CN102875987A - Organic nucleating agent, preparation method thereof and application - Google Patents
Organic nucleating agent, preparation method thereof and application Download PDFInfo
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- CN102875987A CN102875987A CN2012104023342A CN201210402334A CN102875987A CN 102875987 A CN102875987 A CN 102875987A CN 2012104023342 A CN2012104023342 A CN 2012104023342A CN 201210402334 A CN201210402334 A CN 201210402334A CN 102875987 A CN102875987 A CN 102875987A
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Abstract
The invention relates to the field of high-molecular materials, in particular to an organic nucleating agent, a preparation method thereof and application. The organic nucleating agent comprises the following components in parts by weight: 1-100 parts of polylactic acid-polyol block copolymers and 0-50 parts of polylactic acid, wherein the structural general formula of the polylactic acid-polyol block copolymers is PLA-R1-PLA, wherein the R1 is polyol and the PLA is polylactic acid. The organic nucleating agent provided by the invention has the advantages that the copolymerized structure of the product is stable, the molecular weight distribution is even, the eutectic structure is complete, the crystallization rate of polylactic resin can be effectively promoted, the compatibility of polylactic acid blend is improved, the polylactic acid and polylactic acid composition products with excellent chemical resistance, heat resistance and better transparency are obtained, and the development and application prospect in the field of polylactic acid products is wide.
Description
Technical field
The present invention relates to polymeric material field, be specifically related to a kind of organic nucleating agent and preparation thereof and application.
Background technology
Poly(lactic acid) (PLA) is a kind of polymkeric substance with good biocompatibility; it derives from renewable resources farm crop (such as corn); the most outstanding advantage is biodegradability; it can be degradable by the occurring in nature microorganism after using; final carbonic acid gas and the water of generating; free from environmental pollution, highly beneficial to protection of the environment.Poly(lactic acid) has good mechanical property, thermoplasticity, fiberizability, transparency height, is applicable to the various working methods such as blowing, thermoplastic, and is easy to process, is decided to be the most rising type material of new millennium by industrial community.
But as engineering plastics, the shortcoming such as poly(lactic acid) exists crystallization rate slow, and the shrinking percentage of moulded products is large, matter is crisp.For this reason, both at home and abroad to the crystallization rate that how to improve poly(lactic acid), reduce its second-order transition temperature, how to improve the aspect such as its toughness and carried out more widely research.Wherein, adding crystallization nucleation auxiliary agent raising polymer crystallization speed is a kind of method of commonly using in polymer modification processing.Crystallization nucleating agent can be divided into organic and inorganic two large classes.Organic nucleating agent commonly used has alkaline metal salt and the long carbochain aliphatic carboxylic acid metal salt that contains phenyl ring, and research finds that the metal-salt of this class can cause the degraded of polyester, thereby reduces its mechanical property, thermal stability etc.Inorganic nucleator mainly contains polynite, TiO2, CaO, MgO, BaSO4, SiO2, Al2O3 etc., the advantage of this class nucleator is to reach the Nano Particle size, but in use there is agglomeration traits, is difficult in polymkeric substance, keep the Uniform Dispersion of nanoscale.
Patent CN1366004 utilizes twin screw extruder with nucleator and polyester material blend processing, improve the nucleator scattering problem and improved crystallizing polyester speed, but for biodegradable material, in the processing thermal destruction violent, also reduced molecular weight when improving crystallization velocity.
Number of patent application 201080032592.5, prepared polylactic acid stereoscopic composite and stated that it can be used as nucleator and uses, but this stereoscopic composite in building-up process, sneaked into traditional organic system and inorganic be nucleator, therefore being difficult to when using as nucleator proves that its nucleating effect is not the traditional nucleator that derives from these interpolations.And polylactic acid stereoscopic composite contains more end group group, will cause the thermal destruction of self and matrix resin with the polylactic resin melting mixing time, if degraded is violent, will have a strong impact on the use properties of goods.
