CN110066502A - A kind of modified polylactic acid material and the preparation method and application thereof with low-temperature flexibility - Google Patents
A kind of modified polylactic acid material and the preparation method and application thereof with low-temperature flexibility Download PDFInfo
- Publication number
- CN110066502A CN110066502A CN201910338048.6A CN201910338048A CN110066502A CN 110066502 A CN110066502 A CN 110066502A CN 201910338048 A CN201910338048 A CN 201910338048A CN 110066502 A CN110066502 A CN 110066502A
- Authority
- CN
- China
- Prior art keywords
- polylactic acid
- low
- temperature
- modified polylactic
- acid 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.)
- Pending
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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Biological Depolymerization Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of modified polylactic acid material and the preparation method and application thereof with low-temperature flexibility, belongs to biodegradated polymer materal technical field.It solves existing polylactic acid toughening to be only limited to room temperature toughening and do not pay close attention to the technical issues of cryogenic mechanics performance and existing low-temperature resistant plastic product are without biological degradability.Modified polylactic acid material of the invention is made of the polylactic acid of 100 parts by weight and the toughener of 5-40 parts by weight；The weight average molecular weight of polylactic acid is 1.0 × 105‑3.0×105g/mol；Toughener is glass transition temperature in -20 DEG C of polymer below.The modified polylactic acid material still has preferable tensile toughness and impact flexibility under low temperature (- 20 DEG C), material tensile strength with higher simultaneously, and there is biodegradable, it can be used for preparing biodegradable low-temperature resistant plastic product, assign the excellent low-temperature flexibility of such plastic products and biological degradability.
Description
Technical field
The invention belongs to biodegradated polymer materal technical fields, and in particular to a kind of polylactic acid with low-temperature flexibility
Modified material and the preparation method and application thereof.
Background technique
People have pushed demand of the world market to biodegradation material to the concern of plastic refuse in environment.Polylactic acid
It is environmentally protective plastics most with prospects of universally acknowledged 21 century, derives from renewable plant resources, there is biology drop
Solution property good, good biocompatibility, Bioabsorbable is good, mechanical strength is high, the transparency is good, easy processing form the advantages that.However,
Polylactic acid brittleness is serious, and shock resistance is poor, is not able to satisfy application demand, and therefore, people have carried out toughening modifying to polylactic acid
Research.Currently, Blending Toughening Modification method is to improve the technical way of PLA toughness.The use such as Jiang polyadipate/right
Terephtha-late (PBAT) carries out toughening modifying to polylactic acid, so that the tensile toughness of polylactic acid and impact flexibility have one
It is fixed to improve (Biomacromolecules 2006,7,199-207).Li et al. is successfully prepared the PLA/PU intermingling material of high tenacity
(MacromolecularBioscience 2007,7,921-928).In our previous research work, using polyethers-b-
Amide thermoplastic elastomer (TPE) (PEBA) (Polymer Composites 2013,34,122-130) and complete biodegradable it is poly-
(3-hydroxybutyrate ester-co-4- butyric ester) [P (3HB-co-4HB)] (Polymer Composites 2012,33,850-
859) toughening modifying is carried out to polylactic acid, elongation at break and impact strength are significantly improved.Publication No.
The Chinese invention patent of 101914274A has studied modification work of the polyadipate 1,2-PD ester to PLA, polyadipate 1,
The impact strength and tension fracture elongation rate of PLA can be improved in 2- propylene glycol ester.In the patent of Publication No. 109401244A
Disclose a kind of modified polylactic acid material, including polylactic resin, toughener and other auxiliary agents, the modified polylactic acid material of preparation
Solves the lower disadvantage of brittleness existing for existing polylactic acid, poor toughness, impact strength.However, above both at home and abroad to polylactic acid
Whether the toughening modifying of progress is studied, make its room temperature toughness be significantly improved, but improve simultaneously for its low-temperature flexibility
It does not conduct a research.With the expansion that biodegradated polymer materal is applied, low-temperature resistant plastic product is to Biodegradable high molecular material
The demand of material is increasing, such as polylactic acid cold drink suction pipe, cold drink cup disk, ice cream holder and ice cream box, therefore, to the tough of polylactic acid
Property proposes new requirement, and the product for developing biodegradable polylactic acid low-temperature flexibility is beneficial to be further reduced plastic product
White pollution, widen the application range of polylactic acid.
