CN103965493A - Method for preparing high molecular weight vertical structure composite polylactic acid with melt stability characteristics - Google Patents
Method for preparing high molecular weight vertical structure composite polylactic acid with melt stability characteristics Download PDFInfo
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- CN103965493A CN103965493A CN201410195783.3A CN201410195783A CN103965493A CN 103965493 A CN103965493 A CN 103965493A CN 201410195783 A CN201410195783 A CN 201410195783A CN 103965493 A CN103965493 A CN 103965493A
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Abstract
The invention discloses a method for preparing a high molecular weight vertical structure composite polylactic acid with melt stability characteristics. The method comprises the following steps: firstly, carrying out drying treatment on L-polylactide and dextral polylactic acid in vacuum, and then mixing an initiator which can be completely dissolved into absolute ethyl alcohol with a cross-linking agent, and then adding a mixture to a fusion mixer; melting and blending under the conditions that the temperature is 170-200 DEG C and the rotating speed is 20-120 rpm (revolutions per minute) for 2-15 minutes. The prepared high molecular weight vertical structure composite polylactic acid not only has excellent melt stability, but also has strong recrystallization ability, and can ensure that the vertical structure composite polylactic acid crystal with high purity and high content is reformed in a molten product, so as to provide excellent heat resistance and weather fastness to the product. The possibility is also provided for preparation of a PLA product with high performance by virtue of a melt processing technology. Meanwhile, the preparation method provided by the invention is simple in process, high in efficiency, and easy for realization of large-scale industrial production.
Description
Technical field
The invention belongs to poly(lactic acid) preparing technical field, be specifically related to a kind of method that adopts melt blending-solid-state micro-crosslinking technological to prepare to have the high molecular Stereocomplex type poly(lactic acid) of melt stability characteristic.
Background technology
In recent decades, the fast development of macromolecular material provides very big facility for human lives.But, along with the worsening shortages of petroleum resources and day by day increasing the weight of of waste plastic environmental pollution, exploitation taking renewable resources as raw material, biodegradable macromolecular material substitutes the high molecular research of traditional petroleum base and is subject to the great attention of Global Academy and industry member.
Poly(lactic acid) (PLA) is the most potential a kind of bio-based biodegradable polymer.At present, its cost declines to a great extent with the improvement of large-scale industrial production and polymerization technique, will progressively substitute traditional petroleum base polymer and be widely used in the fields such as industrial packaging, electronic apparatus, automotive industry.But the existing some shortcomings part of PLA itself has seriously restricted its large-scale promotion application as general-purpose plastics and engineering plastics.The maximum operation (service) temperature of the PLA goods that the common method for processing forming such as wherein the most outstanding shortcoming is poor heat resistance, employing injection molding make only has 55 DEG C of left and right conventionally, is starkly lower than traditional petroleum base crystalline polymer materials such as polypropylene.
Stereocomplex is that the one that development in recent years is got up can significantly be improved the stable on heating effective way of PLA.It is reported, the fusing point of closely being piled up side by side Stereocomplex type (sc) the poly(lactic acid) crystal forming by Poly-L-lactic acid (PLLA) molecular chain contrary with these two kinds of configurations of dextrorotation poly(lactic acid) (PDLA) can reach 230 DEG C, exceeds approximately 50 DEG C than the fusing point of the single-component of the each self-forming of homopolymer (hc) crystal.In addition, compare with PDLA with simple PLLA, be thisly spaced by left-handed and dextrorotation molecular chain the sc crystal forming and also show more excellent mechanical property and anti-hydrolytic performance, there is very important using value.The Stereocomplex type poly(lactic acid) (sc-PLA) of high purity (more than 95%) can be prepared by solution method and melt-blending process.
Melt-processed is the method that suitability for industrialized production high molecular products is commonly used the most.But (weight-average molecular weight is greater than 1 × 10 for high molecular
4) sc-PLA, because its melt stability is very poor, after melt-processed, be difficult to form again highly purified sc crystal in goods.And the melting of sc crystal forms ability again and significantly weakens with the increase of molecular weight.When weight-average molecular weight is higher than 10
4when gmol, in the melt-processed goods of sc-PLA, tend to form a large amount of sc and hc crystal, and the formation meeting of hc crystal seriously weakens the useful effect that sc crystal should be brought into play in the time giving goods high performance (as heat-resisting in height, high strength and good hydrolytic resistance) simultaneously.Therefore the high molecular sc-PLA that, preparation has an excellent melt stability characteristic is extremely important to the range of application of widening PLA.
