CN101265355A - Polylactic acid mixture and forming articles thereof - Google Patents
Polylactic acid mixture and forming articles thereof Download PDFInfo
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- CN101265355A CN101265355A CNA2007100202785A CN200710020278A CN101265355A CN 101265355 A CN101265355 A CN 101265355A CN A2007100202785 A CNA2007100202785 A CN A2007100202785A CN 200710020278 A CN200710020278 A CN 200710020278A CN 101265355 A CN101265355 A CN 101265355A
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Abstract
The invention discloses a poly lactic acid mixture and a heat-resistant transparent formed product prepared by the poly lactic acid mixture. The poly lactic acid mixture is prepared by poly lactic acid in an amount of 100 parts by weight, an amide compount in an amount of 0.1 to 10 parts by weight, and a sorbitol compound in an amount of 0.01 to 5 parts by weight through mixing. The invention further discloses a poly lactic acid formed product prepared by the poly lactic acid mixture through heat treatment during forming or after forming. In addition, the poly lactic acid formed product has high transparency and heat-resistance.
Description
Technical field
The present invention relates to field of polymer technology, relate to a kind of polylactic acid blend specifically and by the prepared transparent moulding product of this blend with resistance toheat.
Background technology
In recent years, the consumption as the polyethylene of food, beverage-container, pallet etc. and commodity external packing box material, polypropylene, polyester, nylon etc. increases year by year.What accompany therewith is that the amount of using the back waste is also in continuous increase.Because the burning of these wastes and burying has brought various environmental problems.In order to address these problems, in recent years, can to carry out biolytic polymkeric substance and constantly be used.Wherein, poly(lactic acid) is used at industrial quilt widely owing to have relative high melt point and relative higher mechanical properties.
But work as poly(lactic acid) as food, beverage-container, pallet etc. and commodity external packing box, except having required higher transparency, also to have certain hot patience, to prevent encased conveying or the temperature distortion that brought and opaque etc. that raises suddenly.But the thermotolerance of poly(lactic acid) itself is not high, need improve by the two-way stretch crystallization or by adding a large amount of fillers.But the preparation of biaxial stretching film needs huge cost of equipment.And improve stable on heating method by adding filler, can cause the remarkable reduction of the moulding product transparency.
A kind of heat-resistance polylactic acid window membrane by the two-way stretch preparation has been proposed in Japanese Patent 2000-008349.The crystalline polylactic acid membrane has certain thermotolerance by two-way stretch.But the two-way stretch method can't prepare thicker film/sheet material.And the production of biaxial stretching film needs huge equipment and factory building investment.Further, biaxial stretching film is because partially or completely crystallization is not easy to post forming.
Propose injection molding after poly(lactic acid) is mixed talcum powder in Japanese Patent H05-504471, the moulding product have higher heat resisting temperature, but add the transparency that a spot of talcum powder also can influence poly(lactic acid) greatly.And in Japanese Patent H08-193165 talcum powder etc. is added in the poly(lactic acid) as nucleator, when injection molding, actual crystallization velocity is slower, and product is more crisp.
A kind of poly (lactic acid) composition that contains phenolic antioxidant and amides has been described in Chinese patent CN 1539880A, when injection molding, the die temperature of shaper is arranged between the fusion-crystallization starting temperature and glass transition temp of this poly (lactic acid) composition, realizes stable on heating raising by the fusion-crystallization of poly(lactic acid) in the control moulding product.Yet because poly(lactic acid) and fusion-crystallization process slowly thereof, amides is difficult to the fusion-crystallization in the independent control poly(lactic acid) moulding process, must be by adding crystallization velocity, the shortening crystallization time that talcum powder further improve poly(lactic acid).Therefore, prepared moulding product, when improving hot patience, the transparency can not be controlled effectively.
Summary of the invention
The objective of the invention is to overcome poly(lactic acid) cold crystallization temperature height, the slow shortcoming of crystallization velocity, on the basis of the glass transition temp of not obvious reduction poly(lactic acid), provide a kind of polylactic acid blend of comparing, having the crystallization velocity of lower cold crystallization temperature and Geng Gao with the matrix poly(lactic acid).
Another object of the present invention is to provide a kind of this polylactic acid blend through fusion, moulding, and when overmolding and/or the thermal treatment after the moulding is resulting has the good transparency and stable on heating poly(lactic acid) moulding product simultaneously.
Purpose of the present invention can obtain by following means:
A kind of polylactic acid blend, mainly form by following components in part by weight:
100 parts of poly(lactic acid)
0.1～10 part of amides
0.01～5 part of glucitols compound.
