CN108148368A - A kind of full-biodegradable polylactic acid base resin material - Google Patents
A kind of full-biodegradable polylactic acid base resin material Download PDFInfo
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- CN108148368A CN108148368A CN201711377610.3A CN201711377610A CN108148368A CN 108148368 A CN108148368 A CN 108148368A CN 201711377610 A CN201711377610 A CN 201711377610A CN 108148368 A CN108148368 A CN 108148368A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
Abstract
The invention discloses a kind of full-biodegradable polylactic acid base resin materials, are related to resin material technical field.The full-biodegradable polylactic acid base resin material of the present invention includes the raw material of following parts by weight：80~100 parts of poly-lactic acid in high molecular weight, 20~40 parts of low molecular weight, biodegradable 10~25 parts of auxiliary agent, 8~15 parts of reinforcing fiber, 0.02~0.6 part of silane coupling agent, 0.03~0.08 part of heat stabilizer, 0.03~0.06 part of plasticizer.Poly-lactic acid in high molecular weight of the present invention improves the mechanical property of material, and low molecular weight improves the machinability of material, plays respective advantage, reduces cost of material；The good mechanical performances such as tensile strength, notch impact strength, elongation at break, the elasticity modulus of the resin material of preparation, machinability are strong.
Description
Technical field：
The present invention relates to resin material technical fields, and in particular to a kind of full-biodegradable polylactic acid base resin material.
Background technology：
Polylactic acid is as a kind of important biodegradable polymer, with its excellent biocompatibility, biological degradability
It is used widely with Bioabsorbable.It can be decomposed completely in nature under the action of microorganism, water, acid, alkali etc., most
Final product is CO2And H2O, intermediate product lactic acid are also the product of internal normal sugar metabolism, will not be also pollution-free to environment, therefore
It is extremely active to its research as environmental protection macromolecule material.Polylactic acid be often made fiber, film, block, plate etc. for be processed into from
Civilian various plastic products, food packaging, fast food lunch-box, non-woven fabrics, tent cloth, ground pad etc., market prospects are arrived in industry
It is very good.
Although the intensity of polylactic acid and rigidity are high, toughness and impact resistance are poor, are a kind of hard and crisp material under room temperature
Material.In addition, during melt-processed, the molecular weight attenuation of polylactic acid is larger, influence based resin material cost and
Physical property.How in the case where ensureing the requirement of biodegradability of based resin material, its mechanical property and can is improved
Processability is particularly critical.
Invention content：
The technical problems to be solved by the invention are to provide a kind of full-biodegradable polylactic acid base resin material, overcome
The shortcomings that polylactic acid toughness is poor, good mechanical performance, machinability are strong.
The technical problems to be solved by the invention are realized using following technical solution：
The present invention provides a kind of full-biodegradable polylactic acid base resin materials, include the raw material of following parts by weight：High score
80~100 parts of polylactic acid of son amount, 20~40 parts of low molecular weight, biodegradable 10~25 parts of auxiliary agent, reinforcing fiber 8~15
Part, 0.02~0.6 part of silane coupling agent, 0.03~0.08 part of heat stabilizer, 0.03~0.06 part of plasticizer；
The number-average molecular weight of the poly-lactic acid in high molecular weight is 8~90,000 dalton, and the number of the low molecular weight is equal
Molecular weight is 0.8~20,000 dalton.
Preferably, include the raw material of following parts by weight：95 parts of poly-lactic acid in high molecular weight, 25 parts of low molecular weight, life
18 parts of object prodegradant, 12 parts of reinforcing fiber, 0.32 part of silane coupling agent, 0.06 part of heat stabilizer, 0.05 part of plasticizer.
Preferably, the reinforcing fiber is polyacrylonitrile fibre, glass fibre, alumina silicate fibre, high silica fiber, Mo Lai
Mineral wool or carbon fiber.
Preferably, the silane coupling agent is γ aminopropyltriethoxy silane, γ-(methacryloxy) third
One or more combinations in base trimethoxy silane, vinyltriethoxysilane, vinyltrimethoxysilane.
Preferably, the heat stabilizer is dibutyl tin laurate, two maleic acid mono octyl ester di-n-butyl tins, two
One or more combinations in maleic acid mono octyl ester dioctyltin, two cis-butenedioic acid mono ethyl maleate dioctyltins.
Preferably, the plasticizer is epoxidized soybean oil, tributyl citrate, tributyl 2-acetylcitrate, ethylene, propylene
One or more combinations in acid, tricresyl phosphate.
