CN101638508A - Polylactic acid material composite and material prepared from same - Google Patents
Polylactic acid material composite and material prepared from same Download PDFInfo
- Publication number
- CN101638508A CN101638508A CN200810142755A CN200810142755A CN101638508A CN 101638508 A CN101638508 A CN 101638508A CN 200810142755 A CN200810142755 A CN 200810142755A CN 200810142755 A CN200810142755 A CN 200810142755A CN 101638508 A CN101638508 A CN 101638508A
- Authority
- CN
- China
- Prior art keywords
- lactic acid
- poly
- layered silicate
- oxyhydroxide
- 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.)
- Granted
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention discloses a polylactic acid material composite which is characterized in that the composite comprises polylactic acid, layered silicate and hydroxide; the hydroxide is aluminum hydroxideand/or magnesium hydroxide. The invention also discloses a polylactic acid material prepared from the composite of the invention and the polylactic acid material contains the flame retardant materialhydroxide so as to increase the high-temperature resistant and flame resistant properties of the material; owning to the synergistic reaction between the layered silicate and the hydroxide, the mechanical properties of the polylactic acid material can be ensured and the high-temperature resistant and flame resistant properties of the material can be improved significantly.
Description
[technical field]
The material that the present invention relates to a kind of poly-lactic acid material composition and prepare by said composition.
[background technology]
At present, the production method of lectic acid of industrial application all is to adopt the higher agricultural byproducts of starch content, as: rice, potato do, corn and rice bran etc. be raw material, go out lactic acid by gelatinization, saccharification, inoculation, fermentation, precipitation, crystallization, acidolysis, explained hereafter such as concentrated.In above-mentioned operation, fermentation is a vital step.In fermentation procedure, in agricultural byproducts, add bacterial classification through gelatinization and saccharification processing, ferment, generate lactic acid.But generating lactic acid through lactobacillus-fermented is a reversing process, and along with the lactic acid that generates constantly increases, fermenting process tends to balance, and fermentation can become slowly, until stopping.For improving lactic acid production, in fermented liquid, add lime carbonate usually and consume the lactic acid that generates in the fermenting process, make it generate calcium lactate, reduce the content of Lactic Acid from Fermentation Broth, thereby make fermentation proceed.After fermentation is finished, add sulfuric acid in the calcium lactate that generates, acidolysis goes out lactic acid.
Poly(lactic acid) (PLA) is to be raw material with lactic acid, the new polyester material that obtains through polymerization, poly(lactic acid) can be degraded fully by the microorganism of occurring in nature after use and be generated carbonic acid gas and water, can not pollute environment, therefore has good biodegradable performance.But the performance of poly(lactic acid), especially mechanical property can not be satisfied the demand usually, so, the modification technology of poly(lactic acid) is more and more received publicity.
The matrix material that existing polydactyl acid obtains mainly comprises two classes: a class is the matrix material that is obtained by poly(lactic acid) and mineral filler melt blending, as, CN1760265A discloses a kind of preparation method of Nano-composite material of poly lactic acid/montmorillonite, this method comprises that elder generation gets masterbatch with poly(lactic acid), organic modification montmonrillonite blend, again poly(lactic acid) and masterbatch melt blending are promptly got product, adopt less, the poor toughness of lactic acid composite material shock strength at low temperatures of this method preparation, make that this product fragility at low temperatures is bigger; Another kind of is to adopt poly(lactic acid) and other superpolymer such as resins for universal use blend such as polypropylene, polyethylene are prepared lactic acid composite material, but because the matrix material of this lactic acid composite material for can only partly degrading, can not eliminate the pollution of material resin fully, make the environment friendly and pollution-free advantage of poly(lactic acid) weaken greatly environment.
At present, make the mechanical property of lactic acid composite material obtain certain raising, but at some special dimension, as high temperature or inflammable field, conventional lactic acid composite material can not satisfy the use needs by various modifications.
[summary of the invention]
In order to give full play to the biodegradable advantage of poly-lactic acid material, enlarge its Application Areas, the invention provides a kind of poly-lactic acid material composition, when the poly-lactic acid material by said composition preparation has the good mechanical performance, high temperature resistant and flame retardant properties is also very excellent.
The invention discloses a kind of poly-lactic acid material composition, it is characterized in that, said composition contains poly(lactic acid), layered silicate and oxyhydroxide, and described oxyhydroxide is aluminium hydroxide and/or magnesium hydroxide.
