CN103242632A - Polylactic acid degradable foaming material and preparation method thereof - Google Patents
Polylactic acid degradable foaming material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of materials, and relates to a degradable foaming material and a preparation method thereof. The foaming material is prepared from the following components in parts by weight: 100 parts of polylactic acid resin, 0-5 parts of an antioxidant, 3-8 parts of an internal demolding agent, 1-3 parts of a crosslinking agent, 0.5-1.5 parts of an assistant crosslinking agent, 0-2 parts of an air bubble nucleating agent, 1-5 parts of a foaming agent, 0-2.5 parts of an assistant foaming agent and 10-40 parts of a melt strength improving material. According to the preparation method, the foaming material is prepared by using the foaming agent, the preparation process of the foaming material is simple, the application range of the foaming material is wide, biodegradation can be realized, the degradation period is relatively short, and the foaming porosity for preparing the foaming material is 40-98%.
Description
Technical field
The invention belongs to the material technology field, relate to a kind of degradable foam materials and preparation method.
Background technology
The degradative plastics of industrialization at present comprises: poly(lactic acid) (PLA), polyvinyl alcohol (PVA), thermoplastic starch plastic, poly butylene succinate (PBS) etc.PLA generates lactic acid by corn fermentation, generates through polyreaction.PLA has the degradable function, biocompatibility, and processability is outstanding, the performance that permeability is good.The monomer source of PLA is abundant, and its degraded product is CO
2And H
2O not only can participate in the circulation of the Nature, and can participate in the metabolism of human body, therefore has been subjected to paying close attention to widely; Mechanical property and physicals are good, are applicable to blowing, thermoplastic, injection moulding, and its product is applicable to food product pack, medical device, civilian mulch film etc.The second-order transition temperature of PLA is about 50 ℃, and melt temperature is about 150 ℃, and tensile break strength is about 50～70MPa, elongation at break is 5%, and shock strength is 15～30J/m, and its initial degradation temperature is about 320 ℃, similar to PP, its application is promoted on a large scale.
Utilize the preparation method of PLA foam material to mainly contain two kinds of forms at present.First kind is to utilize whipping agent and PLA to carry out blend to extrude, and more than the foaming agent decomposition temperature and below the PLA degradation temperature, makes whipping agent produce gas, forms foaming structure.Second kind is to utilize supercutical fluid (CO
2Or N
2) utilize machining process, prepare the foam of little foaming structure.
Brilliance great achievement company is mixed PLA with the EXPAMCEL microballoon, the extrusion moulding polylactic acid sheet material in forcing machine with PLA particle and foam microspheres.In the extrusion, PLA and foam microspheres fully mix, and microballoon is heated, and produce to expand, and make the melt of PLA present foamed state, obtain smooth smooth PLA foam material through the roll extrusion of twin shaft pressure roller machine.U.S. SEAlAIR company utilizes the blend of amorphous PLA and hemicrystalline PLA and HCFC class whipping agent as starting material, utilizes forcing machine, and extrusion molding prepares the PLA foam sheet continuously.The use temperature of this foam material can not be above 65 ℃.In the patent 200680010446 with PLA, polyolefin resin, polyolefin resin multipolymer, multi-functional monomer, thermolysis type whipping agent joins in the forcing machine, is shaped to sheet material, obtain foamable resin composition, and to this sheet layer material irradiation ionization radial line, make resin crosslinks.Then the flap after crosslinked is heated to more than the decomposition temperature of decomposability whipping agent, whipping agent is decomposed, thereby produce the foam of PLA.Among the patent US20100120932, adopt PLA, polyolefin resin, PP resin, vinyl acetate modified polyolefin resin and AC whipping agent are mediated all resins (comprising linking agent) as foaming raw material by forcing machine, make it mediate the decomposition temperature that temperature is lower than the whipping agent material, these materials are kneaded into thin slice, with under these material fabric ionizing radiations, form crosslinked thin plate then.The PLA resins that ponding changes into product industrial utilization high-crystallinity goes out expanded bead, this kind bead is positioned over foaming in the mould, adopt the material of this prepared under 150 ℃, still can keep mechanical property preferably, improved the high-temperature stability of material greatly.Shanxi Province chemical research institute researches and develops the special-purpose nucleator TMC-328 of successful PLA, belongs to the multiamide compounds of innovation structure, and nonpoisonous and tasteless, to PLA, PET, crystalline materials such as PBT have good nucleation promoter action.