The biodegradation auxiliary agent includes the raw material of following parts by weight：65 parts of cornstarch, polylactic acid/polyethylene block are common
16 parts of polymers, 12 parts of ethylene-vinyl acetate block copolymer, 10 parts of modification infusorial earth, three isostearoyl base metatitanic acid of isopropyl
2.5 parts of ester, 1.6 parts of calgon, 1.3 parts of magnesium stearate, 0.7 part of nano silicon dioxide, 0.6 part of sorbierite, light stabilizer
944 0.08 parts.
The preparation method of the biodegradation auxiliary agent, includes the following steps：
(1) starch hydrophobic is handled：After cornstarch, magnesium stearate are mixed, high-speed stirred is uniform, obtains hydrophobic starch；
(2) material mixes：It is embedding that polylactic acid/polyethylene block co-polymers, ethylene-vinyl acetate are added in into hydrophobic starch
Section copolymer, be warming up to 50 DEG C stir evenly after, sequentially add three isostearoyl base titanate esters of isopropyl, calgon, mountain
Pears alcohol, nano silicon dioxide, modification infusorial earth, light stabilizer 944, after addition, insulated and stirred 30min, then it is placed in microwave
Middle processing 10min, obtains batch mixing；
(3) extruding pelletization：Batch mixing is sent into extruding pelletization in double screw extruder, extrusion temperature is 130~160 DEG C, so
Pelletizing after postcooling traction obtains the biodegradable auxiliary agent that grain size is 20~60 μm.
For the biodegradation auxiliary agent using the excellent cornstarch of degradation property as main component, cooperation lubricant, titanate esters are even
Join a variety of auxiliary agents such as agent, dispersant, light stabilizer, there is good compatibility, machinability, be easily dispersed and biodegradable,
The degradability, toughness and machinability of polylactic acid can be significantly improved.
The preparation method of the modification infusorial earth is：10~40 parts by weight diatomite are added to 400~800 parts by weight
In water, high-speed stirred forms stable diatomite suspension；2~5 parts by weight cation modifier quaternary ammonium salts are dissolved in 100~
In 200 parts by weight of ethanol, add 5~20 parts by weight hydrochloric acid, form cationic solution；Cationic solution is slowly dropped to and is preheated to
In 60~80 DEG C of diatomite aaerosol solution, diatomite colloidal sol is made；Diatomite colloidal sol is filtered, deionized water washing, vacuum
It dry, pulverize.
Above-mentioned modification infusorial earth by diatomite by being configured to suspension, and cation modifier carries out it under strong acid condition
Modified, can replace cations, the improvement diatomite internal structures such as sodium ion, potassium ion in diatomite internal void increases
Porosity so that grain size is more uniform, is suitable as the Modification auxiliary agent of lightweight.
The present invention also provides the processing technologys of above-mentioned full-biodegradable polylactic acid base resin material, include the following steps：
(1) it is dry：Poly-lactic acid in high molecular weight, low molecular weight are weighed according to parts by weight, is dried at 80~100 DEG C
Water content is less than 2%；
(2) it melts：Dried poly-lactic acid in high molecular weight, low molecular weight and biodegradable auxiliary agent, enhancing is fine
Dimension, silane coupling agent, heat stabilizer, plasticizer mixing, high-speed stirred is uniform, is warming up to 160~180 DEG C of heating meltings；
(3) extrusioning shaping：The mixture heated after melting is passed through extruder extruding pelletization, extruder temperature section is
It 160~180 DEG C, squeezes out after 30~40 DEG C of cooling and shapings；
(4) traction post processing：After sizing to be cooled, material is drawn by draft gear, eliminates surface electrostatic, surface coating
Winding obtains the poly-lactic acid ester base resin material afterwards.
Preferably, the screw speed of the extruder be 80~120r/min, screw slenderness ratio 1:30~40.
The number-average molecular weight of polylactic resin is too high, needs higher temperature, the screw rod shearing of bigger in process
Rate, could abundant fusion plastification, but under high temperature high shear effect, molecular weight can hastily be decayed again, both formed the energy with
The waste of material, and it is unfavorable for the stable molding of resin；The number-average molecular weight of polylactic acid is too low, and when processing shows as melt strength
It is too low, it is unfavorable for steady production, and the mechanical property of molding based resin is poor, using being restricted.
The beneficial effects of the invention are as follows：1st, full-biodegradable polylactic acid base resin material of the invention selects high molecular weight
Polylactic acid is matrix with low molecular weight, and using the principle of wide/bimodal molecular weight, the two is fully compatible, poly-lactic acid in high molecular weight
The mechanical property of material is improved, low molecular weight improves the machinability of material, plays respective advantage, reduces original
Expect cost；The mechanical properties such as tensile strength, notch impact strength, elongation at break, the elasticity modulus of the resin material of preparation are excellent
Good, machinability is strong.
