CN106189127A - A kind of modified polylactic acid coblended matter and preparation method thereof - Google Patents
A kind of modified polylactic acid coblended matter and preparation method thereof Download PDFInfo
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- CN106189127A CN106189127A CN201610529647.2A CN201610529647A CN106189127A CN 106189127 A CN106189127 A CN 106189127A CN 201610529647 A CN201610529647 A CN 201610529647A CN 106189127 A CN106189127 A CN 106189127A
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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Abstract
The invention discloses a kind of modified polylactic acid coblended matter, including following components and weight portion thereof: polylactic acid 60 99 parts, anti-impact modifier 1 40 parts, nanometer physical compatibilizer 0.1 5 parts, filler 0 60 parts, 02 parts of antioxidant, antioxygen synergist 02 parts；At least one in the product that described anti-impact modifier is formed by grafting or copolymerization functional group by elastomer matrix polymer and elastomer matrix polymer.Present invention also offers the preparation method of a kind of modified polylactic acid coblended matter.Compared with prior art, the modified polylactic acid coblended matter of the present invention is while strengthening polylactic acid shock resistance, moreover it is possible to ensure that other mechanical performances of polylactic acid are in higher level.
Description
Technical field
The present invention relates to engineering plastics technical field, particularly to a kind of modified polylactic acid coblended matter and preparation method thereof.
Background technology
Polylactic acid belongs to aliphatic thermoplastic polyester, has biodegradability, and its synthesis material is Renewable resource.Make
For the green material that 21 century is most with prospects, become the material of various countries' primary study.Polylactic acid has good adding
Work performance, and the hot strength of excellence and light transmission, available traditional extrusion, be molded, the processing method such as blowing is prepared various
Plastic.
But the shock resistance of polylactic acid is poor, impact strength is less than 5kJ/m2, greatly limits it and extensively applies.Cause
This is around the serious shortcoming of polylactic acid fragility, and domestic and international expansion is studied widely.The modification technology of polylactic acid include modification by copolymerization,
Blending and modifying, composite modified, cross-linking modified etc., wherein, it is main that the method using multicomponent to be blended improves the toughness of polylactic acid
Technological means, as used the low-molecular-weight component such as citrate, epoxy soybean oil to carry out plasticising, improve toughness and also keep high transparency
Property.But, although polylactic acid shock resistance modified in this way enhances, but, other mechanical performances can not get
Ensure.
Summary of the invention
The purpose of the present invention, it is simply that provide a kind of modified polylactic acid coblended matter, this modification in order to solve the problems referred to above
Polylactic acid blend is while strengthening polylactic acid shock resistance, moreover it is possible to ensure that other mechanical performances of polylactic acid are in higher
Level.
Another object of the present invention also resides in a kind of quality guarantee method providing modified polylactic acid coblended matter.
For achieving the above object, technical scheme is implemented as follows:
A kind of modified polylactic acid coblended matter, including following components and weight portion thereof:
Described anti-impact modifier is that elastomer matrix polymer and elastomer matrix polymer are by grafting or copolymerization official
At least one in the product formed can be rolled into a ball；
Described elastomer matrix polymer be polyethylene, polypropylene, polybutene, polyisoprene, ethylene-propylene rubber,
Ethylene-Propylene-Diene rubber, ethylene butylene rubber, ethylene-acrylate rubber, Afpol, butadiene-
Acrylate rubber, Ethylene-octene rubber, acrylonitrile butadiene rubber, ethylene-acrylic acid, ethane-acetic acid ethyenyl ester, ethylene-
Acrylate, acrylonitrile-butadiene-styrene copolymer, styrene ethylene butadiene-styrene block copolymer, benzene second
Alkene-BS or metacrylate-butadiene-styrene；
Described functional group is carboxylic acids functional group, metal carboxylate functional group, ester functional group, ionic polymerization species official's energy
Group, (+)-2,3-Epoxy-1-propanol base class functional group, anhydride functional group, oxazolines functional group or maleimide functional group.
Preferably, described anti-impact modifier is ethylene-acrylate-glycidyl methacrylate trimer, second
Alkene-acrylic acid ionomers, methacrylate butadi ene styrene copolymer, ethylene-butyl acrylate copolymer, second
The grafting of alkene-n-butyl acrylate-glycidyl methacrylate copolymer, ethylene maleic acid anhydride copolymer, maleic anhydride
The styrene-maleimide copolymer of ethylene-propylene-diene copolymer, maleic anhydride grafting, maleic anhydride modified benzene second
The SAN of alkene-ethylene-butylene, Styrene copolymer, maleic anhydride grafting and maleic anhydride are grafted
At least one in acrylonitrile-butadiene-styrene copolymer.
