CN101412842A - Preparation of composition containing polylactic resin and polyacrylacid ester compounds - Google Patents
Preparation of composition containing polylactic resin and polyacrylacid ester compounds Download PDFInfo
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- CN101412842A CN101412842A CNA2007101808665A CN200710180866A CN101412842A CN 101412842 A CN101412842 A CN 101412842A CN A2007101808665 A CNA2007101808665 A CN A2007101808665A CN 200710180866 A CN200710180866 A CN 200710180866A CN 101412842 A CN101412842 A CN 101412842A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/505—Screws
- B29C48/625—Screws characterised by the ratio of the threaded length of the screw to its outside diameter [L/D ratio]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92885—Screw or gear
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Abstract
The invention provides a method for manufacturing a composition comprising polylactic acid resin and polyacrylate compounds. The method utilizes a double-screw extruder to melt and mix the polylactic acid resin and polyacrylate compounds, so as to prepare the composition which is applicable to injection molding and has high light transmittance after molding. The composition comprising the polylactic acid resin and polyacrylate compounds prepared by the method can shorten the processing cycle for injection molding, thereby contributing to the commercialization of the polylactic acid resin.
Description
Technical field
The invention provides a kind of manufacture method that contains the composition of polylactic resin and polyacrylacid ester compounds, more particularly, the invention relates to a kind of polylactic resin of injection molding process-cycle and composition of polyacrylacid ester compounds of shortening.
Background technology
Because most plastic materials does not have can be by the characteristic of natural decomposition, in recent years under the situation that the environmental protection subject under discussion is paid close attention to day by day, can be in physical environment by the resin material of microorganism natural decomposition, promptly so-called biodegradable resin, its related application is promptly extremely paid attention to.In the biodegradable resin that all have been commercially produced, polylactic resin (polylactide resin, PLA) because physical properties excellent and obtain the cause of least cost, attracted attention by the people by its application.The monomer of poly(lactic acid) source can be rich in that conversion obtains the plant of a large amount of starch from corn, yam etc., rely on the situation of petrochemical industry resource fully with respect to the monomer source of most plastic materials, thisly can obtain polymer of monomers from renewable resources (renewable resource) and be considered to make to produce relatively stable, with low cost, needn't worry that not only the petrochemical industry resource exhaustion causes the great effect of monomer source shortage, also more stable on production cost, be not vulnerable to petrochemical industry boom and fluctuate and rise and fall.This base polymer also can reduce the consumption of the energy in process of production simultaneously, and therefore also being considered to it can suppress CO in the industrial manufacturing process
2The generation of gas slows down the rising trend of Global Greenhouse Effect.
Polylactic resin is very slow because of its crystallization rate, therefore often presents with vitreous state at normal temperatures, can make products such as transparent cold drink cup, fresh product pallet via the vacuum forming process method.Yet also because the cause of this characteristic, cause poly(lactic acid) using the injection molding Process to do to add its process-cycle that is shaped in man-hour far above the scope that can be accepted by commerce, the dimensional stability of adding molding is not good, various reasons makes polylactic resin can't use the injection molding Process to carry out the product manufacturing, the possibility that has hindered it to be widely used.Have in the prior art to add nucleus agent and/or toughner technology, yet this technology has no doubt been improved the injection molding characteristic of poly(lactic acid), causes the forfeiture of product transparent characteristic also inevitably with the injection molding characteristic of improving poly(lactic acid).Therefore, how improving the injection molding characteristic of poly(lactic acid) and keep the feature of its transparent material, promptly is the target that the modern laid siege to.
In the research formerly, people such as Eguiburu propose poly(lactic acid) and polymethylmethacrylate (poly (methyl methacrylate) at first, PMMA) can prepare poly(lactic acid)/polymethylmethacrylate constituent [Polymer that any ratio is dissolved each other via solution blending method (solution/precipitationblending) or solution coat method (solution casting), 39,6891-6897,1998].This constituent that dissolves each other scans calorimeter (differential scanning calorimeter with differential, DSC) analyze, can observe single glass tansition temperature (glass transition temperature, Tg), one of characteristic of dissolving each other fully for this constituent.Also because of the cause of dissolving each other fully, the crystallographic property of poly(lactic acid) is suppressed, so this constituent has transparent feature simultaneously.Yet employed resin combination preparation method need consume a large amount of solvent and consuming time in this research, and is not suitable for the commercialization mass production.People such as Le then use single screw extrusion machine, prepare poly(lactic acid) and polymethylmethacrylate constituent [J.Biomater.Sci.Polymer Edn. with the melting mixing processing method, 17,121-137,2006], yet they have but obtained two kinds of immiscible results of interlaminar resin, so the constituent of gained does not have the transparency yet.