2nd, the processing technology of based resin material of the present invention compared with traditional handicraft, increases traction post processing step
Suddenly, although increasing energy consumption, the electrostatic of material surface is eliminated, avoids electrostatic band during processing and use
The harm come, extends service life.
Specific embodiment：
In order to be easy to understand the technical means, the creative features, the aims and the efficiencies achieved by the present invention, tie below
Specific embodiment is closed, the present invention is further explained.
Embodiment 1
A kind of full-biodegradable polylactic acid base resin material includes the raw material of following parts by weight：Poly-lactic acid in high molecular weight 95
Part, 25 parts of low molecular weight, biodegradable 18 parts of auxiliary agent, 12 parts of glass fibre, γ-(methacryloxy) propyl three
0.32 part of methoxy silane, two 0.06 part of maleic acid mono octyl ester dioctyltins, 0.05 part of tributyl 2-acetylcitrate.It is high
The number-average molecular weight of molecular weight polylactic acid is 8~90,000 dalton, and the number-average molecular weight of low molecular weight is 0.8~20,000
Er Dun.
The biodegradation auxiliary agent includes the raw material of following parts by weight：65 parts of cornstarch, polylactic acid/polyethylene block are common
16 parts of polymers, 12 parts of ethylene-vinyl acetate block copolymer, 10 parts of modification infusorial earth, three isostearoyl base metatitanic acid of isopropyl
2.5 parts of ester, 1.6 parts of calgon, 1.3 parts of magnesium stearate, 0.7 part of nano silicon dioxide, 0.6 part of sorbierite, light stabilizer
944 0.08 parts.The preparation method of the biodegradation auxiliary agent, includes the following steps：(1) starch hydrophobic is handled：By cornstarch,
After magnesium stearate mixing, high-speed stirred is uniform, obtains hydrophobic starch；(2) material mixes：Into hydrophobic starch add in polylactic acid/
Polyethylene block co-polymers, ethylene-vinyl acetate block copolymer, be warming up to 50 DEG C stir evenly after, sequentially add isopropyl
Three isostearoyl base titanate esters of base, calgon, sorbierite, nano silicon dioxide, modification infusorial earth, light stabilizer 944, add
After adding, insulated and stirred 30min, then be placed in microwave and handle 10min, obtain batch mixing；(3) extruding pelletization：Batch mixing is sent into
Extruding pelletization in double screw extruder, extrusion temperature are 130~160 DEG C, then pelletizing after cooling traction, obtain grain size for 20~
60 μm of biodegradable auxiliary agent.
The processing technology of above-mentioned full-biodegradable polylactic acid base resin material, includes the following steps：
(1) it is dry：Poly-lactic acid in high molecular weight, low molecular weight are weighed according to parts by weight, is dried at 90 DEG C aqueous
Amount is less than 2%；
(2) it melts：By dried poly-lactic acid in high molecular weight, low molecular weight and biodegradable auxiliary agent, glass fibers
Dimension, γ-(methacryloxy) propyl trimethoxy silicane, two maleic acid mono octyl ester dioctyltins, acetyl lemon
Sour tributyl mixing, high-speed stirred is uniform, is warming up to 166 DEG C of heating meltings；
(3) extrusioning shaping：The mixture heated after melting is passed through extruder extruding pelletization, extruder temperature section is
It 160~180 DEG C, squeezes out after 30~40 DEG C of cooling and shapings；The screw speed of extruder be 80~120r/min, screw slenderness ratio
It is 1:30~40.
(4) traction post processing：After sizing to be cooled, material is drawn by draft gear, eliminates surface electrostatic, surface coating
Winding obtains the poly-lactic acid ester base resin material afterwards.
Embodiment 2
A kind of full-biodegradable polylactic acid base resin material includes the raw material of following parts by weight：Poly-lactic acid in high molecular weight 85
Part, 27 parts of low molecular weight, biodegradable 17 parts of auxiliary agent, 11 parts of mullite fiber, vinyltrimethoxysilane 0.35
Part, two 0.06 part of maleic acid mono octyl ester di-n-butyl tins, 0.03 part of epoxidized soybean oil.The number of poly-lactic acid in high molecular weight is divided equally
Son amount is 8~90,000 dalton, and the number-average molecular weight of low molecular weight is 0.8~20,000 dalton.
