CN108559238A - A kind of polyhydroxycarboxyliacid acid alloy material and its preparation method and application that biology base is degradable - Google Patents
A kind of polyhydroxycarboxyliacid acid alloy material and its preparation method and application that biology base is degradable Download PDFInfo
- Publication number
- CN108559238A CN108559238A CN201810408654.6A CN201810408654A CN108559238A CN 108559238 A CN108559238 A CN 108559238A CN 201810408654 A CN201810408654 A CN 201810408654A CN 108559238 A CN108559238 A CN 108559238A
- Authority
- CN
- China
- Prior art keywords
- acid
- polyhydroxycarboxyliacid
- type polymer
- copoly type
- alloy material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
-
- 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
- C08K2201/018—Additives for biodegradable polymeric composition
-
- 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
-
- 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
-
- 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
Abstract
The present invention discloses the degradable polyhydroxycarboxyliacid acid alloy material of biology base, in terms of mass percentage, raw material includes polylactic acid 50 75%, other polyhydroxycarboxyliacid acids 15 45% in addition to polylactic acid, the first copoly type polymer 0.5 10%, the second copoly type polymer 0.1 1% different from the first copoly type polymer；The monomer of first copoly type polymer includes the first monomer of the functional group that the end group with other polyhydroxycarboxyliacid acids with the end group of polylactic acid and/or in addition to polylactic acid reacts and containing the second comonomer of double bond；Second copoly type polymer is the copolymer of methyl acrylate and glycidyl methacrylate；It prepares：Raw material is weighed by formula, processing is dried to the polyhydroxycarboxyliacid acid weighed, dry polyhydroxycarboxyliacid acid is mixed with surplus stock, extrusion；And the application in producing cold drink cup lid；The present invention realize compared with low temperature exert oneself learn etc. the preferable effect of various aspects of performance, biodegradable, crystalline forming is fast.
Description
Technical field
The invention belongs to polymeric material fields, and in particular to a kind of polyhydroxycarboxyliacid acid alloy material that biology base is degradable
Material and its preparation method and application.
Background technology
Global Oil resource provision day is becoming tight, using oil as the environmental problem caused by the synthetic plastic of primary raw material
In the case of becoming increasingly conspicuous, low-carbon industry is as environmental protection weather and the another main path promoted economic development, low-carbon production
Industry is increasingly paid attention to by developed country and main developing country, and low-carbon economy just becomes world trends.It is passed through in low-carbon
Risen under the guiding of Ji, in world wide research and application biodegradable plastic upsurge, the exploitation of biodegradable plastic with
Using the amblent air temperature problem caused by administering waste plastic (white pollution) promotes to play weight in socio-economic development
Role is wanted, for example, traditional plastic cup cover has non-biodegradable, it is one of the important sources of " white pollution ".
The biodegradated polymer materal produced by biological industry technology using living resources is replaced using oil as raw material
By chemically synthesized conventional polymer material, the annual carbon dioxide that can be achieved to reduce several hundred million tons discharges only.Currently, biological
Degradative plastics is one of the hot spot of global new material, and there are huge growth potentials, according to grinding for Occams Research publications
Study carefully report, whole world biological-based chemicals and high molecular material yield are at 50,000,000 tons or so at present, it is contemplated that can to 2021 annual value of production
Reach 100~15,000,000,000 dollars.The determinant of biodegradable plastic industry development is promoted to be formed, such as national policy branch
It holds, vigorous (such as the demand of cup lid, according to U.S. Cleveland Freedonia groups of market conditions research company of customer demand
Report, cup lid demand are gone up with 4.7% annual growth, and market value estimation at present is up to multi-million dollar), oil price it is continuous
Go up etc., the especially rise of low-carbon economy is that the development of biodegradable plastic brings broader market, is provided more
For fine development blueprint.
Country makes laws biological support degradative plastics in human lives and production in succession in developed country and partial development
Using as the preferential buying biobased products plan in the U.S., the plan of bio-based materials 2020 of Japan, Australia hold
Continuous packaging plan etc..It is contemplated that with the development of Domestic legislation, biodegradable plastic will take the lead in leading in new packaging material
It is popularized in domain.
Biodegradation material can be divided into full-biodegradable material and destructive biodegradation material.Strictly speaking,
Destructive biodegradation material is not belonging to biodegradable plastic scope, as polyolefin/starch composite material, wood plastic composite,
Nondegradable plastics/degradative plastics compound etc..With regard to using starch, sawdust for the composite material of raw material, although shallow lake therein
Powder, sawdust etc. come from reproducible natural resources, but after the degradations such as starch, sawdust, remain polyolefin in the soil very
It is extremely more difficult than the residue of pure plastic products, it is also not possible to be recycled again, burning is the destructive biology drop of processing
The best way of plastics is solved, and the problem of destructive biodegradable plastic is then not present in the post-processing of biological degradation plastics.