Above-mentioned poly(lactic acid) is poly(lactic acid) homopolymer, copolymer of poly lactic acid, polylactic acid stereoscopic composite or the mixture between them.The fusing point of poly(lactic acid) is 120～185 ℃, and weight-average molecular weight is 20,000～800,000.
Above-mentioned amides is selected from one or more in the two alkylamides of ethylene, saturated fatty acid monoamide, unsaturated fatty acids monoamide or the amino acid amide, preferably one or more in lauric amide, stearic amide, amine hydroxybenzene, erucicamide, ricinolic acid acid amides, the bimonthly osmanthus of ethylene acid amides, ethylene bis stearamide, the two amine hydroxybenzenes of ethylene, Methionin laurylamide, Methionin stearylamide, L-glutamic acid laurylamide, L-glutamic acid stearic amide, leucine propylhomoserin laurylamide or leucine stearylamide.
Above-mentioned glucitols compound is selected from the sorbyl alcohol that contains the benzal group, as 1, and 3-benzal sorbyl alcohol, 1,4-benzal sorbyl alcohol, 1,3-alkyl benzal sorbyl alcohol, 1,4-alkyl benzal sorbyl alcohol, 1,3,2,4-dibenzal sorbitol or 1,3,2,4-two (alkyl benzal) sorbyl alcohol (wherein 1,3,2,4-two (alkyl benzal) sorbyl alcohol preferred 1,3,2,4-two (4-methyl benzal) sorbyl alcohol, 1,3,2,4-two (4-ethyl benzal) sorbyl alcohol, 1,3,2,4-two (3,4-dimethyl benzal) sorbyl alcohol) one or more in.
The blend method of above-mentioned polylactic acid blend can be melt blending, mechanical blending etc. or their combination.Can realize by machineries such as high-speed mixer, single screw extrusion machine, twin screw extruder, Banbury mixeies.
A kind of moulding product of polylactic acid blend are obtained by thermal treatment when the moulding and/or after the moulding by above-mentioned polylactic acid blend.Specifically, adopt earlier flow casting molding, calendering formation, injection moulding, blow molding or hot-forming etc. method with the polylactic acid blend melt molding, again through the overmolding neutralization/or moulding after thermal treatment obtain.
The thickness of above-mentioned moulding product is 0.02～5mm.
Heat treated temperature range is below the above fusing point of cold crystallization starting temperature of polylactic acid blend, and heat treatment period is 2 seconds to 10 minutes, preferred 10～120 seconds.
Purpose of the present invention specifically can reach by following measure:
Form blend by per 100 weight part poly(lactic acid) and following (A) with (B) by blend: (A) 0.1～10 weight part amides, (B) 0.01～5 weight part glucitols compound.Reduce the cold crystallization temperature of poly(lactic acid), the crystallization velocity of raising poly(lactic acid) by (A) amides that is added.
Comprise by above-mentioned polylactic acid blend through moulding and the resulting moulding product of thermal treatment, after elder generation adopts flow casting molding, calendering formation, injection moulding, blow molding or hot press molding method with the polylactic acid blend melt molding, promptly through Overheating Treatment.
The polymer shaping goods of concrete above-mentioned polylactic acid blend, for example the thickness that this polylactic acid blend is obtained after fusion, moulding is polylactic acid resin film/sheet material of 0.02～5mm or ampuliform, tubbiness, box-like poly(lactic acid) moulding product, moulding or not once more after the moulding once more, by in the moulding and/or the moulding postheat treatment cause crystallization, improve the transparency of crystallization aftershaping product by (B) glucitols compound in the blend.
As the poly(lactic acid) in the polylactic acid blend among the present invention, its fusing point is 120～185 degree, weight-average molecular weight is 20,000～800,000, as principal constituent, can be the blend of blend, polylactic acid stereoscopic composite (stereocomplex), polylactic acid stereoscopic composite and the poly(lactic acid) homopolymer and/or the copolymer of poly lactic acid of poly(lactic acid) homopolymer, copolymer of poly lactic acid, poly(lactic acid) homopolymer and copolymer of poly lactic acid with L-lactic acid and/or D-lactic acid.The formation mol ratio of L-lactic acid units and D-lactic acid units has no particular limits, and can select in 100/0～0/100 scope.But in order to guarantee the fusing point of poly(lactic acid), any content in preferred L-lactic acid units and the D-lactic acid units is more than 90mol%.