CN103333472A discloses a kind of method of the sc-PLA of improvement melt stability.The method is by solution blended process, polyoxyethylene glycol (PEG) to be incorporated in PLLA/PDLA blend, through vacuum-drying, in nitrogen atmosphere in 250～270 DEG C of meltings, then with after the steps such as the speed Slow cooling of 10 DEG C/min, prepare the PLLA/PDLA/PEG blend with melt stability.But, adopting the method while preparing sc-PLA, need to use a large amount of toxic reagents (as methylene dichloride etc.), and processing step is many, length consuming time, production efficiency is low, is not easy to realize the preparation of industrially scalable.In addition, under the hot conditions of 250～270 DEG C, easily there is thermal destruction in PEG molecular chain, and then cause the degraded of PLLA and PDLA.
Summary of the invention
The object of the invention is the problem existing for prior art, the preparation method that a kind of technique is simple efficiently, be easy to the high molecular Stereocomplex type poly(lactic acid) of suitability for industrialized production, melt stability excellence is provided.
The preparation method of the high molecular Stereocomplex type poly(lactic acid) with melt stability characteristic provided by the invention, comprises following processing step and condition:
(1) by Poly-L-lactic acid and dextrorotation poly(lactic acid) under vacuum tightness is less than 900Pa, in 50～80 DEG C of vacuum-dryings to water ratio lower than 200ppm;
(2) first 0.1-2.0 part linking agent and 0.1～2.0 part of initiator are dissolved in dehydrated alcohol completely, then itself and the Poly-L-lactic acid of 40～60 parts and the dextrorotation poly(lactic acid) of 60～40 parts are uniformly mixed;
(3) mixture is added in melt mixer, melt blending 2～15min under 170～200 DEG C of temperature, rotating speed 20～120rpm, obtains pulverous high molecular sc-PLA with excellent melt stability characteristic.
In above method, the umber of each material is weight part.
Preferably 0.3～1.0 part of the consumption of linking agent used in above method; Preferably 0.3～1.0 part of the consumption of initiator.
In above method, linking agent used is isocyanates linking agent, preferably any in cyanacrylate (TAIC), tolylene diisocyanate (TDI) or diphenylmethanediisocyanate (MDI).
In above method, initiator used is alkyl peroxide or alkyl peroxide thing, any in concrete preferably dicumyl peroxide (DCP), di-t-butyl peroxide (DTBP), hydrogen phosphide cumene (CHP) or tertbutyl peroxide (TBHP).
In above method, the weight-average molecular weight of Poly-L-lactic acid used is 1 × 10
4～5 × 10
5gmol, optical purity are greater than 92%; The weight-average molecular weight of dextrorotation poly(lactic acid) is 1 × 10
4～5 × 10
5gmol, optical purity are greater than 92%.
In above method, melt mixer used can be the small-sized torque rheometer of use for laboratory, can be also industrial large-scale torque rheometer or other other melting mixing devices similar to torque rheometer mixer functionalities.
Preferably 50～100rpm of rotating speed in above method, preferably 2～7min of melt blending time.
The present invention compared with prior art, has the following advantages:
(1) because the present invention is in the time preparing Stereocomplex type poly(lactic acid), solid-state micro-crosslinked technical measures are adopted, thereby it is micro-crosslinked successfully to have realized the right selectivity of PLLA/PDLA molecular chain in the opposition compound crystal of structure non-crystalline region, the formation of this micro-crosslinking structure not only can ensure that the molecular chain that forms in crystal is not to being destroyed when the melting again, and can promote molecular chain again to form the Stereocomplex N-type waferN of high purity (100%) to piling up side by side in melting-process of cooling, thereby make Stereocomplex type poly(lactic acid) obtain excellent melt stability.
(2) because the present invention is to prepare the production rate of the compound crystal of micro-linking agent opposition structure and the impact of degree of crystallinity added in Stereocomplex type poly(lactic acid) very little, in addition its only brings into play optionally effect of the amorphous phase of micro-crosslinked Stereocomplex N-type waferN in melt blending process, thereby can prepare the Stereocomplex type poly(lactic acid) of high-crystallinity (50% left and right).
