CN102212257A - Calcium-carbonate-supported nucleating agent used for poly(lactic acid) crystallization and preparation method thereof - Google Patents
Calcium-carbonate-supported nucleating agent used for poly(lactic acid) crystallization and preparation method thereof Download PDFInfo
- Publication number
- CN102212257A CN102212257A CN2011100886428A CN201110088642A CN102212257A CN 102212257 A CN102212257 A CN 102212257A CN 2011100886428 A CN2011100886428 A CN 2011100886428A CN 201110088642 A CN201110088642 A CN 201110088642A CN 102212257 A CN102212257 A CN 102212257A
- Authority
- CN
- China
- Prior art keywords
- lactic acid
- poly
- lime carbonate
- nucleating agent
- calcium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Abstract
The invention discloses a calcium-carbonate-supported nucleating agent used for poly(lactic acid) crystallization and a preparation method thereof. The nucleating agent comprises the following composition formula: calcium carbonate and phenylphosphonic acid at a weight ratio of (5-40): 1, wherein calcium phenylphosphate generated by reaction of phenylphosphonic acid and calcium carbonate is used as an active ingredient and loaded on the surface of calcium carbonate, and phenyl phosphonic acid has a structural formula shown in the invention, in the formula, R1 and R2, the same or different, represent hydrogen atom, C1-10 alkyl or C1-10 alkoxycarbonyl. The nucleating agent can increase the effective nucleation sites formed by the high-degree dispersion of calcium phenylphosphate on the surface of calcium carbonate, thereby increasing nucleation efficiency as well as strengthening and toughening poly(lactic acid), avoiding the problem that poly(lactic acid) has poor toughness caused by non-supported nucleating agents, and facilitating the wide application of poly(lactic acid). The nucleating agent has a simple preparation method, low consumption of phenylphosphonic acid and significantly low cost.
Description
Technical field
The present invention relates to a kind of crystallization nucleating agent of poly(lactic acid), relate in particular to a kind of lime carbonate load poly(lactic acid) crystallization nucleating agent and preparation method thereof, belong to the biodegradated polymer materal technical field.
Background technology
Poly(lactic acid) (PLA) is a kind of thermoplasticity aliphatics polyester.Because it derives from reproducible plant resources, have excellent biological compatibility and biological degradability, higher mechanical strength and modulus, heigh clarity and workability, therefore poly(lactic acid) is considered to the ideal substitute of petroleum-based plastics, be applied to the general-purpose plastics field, have crucial meaning at aspects such as reducing environmental pollution and saving petroleum resources, caused that at present people pay close attention to widely.
Though polylactic acid based in recent years plastic prod occurs on market gradually, yet, the crystallization velocity of poly(lactic acid) is slow, especially add man-hour by injection moulding, have to improve the injection mold temperature, prolong and annotate the retention time of part in mould, so that it reaches certain degree of crystallinity and intensity, but this method shaping cycle is long, the spherulite size that forms is bigger, and this will cause the bad and fragility fracture of the product transparency.
In order to widen the range of application of poly(lactic acid), improve crystallization velocity and degree of crystallinity, improve forming process and thermotolerance, adding crystallization nucleating agent in poly(lactic acid) is a kind of very effective method.Nucleator when promoting crystalline growth, refinement crystalline size, is being brought into play the effect of the crystallization velocity that improves polymkeric substance as the nucleus of crystalline polymer.The crystallization nucleating agent of poly(lactic acid) mainly comprises inorganic nucleator and organic nucleating agent two classes at present, wherein inorganic nucleator has (Li HB such as talcum powder, polynite, calcium lactate, Huneault MA, Polymer48:6855,2007), the consistency of this class nucleator and poly(lactic acid) is poor, easily reunites in polymkeric substance and disperses inhomogeneous, crystalline rate is low, and how addition also can influence other performance of material.Organic nucleating agent such as lower molecular weight fatty amine, the metal-salt that contains the fatty acid metal salt of long carbochain and contain the phosphonic acids, phosphorous acid etc. of phenyl ring.Chinese patent (application number: 200580010634.4; 200810162837.0) nucleator of the metal-salt of phosphorus compound as poly(lactic acid) disclosed, effectively raise crystallization velocity, the thermotolerance of poly(lactic acid), make its forming process excellence.Yet the metal-salt of this class P contained compound and the consistency of poly(lactic acid) are also relatively poor, easily reunite, and disperse inhomogeneously, and efficient is not high, large usage quantity, and cost is higher, and these all will limit their application.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of lime carbonate load poly(lactic acid) crystallization nucleating agent is provided.This nucleator nucleation efficient height, consumption is few, cost is low and the preparation method is simple.