There are two types of approach in the primary raw materials source of biological degradation plastics：Natural resources and oil/gas.Wherein, gather
Hydroxycarboxylic acid (polyhydroxyalkanoate, PHA) is that one kind being used as polymeric material existing for some microbe carbon sources in nature
Material is a kind of using cornstarch as the polyester-based polymer material of Material synthesis, and PHA can conduct when bad environments
The carbon source of microorganism can also finally be degraded to water and carbon dioxide by the enzyme effect that microorganism generates in the natural environment,
Simultaneously in entire PHA synthesis, application and degradation cycle, the consumption of carbon dioxide is more than discharge capacity, be a kind of performance compared with
For excellent and environmental-friendly high molecular material, the degradable high polymer material, temperature in use such as from renewable resource are than it
The biodegradable plastic of its type is high, has good biocompatibility and gas barrier property, therefore has wide city
Field foreground, still, PHA is slow since there is also crystallization rates, rear crystalline polamer is serious, product brittleness is big, processing rheological property
Difference, heat decomposition temperature it is low, it is not easy to be processed, compared under low temperature environment performance decline it is serious the shortcomings of, make it in actual application process
In be greatly limited, therefore, while those skilled in the art urgently seeks one kind and disclosure satisfy that biodegradable
Can also meet after molding various aspects of performance such as toughness, processing performance, product size stability, compared with low temperature under application performance
The material haveing excellent performance.
Invention content
The technical problem to be solved by the present invention is to overcome deficiency in the prior art, a kind of polyhydroxycarboxyliacid acid conjunction is provided
Golden material not only has biodegradable characteristic, but also can improve the processing rheological property of material, toughness, solves
The problem of product size stability difference, while the stability of material at low ambient temperatures is also improved, and then may make
It can be applied under lower temperature environment.
The present invention also provides the preparation methods of polyhydroxycarboxyliacid acid alloy material.
The present invention also provides purposes of the polyhydroxycarboxyliacid acid alloy material in producing cold drink cup lid.
In order to solve the above technical problems, a kind of technical solution that the present invention takes is as follows：
A kind of polyhydroxycarboxyliacid acid alloy material, raw material include polyhydroxycarboxyliacid acid, and the polyhydroxycarboxyliacid acid includes polylactic acid
With other polyhydroxycarboxyliacid acids in addition to polylactic acid；The raw material further includes the first copoly type polymer, is copolymerized with described first
The second different copoly type polymer of type polymer；
In terms of mass percentage, the polylactic acid, other polyhydroxycarboxyliacid acids in addition to polylactic acid, described
One copoly type polymer and the second copoly type polymer account for respectively the raw material mass percentage be 50-75%,
15-45%, 0.5-10% and 0.1-1%；
Wherein, the monomer of the first copoly type polymer includes the first monomer and the second comonomer containing double bond, described
First monomer has anti-with the end group of the polylactic acid and/or the end group of other polyhydroxycarboxyliacid acids in addition to polylactic acid
The functional group answered；The second copoly type polymer is the copolymer of methyl acrylate and glycidyl methacrylate.
Some preferred aspects according to the present invention, first monomer are sweet selected from maleic anhydride, Glycidyl methacrylate
One or more combinations in grease, acrylic ester compound, oxazole compounds and isocyanate ester compound.
Some preferred aspects according to the present invention, the second comonomer are selected from ethylene, styrene, propylene, non-conjugated two
One or more combinations in alkene, butadiene, amylene, hexene, heptene and octene.
More according to the present invention specific and preferred aspect, the first copoly type polymer are selected from ethylene-propylene
Sour methyl terpolymer, ethylene-butyl acrylate copolymer, ethylene-methyl acrylate-glyceryl methacrylate copolymerization
Object, ethylene maleic acid anhydride copolymer, ethylene-methyl acrylate-copolymer-maleic anhydride, maleic anhydride grafted polyethylene, horse
Maleic anhydride grafted polypropylene, maleic anhydride stem grafting polyolefin elastomer, maleic anhydride grafting ethylene propylene diene rubber and maleic anhydride
The one or more combinations being grafted in hydrogenated butadiene-styrene copolymer.
More according to the present invention specific and preferred aspect, other polyhydroxycarboxyliacid acids in addition to polylactic acid are
Selected from poly 3-hydroxy butyrate, poly- 4 hydroxybutyric acid ester, poly- 3- hydroxyl valerates, poly- (3-hydroxybutyrate -4 hydroxybutyric acid) is total
One in polyester, poly- (3-hydroxybutyrate -3- hydroxypentanoic acids) copolyesters and poly- (4 hydroxybutyric acid -3- hydroxypentanoic acids) copolyesters
Kind or a variety of combinations.
