CN109852037A - Expanded polylactic acid sheet material and preparation method thereof - Google Patents
Expanded polylactic acid sheet material and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to expanded polylactic acid sheet materials and preparation method thereof.The expansion ratio of expanded polylactic acid sheet material of the invention is 20-30 times, and cell density is 10.2 × 109‑13.4×109A/cm3, cell diameter is 4-15 μm, 95-105 DEG C of heat distortion temperature.For the preparation method of the expanded polylactic acid sheet material using polylactic acid as matrix, addition nucleating agent, chain extender obtain mixture, which is squeezed out in double screw extruder, obtains expanded polylactic acid modified resin；Then, the Masterbatch by the modified resin and optionally added is put into the hopper by two-stage extrusion system foam extrusion machine in series, after level-one extrusion system fusion plastification, foaming agent is injected, then, by the mixing of second level extrusion system and it is cooled into low temperature homogeneous melt, it is squeezed out by controllable foaming die, subdivision flattening cooling by sizing, winding, obtains foam sheet.Expanded polylactic acid sheet material expansion ratio of the invention is high, foam performance is good, heat resistance is good, foam structure is good, simple process, and cost is controllable.
Description
Technical field
The present invention relates to a kind of expanded polylactic acid sheet materials and preparation method thereof, belong to polymeric material field.
Background technique
With the high speed development of national economy, the use of high molecular material has penetrated into the every field of people's life,
It brings great convenience to our life.However, high molecular materials many at present is discarded into nature after
It is difficult to degrade, results in serious problem of environmental pollution.Along with the worsening shortages and people of petroleum resources to environmental problem
Highest attention and the desired raising of quality of the life, the high molecular material of exploitation totally biodegradable has become domestic now
Outer research hotspot.
Polylactic acid (PLA) belongs to Biodegradable Polymers, is discarded into nature after this kind of materials'use, energy
It is enough to be finally all degraded to H under nature microorganism effect2O and CO2；Meanwhile the raw material for preparing these biodegradation materials is big
Part can be plant base.Therefore, valuable petroleum resources can not only be saved by promoting the use of this kind of material, but also material makes
Any negative effect, wide market will not be brought after being finished to environment.
Meanwhile polylactic acid also has both the advantages that good biocompatibility, machinability and mechanical property, thus by wide
General concern.However, in practical applications, some defects of polylactic acid itself also limit its large-scale application.Such as melt
Intensity is low, and machinability is bad.Therefore, polylactic acid has the defect for being difficult to foam.
Currently, the foaming agent that expanded polylactic acid uses mainly has: gas foaming agent and production gas foaming agent, such as H2O2、
H2S, argon gas, CO2、N2And H2O2Mixed gas, supercritical CO2And N2Mixed gas and produce CO2Agent etc.；Inorganic salts, such as
Sodium bicarbonate, sodium bicarbonate, inferior ammonium nitrate etc.；Organic compounds category, such as hydrocarbon (such as propane, normal butane, isobutyl
The fat hydrocarbons such as alkane, pentane, isopentane, hexane；Ester ring type hydrocarbons such as pentamethylene, hexamethylene etc.), hydrocarbon fluoride (such as 1,
1,2,2- tetrafluoroethane, 1,1- Difluoroethane etc.), hydrocarbon chlorine fluorine compound (such as monochloro difluoromethane etc.), alkyl chloride (such as
Halogenated hydrocarbons such as methylene chloride, methyl chloride, ethyl chloride etc.), alkyl ether (such as dimethyl ethers), azo (such as azo diformazan
Amide, azo-bis-isobutyl cyanide, diisopropyl azodiformate, Barium azodicarboxylate etc.), organic amine (such as dinitroso five
Tetramine, N, N- dinitrosopentamethlyene tetramine etc.), amides (such as hydrazo diformamide etc.), sulfonyl hydrazines
(such as unifor, 4,4- oxobenzenesulfonyl hydrazide), ureas (such as to toluene sulfoamino-group urea) and substituted benzene (N,
N- dimethyl-N, N dinitroso is to benzene, 5- tetrazolium for benzene) etc..