For reaching better mechanical property, high temperature resistant and flame retardant properties, can also in above-mentioned composition, add anti-impact agent and oxidation inhibitor.
The invention also discloses a kind of poly-lactic acid material,, obtain extruding product under 150-185 ℃, the more described product of extruding is carried out tie rod, pelletizing, injection moulding, obtain poly-lactic acid material by above-mentioned poly-lactic acid material composition is mixed, extrudes.
Wherein, described blending means is in twin screw extruder, in length-to-diameter ratio is 20-40, screw speed is 180-230r/min, each zone temperatures is respectively 150-160 ℃, 150-165 ℃, 160-175 ℃, 160-175 ℃, 160-185 ℃, 155-180 ℃, and the vacuum tightness of each section is to mix under the condition of 0.02-0.06MPa.
Contain fire retardant material oxyhydroxide in the poly-lactic acid material disclosed by the invention, improved the high temperature resistant and flame retardant properties of material, synergy by layered silicate and oxyhydroxide, when having guaranteed the poly-lactic acid material mechanical property, the high temperature resistant and flame retardant properties of material has obtained promoting significantly.
[embodiment]
The invention discloses a kind of poly-lactic acid material composition, it is characterized in that, said composition contains poly(lactic acid), layered silicate and oxyhydroxide, and described oxyhydroxide is aluminium hydroxide and/or magnesium hydroxide.
Weight with poly(lactic acid) is benchmark, and the content of layered silicate is 3-10wt%, and the content of described oxyhydroxide is 10-25wt%.When containing aluminium hydroxide and magnesium hydroxide simultaneously in the described oxyhydroxide, without any relation, only need the oxyhydroxide total content to fall in the above-mentioned scope and get final product between the content of the two.Under the preferable case, be benchmark with the weight of poly(lactic acid), the content of layered silicate is 5-10wt%, and the content of described oxyhydroxide is 12-20wt%.Wherein, oxyhydroxide is magnesium hydroxide and/or aluminium hydroxide.
Poly(lactic acid) is to be the polyester material of raw material production with lactic acid, has good biodegradable performance, mechanical property and physicals preferably, and can be compatible with other material.The structural formula of poly(lactic acid) is as the formula (1):
The viscosity-average molecular weight of described poly(lactic acid) is 100,000-250,000, and fusing point is 150-175 ℃.Being preferably viscosity-average molecular weight is 150,000-230,000, and fusing point is 160-170 ℃.Described poly(lactic acid) can be commercially available, the U.S. natureworks company poly(lactic acid) of producing for example, and the trade mark is 3051D, and injection moulding rank, viscosity-average molecular weight are 180,000, and fusing point is 165 ℃.
Because the moisture in the polylactic acid raw material can exert an influence to the outward appearance and the mechanical property of the material that obtains at last, so the water content of poly(lactic acid) is not higher than 0.025wt% in the poly-lactic acid material composition disclosed by the invention, is not higher than 0.015wt% under the preferable case.
Described oxyhydroxide granularity is 10-50nm, is preferably 15-35nm.Described oxyhydroxide can be aluminium hydroxide and/or magnesium hydroxide.Described oxyhydroxide can be commercially available, for example fire retardant aluminium hydroxide or the magnesium hydroxide that the fire-retardant novel material of section company limited produces in the Hefei.
After the contriver found to add oxyhydroxide in poly(lactic acid), the mechanical property of material can descend rapidly.Under the situation that guarantees the heat-resisting and flame retardant properties of material, the oxyhydroxide of interpolation can cause the mechanical property of material not meet the demands, and under the prerequisite that guarantees material mechanical performance, the not enough again heat-resisting and flame retardant properties of giving the material practicality of the addition of oxyhydroxide.
Unexpected find oxyhydroxide and layered silicate are used of contriver, material is heat-resisting all very excellent with flame retardant properties and mechanical property, has reduced the usage quantity of oxyhydroxide and layered silicate simultaneously.
Layered silicate is one or more in polynite, kaolin, vermiculite, wilkinite or the rectorite leng; Layered silicate granularity is 10-50nm, and wafer thickness is 2-10nm.Under the preferable case, layered silicate is nano imvite, and its granularity is 15-25nm, and wafer thickness is 3-8nm.Layered silicate can be commercially available, for example the nano imvite of Shaanxi Mineral Chemical Engineering Inst.'s production.