Some preferred aspects according to the present invention, the quality percentage of the epoxy group in the second copoly type polymer
Content is 1-10%.It is highly preferred that the mass percentage of the epoxy group in the second copoly type polymer is 4-8%.
The mass percentage of a specific aspect according to the present invention, the epoxy group in the second copoly type polymer is
6.5%.
According to the present invention, the weight average molecular weight of the second copoly type polymer is 5000-20000.It is highly preferred that institute
The weight average molecular weight for stating the second copoly type polymer is 8000-12000.A specific aspect according to the present invention, described second
The weight average molecular weight of copoly type polymer is about 10000.
Some preferred aspects according to the present invention, the polylactic acid, other poly- hydroxyl carboxylics in addition to polylactic acid
The mass percentage that sour, the described first copoly type polymer and the second copoly type polymer account for the raw material respectively is
55-70%, 22-40%, 2-8% and 0.1-0.8%.
According to the present invention, the weight average molecular weight of the polylactic acid is 5~100,000.According to the present invention, it is described except polylactic acid it
The weight average molecular weight of outer other polyhydroxycarboxyliacid acids is 10~600,000.Preferably, other poly- hydroxyls in addition to polylactic acid
The weight average molecular weight of carboxylic acid is 25~350,000.
In the present invention, according to ASTM6866 assay methods, the polylactic acid and other poly- hydroxyls in addition to polylactic acid
Yl carboxylic acid is respectively provided with 100% biomass source.
More according to the present invention specific and preferred aspect, in terms of mass percentage, the raw material further includes accounting for institute
The mass percentage for stating raw material is the lubricant of 0.1-1%.
Some specific aspects according to the present invention, the lubricant be selected from calcium stearate, zinc stearate, odium stearate,
Barium stearate, oxidized polyethylene wax, ethylene vinyl acetate wax, N, N- ethylene bis stearamides, pentaerythritol stearate,
One or more combinations in montanate and silicone powder.
More according to the present invention specific and preferred aspect, in terms of mass percentage, the raw material further includes accounting for institute
The mass percentage for stating raw material is the nucleating agent of 0.1-1%.
Some specific aspects according to the present invention, the nucleating agent are selected from sodium-based montmorillonite, talcum powder, mica, boiling
Stone, vermiculite, wollastonite, sepiolite, aluminium oxide, magnesia, zinc oxide, aluminium nitride, boron nitride, silicon carbide, calcium carbonate, carbonic acid
One or more combinations in barium, barium sulfate.
More according to the present invention specific and preferred aspect, in terms of mass percentage, the raw material further includes accounting for institute
The mass percentage for stating raw material is the antioxidant of 0.1-1%.
Some specific aspects according to the present invention, the antioxidant are selected from four [methylene β-(3,5- di-t-butyl -4- hydroxyls
Base phenyl) propionic acid] pentaerythritol ester (antioxidant 1010), the positive octadecanol of β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid
Ester (antioxidant 1076), three (2,4- di-tert-butyl-phenyls) phosphite esters, 2,6- di-t-butyls are to potassium phenol, bis- (bis- tertiary fourths of 2,4-
Base phenol) pentaerythritol diphosphites (antioxidant 626) and N, N'- it is bis--(3- (3,5- di-tert-butyl-hydroxy phenyls) third
Acyl group) it is one or more in hexamethylene diamine (antioxidant 1098).
Another technical solution provided by the invention：A kind of preparation method of polyhydroxycarboxyliacid acid alloy material described above,
The preparation method includes：Each raw material is weighed by formula rate, processing first is dried in the polyhydroxycarboxyliacid acid weighed,
Then the polyhydroxycarboxyliacid acid after drying is mixed with surplus stock, polyhydroxycarboxyliacid acid alloy material is made in extrusion molding.
Another technical solution provided by the invention：A kind of polyhydroxycarboxyliacid acid alloy material described above is in production cold drink
Purposes in cup lid.
In the present invention, " biology base is degradable " refers to that the primary raw materials of the polylactic acid and polyhydroxycarboxyliacid acid derives from
Starch rather than petroleum-based chemical object, the alloy material biological degradation rate is 90% or more.