The amide compound that the preferred polarity of (A) amides among the present invention is lower, carbochain is long, have suitable consistency with the poly(lactic acid) matrix simultaneously.Thereby this consistency is less when normal temperature, do not play the glass transition temp that plastification does not reduce the poly(lactic acid) matrix; This consistency is big when high temperature, the relative movement of polylactic acid molecule interchain is become easily, thereby reduced cold crystallization temperature, improved crystallization velocity.Above-mentioned amide compound can be the saturated fatty acid monoamide, as lauric amide, stearic amide, amine hydroxybenzene etc.; Also can be the unsaturated fatty acids monoamide, as erucicamide, ricinolic acid acid amides etc.; Also can be the saturated fatty acid bisamide, as two alkylamides of ethylene such as the bimonthly osmanthus of ethylene acid amides, ethylene bis stearamide, the two amine hydroxybenzenes of ethylene; Also can be amino acid amide, as Methionin laurylamide, Methionin stearylamide, L-glutamic acid laurylamide, L-glutamic acid stearic amide, leucine propylhomoserin laurylamide, leucine stearylamide etc.
(B) benzal glucitols compound among the present invention is a kind of well-known polypropylene nucleater, but when using separately, does not have tangible facilitation effect for the crystallization of poly(lactic acid).The present inventor is by discovering, by utilizing (A) amide compound and (B) synergistic effect of these two kinds of nucleators of glucitols compound, by thermal treatment, promoting the poly(lactic acid) crystalline simultaneously, obviously improved the crystalline degree of uniformity again, thereby realized purpose of the present invention.Above-mentioned glucitols compound can be the glucitol derivative that contains the benzal group: as 1, and 3-benzal sorbyl alcohol, 1,4-benzal sorbyl alcohol, 1,3-alkyl benzal sorbyl alcohol, 1,4-alkyl benzal sorbyl alcohol, 1,3,2, the 4-dibenzal sorbitol, 1,2,3,4-two (alkyl benzal) sorbyl alcohol is (as 1,3,2,4-two (4-methyl benzal) sorbyl alcohol, 1,3,2,4-two (4-ethyl benzal) sorbyl alcohol, 1,3,2,4-two (3,4-dimethyl benzal) sorbyl alcohol etc.), the alkyl of the preferred C1 of wherein said alkyl～6, most preferable, ethyl, propyl group or sec.-propyl.
The blend method of polylactic acid blend described in the present invention can be melt blending, mechanical blending etc. or their combination.Can realize by machineries such as high-speed mixer, single screw extrusion machine, twin screw extruder, Banbury mixeies.
Moulding product of the present invention, preferably with described polylactic acid blend in fusion, moulding, moulding and/or the moulding postheat treatment obtain have regular shape or erose, that thickness is 0.02～5mm polylactic acid membrane/sheet material/ampuliform/tubbiness/box-like moulding product, or with lactic acid film/sheet material/ampuliform/tubbiness/box-like moulding product moulding and other moulding product of obtaining once more.
The method of fusion of the present invention, moulding can be extrusion moulding, flow casting molding, calendering formation, injection moulding, blow molding or hot-forming etc.
Thermal treatment of the present invention, can be at convection oven, vacuum drying oven, thus tunnel baking oven etc. have in the airtight of heating function or the semi closed equipment carry out, by regulating treatment temp and treatment time to impel the partially or completely crystallization transparency and the heat-resisting degree of regulating the moulding product of moulding product.The scope of described thermal treatment temp is that heat treatment period is 2 seconds to 10 minutes below the above fusing point of cold crystallization starting temperature that records of differential scanning calorimeter (DSC).The edge of moulding product should be fixed to prevent the influence of thermal contraction when heat-treating.
The present invention is a kind of itself transparent poly-lactic acid mixture (without thermal treatment time) on the whole, this mixture is owing to have special thermal property (than the low cold crystallization temperature of pure poly(lactic acid)), so can after heat-treating, have the transparency and thermotolerance simultaneously concurrently by corresponding special thermal treatment process (treatment temp is below the above fusing point of cold crystallization starting temperature of the polylactic acid blend that differential scanning calorimeter (DSC) records).
After the moulding of this moulding product, by obtaining having concurrently the transparency and stable on heating effect after the processing of special thermal treatment process heat, this thermal treatment process is indispensable for realization stable on heating realization of the present invention, and the adding of glucitol compounds can suppress the transparency decline that thermal treatment causes.
The present invention is on the basis of the glass transition temp of not obvious reduction poly(lactic acid), a kind of polylactic acid blend of comparing, having the crystallization velocity of lower cold crystallization temperature and Geng Gao with the matrix poly(lactic acid) is provided, has the good transparency and thermotolerance simultaneously by the prepared moulding product of this blend.
Embodiment
Thermal treatment and evaluation test method
Thermal treatment:
The film that suppresses is fixed on the steel framework with clip, in pre-set temperature and the convection oven of constant temperature for some time or tunnel baking oven, heated 10～120 seconds.The scope that described temperature is is below the above fusing point of crystallization onset temperature that records of differential scanning calorimeter (DSC).