Summary of the invention
Be only limited to room temperature toughening present invention aim to address existing polylactic acid toughening and do not pay close attention to cryogenic mechanics performance with
And existing low-temperature resistant plastic product does not have the technical issues of biological degradability, provides a kind of polylactic acid with low-temperature flexibility
Modified material and the preparation method and application thereof.
The present invention provides a kind of modified polylactic acid material with low-temperature flexibility, by the polylactic acid and 5-40 of 100 parts by weight
The toughener of parts by weight forms；
The weight average molecular weight of the polylactic acid is 1.0 × 105-3.0×105g/mol；
The toughener is glass transition temperature in -20 DEG C of polymer below；
The modified polylactic acid material with low-temperature flexibility is 17-140%, impact strength in -20 DEG C of elongation at break
For 7-80KJ/m2。
Preferably, the toughener be polycaprolactone, polyethers-b- amide thermoplastic elastomer (TPE) (PEBA), polyadipate/
Butylene terephthalate (PBAT), methyl methacrylate-butadiene-styrene terpolymer (MBS), esters of acrylic acid
Polymer (ACR), epoxychloropropane-ethylene oxide epichlorohydrin binary copolymer, epoxychloropropane-ethylene oxide ternary polymerization
One of epichlorohydrin rubber or a variety of mixing.
Preferably, the toughener is 10-25 parts by weight.
Preferably, the modified polylactic acid material further includes the antioxidant of 0.1-0.5 parts by weight；It is further preferred that institute
Stating antioxidant is three (2,4- di-tert-butyl-phenyl) phosphite esters (irgasfos 168), bis- (2,4- di-tert-butyl-phenyl) Ji Wusi
Alcohol diphosphites (antioxidant AT-626), four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxygens
Agent 1010) one of or a variety of mixing.
Preferably, the elongation at break of the modified polylactic acid material with low-temperature flexibility is 50-140%, impact
Intensity is 13-80KJ/m2。
The present invention also provides the preparation methods of the above-mentioned modified polylactic acid material with low-temperature flexibility, and steps are as follows:
Step 1: weighing the polylactic acid after being dried, toughener and antioxygen after drying process by composition and proportion
Agent, mechanical mixture are uniform；
Step 2: uniformly mixed raw material is added in mixer, melt blending, room temperature is cooling, and cutting is had
The modified polylactic acid material of low-temperature flexibility；
Alternatively,
Uniformly mixed raw material is added in extruder, is squeezed out, it is cooling, it is granulated, obtains the polylactic acid with low-temperature flexibility
Modified material.
Preferably, in the step 1, the churned mechanically time is 1-3min.
Preferably, in the step 2, the temperature of melt blending is 175-190 DEG C, the revolving speed of the temperature of melt blending
It is 50-60 revs/min, the time of the temperature of melt blending is 5-8min.
Preferably, in the step 2, the equipment of extruding pelletization is double screw extruder, the set temperature of extruder
Are as follows: an area: 165-180 DEG C, 2nd area: 170-185 DEG C, 3rd area: 170-190 DEG C, 4th area: 170-190 DEG C, 5th area: 170-190
DEG C, 6th area: 170-190 DEG C, 7th area: 170-190 DEG C, 8th area: 170-190 DEG C, head: 170-190 DEG C；Screw speed is 100-
300rpm。
The present invention also provides the above-mentioned modified polylactic acid material with low-temperature flexibility prepare it is biodegradable low temperature resistant
Application in plastic products.
Preferably, the plastic products are cold drink suction pipe, cold drink cup disk, ice cream holder or ice cream box.
Compared with prior art, the invention has the benefit that
Modified polylactic acid material provided by the invention with low-temperature flexibility, formula is simple, and blend components are few, and raw material is easy
, it is cheap, still there is preferable tensile toughness and impact flexibility under low temperature (- 20 DEG C), highest elongation at break can
Up to 140%, impact strength may be up to 77.1KJ/m2, it is better than high density polyethylene (HDPE), while material stretching with higher is strong
Therefore degree has good resistance to low temperature.Moreover, when test temperature is higher than -20 DEG C and is lower than 0 DEG C, the tensile toughness of material
It can be further increased with impact flexibility.