The report of polylactic acid foam material research aspect is also concentrated mainly on overcome drawbacks described above to be carried out technologic
It explores.For example, Chinese patent CN101151310, CN101362833, CN101619158, CN101880404A etc. disclose it is poly-
Lactic acid foam sheet composition or preparation method.The polylactic acid involved in CN101151310 and polylactic acid are blended with polyolefin resin
Material obtains foamed material by the way that isobutene is added as foaming agent；CN101362833 and CN101619158 are all made of in material
Moulded from foam method is recycled after nucleating agent, foaming agent, blowing promotor are added in material to prepare the chemical blowing side of foamed material
Method；CN101880404A is related to a kind of polylactic acid foaming method, by polylactic acid and polyadipate butylene terephthalate
(PBAT) it is blended then in supercritical CO2The method of middle saturation foaming foams, and is not directed to continuously extrusion or foam-injection
Method.CN 103819885 discloses polylactic acid foam material and preparation method thereof, using biological degradation polyalcohol polylactic acid as base
Body material, by polylactic acid, polyethylene or polypropylene, ethylene-butylene, Styrene (SEBS) block copolymer or maleic anhydride grafting
SEBS be blended, using screw extruder be blended be granulated or squeeze out, then use physical blowing agent, using continuous extrusion foaming,
Foam-injection or batch still foam method carry out foaming or directly that the mixture of above-mentioned material is continuous in screw extruder
Extrusion foaming can prepare the foamed material of the forms such as sheet material, strip, structural member, expanded bead.
However, uneven, foam performance is poor, expansion ratio there are still foaming for obtained expanded polylactic acid sheet material at present
Low, the defects of cost is uncontrollable, preparation process is complicated, need to develop new expanded polylactic acid sheet material and preparation method thereof.
Summary of the invention
To overcome drawbacks described above, as in a first aspect, the present invention provides a kind of expanded polylactic acid sheet material, the polylactic acid hair
The expansion ratio for steeping sheet material is 20-30 times, and cell density is 10.2 × 109-13.4×109A/cm3, cell diameter is 4-15 μ
M, 95-105 DEG C of heat distortion temperature.
As second aspect, the present invention provides a kind of method for preparing expanded polylactic acid sheet material, and the method includes as follows
Step:
(1) polylactic acid, nucleating agent and chain extender are uniformly mixed, obtain mixture；The mixture is added to double spiral shells
In bar extruder, melting, water cooled, pelletizing, drying obtain expanded polylactic acid modified resin；
(2) Masterbatch added by the expanded polylactic acid modified resin that step (1) obtains and optionally is put by two
In the hopper of grade extrusion system foam extrusion machine in series, after level-one extrusion system fusion plastification, foaming agent is injected,
Then, by the mixing and cooling of second level extrusion system, 180-190 DEG C of low temperature homogeneous melt is formed, by the low temperature homogeneous
Melt is squeezed out by controllable foaming die, by cooling with inside and outside hydronic diameter-setting equipment sizing, then by subdivision
Flattening, winding, obtains foam sheet.
The invention further relates to a kind of expanded polylactic acid sheet material as made from method of the invention, wherein the polylactic acid hair
The expansion ratio for steeping sheet material is 20-30 times, and cell density is 10.2 × 109-13.4×109A/cm3, cell diameter is 4-15 μ
M, 95-105 DEG C of heat distortion temperature.
Expanded polylactic acid sheet material of the present invention is high with expansion ratio, heat resistance is good, foam structure is good, abscess
The small and uniform advantage of diameter has good industrial application value.
Detailed description of the invention
Fig. 1 is the preparation flow figure of the expanded polylactic acid sheet material as one of embodiment of the present invention.
Specific embodiment
Specifically, described method includes following steps for the method for preparing expanded polylactic acid sheet material of the invention:
(1) polylactic acid, nucleating agent and chain extender are uniformly mixed, obtain mixture；The mixture is added to double spiral shells
In bar extruder, melting, water cooled, pelletizing, drying obtain expanded polylactic acid modified resin；
(2) Masterbatch added by the expanded polylactic acid modified resin that step (1) obtains and optionally is put by two
In the hopper of grade extrusion system foam extrusion machine in series, after level-one extrusion system fusion plastification, foaming agent is injected,
Then, by the mixing and cooling of second level extrusion system, 180-190 DEG C of low temperature homogeneous melt is formed, by the low temperature homogeneous
Melt is squeezed out by controllable foaming die, by cooling with inside and outside hydronic diameter-setting equipment sizing, then by subdivision
Flattening, winding, obtains foam sheet.