The biodegradation auxiliary agent includes the raw material of following parts by weight：65 parts of cornstarch, polylactic acid/polyethylene block are common
16 parts of polymers, 12 parts of ethylene-vinyl acetate block copolymer, 10 parts of modification infusorial earth, three isostearoyl base metatitanic acid of isopropyl
2.5 parts of ester, 1.6 parts of calgon, 1.3 parts of magnesium stearate, 0.7 part of nano silicon dioxide, 0.6 part of sorbierite, light stabilizer
944 0.08 parts.The preparation method of the biodegradation auxiliary agent, includes the following steps：(1) starch hydrophobic is handled：By cornstarch,
After magnesium stearate mixing, high-speed stirred is uniform, obtains hydrophobic starch；(2) material mixes：Into hydrophobic starch add in polylactic acid/
Polyethylene block co-polymers, ethylene-vinyl acetate block copolymer, be warming up to 50 DEG C stir evenly after, sequentially add isopropyl
Three isostearoyl base titanate esters of base, calgon, sorbierite, nano silicon dioxide, modification infusorial earth, light stabilizer 944, add
After adding, insulated and stirred 30min, then be placed in microwave and handle 10min, obtain batch mixing；(3) extruding pelletization：Batch mixing is sent into
Extruding pelletization in double screw extruder, extrusion temperature are 130~160 DEG C, then pelletizing after cooling traction, obtain grain size for 20~
60 μm of biodegradable auxiliary agent.
The processing technology of above-mentioned full-biodegradable polylactic acid base resin material, includes the following steps：
(1) it is dry：Poly-lactic acid in high molecular weight, low molecular weight are weighed according to parts by weight, is dried at 95 DEG C aqueous
Amount is less than 2%；
(2) it melts：By dried poly-lactic acid in high molecular weight, low molecular weight and biodegradable auxiliary agent, mullite
Fiber, vinyltrimethoxysilane, two maleic acid mono octyl ester di-n-butyl tins, epoxidized soybean oil mixing, high-speed stirred
Uniformly, 170 DEG C of heating meltings are warming up to；
(3) extrusioning shaping：The mixture heated after melting is passed through extruder extruding pelletization, extruder temperature section is
It 160~180 DEG C, squeezes out after 30~40 DEG C of cooling and shapings；The screw speed of extruder be 80~120r/min, screw slenderness ratio
It is 1:30~40.
(4) traction post processing：After sizing to be cooled, material is drawn by draft gear, eliminates surface electrostatic, surface coating
Winding obtains the poly-lactic acid ester base resin material afterwards.
Embodiment 3
A kind of full-biodegradable polylactic acid base resin material includes the raw material of following parts by weight：Poly-lactic acid in high molecular weight 91
Part, 26 parts of low molecular weight, biodegradable 16 parts of auxiliary agent, 13 parts of alumina silicate fibre, γ aminopropyltriethoxy silane
0.42 part, 0.05 part of two cis-butenedioic acid mono ethyl maleate dioctyltin, 0.03 part of tricresyl phosphate.Poly-lactic acid in high molecular weight
Number-average molecular weight is 8~90,000 dalton, and the number-average molecular weight of low molecular weight is 0.8~20,000 dalton.
The biodegradation auxiliary agent includes the raw material of following parts by weight：65 parts of cornstarch, polylactic acid/polyethylene block are common
16 parts of polymers, 12 parts of ethylene-vinyl acetate block copolymer, 10 parts of modification infusorial earth, three isostearoyl base metatitanic acid of isopropyl
2.5 parts of ester, 1.6 parts of calgon, 1.3 parts of magnesium stearate, 0.7 part of nano silicon dioxide, 0.6 part of sorbierite, light stabilizer
944 0.08 parts.The preparation method of the biodegradation auxiliary agent, includes the following steps：(1) starch hydrophobic is handled：By cornstarch,
After magnesium stearate mixing, high-speed stirred is uniform, obtains hydrophobic starch；(2) material mixes：Into hydrophobic starch add in polylactic acid/
Polyethylene block co-polymers, ethylene-vinyl acetate block copolymer, be warming up to 50 DEG C stir evenly after, sequentially add isopropyl
Three isostearoyl base titanate esters of base, calgon, sorbierite, nano silicon dioxide, modification infusorial earth, light stabilizer 944, add
After adding, insulated and stirred 30min, then be placed in microwave and handle 10min, obtain batch mixing；(3) extruding pelletization：Batch mixing is sent into
Extruding pelletization in double screw extruder, extrusion temperature are 130~160 DEG C, then pelletizing after cooling traction, obtain grain size for 20~
60 μm of biodegradable auxiliary agent.
The processing technology of above-mentioned full-biodegradable polylactic acid base resin material, includes the following steps：
(1) it is dry：Poly-lactic acid in high molecular weight, low molecular weight are weighed according to parts by weight, is dried at 100 DEG C aqueous
Amount is less than 2%；
(2) it melts：By dried poly-lactic acid in high molecular weight, low molecular weight and biodegradable auxiliary agent, alumina silicate
Fiber, γ aminopropyltriethoxy silane, two cis-butenedioic acid mono ethyl maleate dioctyltins, tricresyl phosphate mixing, it is high
Speed stirs evenly, and is warming up to 175 DEG C of heating meltings；
(3) extrusioning shaping：The mixture heated after melting is passed through extruder extruding pelletization, extruder temperature section is
It 160~180 DEG C, squeezes out after 30~40 DEG C of cooling and shapings；The screw speed of extruder be 80~120r/min, screw slenderness ratio
It is 1:30~40.