Modified polylactic acid material provided by the invention with low-temperature flexibility has biodegradable, alternative existing
Non-biodegradable material is widely used in low temperature field, solves the problems, such as existing plastic products bring white pollution.
The preparation process of the modified polylactic acid material of low-temperature flexibility of the invention is simple, clean and environmental protection, reduces energy consumption, mentions
High production efficiency.
Modified polylactic acid material with low-temperature flexibility of the invention can prepare biodegradable resistance to low as raw material
Warm plastic products assign the excellent low-temperature flexibility of such plastic products and biological degradability.
Specific embodiment
In order to further appreciate that the present invention, the preferred embodiments of the invention are retouched With reference to embodiment
It states, but it is to be understood that these descriptions are intended merely to further illustrate the features and advantages of the present invention rather than to present invention power
The limitation that benefit requires.
Modified polylactic acid material with low-temperature flexibility of the invention, by the polylactic acid and 5-40 parts by weight of 100 parts by weight
Toughener composition.It can also include the antioxidant of 0.1-0.5 parts by weight.
Wherein, polylactic acid is the substrate of modified material of the invention, can be obtained by those skilled in the art's well-known way.
It is preferred that the weight average molecular weight of polylactic acid is 1.0 × 105-3.0×105g/mol。
Toughener is the core modified material of modified material of the invention, is glass transition temperature at -20 DEG C or less
Polymer.Such as polycaprolactone, polyethers-b- amide thermoplastic elastomer (TPE) (PEBA), polyadipate/butylene terephthalate
(PBAT), methyl methacrylate-butadiene-styrene terpolymer (MBS), acrylic polymer ACR, epoxy chlorine
Oxide-ethylene oxide epichlorohydrin binary copolymer, epoxychloropropane-ethylene oxide ternary polymerization epichlorohydrin rubber etc..Toughener
It can be the mixing that a kind of substance is also possible to many kinds of substance.Above-mentioned polymer can pass through those skilled in the art's well-known way
It obtains.Toughener is preferably 10-25 parts by weight.
Antioxidant is three (2,4- di-tert-butyl-phenyl) phosphite esters (irgasfos 168), bis- (2,4- di-tert-butyl-phenyls)
Pentaerythritol diphosphites (antioxidant AT-626), four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythrites
One of ester (antioxidant 1010) is a variety of.Above-mentioned antioxidant can be obtained by those skilled in the art's well-known way.
Modified polylactic acid material with low-temperature flexibility of the invention is 17-140%, punching in -20 DEG C of elongation at break
Hit intensity is 7-80KJ/m2.It is preferred that elongation at break is 50-140%, impact strength 13-80KJ/m2.More preferable extension at break
Rate is 80-140%, impact strength 30-80KJ/m2.Particularly preferred elongation at break is 120-140%, impact strength 60-
80KJ/m2。
The preparation method of the above-mentioned modified polylactic acid material with low-temperature flexibility, steps are as follows:
The present invention also provides the preparation methods of the above-mentioned modified polylactic acid material with low-temperature flexibility, and steps are as follows:
Step 1: in mass ratio (5-40): 100 weigh the toughener after being dried and the polylactic acid after drying process,
Mechanical mixture is uniform, generally 1-3min；
Wherein, toughener and the drying method of polylactic acid are the technology that those skilled in the art will appreciate that, toughening
The drying process of agent carries out in vacuum drying oven, and drying temperature selects suitable temperature, polylactic acid according to the difference of toughener
Drying process also carried out in vacuum drying oven, be polylactic acid is put in vacuum drying oven in 80 DEG C vacuum drying for 24 hours.
If also containing antioxidant in the formula of modified polylactic acid material, also need to weigh according to the ratio in step 1
Antioxidant.Since the additive amount of antioxidant is little, therefore antioxidant can be by being dried also without drying process.At dry
Reason carries out in vacuum drying oven, and drying temperature selects suitable temperature according to the difference of antioxidant.