A kind of component prescription of lime carbonate load poly(lactic acid) crystallization nucleating agent is: the weight ratio of lime carbonate and phenyl-phosphonic acid is 5～40: 1; The phosphenylic acid calcium (PPCA) that phenyl-phosphonic acid and calcium carbonate reaction generate loads on the lime carbonate surface as activeconstituents; Described phenyl-phosphonic acid structural formula is:
In the formula, R
1And R
2Expression hydrogen atom, carbonatoms are that 1～10 alkyl, carbonatoms are 1～10 carbalkoxy, R
1And R
2Identical or different.
A kind of preparation method of lime carbonate load poly(lactic acid) crystallization nucleating agent is as follows: in reactor, lime carbonate is disperseed in acetone or chloroform, preferred acetone, add phenyl-phosphonic acid again, the weight ratio of lime carbonate and phenyl-phosphonic acid is 5～40: 1, at room temperature stir 4h, centrifugation is then filtered and is obtained white precipitate; Throw out is washed the unreacted phenyl-phosphonic acid of Ex-all, dry sediment with acetone or chloroform; The phosphenylic acid calcium (PPCA) that phenyl-phosphonic acid and calcium carbonate reaction generate loads on the lime carbonate surface as activeconstituents, obtains lime carbonate load poly(lactic acid) crystallization nucleating agent; Described lime carbonate size is any, preferred nanometer grade calcium carbonate.
Load poly(lactic acid) crystallization nucleating agent of the present invention with the lime carbonate of high-specific surface area as carrier, adopt simple blended method phenyl-phosphonic acid to be dispersed in the surface of lime carbonate, utilize the chemical reaction of phenyl-phosphonic acid and lime carbonate to generate P contained compound metal-salt phenyl-phosphonic acid calcium, the surface that the phenyl-phosphonic acid calcium of generation is dispersed in lime carbonate forms effective poly(lactic acid) crystallization nucleating agent.Owing to the high dispersing of the phenyl-phosphonic acid calcium that generates on the lime carbonate surface, and only at the surperficial nucleation site that forms mass efficient of lime carbonate, thereby the consumption of realization minimizing phenyl-phosphonic acid reduces cost, and improves the purpose of nucleation efficient.
A kind of usage of lime carbonate load poly(lactic acid) crystallization nucleating agent is as follows:
With the lime carbonate load poly(lactic acid) crystallization nucleating agent of the present invention preparation and poly(lactic acid) ratio by weight 1: 100～5: 100, join in the Banbury mixer, at 180 ℃, mixed 5-8 minute under 50 rev/mins the condition, mixed sample directly cools off under the air at room temperature state, obtains poly(lactic acid) crystallization product.
The poly(lactic acid) crystallization product of obtaining; cut into fritter and carry out DSC mensuration as testing sample: the testing sample of poly(lactic acid) crystallization product is under nitrogen protection; be raised to 190 ℃ with 50 ℃/min from room temperature; stop 2min and eliminate thermal history; be cooled to 0 ℃ with 10 ℃/min then; last secondary temperature elevation is warming up to 190 ℃ with 10 ℃/min from 0 ℃.The result of test as shown in Figure 3 and Figure 4.