Comprehensive the above as can be known, though the poly(lactic acid) of tool transparent feature and plexiglass constituent are disclosed, but be suitable for the still unmanned proposition of the mass-produced working method of commercialization, and this resin combination is also not evaluated as yet in the characteristic of injection molding processing.
Summary of the invention
Because the disappearance of prior art, the object of the present invention is to provide the manufacture method of the composition of a kind of polylactic resin that can be applicable to injection molding and polyacrylacid ester compounds, replace traditional solution blending method or solution coat method by this.
A kind of preparation of compositions method that comprises polylactic resin and polyacrylacid ester compounds provided by the invention, it comprises that utilizing twin screw extruder (forcing machine) is that the polylactic resin of 2.0～20.0g/10min and the polyacrylacid ester compounds of melt-flow rate 1.5～24g/10min carry out melting mixing processing with melt-flow rate, wherein the length-to-diameter ratio of aforementioned twin screw extruder is 32～42, processing temperature is 175～230 ℃, and screw speed is 200～550rpm.
The composition that utilizes preparation method of the present invention to make, its polylactic resin and polyacrylacid ester compounds height uniform mixing, so mutual solubility height of this polylactic resin constituent, the product appearance that granulation forms behind the particle is the transparent particles shape, can include general use injection molding Process easily in and make the transparent plastics manufacturing process and product, process-cycle that is shaped simultaneously also foreshortens to accepting within the scope of can being commercially produced, and reaches the result who reduces production costs and enhance productivity.
In preparation method of the present invention, the length-to-diameter ratio of described twin screw extruder is preferably 36～42, and processing temperature is preferably 180～210 ℃, and screw speed is preferably 350～550rpm.
Among the preparation method of the present invention, be 100% to calculate with the gross weight of composition, the content of polylactic resin is preferably 70～95% in the composition, and the content of polyacrylacid ester compounds is preferably 5～30%.
In preparation method of the present invention, in order to reach better effect, the melt-flow rate of aforementioned polylactic resin is preferably 3.0～12.0g/10min, and the melt-flow rate of polyacrylacid ester compounds is preferably 5.0～16.0g/10min.
In a preferred embodiment of the invention, polyacrylacid ester compounds is preferably polymethylmethacrylate, polymethyl acrylate, polyethyl methacrylate or polyethyl acrylate.
The present invention also provides a kind of composition that comprises polylactic resin and polyacrylacid ester compounds, it is characterized in that, said composition makes with above-mentioned preparation method, and the injection molding process-cycle among this preparation method is 13～20 seconds.
Above-mentioned composition, its transmittance of test piece of the 1/8 inch thickness that its mode with injection molding is made is more than 80%; Its transmittance of test piece of the 1/4 inch thickness that said composition is made in the injection molding mode is more than 75%.
The composition that the present invention makes with aforesaid method, wherein, the content of polylactic resin is preferably 70～95% in the said composition, and the content of polyacrylacid ester compounds is preferably 5～30%; This polyacrylacid ester compounds is preferably polymethylmethacrylate, polymethyl acrylate, polyethyl methacrylate or polyethyl acrylate.
Above-mentioned composition of the present invention, its polylactic resin and polyacrylacid ester compounds height uniform mixing, the mutual solubility height of polylactic resin constituent, product appearance is the transparent particles shape after the granulation, and this constituent can be included general use injection molding Process easily in and make in the transparent plastics manufacturing process and product, be suitable for the commercialization mass production, reach the result who reduces production costs and enhance productivity.
Description of drawings
Fig. 1: use the differential of the transparent polylactic resin constituent (PLA/PMMA=90/10) that the twin screw extruder of different length-to-diameter ratios makes to scan the calorimeter analysis chart, wherein 28,32,36 and 42 be the length-to-diameter ratio of forcing machine, X-coordinate be temperature (℃), ordinate zou is the trend of hot-fluid and heat release;
Fig. 2: the differential of the transparent polylactic resin constituent of the different ratios that the twin screw extruder of use length-to-diameter ratio 36 makes scans the calorimeter analysis chart, wherein the ratio on right side is the part by weight of polylactic resin and polyacrylacid ester compounds (PLA/PMMA), X-coordinate be temperature (℃), ordinate zou is the trend of hot-fluid and heat release.