Summary of the invention
The object of the invention is to overcome the defective of prior art, a kind of organic nucleating agent and preparation thereof and application are provided.Nucleator of the present invention and poly(lactic acid) and composition resin thereof have good consistency, can overcome traditional nucleator and reunite in polymkeric substance and disperse inhomogeneous disadvantage, effectively improve the crystal property of poly(lactic acid) and composition resin thereof.
The present invention at first discloses a kind of organic nucleating agent, and this organic nucleating agent comprises the component of following weight part:
Poly(lactic acid)-polyvalent alcohol segmented copolymer 1～100 weight part
Poly(lactic acid) 0～50 weight part
Wherein, the general structure of described poly(lactic acid)-polyvalent alcohol segmented copolymer is as follows: PLA-R1-PLA; Wherein R1 is polyvalent alcohol, and PLA is poly(lactic acid).
Further, described organic nucleating agent comprises the component of following weight part:
Poly(lactic acid)-polyvalent alcohol segmented copolymer 1～100 weight part
Poly(lactic acid) 1～50 weight part
Wherein, the general structure of described poly(lactic acid)-polyvalent alcohol segmented copolymer is as follows: PLA-R1-PLA; Wherein R1 is polyvalent alcohol, and PLA is poly(lactic acid).
More excellent, in described poly(lactic acid)-polyvalent alcohol segmented copolymer, the weight percent of poly(lactic acid) block is 50～99%, surplus is the polyvalent alcohol block.Preferably, in described poly(lactic acid)-polyvalent alcohol segmented copolymer, the weight percent of poly(lactic acid) block is 50～90%, and surplus is the polyvalent alcohol block.
More excellent, the acid number of described poly(lactic acid)-polyvalent alcohol segmented copolymer is lower than 10mgKOH/g.More excellent, the acid number of described poly(lactic acid)-polyvalent alcohol segmented copolymer is lower than 1mgKOH/g.Optimum, the acid number of described poly(lactic acid)-polyvalent alcohol segmented copolymer is lower than 0.05mgKOH/g.
More excellent, the monomer of the polyvalent alcohol in described poly(lactic acid)-polyvalent alcohol segmented copolymer is representative examples of saturated aliphatic polyester polyol, unsaturated aliphatic polyester polyvalent alcohol or aromatic polyester polyol.
More excellent, polyvalent alcohol in described poly(lactic acid)-polyvalent alcohol segmented copolymer is selected from polyoxyethylene glycol, poly(propylene oxide) polyvalent alcohol, polybutylene oxide polyvalent alcohol, polyoxypropyleneglycol, polyoxytrimethylene triol, polytetrahydrofuran diol, any one or more segmented copolymer in polybutadiene diol, polyethylene glycol adipate glycol, the poly-hexanodioic acid-BDO esterdiol.
Optimum, the polyvalent alcohol Mn value in described poly(lactic acid)-polyvalent alcohol segmented copolymer is 500～20000.Preferably, the polyvalent alcohol Mn value in described poly(lactic acid)-polyvalent alcohol segmented copolymer is 500～10000.
More excellent, the poly(lactic acid) in described poly(lactic acid)-polyvalent alcohol segmented copolymer is the segmented copolymer of poly (l-lactic acid), poly-D-ALPHA-Hydroxypropionic acid or poly (l-lactic acid) and poly-D-ALPHA-Hydroxypropionic acid.
More excellent, the Mn value of the poly(lactic acid) in described poly(lactic acid)-polyvalent alcohol segmented copolymer is 700～10000.
More excellent, the Mn value of the poly(lactic acid) in described poly(lactic acid)-polyvalent alcohol segmented copolymer is 700～5000.
In poly(lactic acid) of the present invention-polyvalent alcohol segmented copolymer, the poly(lactic acid) (PLA) of polyvalent alcohol (R1) both sides can be the identical poly(lactic acid) of the Nomenclature Composition and Structure of Complexes, also can be the different poly(lactic acid) of the Nomenclature Composition and Structure of Complexes.
