CN103788601A - Polylactic acid resin suitable for rapid injection moulding and preparation method thereof - Google Patents
Polylactic acid resin suitable for rapid injection moulding and preparation method thereof Download PDFInfo
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Abstract
The invention discloses polylactic acid resin suitable for rapid injection moulding and a preparation method thereof. The polylactic acid resin is obtained by blending the following components: 100 parts by weight of polylactic acid resin, 0.5-3 parts by weight of an anhydride type multifunctional monomer, 0.5-3 parts by weight of an epoxy type multifunctional monomer, 5-20 parts by weight of a polyalcohol compound and an antioxidant, wherein the degree of functionality of the anhydride type multifunctional monomer is not less than 3, and the polyalcohol compound is polyethylene glycol and/or polypropylene glycol. The preparation method includes melting and blending the components according to the using amount of each component. According to the polylactic acid resin suitable for rapid injection moulding and the preparation method, the crystallization rate of the polylactic acid material is largely increased; the material achieves good machining and molding effects; and melt viscosity, the crystallization rate and the crystallization temperature of the polylactic acid material can be regulated and controlled by changing the degree of branching of long-chain branches and the using amount of the polyalcohol compound.
Description
Technical field
The present invention relates to polymer processing field, furtherly, relate to a kind of polylactic resin that is applicable to fast injection molding moulding and preparation method thereof.
Background technology
In the last few years, biomass degradable polymer material did not cause the significant advantage of severe contamination to be subject to people's common concern to environment after using with it.Wherein especially comparatively outstanding with polylactic resin material, its back to nature circle of not only can degrading after use, and also its source do not rely on the exploitation of oil, and its application process has realized natural circulation completely, has really reached the demand of low-carbon environment-friendly.In addition, compare with similar polyester material, poly(lactic acid) has mechanical property and thermoplasticity is good, rebound resilience and curling persistence is good, oil-proofness and dyeability is good, glossiness and transparency is high, the flammable plurality of advantages such as low, is a kind of comparatively desirable polymer materials that is expected to be applied to the aspects such as food product pack, disposable plastic apparatus, agricultural film, bio-medical carrier and encapsulation, finery fabric.But the crystallization rate that this material is extremely low at present all makes himself machine-shaping, and especially in injection molding process, difficulty is very big, this finished product that has seriously limited this material is promoted the use of.Therefore improve the crystallization rate of poly(lactic acid) to strengthen the unavoidable problem that its performance is exactly its use range of expansion.By many research, add nucleator and softening agent or lubricant and can slightly improve but effect is limited poly(lactic acid) crystallization rate; And it is also untapped to make at present poly(lactic acid) in machine-shaping process, just can complete the means of rapid crystallization, therefore, seem to there is very much Practical significance and industrial value by simple efficiently, the cheaply processing technology that working method obtains poly(lactic acid) that can rapid crystallization.
Through the literature search of prior art is found, the polylactic resin that obtains rapid crystallization is to pile up this two aspects character of ability by the motion of the nucleation rate of raising poly(lactic acid) and raising polylactic acid chain to realize substantially.Mostly the nucleation rate that improves poly(lactic acid) is to adopt the method for adding nucleator, improve the motion of polylactic acid chain and pile up the methods of adding softening agent or lubricant that adopt of ability more, even but research is found the in the situation that of nucleator and softening agent or lubricant use, the raising of the crystallization rate of poly(lactic acid) is still very limited, and the crystal area proportion that can complete in the natural cooling process after processing is still very low.The nucleator using for poly(lactic acid) is at present mainly the low molecular compound of inorganic or organic, its mechanism of nucleation is heterogeneous nucleation, this depends on the consistency of nucleator and poly(lactic acid) and the deployment conditions in poly(lactic acid) thereof greatly, therefore can not make the crystallization rate of poly(lactic acid) that change in essence occurs.And the softening agent using or lubricant major part except a few compound all can not form compatible system well with poly(lactic acid); In this external product life-time service process, because the molecular weight of this analog assistant is very little, can cause himself moving to product surface.Therefore through the functional group reactions acquisition faster of speed of reaction under high temperature long-chain branch poly(lactic acid), utilize chemical reaction that lubricant keyed jointing is entered in polylactic acid chain, exploitation has the poly-lactic acid material of excellent homogeneous phase crystal property, has huge industrial application value simultaneously.