(4) traction post processing：After sizing to be cooled, material is drawn by draft gear, eliminates surface electrostatic, surface coating
Winding obtains the poly-lactic acid ester base resin material afterwards.
Embodiment 4
A kind of full-biodegradable polylactic acid base resin material includes the raw material of following parts by weight：Poly-lactic acid in high molecular weight 96
Part, 35 parts of low molecular weight, biodegradable 22 parts of auxiliary agent, 14 parts of carbon fiber, 0.25 part of vinyltriethoxysilane, two
0.07 part of dibutyl tin laurate, 0.05 part of tributyl citrate.The number-average molecular weight of poly-lactic acid in high molecular weight is 8~90,000
Er Dun, the number-average molecular weight of low molecular weight is 0.8~20,000 dalton.
The biodegradation auxiliary agent includes the raw material of following parts by weight：65 parts of cornstarch, polylactic acid/polyethylene block are common
16 parts of polymers, 12 parts of ethylene-vinyl acetate block copolymer, 10 parts of modification infusorial earth, three isostearoyl base metatitanic acid of isopropyl
2.5 parts of ester, 1.6 parts of calgon, 1.3 parts of magnesium stearate, 0.7 part of nano silicon dioxide, 0.6 part of sorbierite, light stabilizer
944 0.08 parts.The preparation method of the biodegradation auxiliary agent, includes the following steps：(1) starch hydrophobic is handled：By cornstarch,
After magnesium stearate mixing, high-speed stirred is uniform, obtains hydrophobic starch；(2) material mixes：Into hydrophobic starch add in polylactic acid/
Polyethylene block co-polymers, ethylene-vinyl acetate block copolymer, be warming up to 50 DEG C stir evenly after, sequentially add isopropyl
Three isostearoyl base titanate esters of base, calgon, sorbierite, nano silicon dioxide, modification infusorial earth, light stabilizer 944, add
After adding, insulated and stirred 30min, then be placed in microwave and handle 10min, obtain batch mixing；(3) extruding pelletization：Batch mixing is sent into
Extruding pelletization in double screw extruder, extrusion temperature are 130~160 DEG C, then pelletizing after cooling traction, obtain grain size for 20~
60 μm of biodegradable auxiliary agent.
The processing technology of above-mentioned full-biodegradable polylactic acid base resin material, includes the following steps：
(1) it is dry：Poly-lactic acid in high molecular weight, low molecular weight are weighed according to parts by weight, is dried at 100 DEG C aqueous
Amount is less than 2%；
(2) it melts：By dried poly-lactic acid in high molecular weight, low molecular weight and biodegradable auxiliary agent, carbon fiber,
Vinyltriethoxysilane, dibutyl tin laurate, tributyl citrate mixing, high-speed stirred is uniform, is warming up to 180 DEG C
Heating melting；
(3) extrusioning shaping：The mixture heated after melting is passed through extruder extruding pelletization, extruder temperature section is
It 160~180 DEG C, squeezes out after 30~40 DEG C of cooling and shapings；The screw speed of extruder be 80~120r/min, screw slenderness ratio
It is 1:30~40.
(4) traction post processing：After sizing to be cooled, material is drawn by draft gear, eliminates surface electrostatic, surface coating
Winding obtains the poly-lactic acid ester base resin material afterwards.
Embodiment 5
A kind of full-biodegradable polylactic acid base resin material includes the raw material of following parts by weight：Poly-lactic acid in high molecular weight 95
Part, 34 parts of low molecular weight, biodegradable 22 parts of auxiliary agent, 13 parts of polyacrylonitrile fibre, gamma-amino propyl-triethoxysilicane
0.47 part of alkane, 0.08 part of two cis-butenedioic acid mono ethyl maleate dioctyltin, 0.06 part of tricresyl phosphate.Poly-lactic acid in high molecular weight
Number-average molecular weight for 8~90,000 dalton, the number-average molecular weight of low molecular weight is 0.8~20,000 dalton.