More excellent, the molecular weight distribution of described poly(lactic acid)-polyvalent alcohol segmented copolymer is all less than or equal to 2.More excellent, the molecular weight distribution of described poly (l-lactic acid) and poly-D-ALPHA-Hydroxypropionic acid is all less than or equal to 1.5.
More excellent, described poly(lactic acid)-polyvalent alcohol segmented copolymer can for the poly(lactic acid) of single kind-polyvalent alcohol segmented copolymer, also can be the combination of two or more poly(lactic acid)-polyvalent alcohol segmented copolymer.
More excellent, described poly(lactic acid) is selected from one or more the combination in the segmented copolymer of poly (l-lactic acid), poly-D-ALPHA-Hydroxypropionic acid, poly (l-lactic acid) and poly-D-ALPHA-Hydroxypropionic acid.Be among the present invention, described poly(lactic acid) (poly(lactic acid) in the non-segmented copolymer) as organic one-tenth and agent composition can be the poly (l-lactic acid) of L optically active isomer homopolymerization, it can be the poly-D-ALPHA-Hydroxypropionic acid of D optically active isomer homopolymerization, can be 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 poly(lactic acid).Represent poly (l-lactic acid) by L, the poly-D-ALPHA-Hydroxypropionic acid of D representative, poly(lactic acid) can be expressed as among L, D, LD, DL, LDL, DLD, LDLDL, the DLDLD any one or more combination so.The Mn value of poly(lactic acid) is 700～10000, and preferred Mn value is 700～5000.
The rotational isomerism structure of poly (l-lactic acid) of the present invention is:
The rotational 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: the composition according to aforementioned organic nucleating agent mixes poly(lactic acid)-polyvalent alcohol segmented copolymer with poly(lactic acid), adds in Banbury mixer or the twin screw extruder, and 150～260 ℃ are carried out melt blending, obtains the organic nucleating agent product;
2) following process of organic nucleating agent product or utilization.
More excellent, step 1) adopts twin screw extruder to carry out melt blending, and the screw-rod structure of twin screw extruder is with mixed milling type or shear engagement type spiral shell Duan Weizhu, and screw speed is more than or equal to 50rpm.Preferably, screw speed is 80～200rpm.
More excellent, vacuumize or nitrogen protection in the step 1) melt blending process.
Poly (l-lactic acid) of the present invention and poly-D-ALPHA-Hydroxypropionic acid can adopt following method to be prepared: Pfansteihl or D-ALPHA-Hydroxypropionic acid are joined in the reactor, at first under mechanical stirring, vacuumize, dehydration is 1-3 hour under 70-90 ℃ the temperature, then be warming up to 100-180 ℃, vacuum degree control is reacted and is obtained poly (l-lactic acid) or poly-D-ALPHA-Hydroxypropionic acid after 5-30 hour below 10000Pa.
Wherein,, be preferably greater than and equal 99% respectively more than or equal to 95% for the preparation of the optical purity of the Pfansteihl of poly (l-lactic acid) and poly-D-ALPHA-Hydroxypropionic acid and D-ALPHA-Hydroxypropionic acid.
The raw material poly(lactic acid) of step 1)-polyvalent alcohol segmented copolymer can adopt following method to be prepared: 1) poly (l-lactic acid) and poly-D-ALPHA-Hydroxypropionic acid are mixed to join in the reactor, vacuumize under the agitation condition, temperature 150-240 ℃, vacuum degree control is below 3000Pa, and reaction 1-10 as a child obtained the block polymer of poly (l-lactic acid) and poly-D-ALPHA-Hydroxypropionic acid; 2) a kind of in the block polymer of poly (l-lactic acid), poly-D-ALPHA-Hydroxypropionic acid or poly (l-lactic acid) and poly-D-ALPHA-Hydroxypropionic acid or any two kinds are joined in the reactor, add simultaneously polyvalent alcohol, vacuumize under stirring, temperature 120-240 ℃, vacuum degree control is below 1000Pa, more excellent below 100Pa, react and obtained poly(lactic acid)-polyvalent alcohol segmented copolymer in 1-8 hour.