When the granularity of layered silicate and wafer thickness are in above-mentioned scope, can better form intercalation configuration with polylactic acid molecule, on the molecular chain of poly(lactic acid), form rigid chain segment, assemble between the rigid chain segment and form a microcell, usually this microcell second-order transition temperature is higher, so be called " plastics phase ", and polymer segment has formed flexible phase in most zones, be commonly referred to " rubber phase ".Above-mentioned " plastics phase " distributes in " rubber phase " of poly-lactic acid material inside and forms the state of microphase-separated.As described in composition disclosed by the invention and poly-lactic acid material, after adding above-mentioned oxyhydroxide, oxyhydroxide forms synergy with said structure in poly-lactic acid material, more help improving the heat-resisting and flame retardant properties and the mechanical property of material.
Above-mentioned intercalation configuration is meant that the interlamellar spacing of layered silicate particle increases, and the organic polymer chain runs through whole particle between the lamella of layered silicate, and the interlamellar spacing of layered silicate particle increases but still has strong bonding force each other.This structure be layered silicate particle and macromolecular chain by chemical bond than rock steady structure.
The layered silicate of layered silicate for handling through intercalator; Described intercalator is one or more in 12, cetyl trimethylammonium bromide, the amino undecyl amine acid salt of 11-, cetalkonium chloride, the inferior maple of dimethyl, methane amide and dimethyl formamide, 12-aminolauric acid hydrochloride, the amino tetradecanoic acid amine salt of 14-, the amino hexadecanoic acid amine salt of 16-.Under the preferable case, described intercalator is a 12.Described intercalator can be commercially available, for example the 12 of company's production of the advanced company in Hong Kong production.The method that described intercalator is handled layered silicate is: under 70-90 ℃, layered silicate is placed intercalator 8-15min.Layered silicate and intercalator weight ratio are 1: 0.8-1.2.
When layered silicate is the above-mentioned layered silicate of handling through intercalator, be benchmark with the weight of poly(lactic acid), layered silicate content is the content of the layered silicate handled through intercalator.
For reaching better mechanical property, high temperature resistant and flame retardant properties, can also in above-mentioned composition, add anti-impact agent, oxidation inhibitor.Weight with poly(lactic acid) is benchmark, and the content of described anti-impact agent is 5-10wt%, and the content of described oxidation inhibitor is 0.1-1wt%.Under the preferable case, the content of described anti-impact agent is 6-9wt%, and the content of described oxidation inhibitor is 0.1-0.5wt%.
Described anti-impact agent is one or more in MBS (MBS), silicon-acrylic resin, the methyl methacrylate-ethyl propenoate-butyl acrylate copolymer (ACR); Described oxidation inhibitor is butylated hydroxy anisole, butylated hydroxytoluene, tertiarybutylhydroquinone, phosphorous acid benzene two isodecyl esters, pentaerythritol bis-phosphite, [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] in ten caprylates, four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester one or several.Under the preferable case, described anti-impact agent is silicon-acrylic resin, and described oxidation inhibitor is four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester.Described anti-impact agent and oxidation inhibitor all can be commercially available, for example the anti-impact agent silicon-acrylic resin s-2001 of the Li Yang of Mitsubishi company production.
The invention also discloses a kind of poly-lactic acid material, above-mentioned poly-lactic acid material composition is mixed, extrudes under 150-185 ℃, obtain extruding product, the more described product of extruding is carried out tie rod, pelletizing, injection moulding, obtain described poly-lactic acid material.
Be the water content in the control polylactic acid raw material, so earlier polylactic acid raw material is carried out pre-treatment under the preferable case, pre-treating process is: the raw material poly(lactic acid) is placed vacuum drying oven, at 0.05-0.1MPa, dry 1-4h under 75-90 ℃ obtains the poly(lactic acid) water content and is not higher than 0.025wt%.
After poly(lactic acid) carried out pre-treatment, water content in the poly(lactic acid) can be passed through Ka Shi moisture content tester (the Ka Shi moisture content tester that the plum Teller-Tuo benefit China produces, model MKC-520+ADP-511S) according to ASTM D6869-03 karl Fischer enclosed pasture method and volumetric determination.
In order better to improve the heat-resisting and flame retardant properties and the mechanical property of material, before described mixing, described oxyhydroxide and layered silicate and anti-impact agent can also be carried out earlier just mixing, just the method for mixing is for to join above-mentioned three kinds of components in the high-speed mixer, just silver mixing spare is: under 50-70 ℃, mix 3-10min.Described high-speed mixer is this area high-speed mixer commonly used, as the SHR-5A high-speed mixer of the mechanical company limited of the grand base in Zhangjagang City production.