Due to the use of above technical scheme, the present invention has the following advantages that compared with prior art：
The present invention is on the basis of polylactic acid carries out blending and modifying with other polyhydroxycarboxyliacid acids in addition to polylactic acid, knot
Close the synergistic effect of specific first copoly type polymer and the second copoly type polymer so that polyhydroxycarboxyliacid acid alloy material
The mechanical properties such as toughness can have preferable effect within the scope of -25 DEG C -60 DEG C, both having avoided can give birth in the prior art
The narrow problem in the temperature in use section of object degradable material, and improve the stabilization of material various aspects of performance at a lower temperature
Property, while the modified material of the present invention not only has biodegradable characteristic, and it is environmentally friendly, and crystallization rate is fast, adds
Work is easier.
Specific implementation mode
In the prior art, biodegradable material temperature in use section is narrow, especially various aspects at a lower temperature
Performance such as toughness is poor, it is difficult to realize preferable application.Polyhydroxycarboxyliacid acid (polyhydroxyalkanoate, PHA) gives birth at present
Object degradability is by more and more extensive concern and application, wherein polylactic acid (PLA) is as one kind of polyhydroxycarboxyliacid acid and one
Kind can pass through microbial enzyme under field conditions (factors) with the polyester-based polymer material from cornstarch of complete biodegradable
Effect be decomposed into water and carbon dioxide, with excellent mechanical property, processing rheological property, human society put into practice
In obtain a degree of application, such as field of medicaments and 3D printing field, still, pure PLA crystallization rates are slow, finished product shrinking percentage
Height, poor dimensional stability, essence is brittle, and processing stability is poor, and glass transition temperature is low, and the characteristics such as durability difference are again serious
Limit its application in each field.
In practice, it has been found that when being blended with other polyhydroxycarboxyliacid acids in addition to polylactic acid using polylactic acid
It is modified, in combination with the synergistic effect of specific first copoly type polymer and the second copoly type polymer, and control respective
Content can significantly improve polylactic acid or product that when other polyhydroxycarboxyliacid acids in addition to polylactic acid are used alone has
The big problem of brittleness, so that modified material can be applicable in wider array of temperature range, especially at a lower temperature
Material various aspects of performance such as toughness can also be kept to have the effect of more excellent, so that modified material can should have
In the production of cold drink cup lid.
Based on this, the present invention provides a kind of polyhydroxycarboxyliacid acid alloy materials, and raw material includes polyhydroxycarboxyliacid acid, described
Polyhydroxycarboxyliacid acid includes polylactic acid and other polyhydroxycarboxyliacid acids in addition to polylactic acid；The raw material further includes the first copoly type
Polymer, the second copoly type polymer different from the first copoly type polymer；It is described poly- in terms of mass percentage
Lactic acid, other polyhydroxycarboxyliacid acids, the first copoly type polymer and second copoly type in addition to polylactic acid are poly-
It is 50-75%, 15-45%, 0.5-10% and 0.1-1% to close object and account for the mass percentage of the raw material respectively；Wherein, institute
The monomer for stating the first copoly type polymer includes the first monomer and the second comonomer containing double bond, first monomer have with
The functional group of the end group of the end group of the polylactic acid and/or other polyhydroxycarboxyliacid acids in addition to polylactic acid reaction；It is described
Second copoly type polymer is the copolymer of methyl acrylate and glycidyl methacrylate.
The present invention also provides a kind of method preparing polyhydroxycarboxyliacid acid alloy material, the method includes；By recipe ratio
Example weighs each raw material, processing first is dried in the polyhydroxycarboxyliacid acid weighed, then by the poly- hydroxyl carboxylic after drying
Acid is mixed with surplus stock, and polyhydroxycarboxyliacid acid alloy material is made in extrusion molding.Wherein, it when extrusion molding, can use double
Screw extruder carries out, and controls 80-200 DEG C of the processing temperature of double screw extruder.Preferably, double screw extruder is controlled
120-200 DEG C of processing temperature.It is highly preferred that 150-190 DEG C of the processing temperature of control double screw extruder.Driving screw is controlled to turn
Speed is 200-500 revs/min, preferably 250-350 revs/min.After extrusion molding obtains polyhydroxycarboxyliacid acid alloy material, preferably
So that it is carried out injection molding at 160-200 DEG C, injection molding is more preferably carried out at 160-180 DEG C.
Said program is described further below in conjunction with specific embodiment；It should be understood that these embodiments are for illustrating
The basic principles, principal features and advantages of the present invention, and the present invention is not by the scope limitation of following embodiment；It is adopted in embodiment
Implementation condition can do further adjustment according to specific requirement, and the implementation condition being not specified is usually in routine experiment
Condition.
In following, unless otherwise specified, all raw materials are both from conventional method system commercially available or by this field
It is standby and obtain.
Each performance test methods are substantially as follows：Bending property：ISO 178:2001 plastics bending properties are tested；
Izod notched impact strength：ISO 180:The measurement of 2001 plastics Chalpy impact performances.