In the step 1), in twin screw equipment moment of torsion tolerance range, be lower than the nucleator fusing point by control twin screw the second half temperature, the organic nucleating agent product that twin-screw extrusion is obtained is Powdered nucleator.
More excellent, step 2) described following process obtains the organic nucleating agent powder for the organic nucleating agent product of previous step is pulverized.
More excellent, step 2) described following process obtains the organic nucleating agent powder for pulverizing after the organic nucleating agent product constant temperature of previous step or the crystallization that progressively heats up again.
More excellent, step 2) described following process be organic nucleating agent product with previous step in 80～200 ℃ of temperature ranges, pulverize again behind constant temperature or the crystallization 1～10h that progressively heats up, obtain the organic nucleating agent powder.
If the composition of organic nucleating agent only is poly(lactic acid)-polyvalent alcohol segmented copolymer, then the following process of this organic nucleating agent product be with one or more poly(lactic acid)-polyvalent alcohol segmented copolymer in 80～200 ℃ of temperature ranges, pulverize again behind constant temperature or the crystallization 1～10h that progressively heats up, obtain the organic nucleating agent powder.
Optimum, described organic nucleating agent powder median size is less than or equal to 300 μ m.Preferably less than or equal to 50 μ m; Be more preferably less than and equal 5 μ m.
More excellent, step 2) described following process also comprises common additives is added in the organic nucleating agent product.
More excellent, described common additives is one or more combinations in optothermal stabilizer, oxidation inhibitor, the hydrolysis-resisting agent.
Processing aid commonly used of the present invention also can add in the melt blending process of banburying or twin-screw extrusion, and is together mixing or extrude with organic nucleating agent.
The present invention also discloses aforementioned organic nucleating agent at last as the application of nucleating agent in polylactic acid production in the preparation polylactic resin.
The peak melting point of the organic nucleating agent that the present invention finally obtains is more than or equal to 190 ℃, and minimum acid number is lower than 0.05mgKOH/g, and can improve through further crystallization the eutectic structure of nucleator.Nucleator of the present invention can evenly add in the polylactic resin according to traditional processing mode after being prepared into powder, and the mode by melting mixing prepares becomes polylactic acid resin composition.In the limit of not destroying purpose of the present invention, also nucleator of the present invention can be made into first master batch and add to again in the polylactic resin, the mode by melting mixing prepares becomes polylactic acid resin composition.In the limit of not destroying purpose of the present invention, also can add common additive, such as optothermal stabilizer, oxidation inhibitor, hydrolysis-resisting agent, lubricant, releasing agent, comprise in the tinting material etc. of dyestuff and color one or more, be used for various uses with the form of polylactic acid resin composition together with nucleator of the present invention.The using method of organic nucleating agent of the present invention is: the ratio of organic nucleating agent with 0.1～5wt%(preferred 0.5～2.5wt%) is dispersed in the mixture of pure poly(lactic acid) or pure poly(lactic acid) and other polymkeric substance, and blending extrusion under molten state obtains to contain the polylactic resin polymkeric substance of organic nucleator by twin screw extruder or Banbury mixer.
Nucleator of the present invention can effectively promote the crystallization rate of polylactic resin, helps to improve the consistency of polylactic acid blend, obtains chemical resistant properties, excellent heat resistance, and then the excellent poly(lactic acid) of the transparency and composition article thereof and widespread use.Poly(lactic acid) and composition article thereof refer to the mixture of film, sheet, fiber, cloth, non-woven fabrics, injection-molded article, extrusion molding article, the empty products formed of Vacuum Pressure, blow molding product and other materials etc., can be used for textiles, packing, agricultural material, gardening material, civil construction material, stationery, toy, medical treatment product or other purposes.