Embodiment
Describe the present invention in detail below in conjunction with accompanying drawing, but do not limit practical range of the present invention.
The invention provides the method for compositions that preparation comprises polylactic resin and polyacrylacid ester compounds, its step comprises that to utilize twin screw extruder be that the polyacrylacid ester compounds of the polylactic resin of 2.0～20.0g/10min and melt-flow rate 1.5～24g/10min carries out melting mixing processing with melt-flow rate, wherein the length-to-diameter ratio of aforementioned twin screw extruder is 32～42, processing temperature is 175～230 ℃, and screw speed is 200～550rpm.
In a preferred embodiment, the length-to-diameter ratio of twin screw extruder is 36～42; Processing temperature is 180～210 ℃; Screw speed is 350～550rpm.
In a preferred embodiment, be 100% calculating with the composition gross weight, the content of polylactic resin is 50～99% in the composition, and the content of polyacrylacid ester compounds is 1～50%; More preferably, the content of polylactic resin be 70～95% and the content of polyacrylacid ester compounds be 5～30%.
More preferably among the embodiment, the melt-flow rate that is used for the polylactic resin of melting mixing (also claiming to mix) is 2.5～15.0g/10min, more preferably 3.0～12.0g/10min in the present invention; And the melt-flow rate that is used for the polyacrylacid ester compounds of melting mixing more preferably is 2.0～20.0g/10min, more preferably 5.0～16.0g/10min.
The concrete enforcement aspect of the polyacrylacid ester compounds that the present invention is alleged comprises, but is not limited to polymethylmethacrylate, polymethyl acrylate, polyethyl methacrylate or polyethyl acrylate.
After preparation method of the present invention makes the composition that comprises polylactic resin and polyacrylacid ester compounds; can further comprise with water-cooled or air cooling mode and quicken cooled product; in addition; for the benefit of follow-up injection molding processing, preparation method of the present invention also can further comprise the composition that utilizes tablets press will comprise polylactic resin and polyacrylacid ester compounds and make particle.
The obtained composition that comprises polylactic resin and polyacrylacid ester compounds of preparation method of the present invention, it can further use with antioxidant, UV light stabilizing agent, anti-hydrolysis stabilizer, thermo-stabilizer, agent for slow releasing, static inhibitor, wetting agent, tinting material or lubricant or its mixture jointly, with the characteristic of the product behind improvement or the lifting injection molding.
Utilize method of the present invention can prepare a kind of composition that comprises polylactic resin and polyacrylacid ester compounds, therefore, the present invention also comprises a kind of composition that comprises polylactic resin and polyacrylacid ester compounds with excellent shaping properties simultaneously, and said composition is characterised in that the injection molding process-cycle of said composition is 13～20 seconds.
Wherein, the content of polylactic resin is 50～99% in the foregoing, and the content of polyacrylacid ester compounds is 1～50%, preferably, the content of polylactic resin is 70～95%, and the content of polyacrylacid ester compounds is 5～30%, and it is 100% in the weight of said composition all.
Stating as defined above of polyacrylacid ester compounds.
The present invention is meant that polymer is shaped the required time alleged " the injection molding process-cycle " after operated implement penetrates, if the high molecular injection molding cycle is long, it means needs the long period cooling curing after polymer penetrates, when being understood that easily as if the cooling curing overlong time, to make production efficiency of products low and cause production cost to increase, this will impact and be unfavorable for that this polymer uses at coml volume production quality and volume production speed.
The test piece of the 1/8 inch thickness that the composition of the invention described above is made in the injection molding mode, according to ASTM D1003 normative testing, its transmittance can reach more than 80%, or said composition makes the test piece of 1/4 inch thickness in the injection molding mode, according to ASTM D1003 normative testing, its transmittance can reach more than 75%.
Following examples are used for further understanding advantage of the present invention, are not to be used to limit enforcement of the present invention and protection domain.
Material and equipment
Employed material is as follows in following examples and the comparative example:
(1) polylactic resin:
The U.S.
Corporate system, melt-flow rate 8.0g/10min.