(3) the melt blending temperature adopting in the time preparing Stereocomplex type poly(lactic acid) due to the present invention is between the second-order transition temperature and fusing point of sc-PLA, both can ensure the quick formation of high purity powdered form shape sc crystal in melt blending process, the solid-state micro-crosslinked favourable condition that provides of sc crystal is provided again, thereby can synchronously realize lightly crosslinked to sc crystal amorphous phase of the formation of high purity sc crystal and cross-linker molecules by a step melt blending of PLLA and PDLA, make obtained high molecular sc-PLA can also be completed into sc crystal after melting is repeatedly cooling, and fusing point and the degree of crystallinity of sc crystal remain unchanged substantially.This provides possibility for prepare high performance PLA goods by melt-processed technique.
(4) preparation method's technique provided by the invention is simple, and efficiency is high, is easy to realize large-scale industrial production.
Brief description of the drawings
Fig. 1 is the WAXD collection of illustrative plates of the embodiment of the present invention 1～8 and comparative example.
Fig. 2 is the DSC melting curve of the embodiment of the present invention 2.
Fig. 3 is the DSC melting curve of comparative example.
Fig. 4 is the WAXD collection of illustrative plates of application examples of the present invention and application comparative example.
Fig. 5 is the DMA storage modulus-temperature curve of application examples of the present invention and application comparative example.
Embodiment
Provide embodiment below so that the present invention is specifically described; but be necessary to be pointed out that at this following examples are only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field some nonessential improvement that content is made the present invention according to the present invention and adjustment still belong to protection scope of the present invention.
In addition, umber that what deserves to be explained is following examples and comparative example material used is weight part.
Embodiment 1
Weight-average molecular weight is respectively to 1 × 10
4gmol and 5 × 10
5gmol, optical purity are respectively 92% and 99.5% PLLA and PDLA under vacuum tightness is less than 900Pa, in 50 DEG C of vacuum-dryings to water ratio lower than 200ppm; First 0.3 part of MDI linking agent and 0.3 part of CHP initiator are dissolved in dehydrated alcohol completely, then itself and the PLLA of 60 parts and the PDLA of 40 parts are uniformly mixed; Mixture is added in the melt mixer of torque rheometer, melt blending 2min under 200 DEG C of temperature, rotor speed 120rpm, obtains pulverous sc-PLA.
Embodiment 2
Weight-average molecular weight is respectively to 2.1 × 10
5gmol and 1.2 × 10
5gmol, optical purity are respectively 98.5% and 99.5% PLLA and PDLA under vacuum tightness is less than 900Pa, in 60 DEG C of vacuum-dryings to water ratio lower than 200ppm; First 0.5 part of TAIC linking agent and 0.3 part of DCP initiator are dissolved in dehydrated alcohol completely, then itself and the PLLA of 50 parts and the PDLA of 50 parts are uniformly mixed; Mixture is added in the melt mixer of torque rheometer, melt blending 5min under 180 DEG C of temperature, rotor speed 60rpm, obtains pulverous sc-PLA.
Embodiment 3
Weight-average molecular weight is respectively to 2.1 × 10
5gmol and 1.2 × 10
5gmol, optical purity are respectively 98.5% and 99.5% PLLA and PDLA under vacuum tightness is less than 900Pa, in 60 DEG C of vacuum-dryings to water ratio lower than 200ppm; First 1.0 parts of TAIC linking agents and 1.0 parts of DCP initiators are dissolved in dehydrated alcohol completely, then itself and the PLLA of 50 parts and the PDLA of 50 parts are uniformly mixed; Mixture is added in the melt mixer of torque rheometer, melt blending 7min under 180 DEG C of temperature, rotor speed 50rpm, obtains pulverous sc-PLA.
Embodiment 4
Weight-average molecular weight is respectively to 5 × 10
5gmol and 1 × 10
4gmol, optical purity are respectively 99.5% and 92% PLLA and PDLA under vacuum tightness is less than 900Pa, in 70 DEG C of vacuum-dryings to water ratio lower than 200ppm; First 2.0 parts of TAIC linking agents and 2.0 parts of DCP initiators are dissolved in dehydrated alcohol completely, then itself and the PLLA of 40 parts and the PDLA of 60 parts are uniformly mixed; Mixture is added in the melt mixer of torque rheometer, melt blending 15min under 170 DEG C of temperature, rotor speed 20rpm, obtains pulverous sc-PLA.