In the step (1), the number-average molecular weight of the polylactic acid is preferably 30-40 ten thousand.If number-average molecular weight is too low,
It is low to will lead to melt strength, is not easy to foam；If number-average molecular weight is excessively high, the complex viscosity of material increases, and melt strength increases,
Lead to cell collapse, is unfavorable for forming high performance expanded polylactic acid sheet material.
The nucleating agent is hydrazide compound, preferably more hydrazide compounds, the particularly preferably hexichol of aliphatic dibasic acid
Formyl hydrazine compound, most particularly preferably two hydrazides of decanedioic acid diphenyl.
The chain extender includes 1,4- butanediol, 1,4- butane diisocyanate, toluene di-isocyanate(TDI), six methines two
One of group or more composed by isocyanates, poly methylene poly phenyl poly isocyanate and methyl diphenylene diisocyanate
Kind, preferably 1,4-butanediol or poly methylene poly phenyl poly isocyanate.
Preferably, in the step (1), in parts by weight, the composition of the mixture is as follows: 98-99 parts of polylactic acid, at
0.8-1.0 parts of core agent, 0.15-0.5 parts of chain extender.If the composition of mixture is not in this range, foamed material melt can be made strong
It spends low, is crosslinked between product poor heat resistance or raw material.Wherein, the mixture preferably forms are as follows: polylactic acid 98.8
Part, 1.0 parts of nucleating agent, 0.2 part of chain extender.
It preferably, is preferably 170-195 DEG C by the melting temperature that the mixture melts.If melting temperature is excessively high, can lead
Cause raw material that thermal degradation occurs；If melting temperature is too low, it is uneven to will lead to raw material plasticizing.
Preferably, the screw diameter of the double screw extruder is 75mm, draw ratio 52:1.If screw diameter is excessive
Or it is too small, the power consumption of product per ton increases or yield reduces；If draw ratio is too large or too small, raw material is in screw dwell time
It is long, cause thermal degradation or plasticizing uneven.
In the step (2), the foam extrusion machine is in series by two-stage extrusion system, and the level-one extrusion system will
The resin of melting and the Masterbatch optionally added are sufficiently mixed, and the second level extrusion system squeezes out foaming agent and the level-one
Resin be sufficiently mixed, when reaching suitable blowing temperature, melt is equably cooled down, guarantee foaming quality.Screw diameter
It is preferably fixation with draw ratio parameter, if technical parameter has variation, it will cause melt strength, expansion ratio unstable, shadow
Ring product quality.
The foaming agent is fluorine chloralkane.Wherein, the fluorine chloralkane is preferably by CCl3F、CCl2F2、CClF3、
CHCl2F、CHClF2、FCl2C-CClF2、F2ClC-CClF2、C2H4F2、C2ClF5And C2H3F3One of composed group or several
Kind, preferably CCl3F or CClF3。
Wherein, the screw diameter of two-stage extruder and draw ratio will will affect the property of plasticizing effect or even final foam sheet
Energy.Draw ratio is too small, and extrusion temperature will increase, and will lead to raw material thermal degradation；Draw ratio is excessive, and raw material is when extruder stops
Between it is long, will lead to raw material thermal degradation and molecular weight and molecular weight.
Preferably, screw diameter the φ 90mm, draw ratio 32:1 of the level-one extrusion system；The second level extrusion system
Screw diameter φ 120mm, draw ratio 34:1.
Preferably, the extrusion temperature 180- of 180-205 DEG C of the extrusion temperature of the level-one extrusion system, second level extrusion system
190℃。
As preferred embodiment, the injection of foaming agent is to squeeze out system in the screw end of level-one extrusion system, second level
It is injected before system, the injection is preferably high pressure injection, and injection flow is preferably 22.5-30kg/h.Suitable foaming agent
Range of flow helps to improve the expansion ratio of foam sheet, reduces cell diameter, improves heat distortion temperature, thus enhanced foaming
The performance of sheet material.On the contrary, it is excessive to will lead to foaming agent if injection flow is too fast, expansion ratio is excessive, cell collapse；If injection
Flow is too low, and it is too low to will lead to expansion ratio.