Preferably, the fusing point of described polylactic acid is 120-185 DEG C, number-average molecular weight 5-40 ten thousand.
Preferably, described nanometer physical compatibilizer is in nano silicon, nano imvite, CNT or Graphene
One.
Preferably, described nanometer physical compatibilizer is the nanometer physical compatibilizer of hydrophobically modified.
Further preferably, described nanometer physical compatibilizer is the nano silicon of hydrophobically modified, described hydrophobically modified
Nano silicon is reacted with hydrophobic modifier by nano silicon and is prepared from, and described hydrophobic modifier includes six
Methyl disilazane, trimethoxy-benzene base silane.
Described nanometer physical compatibilizer, is different from reactive compatibilization for the mode of increase-volume, but by physics side
Formula improves the interfacial interaction of anti-impact modifier and polylactic acid.Compatible in order to make between anti-impact modifier and polylactic acid
Property promote further, use nanometer physical compatibilizer dispersion phase broken-coacervation process in play an important role, be distributed in
Anti-impact modifier dispersion phase and polylactic resin flowing boundary, reduce interfacial tension, it is to avoid anti-impact modifier coagulates again
Gathering makes rubber size increase, and is very helpful the impact strength improving blend.
Preferably, during described filler is fibrous filler, Non-fibrous filler and polymer-filled agent at least
A kind of.
Preferably, during described fibrous filler is glass fibre, carbon fiber and organic fiber at least one；Described non-fibre
Dimension shape filler be aluminium oxide, white carbon black, clay, zirconium phosphate, Kaolin, calcium carbonate, copper, kieselguhr, graphite, Muscovitum, Silicon stone, two
In titanium oxide, zeolite, Talcum and wollastonite at least one；Described polymer-filled agent is bead and/or glass powder.
Further preferably, a diameter of 7 μm-14 μm of described glass fibre.
Preferably, described antioxidant is Zhong Fang amine antioxidants, suffocated amine antioxidant, Hinered phenols antioxidant, phosphorous
At least one in esters of gallic acid antioxidant or thioester compound kind antioxidant.
Further preferably, described Zhong Fang amine antioxidants is 4,4'-bis-(propyloxy phenyl base) diphenylamines (CAS:10081-
67-1)；Described suffocated amine antioxidant is poly-{ [6-[(1,1,3,3-tetramethyl butyl) amino]]-1,3,5-triazine-2,4-pair
[(2,2,6,6 ,-tetramethyl-4-piperidyl) imino group]-1,6-oneself two support [(2,2,6,6-tetramethyl-4-piperidyl) imino group]
(CAS:70624-18-9)；Described Hinered phenols antioxidant is 1,1,3-tri-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane
(CAS:1843-03-4), 1,3,5-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid (CAS:27676-62-6), 4,
4'-butylidene double (6-tert-butyl-m-cresol) (CAS:85-60-9), β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid positive ten
Eight carbon alcohol esters (CAS:2082-79-3), four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester (CAS:
6683-19-8), double [1,1-dimethyl-2-[(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy] ethyl]-2 of 3,9-,
4,8,10-tetra-oxaspiro [5.5] hendecane (CAS:90498-90-1) and 1,3,5-trimethyl-2,4,6-three (the tertiary fourth of 3,5-bis-
Base-4-hydroxybenzyl) at least one in benzene (CAS:1709-70-2)；Described phosphite ester kind antioxidant is double octadecyls
Pentaerythritol bis-phosphite (CAS:3806-34-6), double (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphate
(CAS:80693-00-1), 2-2 '-di-2-ethylhexylphosphine oxide (4,6-dibutyl-benzyl)-2-ethylhexyl phosphite ester (CAS:
126050-54-2), tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester (CAS:31570-04-4), trisnonyl phenyl phosphite
(CAS:26523-78-4) and in 4,4'-split isopropyl diphenyl base C12-15-alcohol phosphite ester (CAS:96152-48-6)
At least one；Described thioester compound kind antioxidant is tetramethylolmethane four (3-lauryl thiopropionate) (CAS:29598-76-
3)。
Preferably, at least one during described antioxygen synergist is hydroxylamine or 3-aryl-benzofuranone.
Described hydroxylamine and 3-aryl-benzofuranone are as radical scavenger, it is ensured that polylactic acid blend is in processing
Stability during use, does not affect polylactic acid blend simultaneously and degrades under specific composting conditions, reduces ambient pressure.
Present invention also offers the preparation method of a kind of modified polylactic acid coblended matter as claimed in claim 1, including with
Lower preparation process:
Step 1: according to following components and weight portion preparation raw material thereof: polylactic acid 60-99 part, anti-impact modifier 1-40
Part, nanometer physical compatibilizer 0.1-5 part, filler 0-60 part, antioxidant 0-2 part, antioxygen synergist 0-2 part；
Step 2: the polylactic acid in step 1 is dried to moisture less than 1500ppm；
Step 3: by the anti-impact modifier in polylactic acid dried in step 2 and step 1, nanometer physical compatibilizer,
Antioxidant and the mixing of antioxygen synergist, and add the filler in double screw extruder, step 1 from double screw extruder stage casing
Side spout adds, and extrudes at a temperature of 180-220 DEG C, and simultaneously through supercooling and pelletize, the modification i.e. obtaining the present invention gathers
Lactic acid blend.
Beneficial effects of the present invention is as follows:
1. the anti-impact modifier in the present invention is possible not only to be greatly improved the shock resistance of polyamide, and can make to gather
Other mechanical performances of amide are also protected.
2. the present invention have employed nanometer physical compatibilizer so that anti-impact modifier is able to polylactic acid consistency problem
Solve, thus its shock resistance is higher.
3. the preparation method that the present invention provides is simple, applies more extensive.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described.
In comparative example and embodiment, used raw-material manufacturer and model see table:
Comparative example 1
Step 1: according to following components and weight portion preparation raw material thereof: 90kg polylactic acid and 0.1kg antioxidant 1010.
Step 2: polylactic acid and antioxidant 1010 are mixed, and adds double screw extruder, at a temperature of 180-220 DEG C
Extrusion, simultaneously through supercooling and pelletize, i.e. obtains the polylactic acid blend of comparative example 1.
Comparative example 2
Step 1: according to following components and weight portion preparation raw material thereof: 90kg polylactic acid, 10kg citrate, 0.1kg
Antioxidant 1010 and 1kg nano silicon.
Step 2: by polylactic acid, citrate, antioxidant 1010 mixing and nano silicon mixing, and add double spiral shell
Bar extruder, extrudes at a temperature of 180-220 DEG C, simultaneously through supercooling and pelletize, i.e. obtains the polylactic acid blend of comparative example 2
Thing.
Comparative example 3
Step 1: prepare raw material according to following components and weight portion thereof: 90kg polylactic acid, 10kg epoxy soybean,
0.1kg4,4'-bis-(propyloxy phenyl base) diphenylamines and 1kg hexamethyldisiloxane modified manometer silicon dioxide.
Step 2: by polylactic acid, epoxy soybean oil, 4,4'-bis-(propyloxy phenyl base) diphenylamines and hexamethyldisiloxane
Modified manometer silicon dioxide mixes, and adds double screw extruder, extrudes at a temperature of 180-220 DEG C, simultaneously through supercooling
And pelletize, i.e. obtain the polylactic acid blend of comparative example 3.
Embodiment 1-3 gives the method preparing modified polylactic acid coblended matter of the present invention, and provides and prepare blend
Concrete raw material.
Embodiment 1
Step 1: according to following components and weight portion preparation raw material thereof: 90kg polylactic acid, 10kg ethylene-acrylic acid fourth
Ester-glycidyl methacrylate, 1kg hexamethyldisiloxane modified manometer silicon dioxide and 0.1kg antioxidant 1010；
Step 2: the polylactic acid in step 1 is dried to moisture less than 1500ppm；
Step 3: by polylactic acid dried in step 2 and the Ethylene-butyl acrylate in step 1-methacrylic acid contracting
Water glyceride, hexamethyldisiloxane modified manometer silicon dioxide and antioxidant 1010 mixing, and add double screw extruder,
Extrude at a temperature of 180-220 DEG C, simultaneously through supercooling and pelletize, i.e. obtain the polylactic acid blend of embodiment 1.
Embodiment 2
Step 1: according to following components and weight portion preparation raw material thereof: 90kg polylactic acid, 10kg ethylene-methyl methacrylate
Ionomer, 1kg hexamethyldisiloxane modified manometer silicon dioxide, 0.1kg antioxidant 1010 and 0.1kg4,4'-bis-
(propyloxy phenyl base) diphenylamines；
Step 2: the polylactic acid in step 1 is dried to moisture less than 1500ppm；
Step 3: by the ionomer of the ethylene-methyl methacrylate in polylactic acid dried in step 2 and step 1,
Hexamethyldisiloxane modified manometer silicon dioxide, antioxidant 1010 and 4,4'-bis-(propyloxy phenyl base) diphenylamines mixes, and
Add double screw extruder, extrude at a temperature of 180-220 DEG C, simultaneously through supercooling and pelletize, i.e. obtain the poly-of embodiment 2
Lactic acid blend.
Embodiment 3
Step 1: according to following components and weight portion preparation raw material thereof: 60kg polylactic acid, 40kg methyl methacrylate-
BS, 5kg dimethyldichlorosilane modified manometer silicon dioxide, 0.1kg antioxidant 1010,0.1kg3-
Aryl-benzofuranone and 20kg glass fibre；
Step 2: the polylactic acid in step 1 is dried to moisture less than 1500ppm；
Step 3: by polylactic acid dried in step 2 and the MBS in step 1
Copolymer, dimethyldichlorosilane modified manometer silicon dioxide, antioxidant 1010,3-aryl-benzofuranone mixing, and add
Double screw extruder, glass fibre is fed mouth and is added, extrudes, simultaneously at a temperature of 180-220 DEG C from side, screw extruder stage casing
Through supercooling and pelletize, i.e. obtain the polylactic acid blend of embodiment 3.
Polylactic acid blend prepared by comparative example 1-3 and embodiment 1-3 through relevant test, result such as following table institute
Show:
Note: hot strength according to GB/T1040-1992, impact strength according to GB/T1043-93, low temperature impact strength according to
GB/T1043-93, tests at-40 DEG C, and bending strength is according to GB/T 9341-2008.
According to the test result of upper table, the modified polylactic acid coblended matter that the present invention is obtained compared with prior art,
Its shock resistance is greatly improved, simultaneously as the special anti-impact modifier that the present invention uses so that polylactic acid
Other mechanical performances also ensured.
Above example is used for illustrative purposes only, rather than limitation of the present invention, about the technology people of technical field
Member, without departing from the spirit and scope of the present invention, it is also possible to make various conversion or modification, the most all equivalents
Technical scheme also should belong to scope of the invention, should be limited by each claim.
Claims (10)
1. a modified polylactic acid coblended matter, it is characterised in that include following components and weight portion thereof:
Described anti-impact modifier is that elastomer matrix polymer and elastomer matrix polymer are by grafting or copolymerization functional group
At least one in the product formed；
Described elastomer matrix polymer be polyethylene, polypropylene, polybutene, polyisoprene, ethylene-propylene rubber, ethylene-
Propylenediene rubber, ethylene butylene rubber, ethylene-acrylate rubber, Afpol, butadiene-acrylic acid
Ester rubber, Ethylene-octene rubber, acrylonitrile butadiene rubber, ethylene-acrylic acid, ethane-acetic acid ethyenyl ester, ethylene-acrylic acid
Ester, acrylonitrile-butadiene-styrene copolymer, styrene ethylene butadiene-styrene block copolymer, styrene-fourth two
Alkene-styrol copolymer or metacrylate-butadiene-styrene；
Described functional group is carboxylic acids functional group, metal carboxylate functional group, ester functional group, ionic polymerization species functional group, contracting
Water glycerol base class functional group, anhydride functional group, oxazolines functional group or maleimide functional group.
2. a kind of modified polylactic acid coblended matter as claimed in claim 1, it is characterised in that described anti-impact modifier is second
Alkene-acrylate-glycidyl ester trimer, ethylene-acrylic acid ionomer, methacrylate-fourth
Diene-styrene copolymer, ethylene-butyl acrylate copolymer, ethylene/n-butyl acrylate-methyl propenoic acid glycidyl
The ethylene-propylene-diene copolymer of ester copolymer, ethylene maleic acid anhydride copolymer, maleic anhydride grafting, maleic anhydride connect
The styrene-maleimide copolymer of branch, maleic anhydride modified styrene-ethylene-butylene-styrene copolymer, maleic acid
In the SAN of acid anhydride grafting and the acrylonitrile-butadiene-styrene copolymer of maleic anhydride grafting extremely
Few one.