Described blending means is in twin screw extruder, in length-to-diameter ratio is 20-40, screw speed is 180-230r/min, each zone temperatures is respectively 150-160 ℃, 150-165 ℃, 160-175 ℃, 160-175 ℃, 160-185 ℃, 155-180 ℃, the vacuum tightness of each section is to mix under the condition of 0.02-0.06MPa, extrude then, obtain extruding product.Described vacuum tightness is pounds per square inch absolute (psia).Described twin screw extruder can be this area twin screw extruder commonly used, as the TSSJ25 twin screw extruder of strong company of morning twilight section production.
The described product of extruding is carried out tie rod, pelletizing and injection moulding and can obtain described poly-lactic acid material.Described tie rod, pelletizing and injection moulding process are this area method commonly used; as extruding product by tank cooling carrying out tie rod; with dicing machine (machinery company limited of Zhangjagang City the United Nations General Assembly; model is QLJ-1) under rotating speed 350r/min, carry out pelletizing; after the oven dry of the micelle after cutting, carry out injection moulding with injection moulding machine.
The present invention is further illustrated below by embodiment.
Embodiment 1
Present embodiment is used to illustrate poly-lactic acid material composition provided by the invention and poly-lactic acid material.
1, raw material pre-treatment
Poly(lactic acid) (poly(lactic acid) that U.S. natureworks company produces, the trade mark is 3051D, injection moulding rank, viscosity-average molecular weight are 200,000, fusing point is 168 ℃) is put into vacuum drying oven, at 0.1MPa, 90 ℃ of dry 4h down.Obtaining the poly(lactic acid) water content is 0.02wt%.
2, raw material mixes
Get poly(lactic acid) 100 weight parts of above-mentioned processing, with the 11 weight part aluminium hydroxides (aluminium hydroxide that the fire-retardant novel material of section company limited produces in the Hefei, granularity is 40nm) and the 4 weight part polynites (polynite that company of Shaanxi Mineral Chemical Engineering Inst. produces, granularity is 20nm, wafer thickness is 5nm), 0.4 weight part four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010 that Nanjing Holley bright science, industry and trade company limited produces), place twin screw extruder, in length-to-diameter ratio is 20, screw speed is 200r/min, each zone temperatures is respectively 150 ℃, 160 ℃, 160 ℃, 165 ℃, 170 ℃, 170 ℃, the vacuum tightness of each section is to mix under the condition of 0.05MPa, extrudes then and obtains extruding product.
3, tie rod, pelletizing, injection moulding
To extrude product by tank cooling carrying out tie rod, (machinery company limited of Zhangjagang City the United Nations General Assembly, model is QLJ-1) carries out pelletizing under rotating speed 350r/min with dicing machine, after the oven dry of the micelle after cutting, carries out injection moulding with injection moulding machine.Obtain poly-lactic acid material A1.
Embodiment 2
Present embodiment is used to illustrate poly-lactic acid material composition provided by the invention and poly-lactic acid material.
1, raw material pre-treatment
Poly(lactic acid) (poly(lactic acid) that U.S. natureworks company produces, the trade mark is 3051D, injection moulding rank, viscosity-average molecular weight are 150,000, fusing point is 160 ℃) is put into vacuum drying oven, at 0.08Pa, 85 ℃ of dry 4h down.Obtaining the poly(lactic acid) water content is 0.018wt%.
Under 78 ℃, rectorite leng (rectorite leng that Mingguang City, the Anhui Province strong mining industry of will company limited produces, granularity is 18um, wafer thickness is 6nm) is placed 12 (Hong Kong company of advanced company produces) 10min.Described rectorite leng and 12 weight ratio are 1: 1.
2, raw material mixes
Get poly(lactic acid) 100 weight parts of above-mentioned processing, with the 22 weight part magnesium hydroxides (magnesium hydroxide that the fire-retardant novel material of section company produces in the Hefei, granularity is 20nm), the rectorite leng that 6 weight parts were handled through intercalator, 5 weight part silicon-acrylic resins (s-2001 that Li Yang company of Mitsubishi produces), 0.6 weight part four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010 that Nanjing Holley bright science, industry and trade company limited produces), place twin screw extruder, in length-to-diameter ratio is 40, screw speed is 220r/min, each zone temperatures is respectively 155 ℃, 160 ℃, 160 ℃, 165 ℃, 170 ℃, 170 ℃, the vacuum tightness of each section is to mix under the condition of 0.05MPa, extrudes then and obtains extruding product.