Summary of the invention
Slowly the problem that affects machine-shaping for solving the poly-lactic acid material crystallization rate existing in prior art, the invention provides a kind of polylactic resin that is applicable to fast injection molding moulding and preparation method thereof.Through the functional group reactions acquisition faster of speed of reaction under high temperature long-chain branch poly(lactic acid), utilize chemical reaction that poly alcohol compound is introduced in polylactic acid chain simultaneously, greatly improve the crystallization rate of poly-lactic acid material, make material reach good machine-shaping effect; Can overcome the defect that poly alcohol compound and poly(lactic acid) physical blending easily cause its surface transport simultaneously completely.In addition,, by changing the degree of branching of long-chain branch and the consumption of poly alcohol compound, can realize adjusting and the control of poly-lactic acid material melt viscosity, crystallization rate and Tc.
One of object of the present invention is to provide a kind of polylactic resin that is applicable to fast injection molding moulding.
To obtain by comprising following component blend:
Polylactic resin: 100 weight parts;
Anhydrides polyfunctional monomer 0.5-3 weight part; Preferred: 0.5-2 weight part;
Epoxies polyfunctional monomer 0.5-3 weight part; Preferred: 0.5-2 weight part;
Poly alcohol compound 5-20 weight part; Preferred: 10-15 weight part.
The above polylactic resin is disclosed various polylactic resin in prior art.Because available polylactic resin in currently available technology mostly is linear, so can preferred linear polylactic resin.
Described anhydrides polyfunctional compound can be published various anhydrides polyfunctional compounds in prior art, preferably at least one in following material: Tetra hydro Phthalic anhydride, trimellitic acid 1,2-anhydride, pyromellitic acid anhydride, mellophanic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic acid dianhydride, Succinic anhydried, MALEIC ANHYDRIDE, dodecyl are for MALEIC ANHYDRIDE, inner methylidyne tetrahydric phthalic anhydride, hexahydrophthalic anhydride, glycerine three trimellitic acid 1,2-anhydrides, pentamethylene tetracarboxylic dianhydride etc.
The epoxies functional compound that described epoxies polyfunctional compound is all functionality >=3 in prior art, preferably at least one in following material: three epoxypropyl tricarbimides, glycerin triglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, triglycidyl group p-aminophenol, N, N, N ', N '-four glycidyl group-4, 4 ' diaminodiphenyl-methane, Phloroglucinol monomethyl ether triglycidyl ether, Pyromellitic Acid tetra glycidyl ester, 1, 1 ', 2, 2 '-tetra-(p-hydroxybenzene) ethane, four glycidyl ethers, Resorcinol formal four glycidyl ethers, two Resorcinol formal four glycidyl ethers, glycidyl methacrylate oligopolymer etc.
Described poly alcohol compound is selected from least one in following material: polyoxyethylene glycol, polypropylene glycol.
For overcoming small molecules auxiliary agent defect to surface transport in product use procedure, the poly alcohol compound that choice for use molecular end contains hydroxyl is as the 3rd reactive component, in in being incorporated into polylactic acid chain by covalent linkage, improve poly(lactic acid) crystallization rate.
In the method for the invention, by changing the degree of branching of long-chain branch and the consumption of poly alcohol compound, the preferably melt viscosity of regulating and controlling poly-lactic acid material, crystallization rate and Tc.When anhydrides described in coupling and epoxies polyfunctional compound and weight ratio are (0.5-1): in 1 scope, while using described poly alcohol compound consumption to be the 10-15 part take 100 parts of poly(lactic acid) as base, the crystallization rate that obtains poly-lactic acid material all can reach more excellent effect.
For preventing the oxidative degradation of poly(lactic acid) in this course of processing, in the method, need to add oxidation inhibitor.Described oxidation inhibitor is the conventional various oxidation inhibitor of field of plastics processing in prior art, such as: in Hinered phenols, phosphorous acid esters at least one, its consumption is also conventional amount used, generally, in polylactic resin 100 parts by weight, can be 0.1-0.5 part.The preferably combination of Hinered phenols and phosphite ester kind antioxidant hereinto, more preferably at least one in following Hinered phenols material: 1,3,5-trimethylammonium-2,4,6-tri-(3,5-di-t-butyl-4-hydroxybenzene methyl) benzene, 4,4 '-thiobis (the 6-tertiary butyl-3-methylphenol), four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 2,6 di tert butyl 4 methyl phenol etc.; And more preferably at least one in following phosphorous acid esters material: three (2,4-di-tert-butyl-phenyl) phosphorous acid ester, distearyl pentaerythritol diphosphite; The antioxidant effect the best wherein especially combining with the oxidation inhibitor of four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and three (2,4-di-tert-butyl-phenyl) phosphorous acid ester.
Two of object of the present invention is to provide a kind of preparation method of the polylactic resin that is applicable to fast injection molding moulding.
Comprise: the polylactic resin that is applicable to fast injection molding moulding described in described component makes by described consumption melt blending.
The melt temperature of polylactic resin is melt blending temperature used in common poly(lactic acid) processing, is preferably 190-250 ℃.
In the method for the invention described above, material melt blending equipment can adopt the general melt blending equipment in the rubber and plastic processing industry of prior art, can be twin screw extruder or Banbury mixer etc.
The preferred twin screw extruder of equipment that method of the present invention adopts.Specifically, can under the certain temperature between 190-250 ℃, add the twin screw extruder of 100-300rpm directly to extrude polylactic resin and anhydrides polyfunctional monomer, epoxies polyfunctional monomer, poly alcohol compound and oxidation inhibitor.
The present invention is achieved by the following technical solutions, adopts and by twin screw extruder or Banbury mixer, poly(lactic acid) and anhydrides polyfunctional monomer, epoxies polyfunctional monomer, poly alcohol compound and oxidation inhibitor direct reaction are mixed with.
Compared with original technology, the present invention has following advantage: adopt simple and efficient melt processing method, obtain long-chain branch poly(lactic acid) through high temperature functional group reactions, utilize chemical reaction that poly alcohol compound is introduced in polylactic acid chain simultaneously, greatly improve the crystallization rate of poly(lactic acid), do not need to carry out second annealing moulding, improved 10-100 doubly than the crystallization rate of initial polylactic resin; Gained poly-lactic acid material is due to the existence of the poly alcohol compound part of institute's grafting in long-chain branch product and polylactic acid chain, there are moderate shear viscosity and higher melt strength, make product material can meet the requirement of forming process, can need to easily carry out the processes such as injection moulding, membrane, foaming according to goods; In addition, by changing the degree of branching of long-chain branch and the consumption of poly alcohol compound, can realize adjusting and the control of poly-lactic acid material crystallization rate and Tc.
Accompanying drawing explanation
Fig. 1 is that embodiment 1, comparative example 1, comparative example 3, comparative example 4 and linear original poly(lactic acid) constant temperature at 200 ℃, after 3 minutes, is cooled to the means of differential scanning calorimetry temperature lowering curve of 25 ℃ with 10 ℃/min rate of temperature fall from 200 ℃.In figure, X-coordinate is temperature (° C), and ordinate zou is hot-fluid (W/g).
Embodiment
Below in conjunction with embodiment, further illustrate the present invention.
In following examples, polylactic resin used is raw material with linear polylactic resin (Nature Works LLC company of the U.S., trade mark 2002D), and the density of this raw material is 1.24g/cm
3, melting index is 4-8g/10min (190 ℃/2.16kg), wherein L-type lactic acid content is 96%.
Used 1,3 in following examples, 5-trimethylammonium-2,4,6-tri-(3,5-di-t-butyl-4-hydroxybenzene methyl) benzene is that Ciba company of Sweden produces; Three epoxypropyl tricarbimides and glycerin triglycidyl ether are that lark prestige Chemical Co., Ltd. produces, and pyromellitic acid anhydride and partially benzene tetramethyl dianhydride are that Shanghai brilliant pure reagent company limited produces, and polyoxyethylene glycol is that Chemical Reagent Co., Ltd., Sinopharm Group produces.
Embodiment 1
A kind of polylactic resin that is applicable to fast injection molding moulding
The polylactic resin of 100 weight parts being added at 210 ℃ to rotating speed is the Banbury mixer of 20rpm, constant temperature after its melting, add 0.22 part 1,3,5-trimethylammonium-2,4,6-tri-(3,5-di-t-butyl-4-hydroxybenzene methyl) benzene, the pyromellitic acid anhydride of 1.02 parts, three epoxypropyl tricarbimides of 1.41 parts of three-functionality-degrees, the polyoxyethylene glycol of 11.1 parts, mixes 2 minutes; Then Banbury mixer is risen to 100rpm, melt blending stopped after approximately 3 minutes, made the polylactic resin that is applicable to fast injection molding moulding.The hemihedral crystal time t of isothermal crystallisation process at the poly-lactic acid material obtaining record by means of differential scanning calorimetry method 110 ℃
1/2result is as shown in table 1.See Fig. 1 with 10 ℃/min rate of temperature fall from 200 ℃ of means of differential scanning calorimetry temperature lowering curves that are cooled to 25 ℃.
Embodiment 2
A kind of polylactic resin that is applicable to fast injection molding moulding
It is the Banbury mixer of 20rpm that the linear polylactic resin of 100 weight parts is added to rotating speed at 210 ℃, constant temperature adds four [β-(3 of 0.11 part after its melting, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 0.11 part three (2,4-di-tert-butyl-phenyl) phosphorous acid ester, the pyromellitic acid anhydride of 0.68 part, three epoxypropyl tricarbimides of 0.90 part of three-functionality-degree, the polyoxyethylene glycol of 11.1 parts, mixes 2 minutes; Then Banbury mixer is risen to 100rpm, melt blending stopped after approximately 3 minutes, made the polylactic resin that is applicable to fast injection molding moulding.The hemihedral crystal time t of isothermal crystallisation process at the poly-lactic acid material obtaining record by means of differential scanning calorimetry method 110 ℃
1/2result is as shown in table 1.
Embodiment 3
A kind of polylactic resin that is applicable to fast injection molding moulding
It is the Banbury mixer of 20rpm that the linear polylactic resin of 100 weight parts is added to rotating speed at 210 ℃, constant temperature adds four [β-(3 of 0.12 part after its melting, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 0.12 part three (2,4-di-tert-butyl-phenyl) phosphorous acid ester, the pyromellitic acid anhydride of 0.81 part, three epoxypropyl tricarbimides of 1.07 parts of three-functionality-degrees, the polyoxyethylene glycol of 17.6 parts, mixes 2 minutes; Then Banbury mixer is risen to 100rpm, melt blending stopped after approximately 3 minutes, made the polylactic resin that is applicable to fast injection molding moulding.The hemihedral crystal time t of isothermal crystallisation process at the poly-lactic acid material obtaining record by means of differential scanning calorimetry method 110 ℃
1/2result is as shown in table 1.
Embodiment 4
A kind of polylactic resin that is applicable to fast injection molding moulding
It is the Banbury mixer of 20rpm that the linear polylactic resin of 100 weight parts is added to rotating speed at 220 ℃, constant temperature after its melting, add 0.24 part 1,3,5-trimethylammonium-2,4,6-tri-(3,5-di-t-butyl-4-hydroxybenzene methyl) benzene, the pyromellitic acid anhydride of 1.22 parts, three epoxypropyl tricarbimides of 1.69 parts of three-functionality-degrees, the polyoxyethylene glycol of 17.6 parts, mixes 2 minutes; Then Banbury mixer is risen to 100rpm, melt blending stopped after approximately 5 minutes, made the polylactic resin that is applicable to fast injection molding moulding.The hemihedral crystal time t of isothermal crystallisation process at the poly-lactic acid material obtaining record by means of differential scanning calorimetry method 110 ℃
1/2result is as shown in table 1.
Embodiment 5
A kind of polylactic resin that is applicable to fast injection molding moulding
By the linear polylactic resin of 100 weight parts, 0.22 part 1,3,5-trimethylammonium-2,4,6-tri-(3,5-di-t-butyl-4-hydroxybenzene methyl) benzene, the pyromellitic acid anhydride of 1.02 parts, three epoxypropyl tricarbimides of 1.41 parts of three-functionality-degrees, the polyoxyethylene glycol of 11.1 parts, at 220 ℃, adding rotating speed is the twin screw extruder of 200rpm, directly extrudes the polylactic resin that obtains being applicable to fast injection molding moulding.The hemihedral crystal time t of isothermal crystallisation process at the poly-lactic acid material obtaining record by means of differential scanning calorimetry method 110 ℃
1/2result is as shown in table 1.
Embodiment 6
A kind of polylactic resin that is applicable to fast injection molding moulding
By the linear polylactic resin of 100 weight parts, four [β-(3 of 0.11 part, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, three (2,4-di-tert-butyl-phenyl) phosphorous acid ester of 0.11 part, the pyromellitic acid anhydride of 0.68 part, three epoxypropyl tricarbimides of 0.90 part of three-functionality-degree, the polyoxyethylene glycol of 11.1 parts, at 220 ℃, adding rotating speed is the twin screw extruder of 200rpm, directly extrudes the polylactic resin that obtains being applicable to fast injection molding moulding.The hemihedral crystal time t of isothermal crystallisation process at the poly-lactic acid material obtaining record by means of differential scanning calorimetry method 110 ℃
1/2result is as shown in table 1.
Embodiment 7
A kind of polylactic resin that is applicable to fast injection molding moulding
By the linear polylactic resin of 100 weight parts, four [β-(3 of 0.12 part, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, three (2,4-di-tert-butyl-phenyl) phosphorous acid ester of 0.12 part, the pyromellitic acid anhydride of 0.81 part, three epoxypropyl tricarbimides of 1.07 parts of three-functionality-degrees, the polyoxyethylene glycol of 17.6 parts, at 220 ℃, adding rotating speed is the twin screw extruder of 200rpm, directly extrudes the polylactic resin that obtains being applicable to fast injection molding moulding.The hemihedral crystal time t of isothermal crystallisation process at the poly-lactic acid material obtaining record by means of differential scanning calorimetry method 110 ℃
1/2result is as shown in table 1.
Embodiment 8
A kind of polylactic resin that is applicable to fast injection molding moulding
By the linear polylactic resin of 100 weight parts, 0.24 part 1,3,5-trimethylammonium-2,4,6-tri-(3,5-di-t-butyl-4-hydroxybenzene methyl) benzene, the pyromellitic acid anhydride of 0.81 part, three epoxypropyl tricarbimides of 1.69 parts of three-functionality-degrees, the polyoxyethylene glycol of 17.6 parts, at 220 ℃, adding rotating speed is the twin screw extruder of 200rpm, directly extrudes the polylactic resin that obtains being applicable to fast injection molding moulding.The hemihedral crystal time t of isothermal crystallisation process at the poly-lactic acid material obtaining record by means of differential scanning calorimetry method 110 ℃
1/2result is as shown in table 1.
Embodiment 9
A kind of polylactic resin that is applicable to fast injection molding moulding
The polylactic resin of 100 weight parts being added at 210 ℃ to rotating speed is the Banbury mixer of 20rpm, constant temperature after its melting, add 0.22 part 1,3,5-trimethylammonium-2,4,6-tri-(3,5-di-t-butyl-4-hydroxybenzene methyl) benzene, the inclined to one side benzene tetramethyl dianhydride of 1.86 parts, the glycerin triglycidyl ether of 2.64 parts of three-functionality-degrees, the polypropylene glycol of 11.1 parts, mixes 2 minutes; Then Banbury mixer is risen to 100rpm, melt blending stopped after approximately 3 minutes, made the polylactic resin that is applicable to fast injection molding moulding.The hemihedral crystal time t of isothermal crystallisation process at the poly-lactic acid material obtaining record by means of differential scanning calorimetry method 110 ℃
1/2result is as shown in table 1.
Embodiment 10
A kind of polylactic resin that is applicable to fast injection molding moulding
By the linear polylactic resin of 100 weight parts, 0.24 part 1,3,5-trimethylammonium-2,4,6-tri-(3,5-di-t-butyl-4-hydroxybenzene methyl) benzene, the inclined to one side benzene tetramethyl dianhydride of 1.86 parts, the glycerin triglycidyl ether of 2.64 parts of three-functionality-degrees, the polypropylene glycol of 17.6 parts, at 220 ℃, adding rotating speed is the twin screw extruder of 200rpm, directly extrudes the polylactic resin that obtains being applicable to fast injection molding moulding.The hemihedral crystal time t of isothermal crystallisation process at the poly-lactic acid material obtaining record by means of differential scanning calorimetry method 110 ℃
1/2result is as shown in table 1.
Comparative example 1
The long-chain branch poly(lactic acid) that only uses functional group reactions to prepare
It is the Banbury mixer of 20rpm that the linear polylactic resin of 100 weight parts is added to rotating speed at 210 ℃, constant temperature after its melting, add successively 0.22 part 1,3,5-trimethylammonium-2,4,6-tri-(3,5-di-t-butyl-4-hydroxybenzene methyl) benzene, the pyromellitic acid anhydride of 1.02 parts, the three epoxypropyl tricarbimides of 1.41 parts, mix 2 minutes; Then Banbury mixer is risen to 100rpm, melt blending stopped after approximately 10 minutes, made long-chain branch polylactic resin.The hemihedral crystal time t of isothermal crystallisation process at the poly-lactic acid material obtaining record by means of differential scanning calorimetry method 110 ℃
1/2result is as shown in table 1.See Fig. 1 with 10 ℃/min rate of temperature fall from 200 ℃ of means of differential scanning calorimetry temperature lowering curves that are cooled to 25 ℃.
Comparative example 2
The long-chain branch poly(lactic acid) that only uses functional group reactions to prepare
By the linear polylactic resin of 100 weight parts, four [β-(3 of 0.1 part, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 0.1 part three (2,4-di-tert-butyl-phenyl) phosphorous acid ester, the pyromellitic acid anhydride of 0.37 part, the three epoxypropyl tricarbimides of 0.49 part, at 220 ℃, adding rotating speed is the twin screw extruder of 200rpm, directly extrudes and obtains long-chain branch polylactic resin.The hemihedral crystal time t of isothermal crystallisation process at the poly-lactic acid material obtaining record by means of differential scanning calorimetry method 110 ℃
1/2result is as shown in table 1.
Comparative example 3
The poly(lactic acid) that only uses poly alcohol compound to prepare
By the linear polylactic resin of 100 weight parts, four [β-(3 of 0.12 part, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 0.12 part three (2,4-di-tert-butyl-phenyl) phosphorous acid ester, the polyoxyethylene glycol of 17.6 parts, at 180 ℃, adding rotating speed is the twin screw extruder of 200rpm, directly extrudes the polylactic resin that obtains modification.The hemihedral crystal time t of isothermal crystallisation process at the poly-lactic acid material obtaining record by means of differential scanning calorimetry method 110 ℃
1/2result is as shown in table 1.See Fig. 1 with 10 ℃/min rate of temperature fall from 200 ℃ of means of differential scanning calorimetry temperature lowering curves that are cooled to 25 ℃.
Comparative example 4
Only add poly(lactic acid) prepared by epoxy monomer and poly alcohol compound
It is the Banbury mixer of 20rpm that the linear polylactic resin of 100 weight parts is added to rotating speed at 210 ℃, constant temperature adds successively four [β-(3 of 0.12 part after its melting, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 0.12 part three (2,4-di-tert-butyl-phenyl) phosphorous acid ester, the three epoxypropyl tricarbimides of 1.69 parts, the polyoxyethylene glycol of 17.6 parts, mixes 2 minutes; Then Banbury mixer is risen to 100rpm, melt blending stopped after approximately 10 minutes, made long-chain branch polylactic resin.The hemihedral crystal time t of isothermal crystallisation process at the poly-lactic acid material obtaining record by means of differential scanning calorimetry method 110 ℃
1/2result is as shown in table 1.See Fig. 1 with 10 ℃/min rate of temperature fall from 200 ℃ of means of differential scanning calorimetry temperature lowering curves that are cooled to 25 ℃.
Table 1
Fig. 1 is that embodiment 1, comparative example 1, comparative example 3, comparative example 4 and linear original poly(lactic acid) constant temperature at 200 ℃, after 3 minutes, is cooled to the means of differential scanning calorimetry temperature lowering curve of 25 ℃ with 10 ℃/min rate of temperature fall from 200 ℃.The crystallization situation wherein occurring from temperature lowering curve can reflect the variation of the crystallization rate of each poly-lactic acid material to a certain extent, and in resin system of the present invention, the raising of crystallization rate is mainly that long-chain branch produces and be grafted to both the common contributions of poly alcohol compound in polylactic acid chain.Can find out, prepare the comparative example 1 of long-chain branch poly(lactic acid) only using functional group reactions, only use poly alcohol compound to prepare the comparative example 3 of poly(lactic acid) and only add epoxy monomer and the means of differential scanning calorimetry temperature lowering curve of the comparative example 4 of poly alcohol compound on all there is not crystallization exothermic process, in contrast to this, on the means of differential scanning calorimetry temperature lowering curve of the coefficient embodiment 1 of poly alcohol compound part of institute's grafting in long-chain branch product and polylactic acid chain, there is obvious sharp-pointed crystalline exotherm peak, illustrate that crystallization rate improves greatly, can realize and in natural cooling process, complete whole crystallizations.
Table 1 is the hemihedral crystal time t of isothermal crystallisation process at poly-lactic acid material that each embodiment and comparative example obtain record by means of differential scanning calorimetry method 110 ℃
1/2.The hemihedral crystal time of isothermal crystal process is a kind of common counter of weighing polymer crystallization speed, and in general, crystallization rate is higher, and the hemihedral crystal time of isothermal crystal process is less.In the present invention, the very effective crystallization rate of accelerating poly-lactic acid material of poly alcohol compound part of institute's grafting in the long-chain branch product obtaining by functional group reactions and polylactic acid chain, thus the hemihedral crystal time of its isothermal crystal process is reduced.Therefore, in the present invention, the hemihedral crystal time of the isothermal crystal process recording is less, illustrates that the crystallization rate of poly-lactic acid material is higher, and modified effect is more obvious.Can see, the crystallization rate of the poly-lactic acid material that all embodiment record is all little a lot of than the linear polylactic acid raw material of non-modified, illustrates that the present invention program's enforcement is all reaching the object of improving poly-lactic acid material crystallization rate in varying degrees.Embodiment 1,2,3,4 and comparative example 1, embodiment 5,6,7,8 is compared with comparative example 2, the hemihedral crystal time of isothermal crystal process obviously diminishes, and illustrates that the effect of the crystallization rate that this technological invention improves than the technical scheme that only uses functional group reactions to prepare long-chain branch is good.Embodiment 1,2,3 is compared with comparative example 3, the hemihedral crystal time of isothermal crystal process reduces respectively approximately 75 times, 25 times and 15 times, illustrate that this technological invention is more effective than the crystallization rate that only uses the technical scheme of poly alcohol compound to improve, be more suitable for the requirement of the complete processings such as fast injection molding moulding.Embodiment 4(melting index) compared with comparative example 4, the hemihedral crystal time of isothermal crystal process reduces approximately 25 times, wherein embodiment 4 (records according to ASTMD1238 standard with the melting index of the poly-lactic acid material of comparative example 4, 190 ℃, 2.16kg load) be respectively 2.48g/10min and 4.15g/10min, compare the melting index of linear polylactic acid raw material 5.00g/10min, embodiment 4 has all produced long-chain branch with the poly-lactic acid material of comparative example 4, but due to formula difference separately, long-chain branch structure in bi-material must be different, but the poly(lactic acid) long branched chain structure that the Discrepancy Description of significant crystallization rate produces in the time of anhydrides polyfunctional monomer and the coupling of epoxies polyfunctional monomer is more conducive to the raising of poly(lactic acid) crystallization rate, be not that all poly(lactic acid) long-chain branchs all have the effect that promotes poly(lactic acid) crystal property.The data of comparative example 1 and 2, embodiment 5 and 6, illustrate in the method for the invention, the levels of long chain branching of poly-lactic acid material is larger, and the hemihedral crystal time of its isothermal crystal process is less; The data of comparative example 2 and 3, embodiment 6 and 7, illustrate in the method for the invention, poly alcohol compound content is larger, and the hemihedral crystal time of its isothermal crystal process is less; Add the weight of anhydrides polyfunctional monomer, epoxies polyfunctional monomer and poly alcohol compound by adjustment, successfully reached the object that regulates poly-lactic acid material crystallization rate.
Claims (9)
1. be applicable to a polylactic resin for fast injection molding moulding, it is characterized in that described polylactic resin is comprise following component blend and obtain:
Polylactic resin: 100 weight parts;
Anhydrides polyfunctional monomer 0.5-3 weight part;
Epoxies polyfunctional monomer 0.5-3 weight part;
Poly alcohol compound 5-20 weight part;
Oxidation inhibitor;
Wherein, the epoxies functional monomer that described epoxies polyfunctional monomer is functionality >=3;
Described poly alcohol compound is polyoxyethylene glycol and/or polypropylene glycol.
2. polylactic resin as claimed in claim 1, is characterized in that:
Anhydrides polyfunctional monomer 0.5-2 weight part;
Epoxies polyfunctional monomer 0.5-2 weight part;
Poly alcohol compound 10-15 weight part
Oxidation inhibitor 0.1-0.5 weight part.
3. polylactic resin as claimed in claim 1, is characterized in that:
Described poly(lactic acid) is L-type poly(lactic acid) or the D type poly(lactic acid) of optical purity >=96%.
4. polylactic resin as claimed in claim 1, is characterized in that:
Described anhydrides polyfunctional compound is selected from least one in following material: Tetra hydro Phthalic anhydride, trimellitic acid 1,2-anhydride, pyromellitic acid anhydride, mellophanic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic acid dianhydride, Succinic anhydried, MALEIC ANHYDRIDE, dodecyl are for MALEIC ANHYDRIDE, inner methylidyne tetrahydric phthalic anhydride, hexahydrophthalic anhydride, glycerine three trimellitic acid 1,2-anhydrides, pentamethylene tetracarboxylic dianhydride.
5. polylactic resin as claimed in claim 1, is characterized in that:
Described epoxies polyfunctional compound is at least one being selected from following material: three epoxypropyl tricarbimides, glycerin triglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, triglycidyl group p-aminophenol, N, N, N ', N '-four glycidyl group-4, 4 ' diaminodiphenyl-methane, Phloroglucinol monomethyl ether triglycidyl ether, Pyromellitic Acid tetra glycidyl ester, 1, 1 ', 2, 2 '-tetra-(p-hydroxybenzene) ethane, four glycidyl ethers, Resorcinol formal four glycidyl ethers, two Resorcinol formal four glycidyl ethers, glycidyl methacrylate oligopolymer.
6. polylactic resin as claimed in claim 1, is characterized in that:
Described oxidation inhibitor is at least one in Hinered phenols antioxidant and phosphite ester kind antioxidant.
7. polylactic resin as claimed in claim 1, is characterized in that:
Described anhydrides compound and epoxies polyfunctional compound's weight ratio is (0.5-1): 1.
8. a preparation method for the polylactic resin that is applicable to fast injection molding moulding as described in one of claim 1 ~ 7, is characterized in that described method comprises:
Described in making by described consumption melt blending, described component is applicable to the polylactic resin of fast injection molding moulding.
9. preparation method as claimed in claim 8, is characterized in that:
The temperature of described melt blending is 190-250 ℃.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210422419.7A CN103788601A (en) | 2012-10-29 | 2012-10-29 | Polylactic acid resin suitable for rapid injection moulding and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210422419.7A CN103788601A (en) | 2012-10-29 | 2012-10-29 | Polylactic acid resin suitable for rapid injection moulding and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105199350A (en) * | 2015-11-02 | 2015-12-30 | 浙江工业大学 | Reactive blending and toughening modified polylactic acid based composite material and preparation method thereof |
| WO2023239090A1 (en) * | 2022-06-07 | 2023-12-14 | 주식회사 엘지화학 | Highly branched polylactide resin, and method for preparing same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1749316A (en) * | 2005-10-21 | 2006-03-22 | 中国科学院长春应用化学研究所 | A kind of ternary built poly lactic acid type composite material and application thereof |
-
2012
- 2012-10-29 CN CN201210422419.7A patent/CN103788601A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1749316A (en) * | 2005-10-21 | 2006-03-22 | 中国科学院长春应用化学研究所 | A kind of ternary built poly lactic acid type composite material and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105199350A (en) * | 2015-11-02 | 2015-12-30 | 浙江工业大学 | Reactive blending and toughening modified polylactic acid based composite material and preparation method thereof |
| WO2023239090A1 (en) * | 2022-06-07 | 2023-12-14 | 주식회사 엘지화학 | Highly branched polylactide resin, and method for preparing same |
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Application publication date: 20140514 |