Heat-drawn wire:
It is wide to be cut into 1cm at the film that suppresses, the batten that 5cm is long, be fixed on the sample table shown in figure (accompanying drawing), put into the convection oven (ESPEC) that is warmed up to 65 ℃ in advance, placed 10 minutes, and observed the deformation extent of batten, degree of crook at 10 ° (angles of batten and horizontal direction) with interior being evaluated as " ◎ ", degree of crook is 10-25 ° be evaluated as " △ ", degree of crook is being evaluated as more than 25 ° " * ".For being evaluated as " ◎ ", " △ " and batten, the method above using continues to observe and estimate thermotolerance at 80 ℃, 100 ℃.
The transparency:
Use mist degree to characterize the transparency of moulding product.Mist degree before and after the thermal treatment of moulding product is measured by SugaHZ-1 type haze meter.
Thermal property:
Use the DSC Q100 of TA company, measure Tc.The film that suppresses is downcut about 10mg with blade, preparation sample dish.Nitrogen flow is 50ml/min, at room temperature reaches balance, and temperature rise rate is 20 ℃/min, is warmed up to 200 ℃, reads exothermic peak as cold crystallization temperature (T
Cc), endotherm(ic)peak is as fusing point (T
m), eliminated thermal history in 3 minutes at 200 ℃ of constant temperature, rate of cooling is 20 ℃/min, cools to room temperature, reads endotherm(ic)peak as melt crystallization temperature (T
Mc), at room temperature constant temperature is 2 minutes, heats up with 20 ℃/min once more, reads glass transition temp (T
g).
Embodiment 1
With poly(lactic acid) (4032D, Natureworks, weight-average molecular weight 23.7 ten thousand) places vacuum drying oven, 80 ℃ of dryings are after 10 hours, respectively with the bimonthly osmanthus of ethylene acid amides (EBLA), 1,3,2,4-two (4-methyl benzal) sorbyl alcohol (NC6, Mitsui Chemicals) by the twin screw extruder coextrusion, be a granulated into 4032D: the masterbatch 1 of EBLA=95/5 (weight part), the masterbatch 2 of 4032D/NC6=95/5 (weight part).The feed zone temperature of described twin screw extruder is 170 ℃, and all the other each section temperature are 210 ℃, vacuumizing and exhausting in the extrusion.
Two kinds of masterbatch place vacuum drying oven, 80 ℃ of dryings 10 hours, poly(lactic acid) (the 4032D that crosses with drying again, Natureworks) be mixed into the mixture of 4032D/EBLA/NC6=98/1/1 by a certain percentage, extrude and by casting roller by the single screw extrusion machine that has T pattern head, make thickness and be the film about 0.5mm.The feed zone temperature of described twin screw extruder is 170 ℃, and all the other each section temperature are 210 ℃.
Cold crystallization temperature (the T of film before the test thermal treatment
Cc) be 84.8 ℃, fusing point (T
m) be 164.5 ℃.
With the film that makes with steel framework and clip fixing after, place the tunnel baking oven to heat-treat.
(1) thermal treatment temp is 110 ℃, and heat treatment time is 10 seconds.
The mist degree and the thermotolerance of test thermal treatment rear film.After tested, mist degree is 2.5%, and thermotolerance is 65 ℃ " △ ", 80 ℃ " * ", 100 ℃ " * ".
(2) thermal treatment temp is 110 ℃, and heat treatment time is 20 seconds.
The mist degree and the thermotolerance of test thermal treatment rear film.After tested, mist degree is 5.6%, and thermotolerance is 65 ℃ " ◎ ", 80 ℃ " ◎ ", 100 ℃ " △ ".
(3) thermal treatment temp is 120 ℃, and heat treatment time is 10 seconds.
The mist degree and the thermotolerance of test thermal treatment rear film.After tested, mist degree is 3.8%, and thermotolerance is 65 ℃ " ◎ ", 80 ℃ " ◎ ", 100 ℃ " ◎ ".
(4) thermal treatment temp is 120 ℃, and heat treatment time is 20 seconds.
The mist degree and the thermotolerance of test thermal treatment rear film.After tested, mist degree is 6.5%, and thermotolerance is 65 ℃ " ◎ ", 80 ℃ " ◎ ", 100 ℃ " ◎ ".
Embodiment 2
With poly(lactic acid) (4032D, Natureworks) place vacuum drying oven, 80 ℃ of dryings are after 10 hours, with the bimonthly osmanthus of ethylene acid amides (EBLA), 1,3,2,4-two (4-methyl benzal) sorbyl alcohol (NC6, Mitsui Chemicals) carry out pre-mixing by 100: 1: 1 (weight part) after, by twin screw extruder coextrusion, granulation.The feed zone temperature of described twin screw extruder is 170 ℃, and all the other each section temperature are 210 ℃, vacuumizing and exhausting in the extrusion.