Step 2: uniformly mixed raw material is added in mixer, under conditions of 175-190 DEG C, 50-60 revs/min
Melt blending 5-8min is carried out, it is cooling under air at room temperature state, and it is cut into fritter, obtain modified polylactic acid material；
Alternatively,
Uniformly mixed raw material is added in extruder, is squeezed out, it is cooling, it is granulated, obtains modified polylactic acid material；
Wherein, the equipment of extruding pelletization be double screw extruder, the set temperature of extruder an are as follows: area: 165-180 DEG C,
2nd area: 170-185 DEG C, 3rd area: 170-190 DEG C, 4th area: 170-190 DEG C, 5th area: 170-190 DEG C, 6th area: 170-190 DEG C, seven
Area: 170-190 DEG C, 8th area: 170-190 DEG C, head: 170-190 DEG C；Screw speed is 100-300rpm.
The present invention also provides the above-mentioned modified polylactic acid material with low-temperature flexibility prepare low temperature resistant (- 20 DEG C) can biology
Application in the plastic product of degradation.Modified polylactic acid material with low-temperature flexibility i.e. of the invention can be used in preparing resistance to low
Warm (- 20 DEG C) biodegradable plastics product, preparation process do not have referring to the production technology of the plastic product in the prior art
It is specifically limited.It is usually that the modified polylactic acid material with low-temperature flexibility is made to be in molten state (170-200 DEG C), according to molding work
Skill molding, can be extrusion molding, injection molding, blow molding, compression molding, injection molding, plastics sucking moulding etc..It is common
Plastic product such as cold drink suction pipe, cold drink cup disk, ice cream holder and ice cream box.
To make it is further understood that the present invention, does further the present invention below with reference to embodiment
It is bright.
Embodiment 1
Modified polylactic acid material with low-temperature flexibility, by 100 parts by weight polylactic acid (weight average molecular weight be 2.07 ×
105G/mol), the polyethers-b- amide thermoplastic elastomer (TPE) (PEBA) of 10 parts by weight and the antioxidant 1010 of 0.5 parts by weight composition.
The preparation of the above-mentioned modified polylactic acid material with low-temperature flexibility: polylactic acid and PEBA are first placed in vacuum drying oven
In in 80 DEG C of vacuum drying for 24 hours, then take above-mentioned raw materials by composition and parts by weight, after mechanical mixture 1-3min, be added to mixing
In machine, melt blending 7min under conditions of 175 DEG C, 60 revs/min is finally cold directly under air at room temperature state by intermingling material
But, and it is cut into fritter, obtains modified polylactic acid material.
Embodiment 2
Modified polylactic acid material with low-temperature flexibility, by 100 parts by weight polylactic acid (weight average molecular weight be 2.07 ×
105G/mol), the polyethers-b- amide thermoplastic elastomer (TPE) (PEBA) of 25 parts by weight and the antioxidant 1010 of 0.3 parts by weight composition.
The preparation of the above-mentioned modified polylactic acid material with low-temperature flexibility: polylactic acid and PEBA are first placed in vacuum drying oven
In in 80 DEG C of vacuum drying for 24 hours, then take above-mentioned raw materials by composition and parts by weight, after mechanical mixture 1-3min, be added to mixing
In machine, melt blending 7min under conditions of 175 DEG C, 60 revs/min is finally cold directly under air at room temperature state by intermingling material
But, and it is cut into fritter, obtains modified polylactic acid material.
Embodiment 3
Modified polylactic acid material with low-temperature flexibility, by 100 parts by weight polylactic acid (weight average molecular weight be 2.07 ×
105G/mol), the methyl methacrylate-butadiene-styrene terpolymer (MBS) of 25 parts by weight and 0.3 parts by weight
Antioxidant 1010 composition.
The preparation of the above-mentioned modified polylactic acid material with low-temperature flexibility: polylactic acid and MBS are first placed in vacuum drying oven
In in 80 DEG C of vacuum drying for 24 hours, then take above-mentioned raw materials by composition and parts by weight, after mechanical mixture 1-3min, be added to mixing
In machine, melt blending 7min under conditions of 175 DEG C, 60 revs/min is finally cold directly under air at room temperature state by intermingling material
But, and it is cut into fritter, obtains modified polylactic acid material.
Embodiment 4
Modified polylactic acid material with low-temperature flexibility, by 100 parts by weight polylactic acid (weight average molecular weight be 2.07 ×
105G/mol), the acrylic polymer (ACR) of 25 parts by weight and the antioxidant 1010 of 0.3 parts by weight composition.