Embodiment 5
Weight-average molecular weight is respectively to 5 × 10
5gmol and 1 × 10
4gmol, optical purity are respectively 95% and 95% PLLA and PDLA under vacuum tightness is less than 900Pa, in 70 DEG C of vacuum-dryings to water ratio lower than 200ppm; First 0.5 part of TAIC linking agent and 0.5 part of DCP initiator are dissolved in dehydrated alcohol completely, then itself and the PLLA of 50 parts and the PDLA of 50 parts are uniformly mixed; Mixture is added in the melt mixer of torque rheometer, melt blending 5min under 180 DEG C of temperature, rotor speed 60rpm, obtains pulverous sc-PLA.
Embodiment 6
Weight-average molecular weight is respectively to 5 × 10
5gmol and 1 × 10
4gmol, optical purity are respectively 95% and 95% PLLA and PDLA under vacuum tightness is less than 900Pa, in 80 DEG C of vacuum-dryings to water ratio lower than 200ppm; First 0.1 part of TDI linking agent and 0.1 part of DCP initiator are dissolved in dehydrated alcohol completely, then itself and the PLLA of 50 parts and the PDLA of 50 parts are uniformly mixed; Mixture is added in the melt mixer of torque rheometer, melt blending 5min under 180 DEG C of temperature, rotor speed 60rpm, obtains pulverous sc-PLA.
Embodiment 7
Weight-average molecular weight is respectively to 1.4 × 10
5gmol and 2.0 × 10
4gmol, optical purity are respectively 95% and 95% PLLA and PDLA under vacuum tightness is less than 900Pa, in 80 DEG C of vacuum-dryings to water ratio lower than 200ppm; First 0.5 part of MDI linking agent and 0.5 part of DTBP initiator are dissolved in dehydrated alcohol completely, then itself and the PLLA of 50 parts and the PDLA of 50 parts are uniformly mixed; Mixture is added in the melt mixer of torque rheometer, melt blending 4min under 190 DEG C of temperature, rotor speed 80rpm, obtains pulverous sc-PLA.By 0.1 part of initiator DCP and 0.1 part of linking agent TDI
Embodiment 8
Weight-average molecular weight is respectively to 2.1 × 10
5gmol and 1.2 × 10
5gmol, optical purity are respectively 95% and 95% PLLA and PDLA under vacuum tightness is less than 900Pa, in 50 DEG C of vacuum-dryings to water ratio lower than 200ppm; First 0.6 part of MDI linking agent and 0.6 part of DTBP initiator are dissolved in dehydrated alcohol completely, then itself and the PLLA of 50 parts and the PDLA of 50 parts are uniformly mixed; Mixture is added in the melt mixer of torque rheometer, melt blending 3min under 200 DEG C of temperature, rotor speed 100rpm, obtains pulverous sc-PLA.
Comparative example
Weight-average molecular weight is respectively to 2.1 × 10
5gmol and 1.2 × 10
5gmol, optical purity are respectively 98.5% and 99.5% PLLA and PDLA under vacuum tightness is less than 900Pa, in 60 DEG C of vacuum-dryings to water ratio lower than 200ppm, then PLLA and PDLA by etc. weight part be uniformly mixed; Mixture is added in the melt mixer of torque rheometer, melt blending 5min under 180 DEG C of temperature, rotor speed 60rpm, obtains pulverous sc-PLA.
Application examples
The Powdered sc-PLA that embodiment 2 is made joins in the barrel of micro-injection forming instrument, in the melt temperatures of 245 DEG C, the die temperature condition hemostasis moulding of 170 DEG C, prepares sc-PLA goods.
Application comparative example
The Powdered sc-PLA that comparative example is made joins in the barrel of micro-injection forming instrument, in the melt temperatures of 245 DEG C, the die temperature condition hemostasis moulding of 170 DEG C, prepares sc-PLA goods.