As seen, nucleator preparation method of the present invention is simple, the peak melting point of the organic nucleating agent that finally obtains is more than or equal to 200 ℃, minimum acid number is lower than 0.05mgKOH/g, the crystallization rate that the copolymerization Stability Analysis of Structures of organic nucleating agent product, even molecular weight distribution, eutectic structure be perfect, can effectively promote polylactic resin, help to improve the consistency of polylactic acid blend, obtain chemical resistant properties, excellent heat resistance, and the transparency is poly(lactic acid) and composition article thereof preferably, has wide development and application prospect in polylactic acid-based goods preparation field.
Embodiment
Further set forth the present invention below in conjunction with embodiment.Should be understood that embodiment only is used for explanation the present invention, but not limit the scope of the invention.
Embodiment 1
(1) 100Kg Pfansteihl (optical purity of Pfansteihl equals 99%) raw material is joined in the reactor, at first under mechanical stirring, vacuumize, dehydration is 2 hours under 80 ℃ the temperature, then be warming up to 140 ℃ of temperature of reaction, vacuum degree control is at 5000Pa, react and obtain poly (l-lactic acid) after 8 hours, the Mn value is 715g/mol; Change kind and the reaction parameter of lactic acid, prepare different poly(lactic acid) homopolymer, as shown in table 1.
The preparation of table 1 poly(lactic acid) homopolymer
Embodiment 2
The PLLA-1 and the PDLA-1 that obtain among the embodiment 1 are mixed to join in the reactor, vacuumize under the agitation condition, 200 ℃ of temperature, vacuum tightness 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, and the Mn value is 3249g/mol.
Embodiment 3
The PLLA-2 and the PDLA-2 equimolar ratio that obtain among the embodiment 1 are mixed to join in the reactor, vacuumize under the agitation condition, 210 ℃ of temperature, vacuum tightness 500Pa, reaction 3 as a child obtained the block polymer of poly (l-lactic acid) and poly-D-ALPHA-Hydroxypropionic acid, numbering PLDA-2, and the Mn value is 4158g/mol.
Embodiment 4
PLLA-2 and polytetrahydrofuran diol are mixed to join in the reactor, vacuumize under stirring, 170 ℃ of temperature, vacuum tightness 400Pa reacts and obtained poly(lactic acid)-polyvalent alcohol segmented copolymer in 6 hours.Change poly(lactic acid), polyvalent alcohol and reaction parameter, prepare different poly(lactic acid)-polyvalent alcohol segmented copolymer, as shown in table 2.
The preparation of table 2 polylactic acid poly polyvalent alcohol segmented copolymer
Embodiment 5
With the PLAC-4 grind into powder of embodiment 4 preparations, median size is 30 microns, and fusing point is 201 ℃.Nucleating effect is shown in Table 7.
Embodiment 6
(1) with each 50 weight part of PLAC-1 and PLAC-2 among the embodiment 4, mix, extrude with twin screw extruder, rotating speed 100rpm, extruder temperature arranges as shown in table 3.Extrude rear acquisition nucleating agent in polylactic acid production product.
Table 3 extruder temperature
(2) the nucleating agent in polylactic acid production product grind into powder that step (1) is obtained, median size is 25 microns, fusing point is 205 ℃.Nucleating effect is shown in Table 7.
Embodiment 7
(1) PLLA-2 that embodiment 1 is prepared and each 25 weight part of PDLA-2, and the PLAC-3 of 1 weight part of embodiment 4 preparations mix, extrude with twin screw extruder, and rotating speed 140rpm, extruder temperature arranges as shown in table 4.Extrude rear acquisition nucleating agent in polylactic acid production product.
Table 4: extruder temperature
(2) the nucleating agent in polylactic acid production product grind into powder that step (1) is obtained, median size is 5 microns, fusing point is 215 ℃.Nucleating effect is shown in Table 7.
Embodiment 8
(1) PLAC-4 that embodiment 4 is prepared and each 50 weight part of PLAC-5, and 1 weight part PLDA-1 of embodiment 2 preparations mix, extrude with twin screw extruder, and rotating speed 200rpm, extruder temperature arranges as shown in table 5.Extrude rear acquisition nucleating agent in polylactic acid production product.