The biodegradation auxiliary agent includes the raw material of following parts by weight：65 parts of cornstarch, polylactic acid/polyethylene block are common
16 parts of polymers, 12 parts of ethylene-vinyl acetate block copolymer, 10 parts of modification infusorial earth, three isostearoyl base metatitanic acid of isopropyl
2.5 parts of ester, 1.6 parts of calgon, 1.3 parts of magnesium stearate, 0.7 part of nano silicon dioxide, 0.6 part of sorbierite, light stabilizer
944 0.08 parts.The preparation method of the biodegradation auxiliary agent, includes the following steps：(1) starch hydrophobic is handled：By cornstarch,
After magnesium stearate mixing, high-speed stirred is uniform, obtains hydrophobic starch；(2) material mixes：Into hydrophobic starch add in polylactic acid/
Polyethylene block co-polymers, ethylene-vinyl acetate block copolymer, be warming up to 50 DEG C stir evenly after, sequentially add isopropyl
Three isostearoyl base titanate esters of base, calgon, sorbierite, nano silicon dioxide, modification infusorial earth, light stabilizer 944, add
After adding, insulated and stirred 30min, then be placed in microwave and handle 10min, obtain batch mixing；(3) extruding pelletization：Batch mixing is sent into
Extruding pelletization in double screw extruder, extrusion temperature are 130~160 DEG C, then pelletizing after cooling traction, obtain grain size for 20~
60 μm of biodegradable auxiliary agent.
The processing technology of above-mentioned full-biodegradable polylactic acid base resin material, includes the following steps：
(1) it is dry：Poly-lactic acid in high molecular weight, low molecular weight are weighed according to parts by weight, is dried at 100 DEG C aqueous
Amount is less than 2%；
(2) it melts：By dried poly-lactic acid in high molecular weight, low molecular weight and biodegradable auxiliary agent, polypropylene
Nitrile fiber, γ aminopropyltriethoxy silane, two cis-butenedioic acid mono ethyl maleate dioctyltins, tricresyl phosphate mixing,
High-speed stirred is uniform, is warming up to 175 DEG C of heating meltings；
(3) extrusioning shaping：The mixture heated after melting is passed through extruder extruding pelletization, extruder temperature section is
It 160~180 DEG C, squeezes out after 30~40 DEG C of cooling and shapings；The screw speed of extruder be 80~120r/min, screw slenderness ratio
It is 1:30~40.
(4) traction post processing：After sizing to be cooled, material is drawn by draft gear, eliminates surface electrostatic, surface coating
Winding obtains the poly-lactic acid ester base resin material afterwards.
Embodiment 6
A kind of full-biodegradable polylactic acid base resin material includes the raw material of following parts by weight：Poly-lactic acid in high molecular weight 100
Part, 40 parts of low molecular weight, biodegradable 25 parts of auxiliary agent, 15 parts of alumina silicate fibre, vinyltriethoxysilane 0.55
Part, two 0.08 part of maleic acid mono octyl ester dioctyltins, 0.06 part of epoxidized soybean oil.The number of poly-lactic acid in high molecular weight is divided equally
Son amount is 8~90,000 dalton, and the number-average molecular weight of low molecular weight is 0.8~20,000 dalton.
The biodegradation auxiliary agent includes the raw material of following parts by weight：65 parts of cornstarch, polylactic acid/polyethylene block are common
16 parts of polymers, 12 parts of ethylene-vinyl acetate block copolymer, 10 parts of modification infusorial earth, three isostearoyl base metatitanic acid of isopropyl
2.5 parts of ester, 1.6 parts of calgon, 1.3 parts of magnesium stearate, 0.7 part of nano silicon dioxide, 0.6 part of sorbierite, light stabilizer
944 0.08 parts.The preparation method of the biodegradation auxiliary agent, includes the following steps：(1) starch hydrophobic is handled：By cornstarch,
After magnesium stearate mixing, high-speed stirred is uniform, obtains hydrophobic starch；(2) material mixes：Into hydrophobic starch add in polylactic acid/
Polyethylene block co-polymers, ethylene-vinyl acetate block copolymer, be warming up to 50 DEG C stir evenly after, sequentially add isopropyl
Three isostearoyl base titanate esters of base, calgon, sorbierite, nano silicon dioxide, modification infusorial earth, light stabilizer 944, add
After adding, insulated and stirred 30min, then be placed in microwave and handle 10min, obtain batch mixing；(3) extruding pelletization：Batch mixing is sent into
Extruding pelletization in double screw extruder, extrusion temperature are 130~160 DEG C, then pelletizing after cooling traction, obtain grain size for 20~
60 μm of biodegradable auxiliary agent.