3, tie rod, pelletizing, injection moulding
Tie rod, pelletizing, injection moulding process obtain poly-lactic acid material A2 with embodiment 1.
Embodiment 3
Present embodiment is used to illustrate poly-lactic acid material composition provided by the invention and poly-lactic acid material.
1, raw material pre-treatment
Poly(lactic acid) (poly(lactic acid) that U.S. natureworks company produces, the trade mark is 3051D, injection moulding rank, viscosity-average molecular weight are 200,000, fusing point is 165 ℃) is put into vacuum drying oven, at 0.06MPa, 90 ℃ of dry 4h down.Recording the poly(lactic acid) water content is 0.01wt%.
Under 80 ℃, rectorite leng (rectorite leng that Mingguang City, the Anhui Province strong mining industry of will company limited produces, granularity is 20nm, wafer thickness is 6nm) is placed 12 (Hong Kong company of advanced company produces) 12min.Described rectorite leng and 12 weight ratio are 1: 1.
2, just mix
Poly(lactic acid) with above-mentioned processing is 100 weight parts, (the fire-retardant novel material of section company produces in the Hefei to get 18 weight part magnesium hydroxides, granularity is 25um), 8 weight parts rectorite leng, the 8 weight part silicon-acrylic resins (s-2001 of Li Yang company of Mitsubishi production) handled through intercalator join in the rheometer (AR-G2 of U.S. TA company production), mix 5min down at 60 ℃, obtain just mixing product.
3, raw material mixes
Get poly(lactic acid) 100 weight parts of above-mentioned processing, 20 weight part lime carbonate, with 0.3 weight part four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (1010 oxidation inhibitor that company of Nanjing Holley bright science, industry and trade company limited produces) and the above-mentioned product that just mixes, place high-speed mixer to mix 2 minutes again, place twin screw extruder then, in length-to-diameter ratio is 30, screw speed is 210r/min, each zone temperatures is respectively 155 ℃, 165 ℃, 165 ℃, 170 ℃, 170 ℃, 170 ℃, the vacuum tightness of each section is to mix under the condition of 0.05MPa, extrudes then and obtains extruding product.
4, tie rod, pelletizing, injection moulding
Tie rod, pelletizing, injection moulding process obtain poly-lactic acid material A3 with embodiment 1.
Embodiment 4
Present embodiment is used to illustrate poly-lactic acid material composition provided by the invention and poly-lactic acid material.
1, raw material pre-treatment
The raw material pre-treating process is with embodiment 3, and different is: layered silicate is the blend of polynite and rectorite leng, and intercalator is the blend of 12 and 12-aminolauric acid hydrochloride (rich this specialization worker in Shandong company limited produces).
2, just mix
Just mixing method is with embodiment 3, different is: the poly(lactic acid) with above-mentioned processing is 100 weight parts, oxyhydroxide is the mixture of 10 weight part magnesium hydroxides and 10 weight part aluminium hydroxides, and the anti-impact agent is methyl methacrylate-ethyl propenoate-butyl acrylate copolymer (ACR that U.S. Rhom and Hass produces).
3, raw material mixes
Method for mixing raw materials is with embodiment 3, and different is: oxidation inhibitor is [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (1010 oxidation inhibitor that the abundant Sheng chemical industry in Yantai City company limited produces).
4, tie rod, pelletizing, injection moulding
Tie rod, pelletizing, injection moulding process obtain poly-lactic acid material A4 with embodiment 1.
Comparative Examples 1
This Comparative Examples is used to illustrate poly-lactic acid material of the prior art.
The poly-lactic acid material preparation method is with embodiment 2, and different is not contain oxyhydroxide.Obtain poly-lactic acid material D1.
Comparative Examples 2
This Comparative Examples is used for comparative illustration poly-lactic acid material provided by the invention.
The poly-lactic acid material preparation method is with embodiment 2, and different is not contain layered silicate.Obtain poly-lactic acid material D2.
Comparative Examples 3
This Comparative Examples is used to illustrate poly-lactic acid material of the prior art.
The poly-lactic acid material preparation method is with embodiment 2, and different is not contain layered silicate and oxyhydroxide.Obtain poly-lactic acid material D3.