Wherein, in step (2), the temperature of the controllable foaming die is preferably 180-185 DEG C.If controllable foaming die
Temperature is excessively high, will lead to foam sheet cell collapse；If the temperature of controllable foaming die is too low, it will lead to melt and foaming agent be mixed
It is low to close uneven or expansion ratio.
The expanded polylactic acid sheet surface as made from above-mentioned controllable foaming die is smooth, even width is consistent, high yield rate.
Expanded polylactic acid sheet material of the present invention is high with expansion ratio, heat resistance is good, foam structure is good and bubble
The small and uniform advantage of bore dia has good industrial application value.
Embodiment
Next, being illustrated in further detail by embodiment to the present invention, but the present invention is not limited only to these realities
Apply example.
In following examples, if not specializing, the % refers to wt%.
Wherein, in the present invention, the measuring method of expansion ratio is carried out according to GB/T 6343-2009, and it is close to measure foamed sample
Spend ρfWith unexpanded sample rate ρp, expansion ratio R=ρp/ρf。
The measuring method of cell density is measured according to GB/T 6343-2009 (measurement of foamed plastics apparent density).
The measuring method of cell diameter is according to (the rigid foam average cell size test side GB/T 12811-1991
Method) it is measured.
Heat distortion temperature is measured according to GB/T 1634.2-2004B method and is carried out.
Embodiment 1
(1) by 98.8 parts dry of polylactic acid pellet, 1.0 parts of two hydrazides of nucleating agent decanedioic acid diphenyl, chain extender 1,4-
0.2 part of butanediol, obtained mixture is added into double screw extruder (model TDS-75D), in double screw extruder (spiral shell
Shank diameter is 75mm；Draw ratio is 52:1) in after melting mixing (extruder temperature be 170-195 DEG C), water cooling, pelletizing and drying
Afterwards, expanded polylactic acid modified resin is obtained.
(2) obtained expanded polylactic acid modified resin is put by two-stage extrusion system foam extrusion machine in series
In hopper, wherein screw diameter the φ 90mm, draw ratio 32:1 of the level-one extrusion system；The spiral shell of the second level extrusion system
Shank diameter φ 120mm, draw ratio 34:1 inject foaming agent CCl after level-one extrusion system fusion plastification3F, flow
23.5kg/h by the mixing of second level extrusion system and is cooled into low temperature homogeneous melt, and the level-one extrusion system squeezes out temperature
180-190 DEG C of extrusion temperature of 180-205 DEG C of degree, second level extrusion system.
Then, it is squeezed out by controllable foaming die at 180-185 DEG C, by having inside and outside hydronic diameter-setting equipment
Sizing is cooling, then flattens by subdivision, and winding obtains foam sheet.Sheet material through thermoforming machine preheating, plastic uptake, secondary crystallization,
Punching, obtains foamed products.
After measured, the expansion ratio of thus obtained expanded polylactic acid sheet material is 21 times, and cell density is 12.5 × 109
A/cm3, cell diameter is 6.9 μm, and heat distortion temperature is 95 DEG C.
Embodiment 2
(1) by 98.8 parts dry of polylactic acid pellet, 1.0 parts of two hydrazides of nucleating agent decanedioic acid diphenyl, chain extender 1,4-
0.2 part of butanediol, obtained mixture is added into double screw extruder (model TDS-75D), in double screw extruder (spiral shell
Shank diameter is 75mm；Draw ratio is 52:1) in after melting mixing (extruder temperature be 170-195 DEG C), water cooling, pelletizing, drying obtain
To expanded polylactic acid modified resin.
(2) obtained expanded polylactic acid modified resin is put by two-stage extrusion system foam extrusion machine in series
In hopper, wherein screw diameter the φ 90mm, draw ratio 32:1 of the level-one extrusion system；The spiral shell of the second level extrusion system
Shank diameter φ 120mm, draw ratio 34:1 inject foaming agent CCl after level-one extrusion system fusion plastification3F, flow
28.5kg/h by the mixing of second level extrusion system and is cooled into low temperature homogeneous melt, and the level-one extrusion system squeezes out temperature
180-190 DEG C of extrusion temperature of 180-205 DEG C of degree, second level extrusion system.
