high transparency lactic acid composite material.
Summary of the invention
The technical problem to be solved by the present invention is for solve existing modified polylactic resin cannot combine the transparency,
The technical issues of heat resistance, impact resilience, provides a kind of heat-proof impact-resistant high transparency lactic acid composite material and preparation method thereof.
The technical solution adopted by the present invention to solve the technical problems is:
A kind of heat-proof impact-resistant high transparency lactic acid composite material, the component including following parts by weight: 100 parts of polylactic acid, 1-5
Part toughener, 0.1-0.5 parts of chain extenders, 0.01-1 parts of crystallization nucleating agents, 0.01-0.05 parts of crystallization promoters, 0.1-3 parts resist it is quiet
Electric agent；The polylactic acid is multi-arm branched polylactic acid, and the number-average molecular weight of the polylactic acid is 50,000~200,000, every arm
Number-average molecular weight is 0.2 ten thousand -1 ten thousand.
Preferably, the polylactic acid is the polylactic acid of three arm branchings, and the polylactic acid has following structural formula, wherein n
For 50-1000,
Preferably, melt index of the polylactic acid at 190 DEG C of temperature and load 2.16kg pressure is 2g/10min-
50g/10min, fusing point are 120 DEG C -180 DEG C.
Preferably, the toughener be poly butylene succinate, poly-epsilon-caprolactone, ethylene vinyl acetate copolymer,
One of oil-filled Styrene-Butadiene-Styrene Block Copolymer is a variety of.
Preferably, the oil-filled Styrene-Butadiene-Styrene Block Copolymer is that s-B-S is embedding
The weight ratio of the blend of section copolymer and white oil, the Styrene-Butadiene-Styrene Block Copolymer and white oil is 2: 3-
3∶2。
Preferably, the chain extender is that Styrene-Methyl Methacrylate-Methacrylic Acid ethylene oxidic ester ternary is random
Copolymer, ethylene glycol dimethacrylate, styrene-acrylonitrile-glycidyl methacrylate ternary atactic copolymer
One of or it is a variety of.
Preferably, the crystallization nucleating agent is poly- D lactic acid, 4,6- di-tert-butyl based phosphates, 1,3,5- n-butylbenzenes
One of trimethamide is a variety of, and the poly- D lactic acid is the powder of -3000 mesh of 300 mesh of mesh number.
Preferably, the crystallization promoter is 1,3:2,4- bis- (3,4- dimethyl) benzylidene sorbitol acetal, tri- Benzyl base fork
One of propyl ether dibasic acid esters hexanol, neopentyl ethylene glycol Biphenyl Ester are a variety of.
Preferably, the antistatic agent is bis- (beta-hydroxyethyl) coco amines.
The present invention also provides a kind of preparation method of heat-proof impact-resistant high transparency lactic acid composite material, preparation step is as follows:
By dry polylactic acid, toughener, chain extender, crystallization nucleating agent, crystallization promoter, antistatic agent is blended uniformly,
Raw material must be premixed；
Premix raw material is added twin-screw extrude into mixing, extrusion, granulation, then pellet is dried, obtains drying pellet；
Injection molding machine is added in drying pellet and carries out injection molding.
Preferably, the drying means of the polylactic acid are as follows: polylactic acid is placed on 6~10h of vacuum drying at 60~90 DEG C, directly
It is lower than 300ppm to moisture；The furnace drying method of pellet are as follows: pellet is dried in vacuo 6~10h at 50 DEG C~80 DEG C, until moisture
Lower than 300ppm.
Preferably, the extrusion temperature of the double screw extruder is 160-190 DEG C, engine speed 300-500r/min, is fed
Expect frequency 7-15r/min；The barrel temperature of the injection molding machine is 160-190 DEG C, and pressure is 40MPa~55MPa.
The beneficial effects of the present invention are:
(1) heat-proof impact-resistant high transparency lactic acid composite material of the invention uses multi-arm branched polylactic acid, with routine
Straight chain poly lactic acid resin is compared, and the probability that the long interchain of macromolecular can be intertwined in the molten state of the polylactic acid after branching is more
Height, and the intensity mutually wound is also bigger, so that making polylactic resin inherently has better shock strength, it is anti-for polylactic acid
It rushes toughening modifying and provides excellent basis condition.