Qi Bing places autoclave with the PLA sample, and heats in oil bath.Listening high-pressure metering pump to feed a certain amount of CO2 in autoclave, is sc-CO2 swollen polymer under certain temperature and pressure.Through one hour, fast pressure relief, the supersaturated gas that is dissolved in this moment in the polymeric matrix produces gas nuclear, and the abscess growth forms foam material.Utilize the electronic microscope photos blowing temperature, saturation pressure, the degree of crystallinity of release speed and PLA is to the influence of foam performance.The result shows that blowing temperature is about 108 ℃, and saturation pressure is at 23MPa, and release speed is that PLA can form cavity uniformly under the 300MPa.Temperature continues to raise, and saturation pressure continues to increase, and release speed continues to increase, and then the bubble sky of Xing Chenging subsides easily and forms UNICOM's structure; But temperature reduces, and saturation pressure descends, and release speed reduces, and it is less to form the empty density of bubble, and the aperture is very little; And improve blowing temperature and with the increase saturation pressure identical effect is arranged.The degree of crystallinity of PLA raises, and makes foamable interval narrow down, and PLA is difficult to foaming.Ningbo Material Technology and Engineering Inst. is by carrying out modification and adopting the supercritical CO 2 fluid as whipping agent to the PLA resin, can prepare 20～45 times of PLA foaies with good post forming ability that expansion ratio is controlled, the anti-temperature more than 100 ℃ of material.Japan's clock spins the foam molding of company's exploitation expanded polylactic acid plate and the preparation of expanded bead method as the substitute (Japanese Patent JP2002179832) of polystyrene foamed, at first with PLA expanded bead water steam-heated cal(l)andria, deliver in the forming mould, with the foaming of the water vapour of higher temperature heating essence, the foaming in the progressive type that bonds mutually.This method needs water vapour to produce equipment and mould is had relatively high expectations, and the density refractory of foam material is with control; Toray company adopts micro-/ nano foaming technique and continuous fusion extrusion foaming technology to combine, and realizes the foam material of the frothing percentage of high voidage 98%.Utilize the injection moulding machine micropore plastic product that can be shaped, the PLA raw material is all in the barrel of injection moulding machine, outside screw rod shearing power and heating collar, plastify under the effect of heating, whipping agent directly injects, evenly mix with melt at injection screw melt zone end, and high pressure injects die cavity then.Suddenly step-down is that supersaturated gas a large amount of in the melt emanates out in die cavity, and foaming is expanded, moulding, and typing forms micropore plastic product.
Summary of the invention
The objective of the invention is to provides a kind of PLA foam material and preparation method thereof for the defective that overcomes prior art.
For achieving the above object, the technical solution used in the present invention is as follows:
A kind of foam material, this foam material is made by the component that comprises following weight part:
100 parts of poly(lactic acid) (PLA) resins,
0～5 part of antioxidant,
3～8 parts of inner pattern releasing agent applicables,
1～3 part of linking agent,
0.5～1.5 part of additional crosslinker
0～2 part of bubble nucleating agent,
1～5 part of whipping agent,
0～2.5 part of blowing promotor,
Melt strength improves 10～40 parts of materials.
The melting index of described poly(lactic acid) (PLA) resin is 1～20g/10min, preferred (1～10) * 10 of sticking equal molecular mass
5G/mol;
Described antioxidant is selected from four { β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid } one or more of pentaerythritol ester, (3,5-di-tert-butyl-hydroxy phenyl) propionic acid stearyl alcohol ester, Tyox B or phosphorous acid benzene two isodecyl esters.The purpose of oxidation inhibitor is degraded and/or the oxidation for poly(lactic acid) in the process that is reduced in the preparation matrix material.
Described linking agent is selected from dicumyl peroxide (DCP) or dual-tert-butyl peroxidation diisopropyl benzene (BIBP) etc.
Described additional crosslinker is iso-cyanuric acid triallyl ester (TAIC).