Heat distortion temperature：Measurement-part 1 of ISO 75-1 plastics-load not trip temperature：General Experimental Procedures.
In following, the second copoly type polymer is the copolymer of methyl acrylate and glycidyl methacrylate,
In the second copoly type polymer epoxide epoxy group group content be 6.5% (mass percentage), weight average molecular weight is about 10000.
PHBV：The copolymer of 3-hydroxybutyrate and 3- hydroxypentanoic acids is purchased from Ningbo Tianan Biological Material Co., Ltd.,
The content of 3- hydroxypentanoic acids about 3%, viscosity-average molecular weight about 450,000.The weight average molecular weight of the polylactic acid is 6~80,000.
Embodiment 1
Accurately 2.781 kilograms of PHBV, 6.489 kilograms of PLA, 0.6 kilogram of ethylene-methyl acrylate copolymer is weighed (to be purchased from
French A Kema Lotryl 29MA03), 0.03 kilogram of antioxidant 1010,0.04 kilogram of calcium stearate, 0.03 kilogram of talcum powder,
0.03 kilogram of second copoly type polymer.
Preparation method is as follows：So that PLA and PHBV is dried in vacuo 24 hours at 60 DEG C, is then mixed with remaining raw material
Uniformly, it then is squeezed out (extrusion temperature is 160 ± 5 DEG C), is granulated, it is dry, obtain polyhydroxycarboxyliacid acid alloy material.
It squeezes out sample and test sample (170 ± 5 DEG C of injection temperature) is molded into according to ASTM standard, 23 DEG C of products obtained therefrom
Unnotched impact strength is 199J/m, and -23 DEG C of unnotched impact strengths are 157J/m, bending modulus 2800MPa,
54 DEG C of heat distortion temperature under 0.455MPa.
Embodiment 2
Accurately weigh 2.781 kilograms of PHBV, 6.489 kilograms of PLA, 0.6 kilogram of ethylene-methyl acrylate-metering system
Acid glycidyl ester copolymer (being purchased from France A Kema Lotader 8900), 0.03 kilogram of antioxidant, 626,0.04 kilogram of N,
N- diethylene stearic acid presses, 0.03 kilogram of boron nitride, 0.03 kilogram of second copoly type polymer.
Preparation method is as follows：So that PLA and PHBV is dried in vacuo 24 hours at 60 DEG C, is then mixed with remaining raw material
Uniformly, it then is squeezed out (extrusion temperature is 160 ± 5 DEG C), is granulated, it is dry, obtain polyhydroxycarboxyliacid acid alloy material.
It squeezes out sample and test sample (170 ± 5 DEG C of injection temperature) is molded into according to ASTM standard, 23 DEG C of products obtained therefrom
Unnotched impact strength is 209J/m, and -23 DEG C of unnotched impact strengths are 162J/m, bending modulus 2800MPa,
56 DEG C of heat distortion temperature under 0.455MPa.
Embodiment 3
Accurate 3.708 kilograms of PHBV, 5.562 kilograms of PLA, the 0.6 kilogram of ethylene maleic acid anhydride copolymer of weighing (is purchased from method
State Ah Kerma (unit of kinetic energy) Lotryl 4700), 0.03 kilogram of antioxidant, 1098,0.04 kilograms of pentaerythritol stearates, 0.03 kilogram of sodium
Base montmorillonite, 0.03 kilogram of second copoly type polymer.
Preparation method is as follows：So that PLA and PHBV is dried in vacuo 24 hours at 60 DEG C, is then mixed with remaining raw material
Uniformly, it then is squeezed out (extrusion temperature is 160 ± 5 DEG C), is granulated, it is dry, obtain polyhydroxycarboxyliacid acid alloy material.
It squeezes out sample and test sample (170 ± 5 DEG C of injection temperature) is molded into according to ASTM standard, 23 DEG C of products obtained therefrom
Unnotched impact strength is 165J/m, and -23 DEG C of unnotched impact strengths are 133J/m, bending modulus 2900MPa,
56 DEG C of heat distortion temperature under 0.455MPa.
Embodiment 4
Accurately weigh 3.708 kilograms of PHBV, 5.562 kilograms of PLA, 0.6 kilogram of maleic anhydride stem grafting polyolefin elastomer
(it is purchased from Du Pont493d), 0.03 kilogram of antioxidant 1076,0.04 kilogram of pentaerythritol stearate, 0.03 thousand
Gram boron nitride, 0.03 kilogram of second copoly type polymer.