Table 5: extruder temperature
(2) the nucleating agent in polylactic acid production product that step (2) is obtained grind into powder after 80 ℃ of crystallizations in 6 hours to 200 ℃ that progressively heat up, median size is 16 microns, fusing point is 207 ℃.Nucleating effect is shown in Table 7.
Embodiment 9
(1) the 50 weight part PLAC-4 that embodiment 4 prepared, and 50 weight part PLDA-2 of embodiment 3 preparations mix, extrude with twin screw extruder, and rotating speed 80rpm, extruder temperature arranges as shown in table 7.Extrude rear acquisition nucleating agent in polylactic acid production product.
Table 6: extruder temperature
(2) the nucleating agent in polylactic acid production product that step (2) is obtained grind into powder after 80 ℃ of crystallizations in 6 hours to 200 ℃ that progressively heat up, median size is 300 microns, fusing point is 215 ℃.Nucleating effect is shown in Table 7.
Embodiment 10
1. experiment material
Inorganic nucleator: talcum powder, polynite (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, with various nucleators (inorganic nucleator talcum powder, polynite; And the nucleating agent in polylactic acid production of the present invention's preparation) adds pure PLA resin to (available from U.S. natureworks company according to weight ratio respectively, the poly(lactic acid) of article number 4032D) in company's product, with twin screw extruder or Banbury mixer nucleator is evenly spread in the pure PLA resin, obtain containing the PLA resin sample of nucleator as testing sample (A-F); With the pure PLA resin (available from U.S. natureworks company, the poly(lactic acid) of article number 4032D) that do not contain nucleator as the test comparison sample.
DSC testing method: utilize the U.S. Q100 of TA company type differential scanning calorimeter that above-mentioned sample (testing sample and comparative sample) is carried out respectively heat analysis.Sample quality 0.3 ~ 0.5mg, nitrogen protection in the test process.Test condition is as follows:
(1) be warming up to 180 ℃ from room temperature, temperature rise rate is 40 ℃/min;
(2) 180 ℃ are incubated 10 minutes;
(3) be cooled to 130 ℃, rate of temperature fall is 40 ℃/min;
Isothermal crystal is carried out in (4) 130 ℃ of lower insulations;
(5) obtain complete isothermal crystal peak after, be cooled to room temperature, speed is 40 ℃/min, finishes test.
3. data processing:
The isothermal crystal process can be carried out match with the Avrami equation.The general expression of Avrami equation is as follows:
Xt＝exp（-Kz·t
n）
By each sample resulting isothermal crystal peak in the DSC test is processed with the Avrami equation and converted, can obtain reflecting that each sample is at the data (t of 130 ℃ of isothermal crystal speed
1/2), t
1/2Numerical value is less, and its corresponding crystallization velocity is faster, and concrete outcome is listed in table 7.
Table 7 sample detection
4. experiment conclusion
As shown in Table 7, nucleator of the present invention can significantly improve the crystallization velocity of polylactic resin, obviously is better than traditional inorganic nucleator, such as talcum powder and polynite.
The above; it only is preferred embodiment of the present invention; be not to any formal and substantial restriction of the present invention; should be understood that; for those skilled in the art; under the prerequisite that does not break away from the inventive method, also can make some improvement and replenish, these improvement and replenish and also should be considered as protection scope of the present invention.All those skilled in the art, in the situation that does not break away from the spirit and scope of the present invention, a little change of making when utilizing the disclosed above technology contents, the equivalent variations of modifying and developing are equivalent embodiment of the present invention; Simultaneously, the change of any equivalent variations that all foundations essence technology of the present invention is done above-described embodiment, modify and differentiation, all still belong in the scope of technical scheme of the present invention.