Performance test
Adopt ASTM (U.S.'s test and materials association) standard and UL (American insurance merchant tests authentication) that above-mentioned poly-lactic acid material A1-A4 that makes and D1-D3 are carried out following performance test:
1, tensile strength and elongation at break
Adopt ASTM D638 method to measure the tensile strength and the elongation at break of material;
2, flexural strength and modulus in flexure
Adopt ASTM D790 method to measure the flexural strength and the modulus in flexure of material;
3, notched Izod impact strength
Adopt ASTM D256 method to measure the notched Izod impact strength of material;
4, heat-drawn wire
Adopt ASTM D648 method to measure the heat-drawn wire of material;
5, Vicat softening point
Adopt ASTM D1525 method to measure the Vicat softening point of material;
6, melt flow rate (MFR)
Adopt ASTM D1238 method to measure the melt flow rate (MFR) of material;
7, flame retardant properties
Adopt the UL94 method to measure the flame retardant properties of material.
The plastics flame retardant rating is by HB, V-2, and V-1 increases progressively step by step to V-0:
Minimum flame retardant rating in the HB:UL94 standard.Requirement is for the thick sample of 3-13mm, and combustionvelocity is less than 40mm/min; Less than the thick sample of 3mm, combustionvelocity is less than 70mm/min; Perhaps before the sign of 100mm, extinguish.
V-2: after sample being carried out the combustion testing of twice 10s, flame extinguishes in 60s.Can there be combustionmaterial to fall down.
V-1: after sample being carried out the combustion testing of twice 10s, flame extinguishes in 60s.Can not there be combustionmaterial to fall down.
V-0: after sample being carried out the combustion testing of twice 10s, flame extinguishes in 30s.Can not there be combustionmaterial to fall down.
Test result sees Table 1.
Table 1
| Sample | ??A1 | ??A2 | ??A3 | ??A4 | ??D1 | ??D2 | ??D3 |
| Tensile strength/MPa | ??88.2 | ??85.6 | ??91.4 | ??90.3 | ??86.7 | ??83.4 | ??80.1 |
| Elongation at break/% | ??9.56 | ??11.2 | ??13.1 | ??13.5 | ??8.2 | ??6.51 | ??8.61 |
| Flexural strength/MPa | ??89 | ??91.6 | ??96.2 | ??97.3 | ??85.2 | ??83.7 | ??84.2 |
| Modulus in flexure/MPa | ??2328.3 | ??2375.6 | ??2431.2 | ??2456.8 | ??2265.8 | ??2124.7 | ??2216.8 |
| Notched Izod impact strength/J/m | ??41.3 | ??48.6 | ??56.5 | ??55.3 | ??41.3 | ??37.2 | ??38.9 |
| Heat-drawn wire/℃ | ??59.8 | ??62.3 | ??67.4 | ??67.8 | ??55.7 | ??53.1 | ??50.2 |
| Vicat softening point/℃ | ??55.3 | ??57.2 | ??60.9 | ??59.3 | ??53.1 | ??51.2 | ??50.3 |
| Melt flow rate (MFR) g/10min | ??4.3 | ??3.91 | ??3.55 | ??3.64 | ??4.1 | ??4.72 | ??3.5 |
| Flame retardant properties | ??V1 | ??V1 | ??V0 | ??V0 | Burning has drippage | ??V2 | Burning has drippage |
From the test result of table 1 as can be seen, when containing oxyhydroxide in the poly-lactic acid material (as D2), than pure poly-lactic acid material (as D1), the flame retardant properties of poly-lactic acid material has obtained certain raising, but the modulus in flexure of material and flexural strength and elongation at break obviously descend.When containing layered silicate in the poly-lactic acid material (as D3), the mechanical property of material is improved, but does not have flame retardant properties.
Poly-lactic acid material (as A1) by poly-lactic acid material preparation of compositions disclosed by the invention is than pure poly-lactic acid material (as D1) and contain the poly-lactic acid material (as D2) of oxyhydroxide separately and contain the mechanical property and the flame retardant properties of poly-lactic acid material (as D3) of layered silicate separately all good, illustrates that layered silicate and the oxyhydroxide in poly-lactic acid material has produced synergy.
The test result of contrast A1-A5 as can be seen, by preferred implementation disclosed by the invention, as layered silicate being carried out the intercalator processing and layered silicate, oxyhydroxide and anti-impact agent being carried out just mixing improving the mechanical property of material, heat-resisting and flame retardant properties.