The good mixture of granulation is in vacuum drying oven, and 80 ℃ of dryings were used manual type thermocompressor compacting film forming after 10 hours.The temperature of thermocompressor is 200 ℃, and the fusion time is 3min, and the dwell time is 30 seconds.The melt that suppresses makes the film that thickness is about 0.5mm after using the mixture of ice and water quenching.
After the film thorough drying, the cold crystallization temperature (T of film before the test thermal treatment
Cc) be 84.3 ℃, fusing point (T
m) be 164.5 ℃, after film is fixed with steel framework and clip, place the tunnel baking oven to heat-treat.Thermal treatment temp is 120 ℃, and heat treatment time is 20 seconds.
The mist degree and the thermotolerance of test thermal treatment rear film.After tested, mist degree is 7.6%, and thermotolerance is 65 ℃ " ◎ ", 80 ℃ " ◎ ", 100 ℃ " ◎ ".
Embodiment 3
With poly(lactic acid) (4032D, Natureworks) place vacuum drying oven, 80 ℃ of dryings are after 10 hours, with the bimonthly osmanthus of ethylene acid amides (EBLA), 1,3,2,4-two (4-ethyl benzal) sorbyl alcohol (NC4, Mitsui Chemicals) carry out pre-mixing by 100: 1: 0.5 (weight part) after, by twin screw extruder coextrusion, granulation.The feed zone temperature of described twin screw extruder is 170 ℃, and all the other each section temperature are 210 ℃, vacuumizing and exhausting in the extrusion.
The good mixture of granulation is in vacuum drying oven, and 80 ℃ of dryings were used manual type thermocompressor compacting film forming after 10 hours.The temperature of thermocompressor is 200 ℃, and the fusion time is 3min, and the dwell time is 30 seconds.The melt that suppresses makes the film that thickness is about 0.5mm after using the mixture of ice and water quenching.
After the film thorough drying, the cold crystallization temperature (T of film before the test thermal treatment
Cc) be 87.6 ℃, fusing point (T
m) be 164.5 ℃, after film is fixed with steel framework and clip, place convection oven to heat-treat.Thermal treatment temp is 120 ℃, and heat treatment time is 60 seconds.
The mist degree and the thermotolerance of test thermal treatment rear film.After tested, mist degree is 7.8%, and thermotolerance is 65 ℃ " ◎ ", 80 ℃ " ◎ ", 100 ℃ " ◎ ".
Embodiment 4
(4032D Natureworks) places vacuum drying oven, and 80 ℃ of dryings are after 10 hours with poly(lactic acid), with lauric amide, 1,3,2, after the 4-dibenzal sorbitol carries out pre-mixing by 100: 0.3: 0.1 (weight part), by twin screw extruder coextrusion, granulation.The feed zone temperature of described twin screw extruder is 170 ℃, and all the other each section temperature are 210 ℃, vacuumizing and exhausting in the extrusion.
The good mixture of granulation is in vacuum drying oven, and 80 ℃ of dryings were used manual type thermocompressor compacting film forming after 10 hours.The temperature of thermocompressor is 200 ℃, and the fusion time is 3min, and the dwell time is 30 seconds.The melt that suppresses makes the film that thickness is about 1mm after using the mixture of ice and water quenching.
After the film thorough drying, the cold crystallization temperature (T of film before the test thermal treatment
Cc) be 96.2 ℃, fusing point (T
m) be 164.5 ℃, after film is fixed with steel framework and clip, place convection oven to heat-treat.Thermal treatment temp is 120 ℃, and heat treatment time is 60 seconds.
The mist degree and the thermotolerance of test thermal treatment rear film.After tested, mist degree is 3.3%, and thermotolerance is 65 ℃ " ◎ ", 80 ℃ " △ ", 100 ℃ " * ".
Embodiment 5
With poly(lactic acid) (4032D, Natureworks) place vacuum drying oven, 80 ℃ of dryings are after 10 hours, with the Methionin laurylamide (Amihope LL, Ajimoto), 1,3,2, after 4-two (4-methyl benzal) sorbyl alcohol (NC6, Mitsui Chemicals) carries out pre-mixing by 100: 9: 5 (weight part), by twin screw extruder coextrusion, granulation.The feed zone temperature of described twin screw extruder is 170 ℃, and all the other each section temperature are 210 ℃, vacuumizing and exhausting in the extrusion.