Claims (10)
1. organic nucleating agent, this organic nucleating agent comprises the component of following weight part:
Poly(lactic acid)-polyvalent alcohol segmented copolymer 1～100 weight part
Poly(lactic acid) 0～50 weight part
Wherein, the general structure of described poly(lactic acid)-polyvalent alcohol segmented copolymer is as follows: PLA-R1-PLA; Wherein R1 is polyvalent alcohol, and PLA is poly(lactic acid).
2. organic nucleating agent as claimed in claim 1 is characterized in that, in the composition of described organic nucleating agent, the weight part of poly(lactic acid) is 1～50 weight part.
3. such as claim 1 or the described organic nucleating agent of 2 arbitrary claims, it is characterized in that the monomer of the polyvalent alcohol in described poly(lactic acid)-polyvalent alcohol segmented copolymer is representative examples of saturated aliphatic polyester polyol, unsaturated aliphatic polyester polyvalent alcohol or aromatic polyester polyol.
4. organic nucleating agent as claimed in claim 3, it is characterized in that, polyvalent alcohol in described poly(lactic acid)-polyvalent alcohol segmented copolymer is selected from polyoxyethylene glycol, poly(propylene oxide) polyvalent alcohol, polybutylene oxide polyvalent alcohol, polyoxypropyleneglycol, polyoxytrimethylene triol, polytetrahydrofuran diol, any one or more segmented copolymer in polybutadiene diol, polyethylene glycol adipate glycol, the poly-hexanodioic acid-BDO esterdiol.
5. organic nucleating agent as claimed in claim 4 is characterized in that, the polyvalent alcohol Mn value in described poly(lactic acid)-polyvalent alcohol segmented copolymer is 500～20000.
6. such as claim 1 or the described organic nucleating agent of 2 arbitrary claims, it is characterized in that the poly(lactic acid) in described poly(lactic acid)-polyvalent alcohol segmented copolymer is the segmented copolymer of poly (l-lactic acid), poly-D-ALPHA-Hydroxypropionic acid or poly (l-lactic acid) and poly-D-ALPHA-Hydroxypropionic acid.
7. organic nucleating agent as claimed in claim 6 is characterized in that, the Mn value of the poly(lactic acid) in described poly(lactic acid)-polyvalent alcohol segmented copolymer is 700～10000.
8. such as claim 1 or the described organic nucleating agent of 2 arbitrary claims, it is characterized in that in described poly(lactic acid)-polyvalent alcohol segmented copolymer, the weight percent of poly(lactic acid) block is 50～99%, surplus is the polyvalent alcohol block.
9. the preparation method of the described organic nucleating agent of the arbitrary claim of claim 1-8 comprises the steps:
1) mixing: the composition according to aforementioned organic nucleating agent mixes poly(lactic acid)-polyvalent alcohol segmented copolymer with poly(lactic acid), adds in Banbury mixer or the twin screw extruder, and 150～260 ℃ are carried out melt blending, obtains the organic nucleating agent product;
2) following process of organic nucleating agent product or utilization.
10. the described organic nucleating agent of the arbitrary claim of claim 1-8 is as the application of nucleating agent in polylactic acid production in the preparation polylactic resin.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104327471A (en) * | 2014-11-18 | 2015-02-04 | 中国科学院长春应用化学研究所 | Polylactic acid three-dimensional complex |
| CN113004507A (en) * | 2021-03-08 | 2021-06-22 | 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 |
| CN115449202A (en) * | 2022-10-21 | 2022-12-09 | 合肥工业大学 | Polylactic acid composite material with high heat deformation resistance and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104327471B (en) * | 2014-11-18 | 2017-02-22 | 中国科学院长春应用化学研究所 | Polylactic acid three-dimensional complex |
| CN113004507A (en) * | 2021-03-08 | 2021-06-22 | 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 |
| CN115449202A (en) * | 2022-10-21 | 2022-12-09 | 合肥工业大学 | Polylactic acid composite material with high heat deformation resistance and preparation method thereof |
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| CN102875987B (en) | 2017-03-01 |
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