Claims (11)
1, a kind of poly-lactic acid material composition is characterized in that, said composition contains poly(lactic acid), layered silicate and oxyhydroxide, and described oxyhydroxide is aluminium hydroxide and/or magnesium hydroxide.
2, composition according to claim 1 is characterized in that, is benchmark with the weight of poly(lactic acid), and the content of layered silicate is 3-10wt%, and the content of described oxyhydroxide is 10-25wt%.
3, composition according to claim 1 is characterized in that, the viscosity-average molecular weight of described poly(lactic acid) is 100,000-250,000, and fusing point is 155-175 ℃, and water content is not higher than 0.025wt%.
4, composition according to claim 1 is characterized in that, layered silicate is one or more in polynite, kaolin, vermiculite, wilkinite or the rectorite leng; Layered silicate granularity is 10-50nm, and wafer thickness is 2-10nm.
5, according to claim 1 or 4 described compositions, it is characterized in that the layered silicate of layered silicate for handling through intercalator; Described intercalator is one or more in 12, cetyl trimethylammonium bromide, the amino undecyl amine acid salt of 11-, cetalkonium chloride, the inferior maple of dimethyl, methane amide and dimethyl formamide, 12-aminolauric acid hydrochloride, the amino tetradecanoic acid amine salt of 14-, the amino hexadecanoic acid amine salt of 16-.
6, composition according to claim 1 is characterized in that, described oxyhydroxide granularity is 10-50nm.
7, composition according to claim 1 is characterized in that, described composition also contains anti-impact agent and oxidation inhibitor; Weight with poly(lactic acid) is benchmark, and the content of described anti-impact agent is 5-10wt%, and the content of described oxidation inhibitor is 0.1-1wt%.
8, composition according to claim 7, it is characterized in that described anti-impact agent is one or more in MBS, silicon-acrylic resin, the methyl methacrylate-ethyl propenoate-butyl acrylate copolymer; Described oxidation inhibitor is butylated hydroxy anisole, butylated hydroxytoluene, tertiarybutylhydroquinone, phosphorous acid benzene two isodecyl esters, pentaerythritol bis-phosphite, [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] in ten caprylates, four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester one or several.
9, a kind of poly-lactic acid material by any described composition among the claim 1-8 is mixed, extrudes, obtains extruding product under 150-185 ℃, the more described product of extruding is carried out tie rod, pelletizing, injection moulding, obtains poly-lactic acid material.
10, a kind of poly-lactic acid material, comprise claim 7 or 8 described compositions are mixed, extruded under 150-185 ℃, obtain extruding product, again the described product of extruding is carried out tie rod, pelletizing, injection moulding, obtain poly-lactic acid material, wherein also be included in before the described mixing described oxyhydroxide and layered silicate and anti-impact agent are carried out earlier just mixing, first silver mixing spare is: under 50-70 ℃, and mixing 3-10min.
11, according to claim 9 or 10 described poly-lactic acid materials, it is characterized in that, described blending means is in twin screw extruder, in length-to-diameter ratio is 20-40, screw speed is 180-230r/min, each zone temperatures is respectively 150-160 ℃, 150-165 ℃, 160-175 ℃, 160-175 ℃, 160-185 ℃, 155-180 ℃, and the vacuum tightness of each section is to mix under the condition of 0.02-0.06MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810142755XA CN101638508B (en) | 2008-07-29 | 2008-07-29 | Polylactic acid material composite and material prepared from same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810142755XA CN101638508B (en) | 2008-07-29 | 2008-07-29 | Polylactic acid material composite and material prepared from same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101638508A true CN101638508A (en) | 2010-02-03 |
| CN101638508B CN101638508B (en) | 2011-07-06 |
Family
ID=41613699
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200810142755XA Active CN101638508B (en) | 2008-07-29 | 2008-07-29 | Polylactic acid material composite and material prepared from same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101638508B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102838859A (en) * | 2012-09-28 | 2012-12-26 | 江苏嘉铂新材料有限公司 | Nanometer bentonite composite flame-retardant polylactic acid bioplastics and preparation method thereof |
| CN103013147A (en) * | 2013-01-12 | 2013-04-03 | 天津市市政工程设计研究院 | Flame-retardant modified asphalt and preparation method thereof |