The good mixture of granulation is in vacuum drying oven, and 80 ℃ of dryings were used manual type thermocompressor compacting film forming after 10 hours.The temperature of thermocompressor is 200 ℃, and the fusion time is 3min, and the dwell time is 30 seconds.The melt that suppresses makes the film that thickness is about 0.1mm after using the mixture of ice and water quenching.
After the film thorough drying, the cold crystallization temperature (T of film before the test thermal treatment
Cc) be 105.9 ℃, fusing point (T
m) be 165.9 ℃.With film with steel framework and clip fixing after, place convection oven to heat-treat.Thermal treatment temp is 120 ℃, and heat treatment time is 60 seconds.
The mist degree and the thermotolerance of test thermal treatment rear film.After tested, mist degree is 6.9%, and thermotolerance is 65 ℃ " ◎ ", 80 ℃ " ◎ ", 100 ℃ " ◎ ".
Embodiment 6
With poly(lactic acid) (625 1D, Natureworks, weight-average molecular weight 11.8 ten thousand) places vacuum drying oven, 80 ℃ of dryings are after 10 hours, with the bimonthly osmanthus of ethylene acid amides (EBLA), 1,3,2, after 4-two (4-methyl benzal) sorbyl alcohol (NC6, Mitsui Chemicals) carries out pre-mixing by 100: 1: 1 (weight part), by twin screw extruder coextrusion, granulation.The feed zone temperature of described twin screw extruder is 170 ℃, and all the other each section temperature are 210 ℃, vacuumizing and exhausting in the extrusion.
The good mixture of granulation is in vacuum drying oven, and 80 ℃ of dryings were used manual type thermocompressor compacting film forming after 10 hours.The temperature of thermocompressor is 200 ℃, and the fusion time is 3min, and the dwell time is 30 seconds.The melt that suppresses makes the film that thickness is about 0.5mm after using the mixture of ice and water quenching.
After the film thorough drying, the cold crystallization temperature (T of film before the test thermal treatment
Cc) be 84.0 ℃, fusing point (T
m) be 167.8 ℃, after film is fixed with steel framework and clip, place convection oven to heat-treat.Thermal treatment temp is 120 ℃, and heat treatment time is 60 seconds.
The mist degree and the thermotolerance of test thermal treatment rear film.After tested, mist degree is 8.3%, and thermotolerance is 65 ℃ " ◎ ", 80 ℃ " ◎ ", 100 ℃ " ◎ ".
Embodiment 7
Poly(lactic acid) homopolymer (weight-average molecular weight 9.8 ten thousand) is placed vacuum drying oven, 80 ℃ of dryings are after 10 hours, with the bimonthly osmanthus of ethylene acid amides (EBLA), 1,3,2, after 4-two (4-methyl benzal) sorbyl alcohol (NC6, Mitsui Chemicals) carries out pre-mixing by 100: 1: 1 (weight part), by twin screw extruder coextrusion, granulation.The feed zone temperature of described twin screw extruder is 170 ℃, and all the other each section temperature are 210 ℃, vacuumizing and exhausting in the extrusion.
The good mixture of granulation is in vacuum drying oven, and 80 ℃ of dryings were used manual type thermocompressor compacting film forming after 10 hours.The temperature of thermocompressor is 200 ℃, and the fusion time is 3min, and the dwell time is 30 seconds.The melt that suppresses makes the film that thickness is about 0.5mm after using the mixture of ice and water quenching.
After the film thorough drying, the cold crystallization temperature (T of film before the test thermal treatment
Cc) be 82.4 ℃, fusing point (T
m) be 150.2 ℃, after film is fixed with steel framework and clip, place convection oven to heat-treat.Thermal treatment temp is 120 ℃, and heat treatment time is 60 seconds.
The mist degree and the thermotolerance of test thermal treatment rear film.After tested, mist degree is 8.0%, and thermotolerance is 65 ℃ " ◎ ", 80 ℃ " ◎ ", 100 ℃ " ◎ ".
Comparative example (1)
(4032D Natureworks) places vacuum drying oven, and 80 ℃ of dryings were used manual type thermocompressor compacting film forming after 10 hours with poly(lactic acid).The temperature of thermocompressor is 200 ℃, and the fusion time is 3min, and the dwell time is 30 seconds.The melt that suppresses makes the film that thickness is about 0.5mm after using the mixture of ice and water quenching.
After the film thorough drying, the cold crystallization temperature (T of film before the test thermal treatment
Cc) be 110.5 ℃, fusing point (T
m) be 170.0 ℃.Prepared film is not heat-treated.After tested, the mist degree of this film is 3.0%, and thermotolerance is 65 ℃ " * ", 80 ℃ " * ", 100 ℃ " * ".