The invention effect: 1. lime carbonate load poly(lactic acid) crystallization nucleating agent of the present invention with lime carbonate as carrier, the phenyl-phosphonic acid calcium high dispersing that makes the generation of phenyl-phosphonic acid and calcium carbonate reaction is on the lime carbonate surface, the effective nucleation site that forms increases, thereby has improved the nucleation efficient of nucleator;
2. lime carbonate load poly(lactic acid) crystallization nucleating agent of the present invention with lime carbonate as carrier, the usage quantity of phenyl-phosphonic acid only is 1/5 even 1/40 of a lime carbonate, and the amount less than 5% that the lime carbonate load poly(lactic acid) crystallization nucleating agent that makes only need add poly(lactic acid) just can reach significant nucleating effect, obviously reduce the consumption of phenyl-phosphonic acid, thereby realized the remarkable reduction of nucleator cost.
3. lime carbonate load poly(lactic acid) crystallization nucleating agent of the present invention as carrier, also can play enhancing toughness reinforcing effect to poly(lactic acid) with lime carbonate, has avoided unsupported nucleator to cause the problem of poly(lactic acid) poor toughness, helps the widespread use of poly(lactic acid).
4. lime carbonate load poly(lactic acid) crystallization nucleating agent of the present invention, preparation technology is simple, and used lime carbonate is with low cost.
Description of drawings
Fig. 1 is the DSC figure of phenyl-phosphonic acid (PPOA) and lime carbonate load poly(lactic acid) crystallization nucleating agent NA5.
Fig. 2 is nano-calcium carbonate (nano-CaCO
3), the infrared spectrogram of phenyl-phosphonic acid (PPOA) and nano-calcium carbonate load poly(lactic acid) crystallization nucleating agent NA5.
Fig. 3 is for adopting nano-CaCO
3With the 10 ℃/min decrease temperature crystalline DSC graphic representation of PPOA Different Weight than the load nucleator nucleation poly(lactic acid) of preparation.
Fig. 4 is for adopting nano-CaCO
3With the 10 ℃/min intensification fusion DSC graphic representation of PPOA Different Weight than the load nucleator nucleation poly(lactic acid) of preparation.
NA5, NA10, NA20, NA40 is respectively nano-CaCO
3With the weight ratio of PPOA be 5: 1,10: 1,20: 1, the lime carbonate load poly(lactic acid) crystallization nucleating agent that hybrid reaction after makes at 40: 1.
Embodiment
Embodiment 1 is scattered in nano-calcium carbonate in acetone or the chloroform in reactor, mixed in 5: 1,10: 1,20: 1 and 40: 1 in following ratio with phenyl-phosphonic acid respectively again, and stirring reaction 4h at room temperature, centrifugation is then filtered and is obtained white precipitate; Throw out is washed with acetone or chloroform respectively, the unreacted phenyl-phosphonic acid of Ex-all, dry sediment, the phosphenylic acid calcium (PPCA) that phenyl-phosphonic acid and calcium carbonate reaction generate loads on the lime carbonate surface as activeconstituents, obtains lime carbonate load poly(lactic acid) crystallization nucleating agent respectively.
Fig. 1 and Fig. 2 show that phenyl-phosphonic acid and nano-calcium carbonate react the loading type nucleator that has generated phenyl-phosphonic acid calcium and loaded on the nano-calcium carbonate surface.
A kind of usage of lime carbonate load poly(lactic acid) crystallization nucleating agent is as follows:
With the lime carbonate load poly(lactic acid) crystallization nucleating agent and the trade names of the present invention's preparation is the Natureworks4032D poly(lactic acid), ratio by weight 1: 100～5: 100, join in the Banbury mixer, at 180 ℃, mixed 5-8 minute under 50 rev/mins the condition, mixed sample directly cools off under the air at room temperature state, obtains poly(lactic acid) crystallization product.
The poly(lactic acid) crystallization product of obtaining; cut into fritter and carry out DSC mensuration as testing sample: the testing sample of poly(lactic acid) crystallization product is under nitrogen protection; be raised to 190 ℃ with 50 ℃/min from room temperature; stop 2min and eliminate thermal history; be cooled to 0 ℃ with 10 ℃/min then; last secondary temperature elevation is warming up to 190 ℃ with 10 ℃/min from 0 ℃.The result of test as shown in Figure 3 and Figure 4.