The processing technology of above-mentioned full-biodegradable polylactic acid base resin material, includes the following steps：
(1) it is dry：Poly-lactic acid in high molecular weight, low molecular weight are weighed according to parts by weight, is dried at 100 DEG C aqueous
Amount is less than 2%；
(2) it melts：By dried poly-lactic acid in high molecular weight, low molecular weight and biodegradable auxiliary agent, alumina silicate
Fiber, vinyltriethoxysilane, two maleic acid mono octyl ester dioctyltins, epoxidized soybean oil mixing, high-speed stirred
Uniformly, 177 DEG C of heating meltings are warming up to；
(3) extrusioning shaping：The mixture heated after melting is passed through extruder extruding pelletization, extruder temperature section is
It 160~180 DEG C, squeezes out after 30~40 DEG C of cooling and shapings；The screw speed of extruder be 80~120r/min, screw slenderness ratio
It is 1:30~40.
(4) traction post processing：After sizing to be cooled, material is drawn by draft gear, eliminates surface electrostatic, surface coating
Winding obtains the poly-lactic acid ester base resin material afterwards.
Comparative example 1
A kind of full-biodegradable polylactic acid base resin material includes the raw material of following parts by weight：Poly-lactic acid in high molecular weight 95
Part, biodegradable 18 parts of auxiliary agent, 12 parts of glass fibre, γ -0.32 part of (methacryloxy) propyl trimethoxy silicane, two
0.06 part of maleic acid mono octyl ester dioctyltin, 0.05 part of tributyl 2-acetylcitrate.The number of poly-lactic acid in high molecular weight is equal
Molecular weight is 8~90,000 dalton, and the number-average molecular weight of low molecular weight is 0.8~20,000 dalton.
The biodegradation auxiliary agent includes the raw material of following parts by weight：65 parts of cornstarch, polylactic acid/polyethylene block are common
16 parts of polymers, 12 parts of ethylene-vinyl acetate block copolymer, 10 parts of modification infusorial earth, three isostearoyl base metatitanic acid of isopropyl
2.5 parts of ester, 1.6 parts of calgon, 1.3 parts of magnesium stearate, 0.7 part of nano silicon dioxide, 0.6 part of sorbierite, light stabilizer
944 0.08 parts.The preparation method of the biodegradation auxiliary agent, includes the following steps：(1) starch hydrophobic is handled：By cornstarch,
After magnesium stearate mixing, high-speed stirred is uniform, obtains hydrophobic starch；(2) material mixes：Into hydrophobic starch add in polylactic acid/
Polyethylene block co-polymers, ethylene-vinyl acetate block copolymer, be warming up to 50 DEG C stir evenly after, sequentially add isopropyl
Three isostearoyl base titanate esters of base, calgon, sorbierite, nano silicon dioxide, modification infusorial earth, light stabilizer 944, add
After adding, insulated and stirred 30min, then be placed in microwave and handle 10min, obtain batch mixing；(3) extruding pelletization：Batch mixing is sent into
Extruding pelletization in double screw extruder, extrusion temperature are 130~160 DEG C, then pelletizing after cooling traction, obtain grain size for 20~
60 μm of biodegradable auxiliary agent.
The processing technology of above-mentioned full-biodegradable polylactic acid base resin material, includes the following steps：
(1) it is dry：Poly-lactic acid in high molecular weight is weighed according to parts by weight, water content is dried at 90 DEG C less than 2%；
(2) it melts：By dried poly-lactic acid in high molecular weight and biodegradable auxiliary agent, glass fibre, γ-(metering system
Acyloxy) propyl trimethoxy silicane, two maleic acid mono octyl ester dioctyltins, tributyl 2-acetylcitrate mixing, it is high
Speed stirs evenly, and is warming up to 166 DEG C of heating meltings；
(3) extrusioning shaping：The mixture heated after melting is passed through extruder extruding pelletization, extruder temperature section is
It 160~180 DEG C, squeezes out after 30~40 DEG C of cooling and shapings；The screw speed of extruder be 80~120r/min, screw slenderness ratio
It is 1:30~40.
(4) traction post processing：After sizing to be cooled, material is drawn by draft gear, eliminates surface electrostatic, surface coating
Winding obtains the poly-lactic acid ester base resin material afterwards.
Comparative example 2
A kind of full-biodegradable polylactic acid base resin material includes the raw material of following parts by weight：Poly-lactic acid in high molecular weight 95
Part, 25 parts of low molecular weight, 18 parts of cornstarch, 12 parts of glass fibre, γ-(methacryloxy) propyl trimethoxy
0.32 part of base silane, two 0.06 part of maleic acid mono octyl ester dioctyltins, 0.05 part of tributyl 2-acetylcitrate.Macromolecule
The number-average molecular weight for measuring polylactic acid is 8~90,000 dalton, and the number-average molecular weight of low molecular weight is 0.8~20,000 dongles
.