(2) toughener that heat-proof impact-resistant high transparency lactic acid composite material of the invention uses can be not only polylactic resin
Good toughening effect is provided, does not influence the high transparency of polylactic acid also, transmitance is up to 90% or more；Toughener and expansion simultaneously
Chain agent is used in conjunction with each other, and is made the effect of being cross-linked with each other between polylactic acid branched macromolecules chain and toughener macromolecular chain, is made to increase
Tough dose of toughening effect has obtained better embodiment, while can also reduce between polylactic acid and toughener during subsequent storage
Interlayer phenomenon of phase separation, ensure that the service life of material.
(3) crystallization nucleating agent and crystallization promoter that heat-proof impact-resistant high transparency lactic acid composite material of the invention uses,
The crystallization rate of the lower energy significant increase polylactic acid of synergistic effect, the crystal structure being formed simultaneously all is that spherulite size is nanoscale
" small spherocrystal ", crystal is small and more, make poly-lactic acid material while obtaining high temperature tolerance, it is ensured that its transparency.
(4) heat-proof impact-resistant high transparency lactic acid composite material of the invention additionally uses bis- (beta-hydroxyethyl) coco amine conducts
Antistatic agent substantially improves the antistatic property of polylactic acid, keeps it dust absorption with resisting in the application of packing articles.
(5) heat-proof impact-resistant high transparency lactic acid composite material of the invention is safe and environment-friendly, and low raw-material cost is required
Equipment requirement is low, easy to operate, can be applicable on the packaging product such as takeout food box, plastic pallet, plastic uptake cup lid, perfection substitution
The non-degradables class plastics such as PP, PS can solve white pollution, push the development of Novel environment-friendlymaterial material industry, wide market.
Specific embodiment
The present invention is described in further detail now.
Embodiment 1
The present embodiment provides a kind of heat-proof impact-resistant high transparency lactic acid composite material, the components including following parts by weight: 100
Three arm branched polylactic acids of part (number-average molecular weight is 50,000), 2 parts of toughener poly butylene succinates, 0.2 part of chain extender benzene second
Alkene-methyl methacrylate-glycidyl methacrylate ternary atactic copolymer, the poly- D lactic acid of 0.5 part of crystallization nucleating agent
Powder, 0.03 part of crystallization promoter 1,3:2,4- bis- (3,4- dimethyl) benzylidene sorbitol acetal, the bis- (β-hydroxyl of 0.6 part of antistatic agent
Ethyl) coco amine.
The preparation method of the heat-proof impact-resistant high transparency lactic acid composite material:
Three arm branched polylactic acids are dried in vacuo 10h at 60 DEG C, until moisture is lower than 300ppm；
By dried polylactic acid and toughener, chain extender, crystallization nucleating agent, crystallization promoter and antistatic agent in high speed
Homogeneous blend under blender obtains premix raw material；
Gained premix raw material is added twin-screw extrude into mixing, extrusion, granulation；The double screw extruder is from charging
Mouthful successively it is set as 160 DEG C to each area's heating temperature of discharge port, 165 DEG C, 170 DEG C, 175 DEG C, 180 DEG C, 180 DEG C, 185 DEG C, 190
DEG C, 190 DEG C, engine speed 300r/min, feeding frequency 15r/min；
Gained pellet is dried in vacuo 10h at 50 DEG C, until moisture is lower than 300ppm；
By gained dried granules be added horizontal injection press carry out injection molding, horizontal injection press barrel temperature from feed inlet to
Nozzle temperature is successively set as 160 DEG C, and 165 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 190 DEG C, dwell pressure is 40MPa~55MPa,
Pressure maintaining 25s obtains corresponding batten.
Embodiment 2
The present embodiment provides a kind of heat-proof impact-resistant high transparency lactic acid composite material, the components including following parts by weight: 100
Five arm branched polylactic acids of part (number-average molecular weight is 200,000), 5 parts of toughener poly butylene succinates, 0.5 part of chain extender benzene second
Alkene-methyl methacrylate-glycidyl methacrylate ternary atactic copolymer, the poly- D lactic acid powder of 1 part of crystallization nucleating agent,
0.01 part of crystallization promoter San Benzyl base pitches propyl ether dibasic acid esters hexanol, bis- (beta-hydroxyethyl) coco amines of 1 part of antistatic agent.