The preparation of the above-mentioned modified polylactic acid material with low-temperature flexibility: polylactic acid and ACR are first placed in vacuum drying oven
In in 80 DEG C of vacuum drying for 24 hours, then take above-mentioned raw materials by composition and parts by weight, after mechanical mixture 1-3min, be added to mixing
In machine, melt blending 8min under conditions of 175 DEG C, 60 revs/min is finally cold directly under air at room temperature state by intermingling material
But, and it is cut into fritter, obtains modified polylactic acid material.
Embodiment 5
Modified polylactic acid material with low-temperature flexibility, by 100 parts by weight polylactic acid (weight average molecular weight be 2.07 ×
105G/mol), polyadipate/butylene terephthalate (PBAT) of 25 parts by weight and the antioxidant 1010 group of 0.3 parts by weight
At.
The preparation of the above-mentioned modified polylactic acid material with low-temperature flexibility: polylactic acid and PBAT are first placed in vacuum drying oven
In in 80 DEG C of vacuum drying for 24 hours, then take above-mentioned raw materials by composition and parts by weight, after mechanical mixture 1-3min, be added to mixing
In machine, melt blending 7min under conditions of 175 DEG C, 60 revs/min is finally cold directly under air at room temperature state by intermingling material
But, and it is cut into fritter, obtains modified polylactic acid material.
Embodiment 6
Modified polylactic acid material with low-temperature flexibility, by 100 parts by weight polylactic acid (weight average molecular weight be 2.07 ×
105G/mol), the polycaprolactone (PCL) of 25 parts by weight and the antioxidant 1010 of 0.3 parts by weight composition.
The preparation of the above-mentioned modified polylactic acid material with low-temperature flexibility: first polylactic acid is placed in vacuum drying oven in 80
DEG C vacuum drying for 24 hours, by PCL be placed in vacuum drying oven in 35 DEG C vacuum drying for 24 hours, then by composition and parts by weight take it is above-mentioned
Raw material after mechanical mixture 1-3min, is added in mixer, melt blending 7min under conditions of 175 DEG C, 60 revs/min, finally
Intermingling material is cooling directly under air at room temperature state, and it is cut into fritter, obtain modified polylactic acid material.
Embodiment 7
Modified polylactic acid material with low-temperature flexibility, by 100 parts by weight polylactic acid (weight average molecular weight be 1.0 ×
105G/mol), the methyl methacrylate-butadiene-styrene terpolymer (MBS) of 40 parts by weight and 0.1 parts by weight
Irgasfos 168 composition.
The preparation of the above-mentioned modified polylactic acid material with low-temperature flexibility: polylactic acid and MBS are first placed in vacuum drying oven
In in 80 DEG C of vacuum drying for 24 hours, then take above-mentioned raw materials by composition and parts by weight, after mechanical mixture 1-3min, twin-screw be added
Extruder squeezes out, cooling, is granulated, obtains modified polylactic acid material, the condition of extruding pelletization are as follows: the setting of double screw extruder
Temperature an are as follows: area: 165-180 DEG C, 2nd area: 170-185 DEG C, 3rd area: 170-190 DEG C, 4th area: 170-190 DEG C, 5th area: 170-
190 DEG C, 6th area: 170-190 DEG C, 7th area: 170-190 DEG C, 8th area: 170-190 DEG C, head: 170-190 DEG C；Screw speed is
100-300rpm。
Embodiment 8
Modified polylactic acid material with low-temperature flexibility, by 100 parts by weight polylactic acid (weight average molecular weight be 3.0 ×
105G/mol), the methyl methacrylate-butadiene-styrene terpolymer (MBS) of 5 parts by weight and 0.5 parts by weight is anti-
Oxygen agent AT-626 composition.