In order to investigate the thermal characteristics of high molecular sc-PLA prepared by the inventive method, the present invention first by embodiment 1-8 and comparative example gained for sample wide-angle X ray diffractor (WAXD) test, the results are shown in Figure 1; Secondly comparative example and embodiment 2 gained samples have been analyzed to its melt stability by melting-cooling-melting circulation experiment (intensification, rate of temperature fall are 10 DEG C/min) of differential scanning calorimeter (DSC), the results are shown in Figure 2,3; Characterize application examples and the crystalline texture composition of application comparative example gained sample and the content of sc crystal with WAXD subsequently, the results are shown in Figure 4; Finally use dynamic thermomechanical analysis apparatus (DMA) to evaluate application examples and the next thermotolerance of application comparative example gained sample, the results are shown in Figure 5.
As can be seen from Figure 1, the interpolation of initiator and linking agent is very little on the production rate of sc crystal in PLLA/PDLA blend and the impact of degree of crystallinity, and they are the energy sc crystal of (or 100%) formation high-crystallinity (approximately 50%) completely all.
As can be seen from Figure 3, the melt stability of the sc-PLA forming in high molecular PLLA/PDLA blend very poor (comparative example) after a melting recrystallization, generates a large amount of hc and sc crystal simultaneously; But after having added appropriate initiator and linking agent (embodiment 2), the melt stability of preparation-obtained sc-PLA is largely increased, after twice melting-cooling-melting circulation, sc crystal not only can be completed into, and its fusing point and melting enthalpy substantially remain unchanged (Fig. 2).These results fully show, the formation of micro-crosslinked (gel content is less than 10%) structure has significant strengthening effect to the melt stability of sc-PLA.
As can be seen from Figure 4, the sc-PLA preparing taking conventional scorification is raw material, the crystal generating in melt-processed goods is made up of jointly the hc crystal of 75% sc crystal and 25%, but the sc-PLA with excellent melt stability characteristic described in employing the present invention is raw material, can in melt-processed goods, form 100% sc crystal.DMA result shows, in goods, the existence meeting of a small amount of hc crystal seriously weakens the useful effect (seeing Fig. 5) that sc crystal should be brought into play in the time giving goods high heat resistance.When temperature is during higher than 180 DEG C, goods are lost mechanical strength substantially described in application comparative example, even but application examples resulting product under the hot conditions of 200 DEG C its modulus can also be with application comparative example the modulus 149 DEG C time comparable.
Claims (9)
1. a preparation method with the high molecular Stereocomplex type poly(lactic acid) of melt stability characteristic, processing step and the condition of the method are as follows:
(1) by Poly-L-lactic acid and dextrorotation poly(lactic acid) under vacuum tightness is less than 900Pa, in 50～80 DEG C of vacuum-dryings to water ratio lower than 200ppm;
(2) first 0.1～2.0 part of initiator and 0.1-2.0 part linking agent are dissolved in dehydrated alcohol completely, then itself and the Poly-L-lactic acid of 40～60 parts and the dextrorotation poly(lactic acid) of 60～40 parts are uniformly mixed;
(3) mixture is added in melt mixer, melt blending 2～15min under 170～200 DEG C of temperature, rotating speed 20～120rpm, obtains pulverous high molecular Stereocomplex type poly(lactic acid) with excellent melt stability characteristic.
In above method, the umber of each material is weight part.
2. the preparation method of the high molecular Stereocomplex type poly(lactic acid) with melt stability characteristic according to claim 1, in the method, the consumption of linking agent used is 0.3～1.0 part; The consumption of initiator used is 0.3～1.0 part.
3. the preparation method of the high molecular Stereocomplex type poly(lactic acid) with melt stability characteristic according to claim 1 and 2, in the method, linking agent used is isocyanates linking agent.
4. the preparation method of the high molecular Stereocomplex type poly(lactic acid) with melt stability characteristic according to claim 3, in the method, isocyanates linking agent used is any in cyanacrylate, tolylene diisocyanate or diphenylmethanediisocyanate.
5. the preparation method of the high molecular Stereocomplex type poly(lactic acid) with melt stability characteristic according to claim 1 and 2, in the method, initiator used is any in alkyl peroxide or alkyl peroxide thing.
6. the preparation method of the high molecular Stereocomplex type poly(lactic acid) with melt stability characteristic according to claim 5, in the method, alkyl peroxide used is dicumyl peroxide or di-t-butyl peroxide; Alkyl peroxide thing is hydrogen phosphide cumene or tertbutyl peroxide.