By Fig. 3 and Fig. 4 as can be seen, pure poly(lactic acid) does not have crystallization in 10 ℃/min temperature-fall period, cold crystallization occurs in the secondary temperature elevation process; Add 5% above-mentioned loading type nucleator, occur tangible peak crystallization in the temperature-fall period, and secondary temperature elevation do not have cold crystallization, show that the adding nucleating effect of the lime carbonate load poly(lactic acid) crystallization nucleating agent that the present invention prepares is fine, significantly promoted the crystallization of poly(lactic acid).
Lime carbonate load poly(lactic acid) crystallization nucleating agent and nano-calcium carbonate, the phenyl-phosphonic acid calcium of 1 preparation of embodiment 2 embodiment of the invention compare as nucleator, the nucleation ability of poly(lactic acid) is carried out differential scanning calorimetry (DSC) detect.
The testing method of DSC is: under nitrogen protection; be raised to 190 ℃ with 50 ℃/min from room temperature; stop 2min and eliminate thermal history; then with 45 ℃/min fast cooling to the isothermal crystal temperature; the isothermal crystal temperature is made as 130 ℃ and 140 ℃ herein; at 130 ℃ and 140 ℃ of difference isothermal crystals, test hypocrystalline time t
0.5Test result such as table 1.
Conclusion as can be drawn from Table 1: though nano-calcium carbonate and phenyl-phosphonic acid calcium have all played nucleogenesis to poly(lactic acid), significantly reduced the hypocrystalline time, but compare with the lime carbonate load poly(lactic acid) crystallization nucleating agent of the present invention's preparation, containing identical nucleation active ingredient, and when content is close, the sample hypocrystalline time of the lime carbonate load poly(lactic acid) crystallization nucleating agent of interpolation the present invention preparation is the shortest, for example, when 130 ℃ of isothermal crystals, the sample isothermal hypocrystalline time of adding 1.0%PPCA in PLA is 1.5min, and the lime carbonate load poly(lactic acid) crystallization nucleating agent of interpolation the present invention preparation, when its nucleation active ingredient PPCA was 0.75%, its isothermal hypocrystalline time only was 0.92min.
The nucleating effect of the lime carbonate load poly(lactic acid) crystallization nucleating agent of the present invention's preparation obviously is better than simple phenyl-phosphonic acid calcium.In addition, when identical, the nucleation active ingredient of the lime carbonate load poly(lactic acid) crystallization nucleating agent of required the present invention's preparation is minimum in the poly(lactic acid) hypocrystalline time.For example, when the isothermal hypocrystalline time is 1.5min, the addition of PPCA is 1.0%, and the contained nucleation active ingredient PPCA of the lime carbonate load poly(lactic acid) crystallization nucleating agent of the present invention's preparation only needs 0.096%, promptly under identical nucleating effect, the contained PPCA of the lime carbonate load poly(lactic acid) crystallization nucleating agent of the present invention preparation is 9.6% of a PPCA nucleator only seldom, greatly reduces the cost of nucleator.More than nucleating effects of lime carbonate load poly(lactic acid) crystallization nucleating agent of these explanation the present invention preparations best, obviously promoted the crystallization of poly(lactic acid).
Table 1 contains the poly(lactic acid) of different nucleators respectively 130 and 140 ℃ of isothermal crystal hypocrystalline times
Claims (4)
1. lime carbonate load poly(lactic acid) crystallization nucleating agent, it is characterized in that its component prescription is: the weight ratio of lime carbonate and phenyl-phosphonic acid is 5～40: 1; The phosphenylic acid calcium that phenyl-phosphonic acid and calcium carbonate reaction generate loads on the lime carbonate surface as activeconstituents; Described phenyl-phosphonic acid structural formula is:
In the formula, R
1And R
2Expression hydrogen atom, carbonatoms are that 1～10 alkyl, carbonatoms are 1～10 carbalkoxy, R
1And R
2Identical or different.