Preparation method is as follows：So that PLA and PHBV is dried in vacuo 24 hours at 60 DEG C, is then mixed with remaining raw material
Uniformly, it then is squeezed out (extrusion temperature is 160 ± 5 DEG C), is granulated, it is dry, obtain polyhydroxycarboxyliacid acid alloy material.
It squeezes out sample and test sample (170 ± 5 DEG C of injection temperature) is molded into according to ASTM standard, 23 DEG C of products obtained therefrom
Unnotched impact strength is 172J/m, and -23 DEG C of unnotched impact strengths are 141J/m, bending modulus 2900MPa,
57 DEG C of heat distortion temperature under 0.455MPa.
Embodiment 5
Accurately weigh 3.245 kilograms of PHBV, 6.0255 kilograms of PLA, 0.6 kilogram of maleic anhydride stem grafting polyolefin elastomer
(it is purchased from Du Pont493d), 0.03 kilogram of antioxidant 1076,0.04 kilogram of pentaerythritol stearate, 0.03 thousand
Gram boron nitride, 0.03 kilogram of second copoly type polymer.
Preparation method is as follows：So that PLA and PHBV is dried in vacuo 24 hours at 60 DEG C, is then mixed with remaining raw material
Uniformly, it then is squeezed out (extrusion temperature is 160 ± 5 DEG C), is granulated, it is dry, obtain polyhydroxycarboxyliacid acid alloy material.
It squeezes out sample and test sample (170 ± 5 DEG C of injection temperature) is molded into according to ASTM standard, 23 DEG C of products obtained therefrom
Unnotched impact strength is 183J/m, and -23 DEG C of unnotched impact strengths are 139J/m, bending modulus 2900MPa,
54 DEG C of heat distortion temperature under 0.455MPa.
Comparative example 1
Substantially it with embodiment 1, differs only in and is not added with PHBV, the corresponding additive amount for adjusting PLA is 9.27 kilograms.
It squeezes out sample and test sample (170 ± 5 DEG C of injection temperature) is molded into according to ASTM standard, 23 DEG C of products obtained therefrom
Unnotched impact strength is 116.0J/m, and -23 DEG C of unnotched impact strengths are 108.3J/m, bending modulus 2800MPa,
58 DEG C of heat distortion temperature under 0.455MPa.
Comparative example 2
Substantially it with embodiment 1, differs only in and is not added with PLA, the corresponding additive amount for adjusting PHBV is 9.27 kilograms.
It squeezes out sample and test sample (170 ± 5 DEG C of injection temperature) is molded into according to ASTM standard, 23 DEG C of products obtained therefrom
Unnotched impact strength is 56.4J/m, and -23 DEG C of unnotched impact strengths are 52.1J/m, bending modulus 3050MPa,
140.0 DEG C of heat distortion temperature under 0.455MPa.
Comparative example 3
Substantially it with embodiment 1, differs only in and is not added with ethylene-methyl acrylate copolymer, it is corresponding to adjust PHBV's
Additive amount is 3.381 kilograms.
It squeezes out sample and test sample (170 ± 5 DEG C of injection temperature) is molded into according to ASTM standard, 23 DEG C of products obtained therefrom
Unnotched impact strength is 43.2J/m, and -23 DEG C of unnotched impact strengths are 41.7J/m, bending modulus 2950MPa,
118.3 DEG C of heat distortion temperature under 0.455MPa.
Comparative example 4
Substantially it with embodiment 1, differs only in and is not added with the second copoly type polymer, the corresponding addition for adjusting PHBV
Amount is 2.811 kilograms.
It squeezes out sample and test sample (170 ± 5 DEG C of injection temperature) is molded into according to ASTM standard, 23 DEG C of products obtained therefrom
Unnotched impact strength is 37.8J/m, and -23 DEG C of unnotched impact strengths are 35.5J/m, bending modulus 3000MPa,
123.1 DEG C of heat distortion temperature under 0.455MPa.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow be familiar with technique
Personage cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention, all according to this hair
Equivalent change or modification made by bright Spirit Essence, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of polyhydroxycarboxyliacid acid alloy material, raw material include polyhydroxycarboxyliacid acid, which is characterized in that the polyhydroxycarboxyliacid acid packet
Include polylactic acid and other polyhydroxycarboxyliacid acids in addition to polylactic acid；The raw material further include the first copoly type polymer, with it is described
The second different copoly type polymer of first copoly type polymer；
In terms of mass percentage, the polylactic acid, other polyhydroxycarboxyliacid acids in addition to polylactic acid, first copolymerization
Type polymer and the second copoly type polymer account for respectively the raw material mass percentage be 50-75%, 15-45%,
0.5-10% and 0.1-1%；
Wherein, the monomer of the first copoly type polymer includes the first monomer and the second comonomer containing double bond, and described first
Monomer has the official reacted with the end group of the end group of the polylactic acid and/or other polyhydroxycarboxyliacid acids in addition to polylactic acid
It can group；The second copoly type polymer is the copolymer of methyl acrylate and glycidyl methacrylate.