The preparation of the above-mentioned modified polylactic acid material with low-temperature flexibility: polylactic acid and MBS are first placed in vacuum drying oven
In in 80 DEG C of vacuum drying for 24 hours, then take above-mentioned raw materials by composition and parts by weight, after mechanical mixture 1-3min, twin-screw be added
Extruder squeezes out, cooling, is granulated, obtains modified polylactic acid material, the condition of extruding pelletization are as follows: the setting of double screw extruder
Temperature an are as follows: area: 165-180 DEG C, 2nd area: 170-185 DEG C, 3rd area: 170-190 DEG C, 4th area: 170-190 DEG C, 5th area: 170-
190 DEG C, 6th area: 170-190 DEG C, 7th area: 170-190 DEG C, 8th area: 170-190 DEG C, head: 170-190 DEG C；Screw speed is
100-300rpm。
Comparative example 1
First by polylactic acid, (weight average molecular weight is 2.07 × 105G/mol it) is placed in vacuum drying oven and is dried in vacuo in 80 DEG C
For 24 hours, 100:0.3 in mass ratio weighs polylactic acid and antioxidant 1010 after above-mentioned drying, after mechanical mixture 1-3min, is added to
In mixer, melting mixing 7min under conditions of 175 DEG C, 60 revs/min, then by the material directly under air at room temperature state
It is cooling, and it is cut into fritter, obtain target material.
The target material of modified material and comparative example 1 to embodiment 1-8 is tested for the property, test result such as 1 institute of table
Show.
1 tensile strength of table, Young's modulus and elongation at break, impact strength test result
As it can be seen from table 1 the modified polylactic acid material provided by the invention with low-temperature flexibility still has at -20 DEG C
Good cryogenic tensile and impact flexibility, freezing crack elongation are up to 138.3%, and low temperature impact strength is up to 77.1KJ/m2,
Material tensile strength with higher simultaneously.Moreover, when test temperature be higher than -20 DEG C be lower than 0 DEG C when, the tensile toughness of material and
Impact flexibility can further increase, and poly-lactic acid material is made to possess broader practice space.It is biodegradable suitable for preparing
Low-temperature resistant plastic product.
Specific embodiment described in the present invention only illustrate the spirit of the present invention by way of example.The neck of technology belonging to the present invention
The technical staff in domain can make various modifications or additions to the described embodiments or replace by a similar method
In generation, however, it does not deviate from the spirit of the invention or beyond the scope of the appended claims.
Claims (10)
1. the modified polylactic acid material with low-temperature flexibility, which is characterized in that by the polylactic acid and 5-40 parts by weight of 100 parts by weight
Toughener composition；
The weight average molecular weight of the polylactic acid is 1.0 × 105-3.0×105g/mol；
The toughener is glass transition temperature in -20 DEG C of polymer below；
The modified polylactic acid material with low-temperature flexibility is 17%-140% in -20 DEG C of elongation at break, and impact strength is
7-80KJ/m2。
2. the modified polylactic acid material according to claim 1 with low-temperature flexibility, which is characterized in that the toughener is
Polycaprolactone, polyethers-b- amide thermoplastic elastomer (TPE), polyadipate/butylene terephthalate, methyl methacrylate-fourth
Styrene terpolymer, acrylic polymer, epoxychloropropane-ethylene oxide epichlorohydrin binary copolymer, ring
One of oxygen chloropropane-ethylene oxide ternary polymerization epichlorohydrin rubber or a variety of mixing.
3. the modified polylactic acid material according to claim 1 with low-temperature flexibility, which is characterized in that the toughener is
10-25 parts by weight.
4. the modified polylactic acid material according to claim 1 with low-temperature flexibility, which is characterized in that described that there is low temperature
The elongation at break of the modified polylactic acid material of toughness is 50-140%, impact strength 13-80KJ/m2。
5. the modified polylactic acid material according to claim 1 with low-temperature flexibility, which is characterized in that the polylactic acid changes
Property material further includes the antioxidant of 0.1-0.5 parts by weight.
6. the modified polylactic acid material according to claim 5 with low-temperature flexibility, which is characterized in that the antioxidant is
Three (2,4- di-tert-butyl-phenyl) phosphite esters, bis- (2,4- di-tert-butyl-phenyl) pentaerythritol diphosphites, four [β-(3,
5- di-tert-butyl-hydroxy phenyl) propionic acid] one of pentaerythritol ester or a variety of mixing.
7. the preparation method of the modified polylactic acid material described in claim 1-6 any one with low-temperature flexibility, feature
It is, steps are as follows:
Step 1: weighing the polylactic acid after being dried, toughener and antioxidant after drying process, machine by composition and proportion
Tool is uniformly mixed；
Step 2: uniformly mixed raw material is added in mixer, melt blending, room temperature is cooling, and cutting is obtained with low temperature
The modified polylactic acid material of toughness；
Alternatively,
Uniformly mixed raw material is added in extruder, is squeezed out, it is cooling, it is granulated, obtains that there is the polylactic acid modified of low-temperature flexibility
Material.
8. the preparation method of the modified polylactic acid material according to claim 7 with low-temperature flexibility, which is characterized in that
In the step 1, the churned mechanically time is 1-3min；
In the step 2, the temperature of melt blending is 175-190 DEG C, and the revolving speed of the temperature of melt blending is 50-60 revs/min,
The time of the temperature of melt blending is 5-8min；
In the step 2, the equipment of extruding pelletization is double screw extruder, the set temperature of extruder an are as follows: area: 165-180
DEG C, 2nd area: 170-185 DEG C, 3rd area: 170-190 DEG C, 4th area: 170-190 DEG C, 5th area: 170-190 DEG C, 6th area: 170-190
DEG C, 7th area: 170-190 DEG C, 8th area: 170-190 DEG C, head: 170-190 DEG C；Screw speed is 100-300rpm.
9. described in claim 1-6 any one with low-temperature flexibility modified polylactic acid material prepare it is biodegradable
Application in low-temperature resistant plastic product.
10. the modified polylactic acid material as claimed in claim 9 with low-temperature flexibility is preparing biodegradable low temperature resistant modeling
Application in material products, which is characterized in that the plastic products are cold drink suction pipe, cold drink cup disk, ice cream holder or ice cream box.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910338048.6A CN110066502A (en) | 2019-04-25 | 2019-04-25 | A kind of modified polylactic acid material and the preparation method and application thereof with low-temperature flexibility |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910338048.6A CN110066502A (en) | 2019-04-25 | 2019-04-25 | A kind of modified polylactic acid material and the preparation method and application thereof with low-temperature flexibility |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110066502A true CN110066502A (en) | 2019-07-30 |
Family
ID=67368836
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910338048.6A Pending CN110066502A (en) | 2019-04-25 | 2019-04-25 | A kind of modified polylactic acid material and the preparation method and application thereof with low-temperature flexibility |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110066502A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111534068A (en) * | 2020-06-02 | 2020-08-14 | 中国科学技术大学 | Polylactic acid material with ultrahigh impact strength and preparation method thereof |
| CN111748182A (en) * | 2019-08-19 | 2020-10-09 | 天津大学 | High-transparency high-toughness polylactic acid-based material and preparation method thereof |
| CN111925635A (en) * | 2020-08-14 | 2020-11-13 | 毛澄宇 | Polylactic acid modified material for 3D printing and preparation method and application thereof |
| CN115850932A (en) * | 2022-12-22 | 2023-03-28 | 广东圆融新材料有限公司 | Normal-temperature and low-temperature impact-resistant polylactic acid material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101392093A (en) * | 2008-11-04 | 2009-03-25 | 中国科学院长春应用化学研究所 | High ductility polylactic acid base composite material and preparation method thereof |
| CN103540111A (en) * | 2013-10-12 | 2014-01-29 | 深圳市江之源实业有限公司 | Fully degradable polylactic acid sheet material with high strength and high-temperature resistance, and preparation method thereof |
| CN104530667A (en) * | 2014-12-08 | 2015-04-22 | 安徽聚美生物科技有限公司 | PLA toughening material, PLA toughening plastic-suction sheet and preparation methods of two |
| WO2015067817A1 (en) * | 2013-11-11 | 2015-05-14 | Styrolution Group Gmbh | Blends of styrene butadiene copolymers with poly(lactic acid) |
-
2019
- 2019-04-25 CN CN201910338048.6A patent/CN110066502A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101392093A (en) * | 2008-11-04 | 2009-03-25 | 中国科学院长春应用化学研究所 | High ductility polylactic acid base composite material and preparation method thereof |