(2) plexiglass:
Taiwan Qimei Industry Co., Ltd. system, melt-flow rate 2.1g/10min.
Employed Process Technology of Polymer equipment is as follows in embodiment and the comparative example:
(1) length-to-diameter ratio 28 twin screw extruders:
Germany W﹠amp; P Mechanology Inc. system, screw diameter 30mm.
(2) length-to-diameter ratio 32 twin screw extruders:
The great illuminate Mechanology Inc. in Taiwan system, type: PSM30A.
(3) length-to-diameter ratio 36 twin screw extruders:
Germany section times Long Keya Mechanology Inc. system, type: STS-35.
(4) length-to-diameter ratio 42 twin screw extruders:
Germany W﹠amp; P Mechanology Inc. system, screw diameter 26mm.
(5) emission forming machine:
The rich and powerful prosperous Mechanology Inc. in Taiwan system, type: HT-100.
Characteristic measures and evaluation criteria
(1) glass tansition temperature (Tg) and melt temperature (Tm) (seeing figures.1.and.2):
Use differential to scan calorimeter (U.S. Perkin Elmer corporate system, type: Diamond DSC), allow test portion keep 2 minutes to eliminate hot resume (heat history) under 210 ℃ earlier, then the speed with 10 ℃/min is cooled to 20 ℃, and keeps 2 minutes at 20 ℃.Afterwards, be warming up to 210 ℃ with the speed of 10 ℃/min again.Scanning when as depicted in figs. 1 and 2, acquisition heats up analyzed collection of illustrative plates to read Tg and Tm data.
(2) assessment of injection molding:
Use emission forming machine (the rich and powerful prosperous Mechanology Inc. in Taiwan system, type: HT-100), in the standard dumbbell-shaped test piece mould that meets the ASTMD638 standard, carry out injection molding (200 ℃ of melten gel temperature, 40 ℃ of die temperatures), write down the shortest shaping time process-cycle that this standard test piece can be well release.
(3) Ai Ruode shock strength:
According to the test specification of ASTM D256 method A and method E, carry out the breach (notch) and anti-breach (reversed notch) shock strength of material and measure respectively.
(4) tensile property:
According to the test specification of ASTM D638, carry out the measurement of material maximum strength and elongation.
(5) mould shrinking percentage:
According to the test specification of ASTM D955, carry out the mould shrinking percentage of material and measure.
(6) transmittance and mist degree:
According to the test specification of ASTM D1003, measuring thickness respectively is the transmittance and the mist degree of the test piece of 1/8 inch and 1/4 inch.
Embodiment 1
Weigh the polylactic resin of 90 weight percents (90%wt) and the plexiglass of 10 weight percents (10%wt), mix to do the mode of mixing earlier, import twin screw extruder (the German W﹠amp of length-to-diameter ratio 28 afterwards with the positive displacement feeder; P Mechanology Inc. system, screw diameter 30mm) carry out melting mixing processing in, using processing conditions is 180-205 ℃ of material cylinder temperature, screw speed 250rpm.The bar of extruding of gained is cooled to the solid attitude through cold water after the melting mixing processing, is made into the cylindric particle of diameter 3mm, length 3mm with tablets press.
This resin combination particle of obtaining scans the calorimeter analytical procedure with aforesaid differential, obtains its intensification and scans curve, as shown in fig. 1, analyzes the glass tansition temperature of this resin combination, reads and the results are shown in table 1.
Use emission forming machine (the rich and powerful prosperous Mechanology Inc. in Taiwan system, type: the resin combination particle of HT-100) this being obtained is made into the standard testing test piece that meets the ASTM standard, processing conditions is 190-205 ℃ of melten gel temperature, 40 ℃ of die temperatures, and the shortest shaping time process-cycle that the record standard test piece can be well release.The standard test piece of making comprises microscler test piece, the dumbbell-shaped test piece that meets the ASTMD638 standard that meets ASTM D256 standard, the rectangle test piece that meets ASTM D1003 standard.The standard testing test piece that is obtained is carried out performance with aforesaid standard method of test and is measured, and measurement is listed in table 1.