The preparation method of the heat-proof impact-resistant high transparency lactic acid composite material:
Three arm branched polylactic acids are dried in vacuo 6h at 90 DEG C, until moisture is lower than 300ppm；
By dried polylactic acid and toughener, chain extender, crystallization nucleating agent, crystallization promoter and antistatic agent in high speed
Homogeneous blend under blender obtains premix raw material；
Gained premix raw material is added twin-screw extrude into mixing, extrusion, granulation；The double screw extruder is from charging
Mouthful successively it is set as 160 DEG C to each area's heating temperature of discharge port, 165 DEG C, 170 DEG C, 175 DEG C, 180 DEG C, 180 DEG C, 185 DEG C, 190
DEG C, 190 DEG C, engine speed 500r/min, feeding frequency 7r/min；
Gained pellet is dried in vacuo 6h at 80 DEG C, until moisture is lower than 300ppm；
By gained dried granules be added horizontal injection press carry out injection molding, horizontal injection press barrel temperature from feed inlet to
Nozzle temperature is successively set as 160 DEG C, and 165 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 190 DEG C, dwell pressure is 40MPa~55MPa,
Pressure maintaining 25s obtains corresponding batten.
Embodiment 3
The present embodiment provides a kind of heat-proof impact-resistant high transparency lactic acid composite material, the components including following parts by weight: 100
Three arm branched polylactic acids of part (number-average molecular weight is 100,000), 1 part of toughener poly butylene succinate, 0.1 part of chain extender benzene second
Alkene-methyl methacrylate-glycidyl methacrylate ternary atactic copolymer, the poly- D lactic acid of 0.01 part of crystallization nucleating agent
Powder, 0.05 part of crystallization promoter neopentyl ethylene glycol Biphenyl Ester, bis- (beta-hydroxyethyl) coco amines of 0.1 part of antistatic agent.
The preparation method of the heat-proof impact-resistant high transparency lactic acid composite material:
Three arm branched polylactic acids are dried in vacuo 8h at 80 DEG C, until moisture is lower than 300ppm；
By dried polylactic acid and toughener, chain extender, crystallization nucleating agent, crystallization promoter and antistatic agent in high speed
Homogeneous blend under blender obtains premix raw material；
Gained premix raw material is added twin-screw extrude into mixing, extrusion, granulation；The double screw extruder is from charging
Mouthful successively it is set as 160 DEG C to each area's heating temperature of discharge port, 165 DEG C, 170 DEG C, 175 DEG C, 180 DEG C, 180 DEG C, 185 DEG C, 190
DEG C, 190 DEG C, engine speed 400r/min, feeding frequency 10r/min；
Gained pellet is dried in vacuo 8h at 60 DEG C, until moisture is lower than 300ppm；
By gained dried granules be added horizontal injection press carry out injection molding, horizontal injection press barrel temperature from feed inlet to
Nozzle temperature is successively set as 160 DEG C, and 165 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 190 DEG C, dwell pressure is 40MPa~55MPa,
Pressure maintaining 25s obtains corresponding batten.
Embodiment 4
The present embodiment provides a kind of heat-proof impact-resistant high transparency lactic acid composite material, the components including following parts by weight: 100
Five arm branched polylactic acids of part (number-average molecular weight is 150,000), 3 parts of toughener poly butylene succinates, 0.2 part of chain extender benzene second
Alkene-methyl methacrylate-glycidyl methacrylate ternary atactic copolymer, 0.6 part of crystallization nucleating agent 4, bis- uncle of 6-
Butyl phenyl sodium phosphate, 0.04 part of crystallization promoter 1,3:2,4- bis- (3,4- dimethyl) benzylidene sorbitol acetal, 0.4 part resist it is quiet
Electric bis- (beta-hydroxyethyl) coco amines of agent.
The preparation method of heat-proof impact-resistant high transparency lactic acid composite material batten is the same as embodiment 3.