2. polyhydroxycarboxyliacid acid alloy material according to claim 1, which is characterized in that first monomer is selected from Malaysia
In acid anhydrides, glycidyl methacrylate, acrylic ester compound, oxazole compounds and isocyanate ester compound
One or more combinations.
3. polyhydroxycarboxyliacid acid alloy material according to claim 1, which is characterized in that the second comonomer is selected from second
One or more combinations in alkene, styrene, propylene, non-conjugated diene hydrocarbon, butadiene, amylene, hexene, heptene and octene.
4. according to the polyhydroxycarboxyliacid acid alloy material described in any one of claim 1-3 claims, which is characterized in that described
First copoly type polymer is selected from ethylene-methyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-acrylic acid
Methyl esters-glycidyl methacrylate copolymer, ethylene maleic acid anhydride copolymer, ethylene-methyl acrylate-maleic anhydride
Copolymer, maleic anhydride grafted polyethylene, maleic anhydride inoculated polypropylene, maleic anhydride stem grafting polyolefin elastomer, maleic acid
Acid anhydride is grafted one or more combinations in ethylene propylene diene rubber and maleic anhydride grafting hydrogenated butadiene-styrene copolymer.
5. polyhydroxycarboxyliacid acid alloy material according to claim 1, which is characterized in that described other in addition to polylactic acid
Polyhydroxycarboxyliacid acid is selected from poly 3-hydroxy butyrate, poly- 4 hydroxybutyric acid ester, poly- 3- hydroxyl valerates, poly- (3-hydroxybutyrate -4-
Hydroxybutyric acid) copolyesters, poly- (3-hydroxybutyrate -3- hydroxypentanoic acids) copolyesters and poly- (4 hydroxybutyric acid -3- hydroxypentanoic acids) altogether
One or more combinations in polyester.
6. polyhydroxycarboxyliacid acid alloy material according to claim 1, which is characterized in that in the second copoly type polymer
Epoxy group mass percentage be 1-10%.
7. polyhydroxycarboxyliacid acid alloy material according to claim 1, which is characterized in that the polylactic acid, described remove gather breast
Other polyhydroxycarboxyliacid acids, the first copoly type polymer and the second copoly type polymer except acid account for the original respectively
The mass percentage of material is 55-70%, 22-40%, 2-8% and 0.1-0.8%.
8. polyhydroxycarboxyliacid acid alloy material according to claim 1, which is characterized in that the raw material further includes accounting for the original
The mass percentage of material is the lubricant of 0.1-1%；The raw material also includes selectively the quality for accounting for the raw material respectively
Percentage composition is nucleating agent, the antioxidant of 0.1-1%.
9. the preparation method of the polyhydroxycarboxyliacid acid alloy material described in a kind of any one of claim 1-8 claims, special
Sign is that the preparation method includes：Each raw material is weighed by formula rate, first the polyhydroxycarboxyliacid acid weighed is dried
Processing, then mixes the polyhydroxycarboxyliacid acid after drying with surplus stock, polyhydroxycarboxyliacid acid alloy material is made in extrusion molding
Material.