Described bubble nucleating agent is talcum powder, CaCO
3Or polynite etc., its order number is 1000～5000 orders.
Described inner pattern releasing agent applicable is selected from polyoxyethylene glycol (PEG), low molecular weight polyethylene, Yelkin TTS releasing agent, Zinic stearas, stearin or Tristearoylglycerol, and the melt temperature of described inner pattern releasing agent applicable is 50～70 ℃, and decomposition temperature is greater than 230 ℃.
Described whipping agent is Cellmic C 121, AC whipping agent or expancel whipping agent etc., and the decomposition temperature of described whipping agent is 160～220 ℃.
The zinc oxide (ZnO) that described blowing promotor is selected and the AC whipping agent is used if select the Expancel whipping agent, is not then selected blowing promotor.
Selected melt strength improves material and refers to can form partial cross-linkedly under the linking agent effect with poly(lactic acid), and the material that improves melt strength is selected from vinyl acetate modified olefine kind resin or methyl methacrylate-cinnamic multipolymer.
A kind of preparation method of above-mentioned foam material, it comprises following steps:
(1) takes by weighing each component raw material by said ratio, with poly(lactic acid) (PLA) resin 100 weight parts, oxidation inhibitor 0～5 weight part, 1～3 part of linking agent, 0.5～1.5 part of additional crosslinker, 0～2 part of bubble nucleating agent, 1～5 part of whipping agent, 0～2.5 part of blowing promotor, melt strength improve 10～40 parts of materials, 3～8 parts of inner pattern releasing agent applicables mix above-mentioned substance;
(2) mixture that makes in the step (1) being joined twin screw extruder extrudes pelletizing and obtains modified polylactic resin material grain.
The mixing time of described step (1) is 3～7 minutes.
In the described step (2), screw speed is 10～250r/min, and extrusion temperature is 150～190 ℃.
The present invention utilizes whipping agent to prepare foam material, and this foam material preparation process is simple, has wide range of applications, and can realize biological degradation, and degradation cycle is shorter.The foaming porosity of preparation foam material is 40～98%.Compared with prior art, the present invention has the following advantages and effect:
1, because poly(lactic acid) is a kind of organism-based raw material, its renewable loop cycle is shorter, can effectively substitute petroleum-based foam material.
2, poly(lactic acid) is a kind of raw material of food grade, therefore after the preparation, can be used for food product pack etc.
3, the control that can prepare of the blowing temperature of poly(lactic acid) can guarantee that the blowing temperature range is little.
4, utilize the foam material of this method preparation, can effectively degrade, to alleviate white pollution.
5, utilizing melt strength to improve material can guarantee in foaming process, abscess subside and the hole phenomenon effectively reduce, and utilize the vinyl acetate between to for plastic material that it is improved, can also improve the interface compatibility of material, guarantee the homogeneity of the mixing of foam material.
6, dual-tert-butyl peroxidation diisopropyl benzene (BIBP) linking agent of selecting for use in addition, its toxicity is less, can satisfy the application of food grade.
7, because poly(lactic acid) itself is a kind of hard brittle material, be rigid plastics through the material that obtains after the foaming, improve material by adding melt strength, can prepare the less foam material of hardness.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described, and components contents is weight part among the embodiment.
Following embodiment, if no special instructions, PLA all passed through vacuum-drying before mixing, and drying temperature is 65～90 ℃, and the time is 8h.
Embodiment 1
With 100 parts of polylactic acid PLAs, 3 parts of dual-tert-butyl peroxidation diisopropyl benzene BIBP, 1 part of iso-cyanuric acid triallyl ester TAIC, 5 parts of polyoxyethylene glycol PEG, 2 parts of AC whipping agents, 0.5 part of CaCO
310 parts of vinyl acetate modified olefine kind resins, 0.5 part four { β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid } pentaerythritol ester mixed in mixing tank 3 minutes, join twin screw extruder after fully mixing and extrude pelletizing, screw speed is 80r/min, and extrusion temperature is 150 ℃, obtains the PLA foaming master batch.
The PLA foaming master batch is carried out compression molding, and temperature is 180 ℃, and pressure is 5MPa, time is 3 minutes, it is put pressure, and with after-applied 7MPa pressure, the time is 3 minutes, put pressure, continue to apply 10MPa pressure, the time is 3 minutes, takes out, measure the pore size of foam material, and this moment material density.The performance test results sees Table 1.