Embodiment 5
The present embodiment provides a kind of heat-proof impact-resistant high transparency lactic acid composite material, the components including following parts by weight: 100
Three arm branched polylactic acids of part (number-average molecular weight is 100,000), 4 parts of toughener poly butylene succinates, 0.2 part of chain extender benzene second
Alkene-methyl methacrylate-glycidyl methacrylate ternary atactic copolymer, 0.8 part of crystallization nucleating agent 1,3,5- is just
Butyl benzene trimethamide, 0.02 part of crystallization promoter 1,3:2,4- bis- (3,4- dimethyl) benzylidene sorbitol acetal, 0.8 part resist it is quiet
Electric bis- (beta-hydroxyethyl) coco amines of agent.
The preparation method of heat-proof impact-resistant high transparency lactic acid composite material batten is the same as embodiment 3.
Embodiment 6
The present embodiment provides a kind of heat-proof impact-resistant high transparency lactic acid composite material, the components including following parts by weight: 100
Five arm branched polylactic acids of part (number-average molecular weight is 100,000), 2 parts of toughener poly butylene succinates, 0.2 part of chain extender diformazan
Base acrylic acid glycol ester, the poly- D lactic acid powder of 0.5 part of crystallization nucleating agent, 0.03 part of crystallization promoter 1,3:2,4- bis- (3,4- bis-
Methyl) benzylidene sorbitol acetal, bis- (beta-hydroxyethyl) coco amines of 0.6 part of antistatic agent.
The preparation method of heat-proof impact-resistant high transparency lactic acid composite material batten is the same as embodiment 3.
Embodiment 7
The present embodiment provides a kind of heat-proof impact-resistant high transparency lactic acid composite material, the components including following parts by weight: 100
Three arm branched polylactic acids of part (number-average molecular weight is 150,000), 2 parts of toughener poly butylene succinates, 0.2 part of chain extender benzene second
Alkene-acrylonitrile-methacylate ethylene oxidic ester ternary atactic copolymer, the poly- D lactic acid powder of 0.5 part of crystallization nucleating agent, 0.03 part
Crystallization promoter 1,3:2,4- bis- (3,4- dimethyl) benzylidene sorbitol acetal, bis- (beta-hydroxyethyl) cocounut oil of 0.6 part of antistatic agent
Amine.
The preparation method of heat-proof impact-resistant high transparency lactic acid composite material batten is the same as embodiment 3.
Embodiment 8
The present embodiment provides a kind of heat-proof impact-resistant high transparency lactic acid composite material, the components including following parts by weight: 100
Three arm branched polylactic acids of part (number-average molecular weight is 50,000), 2 parts of toughener poly-epsilon-caprolactones, 0.2 part of chain extender styrene-methyl
Methyl acrylate-glycidyl methacrylate ternary atactic copolymer, the poly- D lactic acid powder of 0.5 part of crystallization nucleating agent, 0.03
Part crystallization promoter 1,3:2,4- bis- (3,4- dimethyl) benzylidene sorbitol acetal, bis- (beta-hydroxyethyl) coconut palms of 0.6 part of antistatic agent
Oleyl amine.
The preparation method of heat-proof impact-resistant high transparency lactic acid composite material batten is the same as embodiment 3.
Embodiment 9
The present embodiment provides a kind of heat-proof impact-resistant high transparency lactic acid composite material, the components including following parts by weight: 100
Three arm branched polylactic acids of part (number-average molecular weight is 200,000), 2 parts of toughener poly-epsilon-caprolactones, 0.2 part of chain extender styrene-methyl
Methyl acrylate-glycidyl methacrylate ternary atactic copolymer, 0.1 part of crystallization nucleating agent 4,6- di-tert-butyl-phenyl
Sodium phosphate, 0.03 part of crystallization promoter 1,3:2,4- bis- (3,4- dimethyl) benzylidene sorbitol acetal, 0.6 part of antistatic agent are double
(beta-hydroxyethyl) coco amine.
The preparation method of heat-proof impact-resistant high transparency lactic acid composite material batten is the same as embodiment 3.
Embodiment 10
The present embodiment provides a kind of heat-proof impact-resistant high transparency lactic acid composite material, the components including following parts by weight: 100
Five arm branched polylactic acids of part (number-average molecular weight is 100,000), 2 parts of toughener poly-epsilon-caprolactones, 0.2 part of chain extender styrene-methyl
Methyl acrylate-glycidyl methacrylate ternary atactic copolymer, 1 part of 1,3,5- n-butylbenzene front three of crystallization nucleating agent
Amide, 0.03 part of crystallization promoter 1,3:2,4- bis- (3,4- dimethyl) benzylidene sorbitol acetal, 0.6 part of bis- (β-of antistatic agent
Ethoxy) coco amine.