Comparative example (2)
The film that makes in the comparative example (1) is heat-treated in convection oven.Thermal treatment temp is 120 ℃, and heat treatment time is 60 seconds.After tested, the mist degree of this film is 3.2%, and thermotolerance is 65 ℃ " * ", 80 ℃ " * ", 100 ℃ " * ".
Comparative example (3)
With poly(lactic acid) (4032D, Natureworks) place vacuum drying oven, 80 ℃ of dryings are after 10 hours, respectively with the bimonthly osmanthus of ethylene acid amides (EBLA), 1,3,2,4-two (4-methyl benzal) sorbyl alcohol (NC6, Mitsui Chemicals) by the twin screw extruder coextrusion, be a granulated into 4032D: the masterbatch 1 of EBLA=95/5 (weight part), the masterbatch 2 of 4032D/NC6=95/5 (weight part).The feed zone temperature of described twin screw extruder is 170 ℃, and all the other each section temperature are 210 ℃, vacuumizing and exhausting in the extrusion.
Two kinds of masterbatch place vacuum drying oven, 80 ℃ of dryings 10 hours, poly(lactic acid) (the 4032D that crosses with drying again, Natureworks) be mixed into the mixture of 4032D/EBLA/NC6=98/1/1 by a certain percentage, extrude and by casting roller by the single screw extrusion machine that has T pattern head, make thickness and be the film about 0.5mm.The feed zone temperature of described twin screw extruder is 170 ℃, and all the other each section temperature are 210 ℃.
After the film thorough drying, the cold crystallization temperature (T of film before the test thermal treatment
Cc) be 89.4 ℃, fusing point (T
m) be 165.5 ℃.Prepared film is not heat-treated.After tested, the mist degree of this film is 2.5%, and thermotolerance is 65 ℃ " * ", 80 ℃ " * ", 100 ℃ " * ".
Comparative example (4)
With poly(lactic acid) (4032D Natureworks) places vacuum drying oven, and 80 ℃ of dryings are after 10 hours, carry out pre-mixing with the bimonthly osmanthus of ethylene acid amides (EBLA) by 100: 1 (weight part) after, by twin screw extruder coextrusion, granulation.The feed zone temperature of described twin screw extruder is 170 ℃, and all the other each section temperature are 210 ℃, vacuumizing and exhausting in the extrusion.
The good mixture of granulation is in vacuum drying oven, and 80 ℃ of dryings were used manual type thermocompressor compacting film forming after 10 hours.The temperature of thermocompressor is 200 ℃, and the fusion time is 3min, and the dwell time is 30 seconds.The melt that suppresses makes the film that thickness is about 0.5mm after using the mixture of ice and water quenching.
After the film thorough drying, the cold crystallization temperature (T of film before the test thermal treatment
Cc) be 84.7 ℃, fusing point (T
m) be 164.5 ℃, after film is fixed with steel framework and clip, place the tunnel baking oven to heat-treat.Thermal treatment temp is 120 ℃, and heat treatment time is 20 seconds.
The mist degree and the thermotolerance of test thermal treatment rear film.After tested, mist degree is 13.3%, and thermotolerance is 65 ℃ " ◎ ", 80 ℃ " ◎ ", 100 ℃ " ◎ ".
By contrasting above embodiment and comparative example, the contriver finds pure polylactic acid film, even by thermal treatment, does not also have 65 ℃ thermotolerance (comparative example 1,2).And when containing the bimonthly osmanthus of ethylene acid amides (EBLA) in the polylactic acid film, cold crystallization temperature (T
Cc) significantly reduce (comparative example 3), thus can make the poly(lactic acid) component in the film can be under the condition of identical thermal treatment temp, faster, easier crystallization.And, by in the polylactic acid film that contains the bimonthly osmanthus of ethylene acid amides (EBLA), further add benzal glucitols compound, the mist degree that thermal treatment caused rises and is obviously suppressed, and the transparency of polylactic acid film has obtained keeping (comparative example 4, embodiment 1).And by control thermal treatment temp and heat treatment time, the present invention is free to regulate the heat-resisting degree and the transparency of goods.
Claims (8)
1. polylactic acid blend is characterized in that described blend mainly is made up of following components in part by weight:
100 parts of poly(lactic acid)
0.1～10 part of amides
0.01～5 part of glucitols compound.
2. polylactic acid blend according to claim 1 is characterized in that described poly(lactic acid) is poly(lactic acid) homopolymer, copolymer of poly lactic acid, polylactic acid stereoscopic composite or the mixture between them.
3. polylactic acid blend according to claim 1, the weight-average molecular weight that it is characterized in that described poly(lactic acid) is 20,000～800,000.