Embodiment 2
With 100 parts of polylactic acid PLAs, 1 part of dicumyl peroxide DCP, 0.5 part iso-cyanuric acid triallyl ester TAIC, 3 parts of low molecular weight polyethylenes, 2 parts of AC whipping agents, 2.5 part zinc oxide, 0.5 part talcum powder, 20 parts of methyl methacrylates and cinnamic multipolymer, 1 part of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid stearyl alcohol ester mixed in mixing tank 5 minutes, join twin screw extruder after fully mixing and extrude pelletizing, screw speed is 40r/min, and extrusion temperature is 180 ℃, obtains the PLA foaming master batch.
The PLA foaming master batch is carried out compression molding, and temperature is 175 ℃, and pressure is 5MPa, and the time is 3 minutes, puts pressure, continues to apply pressure to 10MPa, and pressurize 5 minutes is taken out then, measures the pore size of foam material, and this moment material density.The performance test results sees Table 1.
Embodiment 3
With 100 parts of polylactic acid PLAs, 2 parts of dicumyl peroxide DCP, 1 part of iso-cyanuric acid triallyl ester TAIC, 6 parts of Zinic stearass, 3 parts of AC whipping agents, 1.5 parts of zinc oxide, 0.5 part of polynite, 25 parts of methyl methacrylates and cinnamic multipolymer, 2 parts of Tyox Bs mixed in mixing tank 7 minutes, joined twin screw extruder after fully mixing and extruded pelletizing, and screw speed is 250r/min, extrusion temperature is 170 ℃, obtains the PLA foaming master batch.
The PLA foaming master batch is carried out compression molding, and temperature is 173 ℃, and pressure is 5MPa, and the time is 10 minutes, takes out then, measures the pore size of foam material, and this moment material density.The performance test results sees Table 1.
Embodiment 4
With 100 parts of polylactic acid PLAs, 2 parts of dual-tert-butyl peroxidation diisopropyl benzene DCP, 1 part of iso-cyanuric acid triallyl ester TAIC, 6 parts of Zinic stearass, 5 parts of AC whipping agents, 0.5 part of zinc oxide, 2 parts of polynites, 30 parts of methyl methacrylates and cinnamic multipolymer, 4 parts of phosphorous acid benzene two isodecyl esters mixed in mixing tank 5 minutes, joined twin screw extruder after fully mixing and extruded pelletizing, and screw speed is 60r/min, extrusion temperature is 160 ℃, obtains the PLA foaming master batch.
The PLA foaming master batch is carried out compression molding, and temperature is 173 ℃, and pressure is 5MPa, and the time is 10 minutes, takes out then, measures the pore size of foam material, and this moment material density.The performance test results sees Table 1.
Embodiment 5
With 100 parts of polylactic acid PLAs, 2 parts of dual-tert-butyl dicumyl peroxide BIBP, 1.5 parts of iso-cyanuric acid triallyl ester TAIC, 8 parts of inner pattern releasing agent applicable stearins, 1 part of Expancel whipping agent, 30 parts of vinyl acetate modified olefine kind resins, 5 parts of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid stearyl alcohol esters mixed in mixing tank 5 minutes, join twin screw extruder after fully mixing and extrude pelletizing, screw speed is 60r/min, and extrusion temperature is 160 ℃, obtains the PLA foaming master batch.
The PLA foaming master batch is carried out compression molding, and temperature is 178 ℃, and pressure is 3MPa, and the time is 2 minutes, puts pressure, and pressure increases to 6MPa then, and the time is 5 minutes, takes out then, measures the pore size of foam material, and this moment material density.The performance test results sees Table 1.
Embodiment 6
With 100 parts of polylactic acid PLAs, 2 parts of dicumyl peroxide DCP, 1 part of iso-cyanuric acid triallyl ester TAIC, 4 parts of inner pattern releasing agent applicable Tristearoylglycerols, 5 parts of Expancel whipping agents, 0.5 part of CaCO
3, 40 parts of vinyl acetate modified olefine kind resins mixed in mixing tank 5 minutes, joined twin screw extruder after fully mixing and extruded pelletizing, and screw speed is 10r/min, and extrusion temperature is 160 ℃, obtains the PLA foaming master batch.