The preparation method of heat-proof impact-resistant high transparency lactic acid composite material batten is the same as embodiment 3.
Embodiment 11
The present embodiment provides a kind of heat-proof impact-resistant high transparency lactic acid composite material, the components including following parts by weight: 100
Three arm branched polylactic acids of part (number-average molecular weight is 150,000), the oil-filled s-B-S block copolymerization of 4 parts of toughener
Object, 0.2 part of chain extender ethylene glycol dimethacrylate, the poly- D lactic acid powder of 0.5 part of crystallization nucleating agent, 0.05 part of crystallization promoter
1,3:2,4- bis- (3,4- dimethyl) benzylidene sorbitol acetal, bis- (beta-hydroxyethyl) coco amines of 0.6 part of antistatic agent；It is described oil-filled
Styrene-Butadiene-Styrene Block Copolymer is the blend of Styrene-Butadiene-Styrene Block Copolymer and white oil,
The Styrene-Butadiene-Styrene Block Copolymer and the weight ratio of white oil are 1: 1.
The preparation method of heat-proof impact-resistant high transparency lactic acid composite material batten is the same as embodiment 3.
Embodiment 12
The present embodiment provides a kind of heat-proof impact-resistant high transparency lactic acid composite material, the components including following parts by weight: 100
Three arm branched polylactic acids of part (number-average molecular weight is 100,000), the oil-filled s-B-S block copolymerization of 3 parts of toughener
Object, 0.4 part of chain extender styrene-acrylonitrile-glycidyl methacrylate ternary atactic copolymer, 0.5 part of crystallization nucleation
The poly- D lactic acid powder of agent, 0.03 part of crystallization promoter 1,3:2,4- bis- (3,4- dimethyl) benzylidene sorbitol acetal, 0.6 part antistatic
Bis- (beta-hydroxyethyl) coco amines of agent；The oil-filled Styrene-Butadiene-Styrene Block Copolymer is styrene-butadiene-benzene
The blend of ethylene block copolymer and white oil, the weight ratio of the Styrene-Butadiene-Styrene Block Copolymer and white oil
It is 3: 2.
The preparation method of heat-proof impact-resistant high transparency lactic acid composite material batten is the same as embodiment 3.
Embodiment 13
The present embodiment provides a kind of heat-proof impact-resistant high transparency lactic acid composite material, the components including following parts by weight: 100
Three arm branched polylactic acids of part (number-average molecular weight is 100,000), 2 parts of toughener ethylene vinyl acetate copolymers, 0.2 part of chain extender
Styrene-Methyl Methacrylate-Methacrylic Acid ethylene oxidic ester ternary atactic copolymer, 0.5 part of poly- D of crystallization nucleating agent
Lactic acid powder, 0.03 part of crystallization promoter 1,3:2,4- bis- (3,4- dimethyl) benzylidene sorbitol acetal, 1.6 parts of antistatic agents are double
(beta-hydroxyethyl) coco amine.
The preparation method of heat-proof impact-resistant high transparency lactic acid composite material batten is the same as embodiment 3.
Embodiment 14
The present embodiment provides a kind of heat-proof impact-resistant high transparency lactic acid composite material, the components including following parts by weight: 100
Three arm branched polylactic acids of part (number-average molecular weight is 100,000), the oil-filled s-B-S block copolymerization of 2 parts of toughener
Object, 0.2 part of chain extender Styrene-Methyl Methacrylate-Methacrylic Acid ethylene oxidic ester ternary atactic copolymer, 0.5 part
The poly- D lactic acid powder of crystallization nucleating agent, 0.03 part of crystallization promoter 1,3:2,4- bis- (3,4- dimethyl) benzylidene sorbitol acetal, 3 parts
Bis- (beta-hydroxyethyl) coco amines of antistatic agent；The oil-filled Styrene-Butadiene-Styrene Block Copolymer is styrene-fourth
The blend of styrene block copolymer and white oil, the Styrene-Butadiene-Styrene Block Copolymer and white oil
Weight ratio be 2: 3.