The processing technology of above-mentioned full-biodegradable polylactic acid base resin material, includes the following steps：
(1) it is dry：Poly-lactic acid in high molecular weight, low molecular weight are weighed according to parts by weight, is dried at 90 DEG C aqueous
Amount is less than 2%；
(2) it melts：By dried poly-lactic acid in high molecular weight, low molecular weight and cornstarch, glass fibre,
γ-(methacryloxy) propyl trimethoxy silicane, two maleic acid mono octyl ester dioctyltins, acetyl tributyl citrate three
Butyl ester mixes, and high-speed stirred is uniform, is warming up to 166 DEG C of heating meltings；
(3) extrusioning shaping：The mixture heated after melting is passed through extruder extruding pelletization, extruder temperature section is
It 160~180 DEG C, squeezes out after 30~40 DEG C of cooling and shapings；The screw speed of extruder be 80~120r/min, screw slenderness ratio
It is 1:30~40.
(4) traction post processing：After sizing to be cooled, material is drawn by draft gear, eliminates surface electrostatic, surface coating
Winding obtains the poly-lactic acid ester base resin material afterwards.
The full-biodegradable polylactic acid base resin material prepared to above-described embodiment, comparative example has carried out performance test,
In, tensile strength test is using GB/T 1040-2006 standards, rate of extension 5mm/min；Notch impact strength test execution
GB/T 1043-1993 standards, using simply supported beam notched specimen impact method.Test result see the table below：
As can be seen from the above table, the tensile strength of the full-biodegradable polylactic acid base resin material of the embodiment of the present invention, lack
Good mechanical performances, the machinabilitys such as mouth impact strength, elongation at break, elasticity modulus are strong.
The basic principles, main features and the advantages of the invention have been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (6)
1. a kind of full-biodegradable polylactic acid base resin material, which is characterized in that include the raw material of following parts by weight：High molecular weight
80~100 parts of polylactic acid, 20~40 parts of low molecular weight, biodegradable 10~25 parts of auxiliary agent, 8~15 parts of reinforcing fiber,
0.02~0.6 part of silane coupling agent, 0.03~0.08 part of heat stabilizer, 0.03~0.06 part of plasticizer；
The number-average molecular weight of the poly-lactic acid in high molecular weight be 8~90,000 dalton, the equal molecule of number of the low molecular weight
It measures as 0.8~20,000 dalton.
2. full-biodegradable polylactic acid base resin material according to claim 1, which is characterized in that including following parts by weight
Raw material：95 parts of poly-lactic acid in high molecular weight, 25 parts of low molecular weight, biodegradable 18 parts of auxiliary agent, 12 parts of reinforcing fiber, silicon
0.32 part of alkane coupling agent, 0.06 part of heat stabilizer, 0.05 part of plasticizer.
3. full-biodegradable polylactic acid base resin material according to claim 1, which is characterized in that the reinforcing fiber is
Polyacrylonitrile fibre, glass fibre, alumina silicate fibre, high silica fiber, mullite fiber or carbon fiber.
4. full-biodegradable polylactic acid base resin material according to claim 1, which is characterized in that the silane coupling agent
For γ aminopropyltriethoxy silane, γ-(methacryloxy) propyl trimethoxy silicane, vinyl triethoxyl
One or more combinations in silane, vinyltrimethoxysilane.
5. full-biodegradable polylactic acid base resin material according to claim 1, which is characterized in that the heat stabilizer is
Dibutyl tin laurate, two maleic acid mono octyl ester di-n-butyl tins, two maleic acid mono octyl ester dioctyltins, two
One or more combinations in cis-butenedioic acid mono ethyl maleate dioctyltin.
6. full-biodegradable polylactic acid base resin material according to claim 1, which is characterized in that the plasticizer is ring
It is one or more in oxygen soybean oil, tributyl citrate, tributyl 2-acetylcitrate, ethylene acrylic, tricresyl phosphate
Combination.
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| CN109912988A (en) * | 2019-03-13 | 2019-06-21 | 安庆市泽烨新材料技术推广服务有限公司 | A kind of degradable resin |
| CN112920555A (en) * | 2021-03-01 | 2021-06-08 | 宁波市青湖弹性体科技有限公司 | TPEE composite material suitable for high-speed extrusion and preparation method thereof |
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| CN1239725A (en) * | 1999-06-22 | 1999-12-29 | 沈阳南阳经贸集团有限公司 | Polynary degradable resin composition and its preparation process |
| CN101362853A (en) * | 2008-09-12 | 2009-02-11 | 浙江海正生物材料股份有限公司 | Low cost full-biodegradable polylactic acid sheet material and preparation method thereof |
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| CN112920555A (en) * | 2021-03-01 | 2021-06-08 | 宁波市青湖弹性体科技有限公司 | TPEE composite material suitable for high-speed extrusion and preparation method thereof |
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Application publication date: 20180612 |