The PLA foaming master batch is carried out compression molding, and temperature is 178 ℃, and pressure is 3MPa, and the time is 2 minutes, puts pressure, and pressure increases to 6MPa then, and the time is 5 minutes, takes out then, measures the pore size of foam material, and this moment material density.The performance test results sees Table 1.
Table 1
| Typical case's performance | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Density (kg/m3) | 0.54 | 0.53 | 0.46 | 0.38 | 0.60 | 0.48 |
| Porosity (%) | 56.8 | 57.6 | 63.2 | 69.6 | 52 | 61.6 |
| Tensile strength (MPa) | 15 | 14 | 12 | 10 | 13 | 12 |
| Bubble aperture (μ m) | 703 | 832 | 957 | 980 | 1210 | 1030 |
Annotate: wherein the bubble aperture is mean value.
In embodiment 1 process, because the pressure selection is bigger, so the bubble aperture of foam material is less, and by finding with the contrast of embodiment 2, under the same pressure, foam material is repeatedly put pressure, can reduce the bubble aperture of foam material.
The melt strength that adds improves the tensile strength that material can reduce foam material, this is because melt strength improves the tensile strength that the tensile strength of material is lower than poly(lactic acid), and along with melt strength improves the increase of material, the tensile strength of its foam material can be more and more lower.
From the top data polylactic acid foam material of Expancel whipping agent preparation as can be seen, its density and crafters footpath all are higher than the polylactic acid foam material of the AC whipping agent preparation of equal foaming agents content.
Because the foaming difficulty of poly(lactic acid) is bigger, so its foam material generally belongs to middle low foamed material, and it is also not obvious for the improvement of its expansion ratio to add various materials, and can find in embodiment 4 that by above-mentioned experimental data the expansion ratio of material is the highest.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.The person skilled in the art obviously can easily make various modifications to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and not breaking away from the improvement that category of the present invention makes and revise all should be within protection scope of the present invention.
Claims (10)
1. foam material, it is characterized in that: this foam material is made by the component that comprises following weight part:
100 parts of polylactic resin,
0～5 part of antioxidant,
3～8 parts of inner pattern releasing agent applicables,
1～3 part of linking agent,
0.5～1.5 part of additional crosslinker,
0～2 part of bubble nucleating agent,
1～5 part of whipping agent,
0～2.5 part of blowing promotor,
Melt strength improves 10～40 parts of materials.
2. foam material according to claim 1, it is characterized in that: the melting index of described polylactic resin is 1～20g/10min, preferred (1～10) * 10 of sticking equal molecular mass
5G/mol.
3. foam material according to claim 1, it is characterized in that: described antioxidant is selected from four { β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid } one or more of pentaerythritol ester, (3,5-di-tert-butyl-hydroxy phenyl) propionic acid stearyl alcohol ester, Tyox B or phosphorous acid benzene two isodecyl esters.
4. foam material according to claim 1, it is characterized in that: described linking agent is selected from dicumyl peroxide or dual-tert-butyl peroxidation diisopropyl benzene;
Or described additional crosslinker is iso-cyanuric acid triallyl ester.
5. foam material according to claim 1, it is characterized in that: described bubble nucleating agent is talcum powder, CaCO
3Or polynite, its order number is 1000～5000 orders;
Or described inner pattern releasing agent applicable is selected from polyoxyethylene glycol, low molecular weight polyethylene, Yelkin TTS releasing agent, Zinic stearas, stearin or Tristearoylglycerol, and the melt temperature of described inner pattern releasing agent applicable is 50～70 ℃, and decomposition temperature is greater than 230 ℃.
6. foam material according to claim 1, it is characterized in that: described whipping agent is Cellmic C 121, AC whipping agent or expancel whipping agent, and the decomposition temperature of described whipping agent is 160～220 ℃.
7. foam material according to claim 6 is characterized in that: as blowing promotor when described whipping agent is the AC whipping agent is zinc oxide;
Or described melt strength improves material and is selected from vinyl acetate modified olefine kind resin or methyl methacrylate-cinnamic multipolymer.