The preparation method of heat-proof impact-resistant high transparency lactic acid composite material batten is the same as embodiment 3.
Comparative example 1
The present embodiment provides a kind of heat-proof impact-resistant high transparency lactic acid composite material, the components including following parts by weight: 100
Part straight chain poly lactic acid (number-average molecular weight is 100,000), 2 parts of toughener poly butylene succinates, 0.2 part of chain extender styrene-first
Base methyl acrylate-glycidyl methacrylate ternary atactic copolymer, the poly- D lactic acid powder of 0.5 part of crystallization nucleating agent,
0.03 part of crystallization promoter 1,3:2,4- bis- (3,4- dimethyl) benzylidene sorbitol acetal, the bis- (β-hydroxyl second of 0.6 part of antistatic agent
Base) coco amine.
The preparation method of heat-proof impact-resistant high transparency lactic acid composite material batten is the same as embodiment 3.
Comparative example 2
The present embodiment provides a kind of heat-proof impact-resistant high transparency lactic acid composite material, the components including following parts by weight: 100
Part straight chain poly lactic acid (number-average molecular weight is 50,000), 2 parts of toughener poly-epsilon-caprolactones, 0.2 part of chain extender styrene-methyl propylene
Sour methyl esters-glycidyl methacrylate ternary atactic copolymer, the poly- D lactic acid of 0.5 part of crystallization nucleating agent, 0.03 part of crystallization
Promotor 1,3:2,4- bis- (3,4- dimethyl) benzylidene sorbitol acetal, bis- (beta-hydroxyethyl) coco amines of 0.6 part of antistatic agent.
The preparation method of heat-proof impact-resistant high transparency lactic acid composite material batten is the same as embodiment 3.
Comparative example 3
The present embodiment provides a kind of heat-proof impact-resistant high transparency lactic acid composite material, the components including following parts by weight: 100
Part straight chain poly lactic acid (number-average molecular weight is 150,000), 2 parts of toughener ethylene vinyl acetate copolymers, 0.2 part of chain extender benzene second
Alkene-methyl methacrylate-glycidyl methacrylate ternary atactic copolymer, the poly- D lactic acid of 0.5 part of crystallization nucleating agent
Powder, 0.03 part of crystallization promoter 1,3:2,4- bis- (3,4- dimethyl) benzylidene sorbitol acetal, the bis- (β-hydroxyl of 0.6 part of antistatic agent
Ethyl) coco amine.
The preparation method of heat-proof impact-resistant high transparency lactic acid composite material batten is the same as embodiment 3.
Comparative example 4
The present embodiment provides a kind of heat-proof impact-resistant high transparency lactic acid composite material, the components including following parts by weight: 100
Part straight chain poly lactic acid (number-average molecular weight is 200,000), 2 parts of oil-filled Styrene-Butadiene-Styrene Block Copolymer of toughener,
0.2 part of chain extender Styrene-Methyl Methacrylate-Methacrylic Acid ethylene oxidic ester ternary atactic copolymer, 0.5 part of crystallization
The poly- D lactic acid powder of nucleating agent, 0.03 part of crystallization promoter 1,3:2,4- bis- (3,4- dimethyl) benzylidene sorbitol acetal, 0.6 part anti-
Bis- (beta-hydroxyethyl) coco amines of electrostatic agent.
The preparation method of heat-proof impact-resistant high transparency lactic acid composite material batten is the same as embodiment 3.
Test sample is tested for the property using detail specification process corresponding in iso standard, specific performance such as table
1:
As can be seen from the above Table 1, the present invention obtains the superior height of comprehensive performance by being defined to polylactic resin
Performance polylactic resin material, while keeping original this good characteristic of high transparency, also have both high-impact, high heat resistance and
Antistatic effect has unexpected technical effect；And the polylactic resin of comparative example 1 uses straight chain poly lactic acid, notch
Impact strength is substantially reduced, and brittleness is big, can not be applied in packaging food and drink plastic applications.
Taking the above-mentioned ideal embodiment according to the present invention as inspiration, through the above description, relevant staff is complete
Various changes and amendments can be carried out without departing from the scope of the technological thought of the present invention' entirely.The technology of this invention
Property range is not limited to the contents of the specification, it is necessary to which the technical scope thereof is determined according to the scope of the claim.