7. the preparation method of the high molecular Stereocomplex type poly(lactic acid) with melt stability characteristic according to claim 1 and 2, in the method, the weight-average molecular weight of Poly-L-lactic acid used is 1 × 10
4～5 × 10
5gmol, optical purity are greater than 92%; The weight-average molecular weight of dextrorotation poly(lactic acid) is 1 × 10
4～5 × 10
5gmol, optical purity are greater than 92%.
8. the preparation method of the high molecular Stereocomplex type poly(lactic acid) with melt stability characteristic according to claim 4, in the method, the weight-average molecular weight of Poly-L-lactic acid used is 1 × 10
4～5 × 10
5gmol, optical purity are greater than 92%; The weight-average molecular weight of dextrorotation poly(lactic acid) is 1 × 10
4～5 × 10
5gmol, optical purity are greater than 92%.
9. the preparation method of the high molecular Stereocomplex type poly(lactic acid) with melt stability characteristic according to claim 6, in the method, the weight-average molecular weight of Poly-L-lactic acid used is 1 × 10
4～5 × 10
5gmol, optical purity are greater than 92%; The weight-average molecular weight of dextrorotation poly(lactic acid) is 1 × 10
4～5 × 10
5gmol, optical purity are greater than 92%.
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| CN201410195783.3A CN103965493B (en) | 2014-05-09 | 2014-05-09 | There is the preparation method of the HMW Stereocomplex type PLA of melt stability characteristic |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105133081A (en) * | 2015-10-21 | 2015-12-09 | 浙江海正生物材料股份有限公司 | Thermal resistant polylactic acid fiber and preparation method thereof |
| CN108570145A (en) * | 2018-04-11 | 2018-09-25 | 四川大学 | A kind of preparation method of the miniature product of highly -branched high intensity polylactic acid |
| CN109337308A (en) * | 2018-08-30 | 2019-02-15 | 北京服装学院 | A kind of high Stereocomplex type poly-lactic acid material and preparation method thereof |
| CN111548504A (en) * | 2020-05-27 | 2020-08-18 | 四川大学 | Stereo composite polylactic acid material or product with excellent melt stability and melt processing performance and preparation method thereof |
| CN112300549A (en) * | 2020-11-02 | 2021-02-02 | 河南龙都天仁生物材料有限公司 | Manufacturing method of electronic cigarette filter tip |
| CN113975196A (en) * | 2021-11-06 | 2022-01-28 | 周敏 | Oral health compound and preparation method thereof |
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| CN114230986A (en) * | 2022-01-04 | 2022-03-25 | 浙江宏仕达科技股份有限公司 | Stereo composite crystal reinforced biodegradable material |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105133081A (en) * | 2015-10-21 | 2015-12-09 | 浙江海正生物材料股份有限公司 | Thermal resistant polylactic acid fiber and preparation method thereof |
| CN108570145A (en) * | 2018-04-11 | 2018-09-25 | 四川大学 | A kind of preparation method of the miniature product of highly -branched high intensity polylactic acid |
| CN109337308A (en) * | 2018-08-30 | 2019-02-15 | 北京服装学院 | A kind of high Stereocomplex type poly-lactic acid material and preparation method thereof |
| CN111548504A (en) * | 2020-05-27 | 2020-08-18 | 四川大学 | Stereo composite polylactic acid material or product with excellent melt stability and melt processing performance and preparation method thereof |
| CN111548504B (en) * | 2020-05-27 | 2021-10-22 | 四川大学 | Stereo composite polylactic acid material or product with excellent melt stability and melt processing performance and preparation method thereof |
| CN112300549A (en) * | 2020-11-02 | 2021-02-02 | 河南龙都天仁生物材料有限公司 | Manufacturing method of electronic cigarette filter tip |
| CN113975196A (en) * | 2021-11-06 | 2022-01-28 | 周敏 | Oral health compound and preparation method thereof |
| CN114010536A (en) * | 2021-11-06 | 2022-02-08 | 周敏 | Oral care compositions and methods of making the same |
| CN113975196B (en) * | 2021-11-06 | 2024-03-15 | 周敏 | Oral cavity health care compound and preparation method thereof |
| CN114010536B (en) * | 2021-11-06 | 2024-03-15 | 周敏 | Oral care composition and method of making same |
| CN114230986A (en) * | 2022-01-04 | 2022-03-25 | 浙江宏仕达科技股份有限公司 | Stereo composite crystal reinforced biodegradable material |
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