8. the preparation method of arbitrary described foam material among the claim 1-7 is characterized in that it comprises following steps:
(1) takes by weighing each component raw material by the described proportioning of claim 1, with polylactic resin 100 weight parts, oxidation inhibitor 0～5 weight part, 1～3 part of linking agent, 0.5～1.5 part of additional crosslinker, 0～2 part of bubble nucleating agent, 1～5 part of whipping agent, 0～2.5 part of blowing promotor, melt strength improve 10～40 parts of materials, and inner pattern releasing agent applicable mixes for 3～8 parts;
(2) mixture that makes in the step (1) being joined twin screw extruder extrudes pelletizing and obtains modified polylactic resin material grain.
9. preparation method according to claim 8, it is characterized in that: the mixing time of described step (1) is 3～7 minutes.
10. preparation method according to claim 8, it is characterized in that: in the described step (2), screw speed is 10～250r/min, and extrusion temperature is 150～210 ℃.
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| CN103881222A (en) * | 2014-02-19 | 2014-06-25 | 深圳职业技术学院 | Plastic foam material and preparation method thereof |
| CN105778446A (en) * | 2014-12-26 | 2016-07-20 | 湖南工业大学 | Preparation method of high strength and high buffer POSS hybrid polylactic acid foaming material |
| CN106751611A (en) * | 2016-12-08 | 2017-05-31 | 吉林中粮生化有限公司 | A kind of high fondant-strength expanded polylactic acid is resin dedicated and preparation method thereof |
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| CN103881222A (en) * | 2014-02-19 | 2014-06-25 | 深圳职业技术学院 | Plastic foam material and preparation method thereof |
| CN105778446A (en) * | 2014-12-26 | 2016-07-20 | 湖南工业大学 | Preparation method of high strength and high buffer POSS hybrid polylactic acid foaming material |
| CN107541031B (en) * | 2016-06-29 | 2020-04-28 | 上海浦景化工技术股份有限公司 | Modified PGA or PLGA full-biodegradable foam material and preparation method thereof |
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| CN106751611A (en) * | 2016-12-08 | 2017-05-31 | 吉林中粮生化有限公司 | A kind of high fondant-strength expanded polylactic acid is resin dedicated and preparation method thereof |
| CN110294922A (en) * | 2019-07-03 | 2019-10-01 | 杭州卓普新材料科技有限公司 | Polylactic acid wood materials preparation method |
| CN110591309A (en) * | 2019-08-31 | 2019-12-20 | 佛山碧嘉高新材料科技有限公司 | Biodegradable foamed plastic composite material and preparation method and application thereof |
| CN110591310A (en) * | 2019-09-04 | 2019-12-20 | 常州大学 | Modified polylactic acid foaming material and forming method thereof |
| CN110591310B (en) * | 2019-09-04 | 2021-07-30 | 常州大学 | Modified polylactic acid foaming material and forming method thereof |
| CN110643158A (en) * | 2019-09-29 | 2020-01-03 | 孔令孝 | Polylactic acid foaming material for cigarette filter tip and preparation method thereof |
| CN110643158B (en) * | 2019-09-29 | 2022-03-29 | 孔令孝 | Polylactic acid foaming material for cigarette filter tip and preparation method thereof |
| CN110920018A (en) * | 2019-11-21 | 2020-03-27 | 佛山碧嘉高新材料科技有限公司 | Polylactic acid foaming method |
| CN111234290A (en) * | 2020-03-09 | 2020-06-05 | 东南大学 | Method for preparing bone tissue engineering scaffold by using supercritical fluid foaming technology |
| CN111234290B (en) * | 2020-03-09 | 2022-08-26 | 东南大学 | Method for preparing bone tissue engineering scaffold by using supercritical fluid foaming technology |
| CN112759906A (en) * | 2020-12-23 | 2021-05-07 | 青岛润兴塑料新材料有限公司 | Fully-biodegradable polylactic acid oil-absorbing foaming material for ocean |
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| CN113698746A (en) * | 2021-08-27 | 2021-11-26 | 昌亚新材料科技有限公司 | Degradable heat-resistant polylactic acid pipe and preparation method and application thereof |
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