2. the preparation method of a kind of lime carbonate load poly(lactic acid) crystallization nucleating agent as claimed in claim 1, it is characterized in that, its step is as follows: in reactor, lime carbonate is disperseed in acetone or chloroform, add phenyl-phosphonic acid again, the weight ratio of lime carbonate and phenyl-phosphonic acid is 5～40: 1, at room temperature stirs 4h, centrifugation is then filtered and is obtained white precipitate; Throw out is washed the unreacted phenyl-phosphonic acid of Ex-all, dry sediment with acetone or chloroform; The phosphenylic acid calcium that phenyl-phosphonic acid and calcium carbonate reaction generate loads on the lime carbonate surface as activeconstituents, obtains lime carbonate load poly(lactic acid) crystallization nucleating agent; Described lime carbonate size is any; Described organic solvent is acetone or chloroform.
3. the preparation method of a kind of lime carbonate load poly(lactic acid) crystallization nucleating agent as claimed in claim 2 is characterized in that, described calcium carbonate nano level lime carbonate.
4. the preparation method of a kind of lime carbonate load poly(lactic acid) crystallization nucleating agent as claimed in claim 2 is characterized in that described organic solvent is an acetone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100886428A CN102212257A (en) | 2011-04-11 | 2011-04-11 | Calcium-carbonate-supported nucleating agent used for poly(lactic acid) crystallization and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100886428A CN102212257A (en) | 2011-04-11 | 2011-04-11 | Calcium-carbonate-supported nucleating agent used for poly(lactic acid) crystallization and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102212257A true CN102212257A (en) | 2011-10-12 |
Family
ID=44743808
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011100886428A Pending CN102212257A (en) | 2011-04-11 | 2011-04-11 | Calcium-carbonate-supported nucleating agent used for poly(lactic acid) crystallization and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102212257A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262917A (en) * | 2014-09-18 | 2015-01-07 | 浙江大学 | Preparation method of high-molecular polylactic acid (PLA) three-dimensional composite material capable of being crystallized rapidly |
| CN106565991A (en) * | 2017-01-03 | 2017-04-19 | 湖北光合生物科技有限公司 | Organized calcium based montmorillonite loaded polylactic acid crystal nucleating agent and preparation method thereof |
| CN106565992A (en) * | 2017-01-03 | 2017-04-19 | 湖北光合生物科技有限公司 | Starch loaded polylactic acid crystallization nucleating agent and preparation method thereof |
| CN113956640A (en) * | 2021-12-15 | 2022-01-21 | 中化泉州能源科技有限责任公司 | Biodegradable PLA film and preparation method thereof |
| CN116769253A (en) * | 2023-08-24 | 2023-09-19 | 山东路德新材料股份有限公司 | Geogrid modified polypropylene engineering plastic and preparation method and application thereof |
| WO2024047187A1 (en) * | 2022-09-02 | 2024-03-07 | Omya International Ag | Nucleating agent for polylactic acid formulation |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101020780A (en) * | 2007-03-15 | 2007-08-22 | 上海交通大学 | Prepn process of polylactic acid-base thermoplastic wood-plastic composite material |
| CN101792596A (en) * | 2010-03-25 | 2010-08-04 | 从化市聚赛龙工程塑料有限公司 | Composite material for recycling waste vehicle nylon products and preparation method thereof |
| WO2011030822A1 (en) * | 2009-09-09 | 2011-03-17 | 日産化学工業株式会社 | Method for producing phosphonic acid metal salt and thermoplastic resin composition containing phosphonic acid metal salt |
-
2011
- 2011-04-11 CN CN2011100886428A patent/CN102212257A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101020780A (en) * | 2007-03-15 | 2007-08-22 | 上海交通大学 | Prepn process of polylactic acid-base thermoplastic wood-plastic composite material |
| WO2011030822A1 (en) * | 2009-09-09 | 2011-03-17 | 日産化学工業株式会社 | Method for producing phosphonic acid metal salt and thermoplastic resin composition containing phosphonic acid metal salt |