Embodiment 2,3 and 4
Use and identical resin combination ratio and melt-processed condition described in the embodiment 1, in embodiment 2,3 and 4, use the twin screw extruder of length-to-diameter ratio 32, length-to-diameter ratio 36, length-to-diameter ratio 42 to process respectively, and obtain resin particle with the melting mixing that carries out resin combination.The intensification that the differential of the resin combination particle of obtaining scans calorimeter scans curve as shown in Figure 1, and the glass tansition temperature that reads the results are shown in table 1.The resin combination particle of obtaining is made into the standard test piece that meets the ASTM standard and measures to carry out performance with emission forming machine, the measurement that is obtained is listed in table 1.
Embodiment 5
Use and identical melt-processed condition described in the embodiment 1, weigh (80%wt) polylactic resin of 80 weight percents and the plexiglass of 20 weight percents (20%wt), mix to do the mode of mixing earlier, import twin screw extruder (German section times Long Keya Mechanology Inc. system, the type: carry out melting mixing processing STS-35) of length-to-diameter ratio 36 afterwards with the positive displacement feeder.The extrusion bar of gained is cooled to the solid attitude through cold water after the melting mixing processing, is made into the cylindric particle of diameter 3mm, length 3mm with tablets press.
This resin combination particle of obtaining scans the calorimeter analytical procedure with aforesaid differential, obtains its intensification and scans curve, as shown in Figure 2, analyzes the glass tansition temperature of this resin combination, reads and the results are shown in table 1.
Use and identical ASTM standard test piece manufacturing process described in the embodiment 1, this resin combination particle of obtaining is made into the standard testing test piece that meets the ASTM standard.The standard testing test piece that is obtained is carried out performance with aforesaid standard method of test and is measured, and measurement is listed in table 1.
Embodiment 6,7 and 8
Use and identical method for melt processing and condition described in the embodiment 5, the different blending ratio of change resin combination is to obtain resin particle.The intensification that the differential of the resin combination particle of obtaining scans calorimeter scans curve as shown in Figure 2, and the glass tansition temperature that reads the results are shown in table 1.The resin combination particle of obtaining is made into the standard test piece that meets the ASTM standard and measures to carry out performance with emission forming machine, the measurement that is obtained is listed in table 1.
Comparative example 1
Get 3, the pure polylactic resin particle of 000g uses vacuum drying oven to carry out drying treatment with 50 ℃ and the condition that vacuumizes, and the time is more than 4 hours.Take out afterwards with emission forming machine (the rich and powerful prosperous Mechanology Inc. in Taiwan system, type: HT-100) make the standard testing test piece that meets the ASTM standard, processing conditions is 195-210 ℃ of melten gel temperature, 40 ℃ of die temperatures, and the shortest shaping time process-cycle that the record standard test piece can be well release.The standard test piece of making comprises microscler test piece, the dumbbell-shaped test piece that meets ASTM D638 standard that meets ASTM D256 standard, the rectangle test piece that meets ASTM D1003 standard.The standard testing test piece that is obtained is carried out performance with aforesaid standard method of test and is measured, and measurement is listed in table 1.
Pure polylactic resin particle scans the calorimeter analytical procedure with aforesaid differential, obtains its intensification and scans curve, as shown in Figure 2, analyzes the glass tansition temperature of this resin combination, reads and the results are shown in table 1.
Comparative example 2
Get 3, the pure plexiglass particle of 000g uses Hotaircirculatingoven to carry out drying treatment with 80 ℃ condition, and the time is more than 4 hours.Take out afterwards with emission forming machine (the rich and powerful prosperous Mechanology Inc. in Taiwan system, type: HT-100) make the standard testing test piece that meets the ASTM standard, processing conditions is 195-210 ℃ of melten gel temperature, 40 ℃ of die temperatures, but and the shortest shaping time process-cycle of record standard test piece good separation type.The standard test piece of making comprises microscler test piece, the dumbbell-shaped test piece that meets ASTM D638 standard that meets ASTM D256 standard, the rectangle test piece that meets ASTM D1003 standard.The standard testing test piece that is obtained is carried out performance with aforesaid standard method of test and is measured, and measurement is listed in table 1.
Pure plexiglass particle scans the calorimeter analytical procedure with aforesaid differential, obtains its intensification and scans curve, as shown in Figure 2, analyzes the glass tansition temperature of this resin combination, reads and the results are shown in table 1.
Fig. 1 is that poly(lactic acid) and plexiglass constituent are under the condition of 90/10 weight percent in blending ratio, and the intensification that the differential that uses the twin screw extruder of different length-to-diameter ratios to carry out the constituent particle of melting mixing processing gained scans calorimeter scans curve.Can know and see, use the constituent of the twin screw extruder gained of length-to-diameter ratio 28 tangible Tg point to be arranged at 60 ℃, and tangible melting peak is also arranged at 165 ℃, the repressed degree of crystallization property of explanation poly(lactic acid) in this constituent is very limited, the transmittance of material will be affected, and the transmittance that this can the 1/8 inch thickness test piece of embodiment 1 from table 1 only has 72.5% to obtain evidence.When the length-to-diameter ratio of the twin screw extruder that uses is increased to 32, the intensification of constituent at this moment scans on the curve and only can obviously observe the Tg point at 60 ℃, become atomic weak signal at 165 ℃ melting peaks, the two obtains the melting mixing and the characteristic of dissolving each other preferably because the increase of length-to-diameter ratio allows poly(lactic acid) and polymethylmethacrylate in this constituent in explanation, make the crystallization property of poly(lactic acid) be subjected to obvious inhibition, transmittance is also brought up to 79.8% (the 1/8 inch thickness test piece of embodiment 2 in the table 1) simultaneously.Along with the length-to-diameter ratio of twin screw extruder is increased to more than 36, further to be restrained especially at 165 ℃ melting peaks, transmittance is also further brought up to 83.2% and 82.8% (embodiment 3,4).
Fig. 2 is that the intensification that the differential of the poly(lactic acid) of different mixing proportion and polymethylmethacrylate constituent scans calorimeter scans curve under the condition of the twin screw extruder that uses length-to-diameter ratio 36.Can know and see, under different blending ratios, it all is only to observe the tangible Tg point in a place that the intensification of these resin combinations scans on the curve, and along with the content of polymethylmethacrylate in the resin combination increases, the Tg of resin combination draws close to the Tg of pure polymethylmethacrylate gradually, is one of characteristic of dissolving each other fully for two kinds of polymkeric substance knowing.At this moment, the crystallization property of poly(lactic acid) is also suppressed effectively, therefore these resin combinations also have good transmittance, the transmittance of 1/8 inch thickness test piece that can see embodiment 3,5,6,7,8 from table 1 is between 83～86%, and the transmittance of 1/4 inch thickness test piece is also more than 75%.
Simultaneously, can find out the injection molding characteristic that this transparent polylactic resin constituent obviously improves from table 1.Under identical processing conditions, the injection molding process-cycle of the transparent polylactic resin constituent among all embodiment (13～20 seconds) is much smaller than pure poly(lactic acid) (45～50 seconds), and only exceed than pure polymethylmethacrylate (10～13 seconds), this can be accepted in the commercially producing of majority.In addition, the mechanical property of this transparent polylactic resin constituent is also equally matched with the performance of the general transparent plastic material of using always, therefore can be used in the application of daily plastic prod.Add after polylactic resin is dropped, can be in physical environment by the characteristic of microorganism natural decomposition, the product made from this transparent polylactic resin constituent also has the contribution that alleviates environmental pressure after being dropped.
Comprehensively above-mentioned, the present invention is by the use of twin screw extruder, evenly melting mixing goes out to comprise the composition of polylactic resin and polyacrylacid ester compounds, use in solutions with high amounts of solvents fusion method or the preparation of solution coat method more environmental protection and save time compared to need, and polylactic resin and polyacrylacid ester compounds dissolve each other in good condition, and has a good transparent characteristic, therefore can behind injection molding, make opaque products or container, the process-cycle of injection molding also shortens in addition, thereby helps commercially producing.
Other implements aspect
Disclosed in this manual all features all may combine with other method, disclosed each feature all may optionally be replaced with identical, equal or similar purpose feature in this specification sheets, therefore, except special notable attribute, the disclosed feature of this all specification sheetss only is an example in equal or the similar features.
Though the present invention discloses as above with embodiment more preferably, so it is not in order to limiting the present invention, any those skilled in the art, without departing from the spirit and scope of the present invention, when being used for a variety of modifications and variations.
Claims (13)
1. preparation of compositions method that comprises polylactic resin and polyacrylacid ester compounds, this method comprises that utilizing twin screw extruder is that the polylactic resin of 2.0～20.0g/10min and the polyacrylacid ester compounds of melt-flow rate 1.5～24g/10min carry out melting mixing processing with melt-flow rate, wherein, the length-to-diameter ratio of twin screw extruder is 32～42, processing temperature is 175～230 ℃, and screw speed is 200～550rpm.
2. preparation method as claimed in claim 1, wherein, the length-to-diameter ratio of twin screw extruder is 36～42.
3. preparation method as claimed in claim 1, wherein, processing temperature is 180～210 ℃.
4. preparation method as claimed in claim 1, wherein, screw speed is 350～550rpm.
5. preparation method as claimed in claim 1, wherein, the weight content of polylactic resin is 70～95% in the described composition, the weight content of polyacrylacid ester compounds is 5～30%.
6. preparation method as claimed in claim 1, wherein, the melt-flow rate of described polylactic resin is 3.0～12.0g/10min.
7. preparation method as claimed in claim 1, wherein, the melt-flow rate of described polyacrylacid ester compounds is 5.0～16.0g/10min.
8. preparation method as claimed in claim 1, wherein, described polyacrylacid ester compounds is polymethylmethacrylate, polymethyl acrylate, polyethyl methacrylate or polyethyl acrylate.
9. the composition that comprises polylactic resin and polyacrylacid ester compounds that the described method of claim 1 makes is characterized in that, the injection molding process-cycle of said composition is 13～20 seconds.
10. composition as claimed in claim 9, wherein, its transmittance of test piece of the said composition of the 1/8 inch thickness that makes in the injection molding mode is more than 80%.
11. composition as claimed in claim 9, wherein, its transmittance of test piece of the said composition of the 1/4 inch thickness that makes in the injection molding mode is more than 75%.
12. composition as claimed in claim 9, wherein, the weight content of polylactic resin is 70～95% in the described composition, and the weight content of polyacrylacid ester compounds is 5～30%.
13. composition as claimed in claim 9, wherein, described polyacrylacid ester compounds is polymethylmethacrylate, polymethyl acrylate, polyethyl methacrylate or polyethyl acrylate.
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| CNA2007101808665A CN101412842A (en) | 2007-10-19 | 2007-10-19 | Preparation of composition containing polylactic resin and polyacrylacid ester compounds |
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2007101808665A CN101412842A (en) | 2007-10-19 | 2007-10-19 | Preparation of composition containing polylactic resin and polyacrylacid ester compounds |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101983986A (en) * | 2010-10-26 | 2011-03-09 | 中国科学院长春应用化学研究所 | Transparent and toughening polylactic acid resin and method for preparing the same |
| CN102206407A (en) * | 2011-04-21 | 2011-10-05 | 上海锦湖日丽塑料有限公司 | Biodegradable free-spraying aesthetic resin and preparation method thereof |
| CN106633709A (en) * | 2016-09-22 | 2017-05-10 | 无锡海特新材料研究院有限公司 | High-temperature-resistance polylactic acid composite material for spinning and preparation method thereof |
| CN115477835A (en) * | 2022-09-30 | 2022-12-16 | 武汉工程大学 | Calcium lignosulfonate thermoplastic elastomer modified polylactic acid material and preparation method thereof |
-
2007
- 2007-10-19 CN CNA2007101808665A patent/CN101412842A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101983986A (en) * | 2010-10-26 | 2011-03-09 | 中国科学院长春应用化学研究所 | Transparent and toughening polylactic acid resin and method for preparing the same |
| CN101983986B (en) * | 2010-10-26 | 2012-05-23 | 中国科学院长春应用化学研究所 | Transparent and toughening polylactic acid resin and method for preparing the same |
| CN102206407A (en) * | 2011-04-21 | 2011-10-05 | 上海锦湖日丽塑料有限公司 | Biodegradable free-spraying aesthetic resin and preparation method thereof |
| CN102206407B (en) * | 2011-04-21 | 2013-09-18 | 上海锦湖日丽塑料有限公司 | Biodegradable free-spraying aesthetic resin and preparation method thereof |
| CN106633709A (en) * | 2016-09-22 | 2017-05-10 | 无锡海特新材料研究院有限公司 | High-temperature-resistance polylactic acid composite material for spinning and preparation method thereof |
| CN115477835A (en) * | 2022-09-30 | 2022-12-16 | 武汉工程大学 | Calcium lignosulfonate thermoplastic elastomer modified polylactic acid material and preparation method thereof |
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Open date: 20090422 |