Then, it is squeezed out by controllable foaming die at 180-185 DEG C, by having inside and outside hydronic diameter-setting equipment
Sizing is cooling, then flattens by subdivision, and winding obtains foam sheet.Sheet material through thermoforming machine preheating, plastic uptake, secondary crystallization,
Punching, obtains foamed products.
After measured, the expansion ratio of thus obtained expanded polylactic acid sheet material is 26 times, and cell density is 11.4 × 109
A/cm3, cell diameter is 5.2 μm, and heat distortion temperature is 101 DEG C.
Comparative example 1
(1) by 98.0 parts dry of polylactic acid pellet, 1.0 parts of two hydrazides of nucleating agent decanedioic acid diphenyl, chain extender 1,4-
1.0 parts of butanediol, obtained mixture is added into double screw extruder (the model TDS-75D of extruder), in twin-screw
Extruder (screw diameter 75mm；Draw ratio is 52:1) in after melting mixing (extruder temperature be 170-195 DEG C), water cooling is cut
After grain and drying, expanded polylactic acid modified resin is obtained.
(2) obtained expanded polylactic acid modified resin is put by two-stage extrusion system foam extrusion machine in series
In hopper, wherein screw diameter the φ 90mm, draw ratio 32:1 of the level-one extrusion system；The spiral shell of the second level extrusion system
Shank diameter φ 120mm, draw ratio 34:1 inject foaming agent CCl after level-one extrusion system fusion plastification3F, flow
23.5kg/h by the mixing of second level extrusion system and is cooled into low temperature homogeneous melt, and the level-one extrusion system squeezes out temperature
180-190 DEG C of extrusion temperature of 180-205 DEG C of degree, second level extrusion system.
Then, it is squeezed out by controllable foaming die at 180-185 DEG C, by having inside and outside hydronic diameter-setting equipment
Sizing is cooling, then flattens by subdivision, and winding obtains foam sheet.
Modified materials crosslinking is serious, fails to obtain qualified samples.
Comparative example 2
(1) by 99.5 parts dry of polylactic acid pellet, 0.5 part of chain extender 1,4-butanediol, mixed material is added
Into double screw extruder, in double screw extruder (screw diameter 75mm；Draw ratio is 52:1) in melting mixing (screw rod temperature
Degree is 170-195 DEG C) after, after water cooling, pelletizing and drying, obtain expanded polylactic acid modified resin.
(2) obtained expanded polylactic acid modified resin is put by two-stage extrusion system foam extrusion machine in series
In hopper, wherein screw diameter the φ 90mm, draw ratio 32:1 of the level-one extrusion system；The spiral shell of the second level extrusion system
Shank diameter φ 120mm, draw ratio 34:1 inject foaming agent CCl after level-one extrusion system fusion plastification3F, flow
28.5kg/h by the mixing of second level extrusion system and is cooled into low temperature homogeneous melt, and the level-one extrusion system squeezes out temperature
180-190 DEG C of extrusion temperature of 180-205 DEG C of degree, second level extrusion system.
Then, it is squeezed out by controllable foaming die at 180-185 DEG C, by having inside and outside hydronic diameter-setting equipment
Sizing is cooling, then flattens by subdivision, and winding obtains foam sheet.Sheet material through thermoforming machine preheating, plastic uptake, secondary crystallization,
Punching obtains foamed products.
After measured, the expansion ratio of thus obtained expanded polylactic acid sheet material is 22 times, and cell density is 10.5 × 109
A/cm3, cell diameter is 10.2 μm, and heat distortion temperature is 65 DEG C.
In the comparative example, step (1) does not add nucleating agent, and the cell diameter of obtained foamed material is 10.2 μm, heat
Deformation temperature is 65 DEG C, studies have shown that the crystallinity of polylactic acid is low, poor heat resistance in the case where no addition nucleating agent, is produced
Product heat distortion temperature is down to 55-65 DEG C, using there is limitation.On the contrary, polylactic acid knot can be significantly improved after appropriate nucleating agent is added
Brilliant degree, after thermoforming secondary crystallization, 95-105 DEG C of product heat distortion temperature has largely widened the application neck of product
Domain.