Claims (10)
1. a kind of heat-proof impact-resistant high transparency lactic acid composite material, which is characterized in that the component including following parts by weight: 100 parts
Polylactic acid, 1-5 parts of toughener, 0.1-0.5 parts of chain extenders, 0.01-1 parts of crystallization nucleating agents, 0.01-0.05 parts of crystallization promoters,
0.1-3 parts of antistatic agents；The polylactic acid is multi-arm branched polylactic acid, and the number-average molecular weight of the polylactic acid is 50,000~20
Ten thousand, the number-average molecular weight of every arm is 0.2 ten thousand -1 ten thousand.
2. heat-proof impact-resistant high transparency lactic acid composite material according to claim 1, which is characterized in that the polylactic acid is
The polylactic acid of three arm branchings, the polylactic acid have following structural formula, and wherein n is 50-1000,
3. heat-proof impact-resistant high transparency lactic acid composite material according to claim 1 or 2, which is characterized in that the poly- cream
Melt index of the acid at 190 DEG C of temperature and load 2.16kg pressure is 2g/10min-50g/10min, and fusing point is 120 DEG C -180
℃。
4. heat-proof impact-resistant high transparency lactic acid composite material according to claim 1-3, which is characterized in that described
Toughener is poly butylene succinate, poly-epsilon-caprolactone, ethylene vinyl acetate copolymer, oil-filled styrene-butadiene-benzene
One of ethylene block copolymer is a variety of, and the oil-filled Styrene-Butadiene-Styrene Block Copolymer is styrene-
The blend of butadiene-styrene block copolymer and white oil, the Styrene-Butadiene-Styrene Block Copolymer with it is white
The weight ratio of oil is 2: 3-3: 2.
5. heat-proof impact-resistant high transparency lactic acid composite material according to claim 1-4, which is characterized in that described
Chain extender is Styrene-Methyl Methacrylate-Methacrylic Acid ethylene oxidic ester ternary atactic copolymer, dimethacrylate
One of glycol ester, styrene-acrylonitrile-glycidyl methacrylate ternary atactic copolymer is a variety of.
6. heat-proof impact-resistant high transparency lactic acid composite material according to claim 1-5, which is characterized in that described
Crystallization nucleating agent be one of poly- D lactic acid, 4,6- di-tert-butyl based phosphates, 1,3,5- n-butylbenzene trimethamides or
A variety of, the poly- D lactic acid is the powder of -3000 mesh of 300 mesh of mesh number；The crystallization promoter is the (3,4- bis- of 1,3:2,4- bis-
Methyl) benzylidene sorbitol acetal, tri- Benzyl base fork propyl ether dibasic acid esters hexanol, one of neopentyl ethylene glycol Biphenyl Ester or a variety of.
7. a kind of heat-proof impact-resistant high transparency lactic acid composite material described in any one of claims 1-6, which is characterized in that described
Antistatic agent is bis- (beta-hydroxyethyl) coco amines.
8. a kind of preparation method of the described in any item heat-proof impact-resistant high transparency lactic acid composite materials of claim 1-7, special
Sign is that preparation step is as follows:
By dry polylactic acid, toughener, chain extender, crystallization nucleating agent, crystallization promoter, antistatic agent is blended uniformly, obtains pre-
Mixed raw material；
Premix raw material is added twin-screw extrude into mixing, extrusion, granulation, then pellet is dried, obtains drying pellet；
Injection molding machine is added in drying pellet and carries out injection molding.
9. the preparation method of heat-proof impact-resistant high transparency lactic acid composite material according to claim 8, which is characterized in that institute
State the drying means of polylactic acid are as follows: polylactic acid is placed on 6~10h of vacuum drying at 60~90 DEG C, until moisture is lower than 300ppm；
The furnace drying method of pellet are as follows: pellet is dried in vacuo 6~10h at 50 DEG C~80 DEG C, until moisture is lower than 300ppm.
10. the preparation method of heat-proof impact-resistant high transparency lactic acid composite material according to claim 8 or claim 9, feature exist
In the extrusion temperature of the double screw extruder is 160-190 DEG C, engine speed 300-500r/min, feeding frequency 7-15r/
min；The barrel temperature of the injection molding machine is 160-190 DEG C, and pressure is 40MPa~55MPa.
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