4. polylactic acid blend according to claim 1 is characterized in that described amides is selected from one or more in the two alkylamides of ethylene, saturated fatty acid monoamide, unsaturated fatty acids monoamide or the amino acid amide.
5. polylactic acid blend according to claim 1 is characterized in that described glucitols compound is selected from one or more in the glucitols compound that contains the benzal group.
6. the moulding product of a polylactic acid blend is characterized in that being obtained by thermal treatment when the moulding and/or after the moulding by any described polylactic acid blend of claim 1～5.
7. moulding product according to claim 6 is characterized in that described moulding product thickness is 0.02～5mm.
8. moulding product according to claim 6 is characterized in that heat treated temperature range is below the above fusing point of cold crystallization starting temperature of polylactic acid blend, and heat treatment period is 2 seconds to 10 minute.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100202785A CN101265355A (en) | 2007-03-16 | 2007-03-16 | Polylactic acid mixture and forming articles thereof |
| JP2008515779A JP5493355B2 (en) | 2007-03-16 | 2008-03-12 | Aliphatic polyester sheet and molded article comprising the same |
| KR1020097019221A KR101471220B1 (en) | 2007-03-16 | 2008-03-12 | Aliphatic polyester sheet and molded body composed of the same |
| PCT/JP2008/054456 WO2008126581A1 (en) | 2007-03-16 | 2008-03-12 | Aliphatic polyester sheet and molded body composed of the same |
| EP08721872A EP2123700A4 (en) | 2007-03-16 | 2008-03-12 | Aliphatic polyester sheet and molded body composed of the same |
| US12/529,819 US8673432B2 (en) | 2007-03-16 | 2008-03-12 | Aliphatic polyester sheet and molded body composed of the same |
| CN2008800083007A CN101631821B (en) | 2007-03-16 | 2008-03-12 | Aliphatic polyester sheet and molded body composed of the same |
| TW97108966A TWI448506B (en) | 2007-03-16 | 2008-03-14 | Aliphatic polyester film and formed body formed therefrom |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100202785A CN101265355A (en) | 2007-03-16 | 2007-03-16 | Polylactic acid mixture and forming articles thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101265355A true CN101265355A (en) | 2008-09-17 |
Family
ID=39988055
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007100202785A Pending CN101265355A (en) | 2007-03-16 | 2007-03-16 | Polylactic acid mixture and forming articles thereof |
| CN2008800083007A Expired - Fee Related CN101631821B (en) | 2007-03-16 | 2008-03-12 | Aliphatic polyester sheet and molded body composed of the same |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008800083007A Expired - Fee Related CN101631821B (en) | 2007-03-16 | 2008-03-12 | Aliphatic polyester sheet and molded body composed of the same |
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| CN (2) | CN101265355A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857715A (en) * | 2010-05-26 | 2010-10-13 | 上海大学 | Method for quickly crystallizing polylactic acid |
| US9951184B2 (en) | 2013-10-10 | 2018-04-24 | International Business Machines Corporation | Methods of preparing polyhemiaminals and polyhexahydrotriazines |
| CN108409985A (en) * | 2018-04-09 | 2018-08-17 | 山东大学 | A method of it is handled by pre- isothermal cold crystallization and improves expanded polylactic acid multiplying power |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106189129B (en) * | 2016-07-07 | 2018-08-03 | 威海聚衍新型材料有限公司 | A kind of PLA sheet materials and preparation method thereof |
| CN107216451B (en) * | 2017-06-14 | 2019-04-23 | 江南大学 | A kind of method of polylactic acid spontaneous nucleation |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003253009A (en) * | 2002-03-06 | 2003-09-10 | Unitika Ltd | Polylactic acid based molded product and production method therefor |
| KR100948720B1 (en) * | 2005-05-12 | 2010-03-22 | 미쓰이 가가쿠 가부시키가이샤 | Lactic acid polymer composition, molded article made of same, and method for producing such molded article |
-
2007
- 2007-03-16 CN CNA2007100202785A patent/CN101265355A/en active Pending
-
2008
- 2008-03-12 CN CN2008800083007A patent/CN101631821B/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857715A (en) * | 2010-05-26 | 2010-10-13 | 上海大学 | Method for quickly crystallizing polylactic acid |
| US9951184B2 (en) | 2013-10-10 | 2018-04-24 | International Business Machines Corporation | Methods of preparing polyhemiaminals and polyhexahydrotriazines |
| CN108409985A (en) * | 2018-04-09 | 2018-08-17 | 山东大学 | A method of it is handled by pre- isothermal cold crystallization and improves expanded polylactic acid multiplying power |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101631821A (en) | 2010-01-20 |
| CN101631821B (en) | 2012-02-29 |
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