3. a kind of modified polylactic acid coblended matter as claimed in claim 1, it is characterised in that the fusing point of described polylactic acid is 120-
185 DEG C, number-average molecular weight 5-40 ten thousand.
4. a kind of modified polylactic acid coblended matter as claimed in claim 1, it is characterised in that described nanometer physical compatibilizer is for receiving
One in rice silicon dioxide, nano imvite, CNT or Graphene.
5. a kind of modified polylactic acid coblended matter as claimed in claim 1, it is characterised in that described nanometer physical compatibilizer is thin
The nanometer physical compatibilizer that water is modified.
6. a kind of modified polylactic acid coblended matter as claimed in claim 1, it is characterised in that described filler is fibrous filler
At least one in agent, Non-fibrous filler and polymer-filled agent.
7. a kind of modified polylactic acid coblended matter as claimed in claim 6, it is characterised in that described fibrous filler is glass
In fiber, carbon fiber and organic fiber at least one；Described Non-fibrous filler be aluminium oxide, white carbon black, clay, zirconium phosphate,
In Kaolin, calcium carbonate, copper, kieselguhr, graphite, Muscovitum, Silicon stone, titanium dioxide, zeolite, Talcum and wollastonite at least one；
Described polymer-filled agent is bead and/or glass powder.
8. a kind of modified polylactic acid coblended matter as claimed in claim 1, it is characterised in that described antioxidant is that Zhong Fang amine resists
In oxygen agent, suffocated amine antioxidant, Hinered phenols antioxidant, phosphite ester kind antioxidant or thioester compound kind antioxidant extremely
Few one.
9. a kind of modified polylactic acid coblended matter as claimed in claim 1, it is characterised in that described antioxygen synergist is hydroxylamine
Or at least one in 3-aryl-benzofuranone.
10. the preparation method of a modified polylactic acid coblended matter as claimed in claim 1, it is characterised in that include following system
Standby step:
Step 1: prepare raw material according to following components and weight portion thereof: polylactic acid 60-99 part, anti-impact modifier 1-40 part,
Nanometer physical compatibilizer 0.1-5 part, filler 0-60 part, antioxidant 0-2 part, antioxygen synergist 0-2 part；
Step 2: the polylactic acid in step 1 is dried to moisture less than 1500ppm；
Step 3: by polylactic acid dried in step 2 and the anti-impact modifier in step 1, nanometer physical compatibilizer, antioxygen
Agent and antioxygen synergist mixing, and add the filler in double screw extruder, step 1 from the side in double screw extruder stage casing feed
Material mouth adds, and extrudes at a temperature of 180-220 DEG C, simultaneously through supercooling and pelletize, i.e. obtains the polydactyl acid of the present invention
Blend.
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| CN109294185A (en) * | 2018-09-10 | 2019-02-01 | 武汉金发科技有限公司 | A kind of automotive bumper material and the preparation method and application thereof |
| CN109627715A (en) * | 2018-11-22 | 2019-04-16 | 南通大学 | A kind of impact-resisting and heat resistant antibacterial polylactic acid composition and preparation method thereof |
| CN110183729A (en) * | 2019-05-16 | 2019-08-30 | 华南理工大学 | N- alkoxy hindered amine modifies laminar nano basic zirconium phosphate and the preparation method and application thereof |
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| CN110183729A (en) * | 2019-05-16 | 2019-08-30 | 华南理工大学 | N- alkoxy hindered amine modifies laminar nano basic zirconium phosphate and the preparation method and application thereof |
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| CN114702803A (en) * | 2022-04-28 | 2022-07-05 | 深圳烯湾科技有限公司 | Antistatic polylactic acid material and preparation method thereof |
| CN114702803B (en) * | 2022-04-28 | 2023-08-18 | 深圳烯湾科技有限公司 | Antistatic polylactic acid material and preparation method thereof |
| WO2024069161A1 (en) * | 2022-09-26 | 2024-04-04 | Colloids Limited | Phonograph records |
| CN116355373A (en) * | 2023-04-20 | 2023-06-30 | 四川大学 | Polylactic acid-based composite material and preparation method thereof |
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