| CN103540111A (en) * | 2013-10-12 | 2014-01-29 | 深圳市江之源实业有限公司 | Fully degradable polylactic acid sheet material with high strength and high-temperature resistance, and preparation method thereof |
| WO2015067817A1 (en) * | 2013-11-11 | 2015-05-14 | Styrolution Group Gmbh | Blends of styrene butadiene copolymers with poly(lactic acid) |
| CN104530667A (en) * | 2014-12-08 | 2015-04-22 | 安徽聚美生物科技有限公司 | PLA toughening material, PLA toughening plastic-suction sheet and preparation methods of two |
Non-Patent Citations (2)
| Title |
|---|
| 任淑英: "抗冲改性剂改性聚乳酸的研究进展", 《塑料助剂》 * |
| 肖伟娜等: "聚乳酸增韧改性研究进展", 《化工进展》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111748182A (en) * | 2019-08-19 | 2020-10-09 | 天津大学 | High-transparency high-toughness polylactic acid-based material and preparation method thereof |
| CN111748182B (en) * | 2019-08-19 | 2022-11-04 | 天津大学 | High-transparency high-toughness polylactic acid-based material and preparation method thereof |
| CN111534068A (en) * | 2020-06-02 | 2020-08-14 | 中国科学技术大学 | Polylactic acid material with ultrahigh impact strength and preparation method thereof |
| CN111925635A (en) * | 2020-08-14 | 2020-11-13 | 毛澄宇 | Polylactic acid modified material for 3D printing and preparation method and application thereof |
| CN115850932A (en) * | 2022-12-22 | 2023-03-28 | 广东圆融新材料有限公司 | Normal-temperature and low-temperature impact-resistant polylactic acid material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110066502A (en) | A kind of modified polylactic acid material and the preparation method and application thereof with low-temperature flexibility | |
| CN105623214B (en) | One kind plasticising Biodegradable polyester film and preparation method thereof | |
| CN108822514B (en) | Completely biodegradable polylactic acid based blown film and preparation method thereof | |
| CN101280095A (en) | Glass fiber reinforced polyethylene glycol terephthalate composite material and preparation thereof | |
| TWI330649B (en) | Biodegradable resin composition with improved toughness and thermal resistance and production method thereof | |
| CN1216101C (en) | Preparation method of toughness enhanced and reinforced polybutanediol terephthalate nanometer composition | |
| CN101205356A (en) | Polyhydroxylkanoates as well as blending modification for copolymer thereof and polylactic acid | |
| CN110698822B (en) | Full-biodegradable composite material for tableware and preparation method and application thereof | |
| US8691913B2 (en) | Polylactic acid compositions, polylactic acid materials and methods of preparing the same | |
| CN103965596B (en) | A kind of biodegradable polylactic acid based composites and application | |
| CN101649072B (en) | Full-degradable biological material and film product thereof | |
| CN104072957A (en) | Food grade biodegradable polylactic acid-based composite material and application thereof | |
| CN106916424A (en) | A kind of high-tenacity heat-resistant type full-biodegradable polylactic acid material and preparation method thereof | |
| CN104387732A (en) | Transparent, tear-resistant and biodegradable polylactic acid thin film and preparation method thereof | |
| JP2014503678A (en) | Biodegradable polymer composite | |
| CN106467657A (en) | High heat-resisting PLA/PHA composite and preparation method thereof | |
| CN108017887A (en) | A kind of PLA-PBSA inflation films and preparation method thereof | |
| JP5300395B2 (en) | Polyester resin composition, fiber obtained from the resin composition, and method for producing the fiber | |
| CN1072246C (en) | Polyethylene terephthalate resin composition | |
| CN114369347B (en) | Degradable flow modification auxiliary agent and preparation method and application thereof | |
| CN114231005A (en) | PC/ABS alloy material suitable for INS membrane substrate and preparation method thereof | |
| CN106751568B (en) | A kind of antibacterial PBAT/PLA composite membranes and preparation method thereof | |
| CN113429762A (en) | Starch/polylactic acid/PBAT nano composite material and preparation method thereof | |
| CN102153844A (en) | High-impact heat-resisting polylactic resin with high light transmittance and preparation method of high-impact heat-resisting polylactic resin | |
| US20230303829A1 (en) | Biodegradable material, preparation method and application thereof |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190730 |
|
| RJ01 | Rejection of invention patent application after publication |