Claims (7)
1. a kind of expanded polylactic acid sheet material, which is characterized in that the expansion ratio of the expanded polylactic acid sheet material is 20-30 times, bubble
Hole density is 10.2 × 109-13.4×109A/cm3, cell diameter is 4-15 μm, 95-105 DEG C of heat distortion temperature.
2. a kind of method for preparing expanded polylactic acid sheet material, described method includes following steps:
(1) polylactic acid, nucleating agent and chain extender are uniformly mixed, obtain mixture；The mixture is added to twin-screw to squeeze
Out in machine, melting, water cooled, pelletizing, drying obtain expanded polylactic acid modified resin；
(2) Masterbatch added by the expanded polylactic acid modified resin that step (1) obtains and optionally is put into is squeezed by two-stage
In the hopper for the foam extrusion machine that Cascade System is constituted out, after level-one extrusion system fusion plastification, foaming agent is injected, so
Afterwards, by the mixing and cooling of second level extrusion system, 180-190 DEG C of low temperature homogeneous melt is formed, the low temperature homogeneous is melted
Body is squeezed out by controllable foaming die, by cooling with inside and outside hydronic diameter-setting equipment sizing, then by subdivision exhibition
Flat, winding obtains foam sheet.
3. method according to claim 2, wherein in the step (1),
The number-average molecular weight of the polylactic acid is 30-40 ten thousand；
The nucleating agent is hydrazide compound, preferably more hydrazide compounds, the particularly preferably dibenzoyl of aliphatic dibasic acid
Hydrazine compound, most particularly preferably two hydrazides of decanedioic acid diphenyl；
The chain extender is 1,4- butanediol, 1,4- butane diisocyanate, toluene di-isocyanate(TDI), six methine diisocyanates
One of group or a variety of, excellent composed by ester, poly methylene poly phenyl poly isocyanate and methyl diphenylene diisocyanate
It is selected as 1,4- butanediol or poly methylene poly phenyl poly isocyanate；
In parts by weight, the group of the mixture become polylactic acid 98-99 parts, 0.8-1.0 parts of nucleating agent, chain extender 0.15-0.5
Part；Preferably, the group of the mixture becomes 98.8 parts of polylactic acid, 1.0 parts of nucleating agent, 0.2 part of chain extender；
The melting temperature is 170-195 DEG C；
The screw diameter of the double screw extruder is 75mm, draw ratio 52:1.
4. method as claimed in claim 2 or claim 3, wherein in the step (2),
The level-one extrusion system is abundant by the expanded polylactic acid modified resin of melting and the Masterbatch optionally added
The resin that foaming agent is squeezed out with the level-one is sufficiently mixed by mixing, the second level extrusion system；
The foaming agent is fluorine chloralkane, preferably by CCl3F、CCl2F2、CClF3、CHCl2F、CHClF2、FCl2C-CClF2、
F2ClC-CClF2、C2H4F2、C2ClF5And C2H3F3One or more of composed group, more preferable CCl3F or CClF3；
Screw diameter the φ 90mm, draw ratio 32:1 of the level-one extrusion system；The screw diameter φ of the second level extrusion system
120mm, draw ratio 34:1；
180-190 DEG C of extrusion temperature of 180-205 DEG C of the extrusion temperature of the level-one extrusion system, second level extrusion system.
5. such as the described in any item methods of claim 2-4, wherein the injection of the foaming agent is the spiral shell in level-one extrusion system
It is injected before bar end, second level extrusion system, described to be injected to high pressure injection, injection flow is selected as 22.5-30kg/h.
6. such as the described in any item methods of claim 2-5, wherein the temperature of the controllable foaming die is 180-185 DEG C.
7. a kind of expanded polylactic acid sheet material as made from claim 2-6 described in any item methods, wherein the polylactic acid hair
The expansion ratio for steeping sheet material is 20-30 times, and cell density is 10.2 × 109-13.4×109A/cm3, cell diameter is 4-15 μ
M, 95-105 DEG C of heat distortion temperature.
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