10. polyhydroxycarboxyliacid acid alloy material as claimed in any one of claims 1-8 is in producing cold drink cup lid
Application.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810408654.6A CN108559238B (en) | 2018-05-02 | 2018-05-02 | Biodegradable polyhydroxycarboxylic acid alloy material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810408654.6A CN108559238B (en) | 2018-05-02 | 2018-05-02 | Biodegradable polyhydroxycarboxylic acid alloy material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108559238A true CN108559238A (en) | 2018-09-21 |
| CN108559238B CN108559238B (en) | 2020-11-13 |
Family
ID=63537421
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810408654.6A Active CN108559238B (en) | 2018-05-02 | 2018-05-02 | Biodegradable polyhydroxycarboxylic acid alloy material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108559238B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114605795A (en) * | 2022-03-04 | 2022-06-10 | 大连海事大学 | Preparation method of biochar polylactic acid composite 3D printing material |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1898326A (en) * | 2003-12-22 | 2007-01-17 | 伊斯曼化学公司 | Compatibilized blends of biodegradable polymers with improved rheology |
| CN102131868A (en) * | 2008-01-09 | 2011-07-20 | 纳幕尔杜邦公司 | Polyester composition resistant to hydrolysis |
| CN103013070A (en) * | 2012-12-11 | 2013-04-03 | 奇瑞汽车股份有限公司 | Polylactic acid composite material and preparation method thereof |
| CN103122129A (en) * | 2003-12-22 | 2013-05-29 | 伊士曼化工公司 | Polymer blends with improved notched impact strength |
| CN103319865A (en) * | 2013-06-08 | 2013-09-25 | 上海博疆新材料科技有限公司 | Polylactic acid alloy membrane and application thereof |
| CN104379671A (en) * | 2012-06-05 | 2015-02-25 | 梅塔玻利克斯公司 | Biobased rubber modified biodegradable polymer blends |
-
2018
- 2018-05-02 CN CN201810408654.6A patent/CN108559238B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1898326A (en) * | 2003-12-22 | 2007-01-17 | 伊斯曼化学公司 | Compatibilized blends of biodegradable polymers with improved rheology |
| CN103122129A (en) * | 2003-12-22 | 2013-05-29 | 伊士曼化工公司 | Polymer blends with improved notched impact strength |
| CN102131868A (en) * | 2008-01-09 | 2011-07-20 | 纳幕尔杜邦公司 | Polyester composition resistant to hydrolysis |
| CN104379671A (en) * | 2012-06-05 | 2015-02-25 | 梅塔玻利克斯公司 | Biobased rubber modified biodegradable polymer blends |
| CN103013070A (en) * | 2012-12-11 | 2013-04-03 | 奇瑞汽车股份有限公司 | Polylactic acid composite material and preparation method thereof |
| CN103319865A (en) * | 2013-06-08 | 2013-09-25 | 上海博疆新材料科技有限公司 | Polylactic acid alloy membrane and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| 曾人泉: "《塑料加工助剂》", 31 December 1997 * |
| 杨桂生: "《工程塑料》", 31 December 2017 * |
| 章峻，司玲，杨继全: "《3D打印成型材料》", 31 December 2016 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114605795A (en) * | 2022-03-04 | 2022-06-10 | 大连海事大学 | Preparation method of biochar polylactic acid composite 3D printing material |
| CN114605795B (en) * | 2022-03-04 | 2024-02-06 | 大连海事大学 | Preparation method of biochar polylactic acid composite 3D printing material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108559238B (en) | 2020-11-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Singh et al. | Thermal properties and degradation characteristics of polylactide, linear low density polyethylene, and their blends | |
| Zhao et al. | Biodegradation behavior of polycaprolactone/rice husk ecocomposites in simulated soil medium | |
| TWI396712B (en) | Resin composition and the molding article | |
| CN108047658B (en) | Biodegradable polyester agricultural mulching film | |
| JP4987312B2 (en) | Thermoplastic resin composition and molded article thereof | |
| JP5567129B2 (en) | Polyhydroxyalkanoate composition exhibiting improved impact resistance | |
| CN111718566A (en) | PLA/PBAT biodegradable composite material and product thereof | |
| CN109337312B (en) | Polylactic acid composite material and preparation method thereof | |
| CN108948690B (en) | Polylactic acid-lignin-starch composite material and preparation method thereof | |
| CN101475735A (en) | Completely biodegradable polyhydroxyalkanote / poly(butylene succinate) blending alloy | |
| CN107619584A (en) | Lactic acid composite material, tableware and preparation method thereof | |
| CN102719063A (en) | Polylactic acid material composition, polylactic acid material and its preparation method | |
| JP2007191695A (en) | Resin composition and molded article comprising the same | |
| CN102295831A (en) | Special material for fully biodegradable rigid sheet and preparation method thereof | |
| JP2007161837A (en) | Styrene-based resin composition | |
| CN108641318A (en) | A kind of polyhydroxycarboxyliacid acid alloy material and preparation method thereof that biology base is degradable | |
| JP2010143978A (en) | Resin composition and molded product using the same | |
| CN108559238A (en) | A kind of polyhydroxycarboxyliacid acid alloy material and its preparation method and application that biology base is degradable | |
| EP2251378A1 (en) | Biodegradable polyester resin composition and molded body composed of the same | |
| JP2007063540A (en) | Styrene-based resin composition and molded product made of the same | |
| Valerio et al. | Improvement of impact toughness of biodegradable poly (butylene succinate) by melt blending with sustainable biobased glycerol elastomers | |
| CN108587092A (en) | The degradable polyhydroxycarboxyliacid acid alloy material and its preparation method and application of biology base | |
| CN108841153B (en) | High-toughness and high-heat-deformation-temperature polylactic acid composition and preparation method thereof | |
| US20230303829A1 (en) | Biodegradable material, preparation method and application thereof | |
| CN114836012A (en) | Completely biodegradable garbage bag film material and preparation method of garbage bag film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |