CN102875987B - A kind of organic nucleating agent and its preparation and application - Google Patents
A kind of organic nucleating agent and its preparation and application Download PDFInfo
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Abstract
The present invention relates to polymeric material field is and in particular to a kind of organic nucleating agent and its preparation and application.The organic nucleating agent of the present invention includes the component of following weight portion：Polylactic acid poly polyol blocks copolymer 1～100 weight portion；Polylactic acid 0～50 weight portion；Wherein, the general structure of described polylactic acid poly polyol blocks copolymer is as follows：PLA‑R1‑PLA；Wherein R1 is polyvalent alcohol, and PLA is polylactic acid.The copolymeric structure of the organic nucleating agent product of the present invention is stable, even molecular weight distribution, eutectic structure are perfect, crystalline rate that is can effectively lifting polylactic resin, it is favorably improved the compatibility of polylactic acid blend, obtain chemical resistance, excellent heat resistance, and the transparency preferably polylactic acid and combinations thereof Tetramune, has wide development and application prospect in polylactic acid-based product preparation field.
Description
Technical field
The present invention relates to polymeric material field is and in particular to a kind of organic nucleating agent and its preparation and application.
Background technology
Polylactic acid (PLA) is a kind of polymer with excellent biocompatibility, and it derives from Renewable resource farming
Thing（As Semen Maydiss）, advantage the most prominent is biodegradability, can be degradable by microorganism in nature after its use, finally
Generate carbon dioxide and water, free from environmental pollution, highly beneficial to environmental protection.Polylactic acid has good mechanical property, thermoplastic
Property, fibre forming property, transparency high it is adaptable to the various processing method such as blowing, thermoplastic, easy to process, new century is defined as by industry
New material the most rising.
But as engineering plastics, there is the shortcomings of crystalline rate is slow, and the shrinkage factor of moulded products is big, matter is crisp in polylactic acid.
For this reason, both at home and abroad to how improving the crystalline rate of polylactic acid, reduce its glass transition temperature, how to improve the side such as its toughness
Face has carried out wide research.Wherein, adding crystallization nucleation auxiliary agent and improving polymer crystallization speed is that one kind changes in polymer
Property processing in conventional method.Crystallization nucleating agent can be divided into organic and inorganic two big class.Conventional organic nucleating agent has containing phenyl ring
Alkaline metal salt and Long carbon chain aliphatic carboxylic acid metal salt, research finds that this kind of slaine can cause the degraded of polyester, thus
Reduce its mechanical property, thermal stability etc..Inorganic nucleator mainly have montmorillonite, TiO2, CaO, MgO, BaSO4, SiO2,
Al2O3 etc., the advantage of this kind of nucleator is to reach Nano Particle size, but there are agglomeration traits in use it is difficult to
Keep the dispersed of nanoscale in the polymer.
Patent CN1366004 utilizes double screw extruder by nucleator and polyester material blending processing, improves nucleator
Scattering problem and improve crystallizing polyester speed, but for biodegradation material, thermal degradation in processing acutely, improves knot
Molecular weight is also reduced while brilliant speed.
Number of patent application 201080032592.5, be prepared for polylactic acid stereoscopic composite and state it can be used as nucleator
Use, but this stereoscopic composite has been mixed into traditional organic system and inorganic system nucleator in building-up process, therefore as one-tenth
Core agent is difficult to when using prove that its nucleating effect is not derived from the traditional nucleating agents of these interpolations.And, polylactic acid stereoscopic is multiple
Compound contains more end moieties, will cause the heat drop of itself and matrix resin when with polylactic resin melting mixing
Solution, if degraded is acutely, will have a strong impact on the serviceability of product.
Content of the invention
It is an object of the invention to overcoming the defect of prior art, provide a kind of organic nucleating agent and its preparation and application.
The nucleator of the present invention has the good compatibility with polylactic acid and combinations thereof resin, can overcome traditional nucleating agents in polymerization
Reunite and disperse uneven disadvantage in thing, effectively improve the crystal property of polylactic acid and combinations thereof resin.
The present invention discloses a kind of organic nucleating agent first, and this organic nucleating agent includes the component of following weight portion：
Polylactic acid-polyvalent alcohol block copolymer 1～100 weight portion
Polylactic acid 0～50 weight portion
Wherein, the general structure of described polylactic acid-polyvalent alcohol block copolymer is as follows：PLA-R1-PLA；Wherein R1 is
Polyvalent alcohol, PLA is polylactic acid.
Further, described organic nucleating agent includes the component of following weight portion：
Polylactic acid-polyvalent alcohol block copolymer 1～100 weight portion
Polylactic acid 1～50 weight portion
Wherein, the general structure of described polylactic acid-polyvalent alcohol block copolymer is as follows：PLA-R1-PLA；Wherein R1 is
Polyvalent alcohol, PLA is polylactic acid.
Preferably, in described polylactic acid-polyvalent alcohol block copolymer, the percentage by weight of polylactic acid block is 50～
99%, balance of polyvalent alcohol block.Preferably, in described polylactic acid-polyvalent alcohol block copolymer, the weight of polylactic acid block
Amount percentage ratio is 50～90%, balance of polyvalent alcohol block.
Preferably, the acid number of described polylactic acid-polyol blocks copolymer is less than 10mgKOH/g.More excellent, described poly- breast
The acid number of acid-polyol blocks copolymer is less than 1mgKOH/g.Optimum, the acid of described polylactic acid-polyol blocks copolymer
Value is less than 0.05mgKOH/g.
Preferably, the monomer of the polyvalent alcohol in described polylactic acid-polyvalent alcohol block copolymer is saturated fat adoption
Ester polyol, unsaturated aliphatic polyester polyhydric alcohol or aromatic polyester polyol.
More excellent, the polyvalent alcohol in described polylactic acid-polyvalent alcohol block copolymer is selected from Polyethylene Glycol, polycyclic oxygen third
Alkane polyhydric alcohol, polybutylene oxide polyhydric alcohol, polyoxypropyleneglycol, polypropylene oxide triol, polytetrahydrofuran diol, polybutadiene
The block copolymerization of any one or more in enediol, 10PE27 glycol, polyadipate -1,4- butyl glycol ester diol
Thing.
Optimum, the polyvalent alcohol Mn value in described polylactic acid-polyvalent alcohol block copolymer is 500～20000.Preferably
, the polyvalent alcohol Mn value in described polylactic acid-polyvalent alcohol block copolymer is 500～10000.
Preferably, the polylactic acid in described polylactic acid-polyvalent alcohol block copolymer be poly (l-lactic acid), poly- D-ALPHA-Hydroxypropionic acid or poly-
Pfansteihl and the block copolymer of poly- D-ALPHA-Hydroxypropionic acid.
Preferably, the Mn value of the polylactic acid in described polylactic acid-polyvalent alcohol block copolymer is 700～10000.
More excellent, the Mn value of the polylactic acid in described polylactic acid-polyvalent alcohol block copolymer is 700～5000.
In the polylactic acid of the present invention-polyvalent alcohol block copolymer, polyvalent alcohol（R1）The polylactic acid of both sides（PLA）Permissible
For the Nomenclature Composition and Structure of Complexes identical polylactic acid or the different polylactic acid of the Nomenclature Composition and Structure of Complexes.
Preferably, the molecular weight distribution of described polylactic acid-polyvalent alcohol block copolymer is respectively less than and is equal to 2.More excellent, institute
State poly (l-lactic acid) and the molecular weight distribution of poly- D-ALPHA-Hydroxypropionic acid is respectively less than equal to 1.5.
Preferably, described polylactic acid-polyvalent alcohol block copolymer can be embedding for the polylactic acid-polyvalent alcohol of single kind
Section copolymer or the combination of two or more polylactic acid-polyvalent alcohol block copolymer.
Preferably, described polylactic acid is selected from poly (l-lactic acid), the block copolymer of poly- D-ALPHA-Hydroxypropionic acid, poly (l-lactic acid) and poly- D-ALPHA-Hydroxypropionic acid
One or more of combination.I.e. in the present invention, as the described polylactic acid of organic one-tenth mediating recipe composition（In non-block copolymer
Polylactic acid）Can be the poly (l-lactic acid) of L optical isomer homopolymerization, can be the poly- D-ALPHA-Hydroxypropionic acid of D optical isomer homopolymerization, permissible
It is two blocks or the segmented copolymer of poly (l-lactic acid) and poly- D-ALPHA-Hydroxypropionic acid, can also be the combination of aforementioned multiple polylactic acid.By L
Represent poly (l-lactic acid), D represents poly- D-ALPHA-Hydroxypropionic acid, then polylactic acid can be expressed as L, D, LD, DL, LDL, DLD, LDLDL, DLDLD
In the combination of any one or more.The Mn value of polylactic acid is 700～10000, and preferably Mn value is 700～5000.
The optical isomerism structure of the poly (l-lactic acid) of the present invention is：The optical isomerism structure of poly- D-ALPHA-Hydroxypropionic acid is：The structure of the block polymer of poly (l-lactic acid) and poly- D-ALPHA-Hydroxypropionic acid is：
Secondly, the invention discloses the preparation method of aforementioned organic nucleating agent, comprise the steps：
1）Mixing：Polylactic acid-polyvalent alcohol block copolymer is mixed by the composition according to aforementioned organic nucleating agent with polylactic acid
Close, add in banbury or double screw extruder, 150～260 DEG C carry out melt blending, obtain organic nucleating agent product；
2）The following process of organic nucleating agent product or utilization.
Preferably, step 1）Melt blending is carried out using double screw extruder, the screw-rod structure of double screw extruder is with mixed
Based on refining type or shearing engagement type spiral shell section, screw speed is more than or equal to 50rpm.Preferably, screw speed is 80～200rpm.
Preferably, step 1）Carry out evacuation or nitrogen protection during melt blending.
Poly (l-lactic acid) of the present invention and poly- D-ALPHA-Hydroxypropionic acid can be prepared using following methods：Pfansteihl or D-ALPHA-Hydroxypropionic acid are added
To in reactor, evacuation under mechanical stirring first, it is dehydrated 1-3 hour at a temperature of 70-90 DEG C, then heat to 100-
180 DEG C, vacuum degree control, in below 10000Pa, obtains poly (l-lactic acid) or poly- D-ALPHA-Hydroxypropionic acid after reacting 5-30 hour.
Wherein, respectively greater than it is equal to for preparing poly (l-lactic acid) and the Pfansteihl of poly- D-ALPHA-Hydroxypropionic acid and the optical purity of D-ALPHA-Hydroxypropionic acid
95%, preferably greater than or equal to 99%.
Step 1）Raw material polylactic acid-polyvalent alcohol block copolymer can be prepared using following methods：1）To gather
Pfansteihl and poly- D-ALPHA-Hydroxypropionic acid are mixed to join in reactor, evacuation under stirring condition, temperature 150-240 DEG C, vacuum degree control
In below 3000Pa, react 1-10 and as a child obtained poly (l-lactic acid) and the block polymer of poly- D-ALPHA-Hydroxypropionic acid；2）By poly (l-lactic acid), gather
One of block polymer of D-ALPHA-Hydroxypropionic acid or poly (l-lactic acid) and poly- D-ALPHA-Hydroxypropionic acid or any two kinds are added in reactor, simultaneously plus
Enter polyvalent alcohol, the lower evacuation of stirring, temperature 120-240 DEG C, vacuum degree control in below 1000Pa, more excellent 100Pa with
Under, reaction 1-8 hour obtains polylactic acid-polyvalent alcohol block copolymer.
Step 1）In, in twin screw device moment of torsion tolerance range, it is less than nucleation by controlling twin screw the second half temperature
Agent fusing point, makes the organic nucleating agent product that twin-screw extrusion obtains be powder nucleator.
Preferably, step 2）Described following process is to be pulverized the organic nucleating agent product of previous step, and acquisition has
Machine nucleant powder.
Preferably, step 2）Described following process is to heat up or progressively the organic nucleating agent product constant temperature of previous step
Pulverize again after crystallization, obtain organic nucleating agent powder.
More excellent, step 2）Described following process is in 80～200 DEG C of temperature by the organic nucleating agent product of previous step
In the range of, pulverize again after constant temperature or progressively intensification crystallization 1～10h, obtain organic nucleating agent powder.
If the composition of organic nucleating agent is only polylactic acid-polyvalent alcohol block copolymer, this organic nucleating agent product
Following process be by one or more polylactic acid-polyol blocks copolymer in 80～200 DEG C of temperature ranges, constant temperature or by
Pulverize again after step intensification crystallization 1～10h, obtain organic nucleating agent powder.
Optimum, described organic nucleating agent powder average particle size is less than or equal to 300 μm.Preferably smaller than it is equal to 50 μm；More excellent
Choosing is less than or equal to 5 μm.
Preferably, step 2）Described following process also includes typical additives are added in organic nucleating agent product.
More excellent, described typical additives are that one or more of optothermal stabilizer, antioxidant, hydrolysis-resisting agent combine.
The conventional processing aid of the present invention can also add during the melt blending of banburying or twin-screw extrusion, and has
Machine nucleator together kneads or extrudes.
The present invention finally also discloses aforementioned organic nucleating agent and is preparing in polylactic resin as nucleating agent in polylactic acid production
Application.
The peak melting point of the organic nucleating agent that the present invention finally gives is more than or equal to 190 DEG C, and minimum acid number is less than
0.05mgKOH/g, and may also pass through the eutectic structure that nucleator is improved in crystallization further.Nucleator of the present invention is prepared into powder
Last uniformly can be added in polylactic resin according to traditional processing mode, prepared by way of melting mixing and become poly- breast
Acid resin compositionss.In the limit not destroying the purpose of the present invention, also nucleator of the present invention first can be fabricated to master batch and add again
It is added in polylactic resin, being prepared by way of melting mixing becomes polylactic acid resin composition.Do not destroying the present invention's
In the limit of purpose, also can add common additive, such as optothermal stabilizer, antioxidant, hydrolysis-resisting agent, lubricant, the demoulding
Agent, comprise one of coloring agent of dyestuff and color etc. or two or more, with nucleator of the present invention together with polylactic resin
The form of compositionss is used for various uses.The using method of organic nucleating agent of the present invention is：By organic nucleating agent with 0.1～5wt%
（Preferably 0.5～2.5wt%）Ratio uniform be dispersed in pure polylactic acid or pure polylactic acid and the mixture of other polymers, lead to
Cross double screw extruder or the banbury polylactic resin polymer containing organic nucleating agent for the blending extrusion acquisition in the molten state.
The nucleator of the present invention can effectively lift the crystalline rate of polylactic resin, is favorably improved polylactic acid blend
The compatibility, obtain chemical resistance, excellent heat resistance, so the excellent polylactic acid of the transparency and combinations thereof Tetramune and extensively should
With.Polylactic acid and combinations thereof Tetramune refers to film, piece, fiber, cloth, non-woven fabrics, injection-molded article, extrusion molding article, vacuum pressure
Complex of empty products formed, blow molding product and other materials etc., can be used for textile, packaging, agricultural material, gardening
With material, civil construction material, stationery, toy, medical supplies or other purposes.
It can be seen that, the nucleator preparation method of the present invention is simple, and the peak melting point of the organic nucleating agent finally giving is more than etc.
In 200 DEG C, minimum acid number is less than 0.05mgKOH/g, the copolymeric structure of organic nucleating agent product is stable, even molecular weight distribution,
Eutectic structure is perfect, crystalline rate that is can effectively lifting polylactic resin, is favorably improved the compatibility of polylactic acid blend,
Obtain chemical resistance, excellent heat resistance, and the transparency preferably polylactic acid and combinations thereof Tetramune, in polylactic acid-based product system
Standby field has wide development and application prospect.
Specific embodiment
The present invention is expanded on further with reference to embodiment.It should be understood that embodiment is merely to illustrate the present invention, and unrestricted
The scope of the present invention.
Embodiment 1
（1）By 100Kg Pfansteihl（The optical purity of Pfansteihl is equal to 99%）Raw material is added in reactor, first in machine
The lower evacuation of tool stirring, is dehydrated 2 hours at a temperature of 80 DEG C, then heats to 140 DEG C of reaction temperature, vacuum degree control exists
5000Pa, reaction obtained poly (l-lactic acid) after 8 hours, and Mn value is 715g/mol；Change species and the response parameter of lactic acid, be prepared into
To different polylactic acid homopolymer, as shown in table 1.
The preparation of table 1 polylactic acid homopolymer
Embodiment 2
PLLA-1 and PDLA-1 obtaining in embodiment 1 is mixed to join in reactor, evacuation under stirring condition, temperature
200 DEG C of degree, vacuum 1000Pa, reaction 5 as a child obtained the multi-block polymer of poly (l-lactic acid) and poly- D-ALPHA-Hydroxypropionic acid, numbering
PLDA-1, Mn value is 3249g/mol.
Embodiment 3
PLLA-2 the and PDLA-2 equimolar obtaining in embodiment 1 ratio is mixed to join in reactor, under stirring condition
Evacuation, 210 DEG C of temperature, vacuum 500Pa, reaction 3 as a child obtained the block polymer of poly (l-lactic acid) and poly- D-ALPHA-Hydroxypropionic acid, compiled
Number PLDA-2, Mn value is 4158g/mol.
Embodiment 4
PLLA-2 and polytetrahydrofuran diol are mixed to join in reactor, the lower evacuation of stirring, 170 DEG C of temperature, very
Reciprocal of duty cycle 400Pa, reaction obtains polylactic acid-polyvalent alcohol block copolymer for 6 hours.Change polylactic acid, polyvalent alcohol and reaction ginseng
Number, prepares different polylactic acid-polyvalent alcohol block copolymers, as shown in table 2.
The preparation of table 2 polylactic acid poly polyol blocks copolymer
Embodiment 5
PLAC-4 grind into powder prepared by embodiment 4, mean diameter is 30 microns, and fusing point is 201 DEG C.Nucleating effect
It is shown in Table 7.
Embodiment 6
（1）By each for PLAC-1 and PLAC-2 in embodiment 4 50 weight portions, mix, with double screw extruder extrusion, rotating speed
100rpm, extruder temperature setting is as shown in table 3.Nucleating agent in polylactic acid production product is obtained after extrusion.
Table 3 extruder temperature
（2）By step（1）The nucleating agent in polylactic acid production product grind into powder obtaining, mean diameter is 25 microns, and fusing point is
205℃.Nucleating effect is shown in Table 7.
Embodiment 7
（1）Each 25 weight portions of PLLA-2 and PDLA-2 prepared by embodiment 1, and 1 weight portion of embodiment 4 preparation
PLAC-3, mixing, with double screw extruder extrusion, rotating speed 140rpm, extruder temperature setting is as shown in table 4.Obtain after extrusion
Nucleating agent in polylactic acid production product.
Table 4：Extruder temperature
（2）By step（1）The nucleating agent in polylactic acid production product grind into powder obtaining, mean diameter is 5 microns, and fusing point is
215℃.Nucleating effect is shown in Table 7.
Embodiment 8
（1）Each 50 weight portions of PLAC-4 and PLAC-5 prepared by embodiment 4, and 1 weight portion of embodiment 2 preparation
PLDA-1, mixing, with double screw extruder extrusion, rotating speed 200rpm, extruder temperature setting is as shown in table 5.Obtain after extrusion
Nucleating agent in polylactic acid production product.
Table 5：Extruder temperature
（2）By step（2）The nucleating agent in polylactic acid production product obtaining grinds from after 80 DEG C of crystallizations in 6 hours to 200 DEG C that progressively heat up
Clay into power, mean diameter is 16 microns, fusing point is 207 DEG C.Nucleating effect is shown in Table 7.
Embodiment 9
（1）50 weight portion PLAC-4 prepared by embodiment 4, and 50 weight portion PLDA-2 of embodiment 3 preparation, mixing,
With double screw extruder extrusion, rotating speed 80rpm, extruder temperature setting is as shown in table 7.Obtain nucleating agent in polylactic acid production after extrusion to produce
Product.
Table 6：Extruder temperature
（2）By step（2）The nucleating agent in polylactic acid production product obtaining grinds from after 80 DEG C of crystallizations in 6 hours to 200 DEG C that progressively heat up
Clay into power, mean diameter is 300 microns, fusing point is 215 DEG C.Nucleating effect is shown in Table 7.
Embodiment 10
1. experiment material
Inorganic nucleator：Pulvis Talci, montmorillonite（MMT）.
Organic nucleating agent：The nucleating agent in polylactic acid production of embodiment 5-8 preparation.
2. experimental technique
By the method for general melt blending, by various nucleators（Inorganic nucleator Pulvis Talci, montmorillonite；And the present invention
The nucleating agent in polylactic acid production of preparation）It is added to pure PLA resin according to weight ratio respectively（Purchased from natureworks company of the U.S., commodity
The polylactic acid of number 4032D）In Products, make nucleator equal in the range of 150-190 DEG C with double screw extruder or banbury
Even be distributed in pure PLA resin, obtain PLA resin sample containing nucleator as testing sample（A-F）；With without nucleator
Pure PLA resin（Purchased from natureworks company of the U.S., the polylactic acid of article number 4032D）As test control sample.
DSC method of testing：Using U.S.'s TA company Q100 type differential scanning calorimeter to above-mentioned sample（Testing sample and right
Compare sample）Carry out heat analysis respectively.Sample quality 0.3 ~ 0.5mg, nitrogen protection in test process.Test condition is as follows：
（1）From room temperature to 180 DEG C, heating rate is 40 DEG C/min；
（2）180 DEG C are incubated 10 minutes；
（3）It is cooled to 130 DEG C, rate of temperature fall is 40 DEG C/min；
（4）It is incubated at 130 DEG C, carry out isothermal crystal；
（5）After obtaining complete isothermal crystal peak, it is cooled to room temperature, speed is 40 DEG C/min, terminates test.
3. data processing：
Isothermal crystal process can be fitted with Avrami equation.The general expression of Avrami equation is as follows：
Xt=exp（-Kz·tn）
By each sample is processed with Avrami equation and is changed in obtained isothermal crystal peak in DSC test
Calculate, can obtain reflecting the data in 130 DEG C of isothermal crystal speed for each sample（t1/2）, t1/2Numerical value is less, its corresponding knot
Brilliant speed is faster, and concrete outcome is listed in table 7.
Table 7 sample detection
4. experiment conclusion
As shown in Table 7, the nucleator of the present invention can significantly improve the crystallization rate of polylactic resin hence it is evident that being better than tradition
Inorganic nucleator, such as Pulvis Talci and montmorillonite.
The above, only presently preferred embodiments of the present invention, not any to the present invention formal and substantial restriction,
It should be pointed out that for those skilled in the art, on the premise of without departing from the inventive method, also can make
Some improvement and supplement, these improve and supplement also should be regarded as protection scope of the present invention.All those skilled in the art,
Without departing from the spirit and scope of the present invention, when available disclosed above technology contents make a little more
Equivalent variations that are dynamic, modifying and develop, are the Equivalent embodiments of the present invention；Meanwhile, all substantial technological pair according to the present invention
The change of any equivalent variations, modification and differentiation that above-described embodiment is made, all still fall within the scope of technical scheme
Interior.
Claims (7)
1. a kind of organic nucleating agent, this organic nucleating agent includes the component of following weight portion：
Polylactic acid-polyvalent alcohol block copolymer 1～100 weight portion
Polylactic acid 1～50 weight portion
Wherein, the general structure of described polylactic acid-polyvalent alcohol block copolymer is as follows：PLA-R1-PLA；
Wherein R1 is the residue of polyvalent alcohol, and PLA is the residue of polylactic acid；The acid of described polylactic acid-polyol blocks copolymer
Value is less than 10mgKOH/g；
Polyvalent alcohol in described polylactic acid-polyvalent alcohol block copolymer is selected from Polyethylene Glycol, polyoxypropyleneglycol, polyoxy
Change propylene triol, polytetrahydrofuran diol, appoint in 10PE27 glycol, polyadipate-BDO esterdiol
One or more of block copolymer.
2. organic nucleating agent as claimed in claim 1 is it is characterised in that be used for synthesizing described polylactic acid-polyvalent alcohol block
Polyvalent alcohol Mn value in copolymer is 500～20000.
3. organic nucleating agent as claimed in claim 1 is it is characterised in that in described polylactic acid-polyvalent alcohol block copolymer
Polylactic acid be poly (l-lactic acid), poly- D-ALPHA-Hydroxypropionic acid or poly (l-lactic acid) and poly- D-ALPHA-Hydroxypropionic acid block copolymer.
4. organic nucleating agent as claimed in claim 1 is it is characterised in that be used for synthesizing described polylactic acid-polyvalent alcohol block
The Mn value of the polylactic acid in copolymer is 700～10000.
5. organic nucleating agent as claimed in claim 1 is it is characterised in that in described polylactic acid-polyvalent alcohol block copolymer,
The percentage by weight of polylactic acid block is 50～99%, balance of polyvalent alcohol block.
6. the preparation method of organic nucleating agent described in claim 1-5 any claim, comprises the steps：
1) knead：Polylactic acid-polyvalent alcohol block copolymer is mixed by the composition according to aforementioned organic nucleating agent with polylactic acid, plus
Enter in banbury or double screw extruder, 150～260 DEG C carry out melt blending, obtain organic nucleating agent product；
2) following process of organic nucleating agent product or utilization.
7. described in claim 1-5 any claim, organic nucleating agent is being prepared in polylactic resin as nucleating agent in polylactic acid production
Application.
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| CN113004507B (en) * | 2021-03-08 | 2022-12-20 | 中国科学院长春应用化学研究所 | Rapidly-crystallized poly-L-lactic acid and preparation method thereof, and polylactic acid foam material and preparation method thereof |
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| CN101899139B (en) * | 2010-07-23 | 2012-02-29 | 同济大学 | Method for preparing polylactic acid-based high-elasticity copolymer |
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