| CN101792596A (en) * | 2010-03-25 | 2010-08-04 | 从化市聚赛龙工程塑料有限公司 | Composite material for recycling waste vehicle nylon products and preparation method thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262917A (en) * | 2014-09-18 | 2015-01-07 | 浙江大学 | Preparation method of high-molecular polylactic acid (PLA) three-dimensional composite material capable of being crystallized rapidly |
| CN106565991A (en) * | 2017-01-03 | 2017-04-19 | 湖北光合生物科技有限公司 | Organized calcium based montmorillonite loaded polylactic acid crystal nucleating agent and preparation method thereof |
| CN106565992A (en) * | 2017-01-03 | 2017-04-19 | 湖北光合生物科技有限公司 | Starch loaded polylactic acid crystallization nucleating agent and preparation method thereof |
| CN113956640A (en) * | 2021-12-15 | 2022-01-21 | 中化泉州能源科技有限责任公司 | Biodegradable PLA film and preparation method thereof |
| CN113956640B (en) * | 2021-12-15 | 2023-02-21 | 中化泉州能源科技有限责任公司 | Biodegradable PLA film and preparation method thereof |
| WO2024047187A1 (en) * | 2022-09-02 | 2024-03-07 | Omya International Ag | Nucleating agent for polylactic acid formulation |
| CN116769253A (en) * | 2023-08-24 | 2023-09-19 | 山东路德新材料股份有限公司 | Geogrid modified polypropylene engineering plastic and preparation method and application thereof |
| CN116769253B (en) * | 2023-08-24 | 2023-12-12 | 山东路德新材料股份有限公司 | Geogrid modified polypropylene engineering plastic and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102212257A (en) | Calcium-carbonate-supported nucleating agent used for poly(lactic acid) crystallization and preparation method thereof | |
| CN101490127B (en) | Aliphatic polyester resin composition and process for producing the same | |
| CN101544813B (en) | Rapid crystallization polylactic acid composite material and preparation method thereof | |
| CN103044872B (en) | Polylactic acid composition | |
| CN101845187B (en) | Oil-based viscosity reducer for raw oil conveyed through pipeline | |
| CN103396659B (en) | A kind of method accelerating crystallization of polylactic acid resin | |
| CN105001122A (en) | Polylactic acid organic nucleating agent as well as preparation method therefor and application thereof | |
| CN105062024B (en) | High transparency high-temperature resistant lactic acid composite material and preparation method thereof | |
| CN108424626A (en) | A kind of polylactic acid poly propylene carbonate composite material and preparation method | |
| CN103265797B (en) | Lactic acid composite material of a kind of high-crystallinity Wholly-degradable and preparation method thereof | |
| CN101622311A (en) | Polyester mixture comprising biodiesel | |
| CN102391635A (en) | Biological degradation foamed plastic and preparation method thereof | |
| Chen et al. | Sustainable composites from biodegradable polyester modified with camelina meal: synergistic effects of multicomponents on ductility enhancement | |
| CN102838858B (en) | Polylactic acid nucleating agent, preparation method and application thereof | |
| JP4996668B2 (en) | POLYLACTIC ACID RESIN COMPOSITION, PROCESS FOR PRODUCING POLYLACTIC ACID RESIN COMPOSITION, MOLDED ARTICLE, DESK HOLDER FOR MOBILE PHONE, MOBILE PHONE INTERNAL CHASSIS COMPONENT, ELECTRONIC DEVICE CASE, ELECTRONIC DEVICE INTRODUCTION COMPONENT | |
| CN104194293B (en) | Biological poly ester composition of a kind of rapid crystallization and preparation method thereof | |
| CN103102661B (en) | Rapid nucleating agent for polylactic resin | |
| CN104558847A (en) | Homo-polypropylene beta nucleating agent and preparation method thereof | |
| JP2008201863A (en) | Method for producing molded article of polylactic acid resin | |
| CN102190813B (en) | Nucleating agent, its preparation method and application | |
| Zhang et al. | Enhancement of the properties of poly (L-lactide)/poly (butylene adipate-co-terephthalate) blends by introduction of stereocomplex polylactide crystallites | |
| JP2010070621A (en) | Masterbatch and method for manufacturing the same | |
| CN109134293A (en) | A kind of polylactic acid efficient nucleation agent and the preparation method and application thereof | |
| CN106565992B (en) | A kind of starch load polylactic acid crystal nucleating agent and preparation method thereof | |
| CN110684288B (en) | Preparation method and application of special aid for improving polybutene-1 crystal form conversion rate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20111012 |