| CN107814956A (en) * | 2017-10-16 | 2018-03-20 | 王欣 | A kind of production method of sodium alginate polyvinyl alcohol bentonite slow release fertilizer coating liquid |
| CN113980445A (en) * | 2021-12-09 | 2022-01-28 | 王玲芝 | Special biomass color master batch for degradable plastics and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5036318B2 (en) * | 2004-11-15 | 2012-09-26 | ユニチカ株式会社 | Flame retardant polylactic acid resin composition, method for producing the same, and molded product obtained therefrom |
| CN1760265A (en) * | 2005-10-13 | 2006-04-19 | 同济大学 | A kind of preparation method of Nano-composite material of poly lactic acid/montmorillonite |
| CN101003667A (en) * | 2006-01-20 | 2007-07-25 | 东丽纤维研究所（中国）有限公司 | Composite material of poly lactic acid / natural faric, and production method |
| CN101143962A (en) * | 2006-09-15 | 2008-03-19 | 奇钛科技股份有限公司 | Biodegradable resin composition for modifying toughness and heat resistance and preparation method thereof |
-
2008
- 2008-07-29 CN CN200810142755XA patent/CN101638508B/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102838859A (en) * | 2012-09-28 | 2012-12-26 | 江苏嘉铂新材料有限公司 | Nanometer bentonite composite flame-retardant polylactic acid bioplastics and preparation method thereof |
| CN103013147A (en) * | 2013-01-12 | 2013-04-03 | 天津市市政工程设计研究院 | Flame-retardant modified asphalt and preparation method thereof |
| CN107814956A (en) * | 2017-10-16 | 2018-03-20 | 王欣 | A kind of production method of sodium alginate polyvinyl alcohol bentonite slow release fertilizer coating liquid |
| CN113980445A (en) * | 2021-12-09 | 2022-01-28 | 王玲芝 | Special biomass color master batch for degradable plastics and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101638508B (en) | 2011-07-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101747639B (en) | Wood plastic composite composition, wood plastic composite and preparation method thereof | |
| CN101974218B (en) | Special plastic/acrylonitrile butadiene styrene (PC/ABS) alloy for notebook computer shell | |
| CN102719063A (en) | Polylactic acid material composition, polylactic acid material and its preparation method | |
| CN106751607A (en) | A kind of FDM printings use graininess PLA material modified and preparation method | |
| CN103113727B (en) | A kind of completely biological degradation polylactic acid matrix material and its preparation method and application | |
| JP2011528043A (en) | Thermoplastic flame retardant alloy and process for its preparation | |
| CN103087460B (en) | A kind of toughening polyoxymethylene composition and preparation method thereof | |
| CN102911454B (en) | PVC (polyvinyl chloride)/ABS (acrylonitrile butadiene styrene copolymer)/CPE (chlorinated polyethylene) pipe with high impact resistance and method for preparing same | |
| CN101638508B (en) | Polylactic acid material composite and material prepared from same | |
| CN105038163A (en) | Fully-biodegradable material as well as preparation method and application thereof | |
| CN102367308A (en) | Flame retardant polypropylene composite material and its preparation method | |
| CN106189127A (en) | A kind of modified polylactic acid coblended matter and preparation method thereof | |
| CN102250389B (en) | Biodegradable polymer material compatibilized and blended by lignocellulose and preparation method thereof | |
| CN104558818B (en) | Polypropene composition of dimensionally stable and preparation method thereof | |
| CN106189128A (en) | A kind of polylactic acid polyamide blend and preparation method thereof | |
| CN106479143A (en) | A kind of attapulgite/poly lactic acid nano composite material and preparation method thereof | |
| CN103571182A (en) | High-fluidity toughened filling nylon and preparation method thereof | |
| CN103724958B (en) | A kind of high-toughness polylactic acid matrix material and preparation method thereof | |
| CN105086393B (en) | Plastic allowing PLA to be fully degraded and production method thereof | |
| CN104974487A (en) | Preparation method of high-toughness polylactic acid-based composite material | |
| CN103965599B (en) | PLA (polylactic acid)/ABS (acrylonitrile-butadiene-styrene copolymers) alloy material and preparation method thereof | |
| CN114407471B (en) | Three-layer co-extrusion biodegradable automatic packaging film material and manufacturing method thereof | |
| CN103224695A (en) | High impact recycled PET/ABS alloy composition and preparation method thereof | |
| CN102167891B (en) | Polylactic acid material and preparation method thereof | |
| CN113683870A (en) | High-strength high-toughness polylactic acid material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |