CN102408688A - Polylactic acid composite material and preparation method thereof - Google Patents
Polylactic acid composite material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a polylactic acid composite material. The polylactic acid composite material contains polylactic acid, polydiethylene butylene terephthalate, a compatability and glass fiber, wherein the glass fiber is glass fiber subjected to surface treatment with a silane coupling agent. The invention also provides a preparation method of the polylactic acid composite material. The polylactic acid composite material provided by the invention can be completely degraded; in addition, the polylactic acid composite material has high mechanical property and heat resistance.
Description
Technical field
The invention belongs to the biological degradable composite material field, relate in particular to a kind of lactic acid composite material and preparation method thereof.
Background technology
POLYACTIC ACID (PLA) is a kind of biodegradable polymers, derives from reproducible starch based resource, has good biocompatibility, bacterinertness, mechanical property and processing characteristics, is the environment-friendly type plastic that has application prospect most at present.But PLA matter is hard and toughness is not enough, and shock resistance is poor, thermotolerance is also relatively poor, and present most companies still are applied in the wrapping material aspect to its modification.
Gather hexanodioic acid mutual-phenenyl two acid bromide two alcohol ester (PBAT) and be the aliphatic-aromatic copolyester that hexanodioic acid, terephthalic acid and butyleneglycol terpolymer form, finally can under the soil of standard or composting conditions, be converted into carbonic acid gas (CO
2), water and biomass, and its conversion rate is very fast.PBAT has stronger toughness and good thermostability, but its mechanical property is relatively poor.Adopt PBAT can improve the toughness of PLA, but can reduce the mechanical strength of co-mixing system greatly; And the PLA/PBAT blend is an inconsistent two-phase system, and wherein PBAT is scattered in the PLA matrix about with about 300nm.
Select for use high reaction activity oligopolymer (HO) that the consistency of the incompatible blend of PLA/PBAT is improved in the prior art; The isocyanate functional group of containing high reaction activity in the HO molecule; Pass through in-situ copolymerization; Play the effect of emulsifying agent at the phase interface place, reduce surface tension, thereby improve the consistency of PLA and PBAT.But contain the isocyanate functional group in the PLA/PBAT system that this method obtains, need in the making processes of matrix material to use toxic substance, so its application is restricted.
Also disclose a kind of expanding material in the prior art, this expanding material has been added in the PLA/PBAT co-mixing system, thereby improved the consistency of PLA and PBAT; This expanding material is polycaprolactone (PCL).Through in the PLA/PBAT co-mixing system, introducing PCL, can improve shock strength, tensile strength and the modulus in tension of blend; But the PLA/PBAT system that this method obtains still exists mechanical property and the relatively poor defective of thermotolerance.
Summary of the invention
The invention solves the technical problem of mechanical performance of the PLA/PBAT matrix material that exists in the prior art and poor heat resistance.
The invention provides a kind of lactic acid composite material, contain POLYACTIC ACID in the said lactic acid composite material, gather hexanodioic acid mutual-phenenyl two acid bromide two alcohol ester, compatilizer and spun glass; Wherein said spun glass is process silane coupling agent surface-treated spun glass.
The present invention also provides the preparation method of said lactic acid composite material, may further comprise the steps:
1) with silane coupling agent spun glass is carried out surface treatment;
2) with POLYACTIC ACID, gather the hexanodioic acid mutual-phenenyl two acid bromide two alcohol ester and compatilizer mixes, obtain pre-composition; With the product of pre-composition and step 1) mix, coextrusion, obtain said lactic acid composite material.
Lactic acid composite material provided by the invention can be degraded fully, and wherein PLA and PBAT have good consistency, makes lactic acid composite material of the present invention both have mechanical property and the processing characteristics of PLA, has toughness and the thermostability of PBAT again; Spun glass through adopting silane coupling agent to handle in the lactic acid composite material of the present invention makes lactic acid composite material have higher mechanical properties and resistance toheat.
Embodiment
The invention provides a kind of lactic acid composite material, contain POLYACTIC ACID in the said lactic acid composite material, gather hexanodioic acid mutual-phenenyl two acid bromide two alcohol ester, compatilizer and spun glass; Wherein said spun glass is process silane coupling agent surface-treated spun glass.
Contriver of the present invention finds through a large amount of experiments, among the present invention, improves the consistency of PLA/PBAT co-mixing system through compatilizer, makes lactic acid composite material of the present invention have the mechanical property of PLA and toughness, the thermostability of PBAT simultaneously; In addition; The spun glass of handling through the introducing silane coupling agent among the present invention; Guarantee that spun glass and PLA, PBAT have good consistency on the one hand; Improve the mechanical strength of lactic acid composite material on the other hand, erosion-resisting characteristics, thus make lactic acid composite material of the present invention have the favorable mechanical performance; In addition, resistance toheat also is greatly improved.
Among the present invention, through spun glass is carried out the silane coupling agent surface-treated, thereby improve the consistency of spun glass and PLA, PBAT.Wherein, said silane coupling agent is to well known to a person skilled in the art the silane with active reactive group, thereby through the Chemical bond of the realization of the active reactive group on the silane with other materials.Among the present invention, PLA is last to have terminal hydroxy group and an end carboxyl, and PBAT is last to have the end carboxyl, and for improving the consistency of spun glass and PLA, PBAT, said silane coupling agent preferably adopts the silane coupling agent that contains amino, carbonyl, carboxyl or epoxy group(ing).Among the present invention, said silane coupling agent can directly adopt and be purchased product, for example can adopt KH550, KH560, KH570, KH792, DL602, DL171, at least a among the A186.
Spun glass is used for the thermotolerance that the PLA system can improve PLA, along with the increase of content of glass fiber, and the raising of material modulus, the heat-drawn wire that strengthens PLA also increases thereupon.But because spun glass and PLA, PBAT have relatively poor consistency, so the spun glass that adopts among the present invention is the spun glass through surface modification treatment.The diameter of said spun glass is 8-20 μ m, and the length of spun glass is 2-3mm.Among the present invention, said spun glass can directly adopt and be purchased product.
Among the present invention,, therefore contain compatilizer in the lactic acid composite material of the present invention, be used to improve the consistency of PLA and PBAT because PLA and PBAT consistency are relatively poor.Said compatilizer is at least a in ethylene-propylene acetoacetic ester-SY-Monomer G terpolymer (E-MA-GMA), ethylene-propylene acid butyl ester-SY-Monomer G terpolymer, the SEBS-g-glycidyl methacrylate copolymer.For example; E-MA-GMA can adopt the product of French Arkema; Ethylene-propylene acid butyl ester-SY-Monomer G terpolymer can adopt the product of du pont company, and the SEBS-g-glycidyl methacrylate copolymer can adopt the product of the company that rises of Shanghai day.
Among the present invention, the various PLA that said PLA uses always for those skilled in the art.Under the preferable case, the weight-average molecular weight of said PLA is 50000-500000, more preferably 70000-300000.Among the present invention, said PLA can adopt the 3051D of Nature Works company or the injection grade polylactic acid raw material of Shenzhen brilliance great achievement company.The weight-average molecular weight of said PBAT is 100000-250000.Among the present invention, said PBAT can oneself synthesize, and also can directly adopt and be purchased product; For example, can directly adopt the Ecoflex F BX7011 of BASF Aktiengesellschaft.
The total mass of lactic acid composite material is a benchmark, and POLYACTIC ACID content is 25-60wt%, and the content that gathers the hexanodioic acid mutual-phenenyl two acid bromide two alcohol ester is 15-40wt%, and the content of compatilizer is 1-10 wt%, and the content of spun glass is 10-30 wt%.Under the preferable case, be benchmark with the total mass of lactic acid composite material, the content of POLYACTIC ACID is 30-45wt%, and the content that gathers the hexanodioic acid mutual-phenenyl two acid bromide two alcohol ester is 20-30 wt%, and the content of compatilizer is 5-8wt%, and the content of spun glass is 20-28wt%.
As a kind of preferred implementation of the present invention, also contain nucleator in the lactic acid composite material of the present invention.Said nucleator can effectively improve the crystallization velocity of PLA, PBAT, thereby improves the resistance toheat of lactic acid composite material.Total mass with lactic acid composite material is a benchmark, and the content of nucleator is 1-5wt%, is preferably 3-5wt%.Said nucleator is methylene-bis (2,4-di-t-butyl phenoxy) sodium phosphate or an active talcum powder.Wherein, methylene-bis (2,4-di-t-butyl phenoxy) sodium phosphate can directly adopt and be purchased product, for example can adopt the NA-11 of the electrochemical company of the Japanese rising sun.
As those skilled in the art's common practise, oxygenolysis takes place when the high temperature coextrusion for avoiding lactic acid composite material, also contain oxidation inhibitor in the lactic acid composite material of the present invention.Total mass with lactic acid composite material is a benchmark, and the content of oxidation inhibitor is 0.1-0.5wt%, is preferably 0.2-0.4wt%.Said oxidation inhibitor can adopt and well known to a person skilled in the art various oxidation inhibitor; Four [methyl-β-(3 for example; The 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, butylated hydroxy anisole, butylated hydroxytoluene, tertiarybutylhydroquinone, phosphorous acid benzene two isodecyl esters, pentaerythritol bis-phosphite, [3-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, tricresyl phosphite (2; 4-di-tert-butyl-phenyl) ester or [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] ten caprylates.Among the present invention, said oxidation inhibitor can directly adopt and be purchased product, for example adopts 1010 of Switzerland Ciba company.
The present invention also provides the preparation method of said lactic acid composite material, may further comprise the steps:
1) with silane coupling agent spun glass is carried out surface treatment;
2) PLA, PBAT and compatilizer are mixed, obtain pre-composition; With the product of pre-composition and step 1) mix, coextrusion, obtain said lactic acid composite material.
Preparation in accordance with the present invention needs to carry out surface treatment to spun glass earlier, thereby can improve the consistency of spun glass and PLA, PBAT, and wherein, the surface treatment agent that is adopted is a silane coupler solution.Spun glass is carried out the surface-treated method for directly spun glass being soaked in the silane coupling agent solvent, and soak time is 1-3h.The water of pure and mild 5-10wt% that contains silane coupling agent, the 70-80wt% of 15-25wt% in the said silane coupler solution.
Under the preferable case, also contain the pH regulator agent in the said silane coupler solution, the pH value of regulating silane coupler solution is 4-5.Wherein, said pH regulator agent is an acetic acid.
Prepare lactic acid composite material of the present invention, need earlier PLA, PBAT and compatilizer to be mixed, obtain pre-composition.Wherein, PLA, PBAT and compatilizer blended temperature are 30-40 ℃.Pre-composition with 100 weight parts is a benchmark, and wherein the content of PLA is the 30-80 weight part, and the content of PBAT is the 17-56 weight part, and the content of compatilizer is the 2-14 weight part.Under the preferable case, be benchmark with the pre-composition of 100 weight parts, wherein the content of PLA is the 38-65 weight part, and the content of PBAT is the 26-50 weight part, and the content of compatilizer is the 6-12 weight part.
As preferred implementation of the present invention, nucleator and/or oxidation inhibitor can be mixed together evenly with PLA, PBAT, compatilizer, are also contained the pre-composition of nucleator and/or oxidation inhibitor.Pre-composition with 100 weight parts is a benchmark, and the content of nucleator is the 1-7 weight part, and the content of oxidation inhibitor is the 0.1-0.7 weight part.Under the preferable case, be benchmark with the pre-composition of 100 weight parts, the content of nucleator is the 3-7 weight part, and the content of oxidation inhibitor is the 0.2-0.6 weight part.
Pre-composition and process silane coupling agent surface-treated spun glass are mixed, and coextrusion then can obtain lactic acid composite material of the present invention.Pre-composition with 100 weight parts is a benchmark, and the consumption of silane coupling agent surface-treated spun glass is the 10-30 weight part, is preferably the 20-28 weight part.The temperature of the coextrusion of pre-composition and silane coupling agent surface-treated spun glass is 200-230 ℃.
Said coextrusion can be accomplished through twin screw extruder, for example can adopt the twin screw extruder of Nanjing New Time Co., and length-to-diameter ratio is 30-40:1.Wherein, silane coupling agent surface-treated spun glass is from the side hello barrel charging of twin screw extruder, and pre-composition is from the main hello barrel charging of forcing machine.The twin screw extruder setup parameter is: main hello barrel rate of feeding 35-55r/min, preferred 38-44r/min; Main feed screw rotating speed 160-220r/min, preferred 170-200r/min; Side hello barrel inlet is positioned at the 6th district, side hello barrel rate of feeding 50-80 r/min, preferred 60-72r/min; Side feed screw rotating speed 80-120r/min, preferred 96-110r/min.The temperature subregion of twin screw extruder from the spout to the extrusion is provided with as follows:
| 1 district | 2 districts | 3 districts | 4 districts | 5 districts | 6 districts | 7 districts | 8 districts | 9 districts | 10 districts |
| 160℃ | 160℃ | 170℃ | 170℃ | 180℃ | 200℃ | 220℃ | 230℃ | 230℃ | 230℃ |
The sample that comes out from extrusion is through the recirculated water cooling tie rod, and blower fan dries up, and through the dicing machine pelletizing, promptly obtains lactic acid composite material at last.
Below in conjunction with embodiment and Comparative Examples lactic acid composite material of the present invention and preparation method thereof is further described.The raw material that is adopted in embodiment and the Comparative Examples all is commercially available.
Embodiment 1
(1) by following quality percentage composition preparation silane coupler solution: silane coupling agent KH560,20wt%; Ethanol, 72wt%; Water, 8wt% splashes into acetic acid then, regulates pH=4.0.Spun glass (diameter is 10-15 μ m, and length is 2-3mm) is soaked in 1h in the silane coupler solution, takes out the back drying at room temperature.
(2) with exsiccant PLA (Natureworks; 3051D, weight-average molecular weight is 180000), PBAT (BASF, Ecoflex F BX7011; Weight-average molecular weight is 145000), compatilizer E-MA-GMA (French Arkema), nucleator NA-11 (Japanese the rising sun electrification company) and antioxidant 1010 mix below 40 ℃ in high-speed mixer; The high-speed mixer rotating speed is 1200r/min, revolution 30s stall 1min, and circulating obtains pre-composition after 5 times.In the pre-composition, each component concentration is as shown in table 1.
(3) product of step (1) is dropped into the side hello barrel of twin screw extruder (Nanjing New Times), the product pre-composition of step (2) drops into main hello barrel; Pre-composition with 100 weight parts is a benchmark, and the feeding capacity of the product of step (1) is 25 weight parts.Main hello barrel rate of feeding is 40r/min, and main feed screw rotating speed is 190r/min; Side hello barrel inlet is positioned at temperature subregion the 6th district, and side hello barrel rate of feeding is 70r/min, and side feed screw rotating speed is 100r/min; Be set to from the temperature subregion of spout to extrusion:
| 1 district | 2 districts | 3 districts | 4 districts | 5 districts | 6 districts | 7 districts | 8 districts | 9 districts | 10 districts |
| 160℃ | 160℃ | 170℃ | 170℃ | 180℃ | 200℃ | 220℃ | 230℃ | 230℃ | 230℃ |
From the sample that extrusion obtains, water-cooled, drying, pelletizing obtain the lactic acid composite material of present embodiment, are designated as S1.
Embodiment 2-5
Adopt to prepare lactic acid composite material S2-S5 with embodiment 1 identical method, difference is:
In the step (2), each component concentration of premix species (weight part) is as shown in table 1.
Table 1
| ? | S1 | S2 | S3 | S4 | S5 |
| PLA | 60 | 38 | 65 | 30 | 79.7 |
| PBAT | 26.5 | 50 | 24.5 | 56 | 17 |
| Compatilizer | 8 | 6 | 10 | 11.7 | 3 |
| Nucleator | 5 | 5.5 | - | 2 | - |
| Oxidation inhibitor | 0.5 | 0.5 | 0.5 | 0.3 | 0.3 |
In the last table 1, the compatilizer of S2 is ethylene-propylene acid butyl ester-SY-Monomer G terpolymer; The nucleator of S3 is an active talcum powder; The PLA of S4 is the injection grade polylactic acid raw material of Shenzhen brilliance great achievement company.
Embodiment 6
Adopt to prepare lactic acid composite material S2-S5 with embodiment 1 identical method, difference is:
In the step (1), silane coupler solution: silane coupling agent KH560,20wt%; Ethanol, 72wt%; Water, 8wt%; The diameter of spun glass is 8-12 μ m, and length is 2-3mm;
In the step (3), be benchmark with the pre-composition of 100 weight parts, the feeding capacity of the product of step (1) is 32 weight parts.
Through above-mentioned steps, obtain lactic acid composite material S6.
Comparative Examples 1
PLA, the PBAT that will pass through hydroxy-end capped processing join in the reactor drum, with dissolved in chloroform evenly after, remove chloroform.Mixture with PLA, PBAT changes in the there-necked flask then, is warming up to PLA, the complete fusion of PBAT under the nitrogen protection, adds inferior tin of liquid hexamethylene diisocyanate (HDI) and octoate catalyst and antioxidant 1010 then, reacts 30 min.Again successively with dissolved in chloroform, dissolve with methanol, stir, leave standstill, dry, obtain the product of this Comparative Examples, be designated as DS1.
Comparative Examples 2
With exsiccant PLA (weight-average molecular weight 180000; Tongji University's Materials Academy), PBAT (BASF; Ecoflex, weight-average molecular weight 145000), Triple Pressed Stearic Acid, calcium stearate, antioxidant 1010 mix by the mass ratio of 85:15:1:1, adds the PCL (weight-average molecular weight 68000 of 2 weight parts again; Belgium Solvay Caprolactones company), extrude through the twin screw extruder blend.The temperature 145-170 of forcing machine ℃ (being divided into 11 districts), screw speed is 150r/min, and rate of feeding is 30r/min.After extruding, water-cooled, granulation obtains matrix material, is designated as DS2.
Performance test:
(1) measuring mechanical property:
Adopt tensile strength and the tensile modulus of ASTM D638 disclosed method each composite sample S1-S6 of test and DS1-DS2;
Adopt the cantilever beam impact strength of ASTM D256 disclosed method each composite sample S1-S6 of test and DS1-DS2;
Adopt flexural strength and the modulus in flexure of ASTM D790 disclosed method each composite sample S1-S6 of test and DS1-DS2.
(2) resistance toheat test:
Adopt the heat-drawn wire of ASTM D648 disclosed method each composite sample S1-S6 of test and DS1-DS2.
Test result is as shown in table 2.
Table 2
| ? | Tensile strength (Mpa) | Tensile modulus (Mpa) | Cantilever beam impact strength (J/M) | Flexural strength (Mpa) | Modulus in flexure (Mpa) | Heat-drawn wire (℃) |
| S1 | 55.87 | 2208 | 202 | 66.83 | 2976 | 81 |
| S2 | 43.27 | 1726 | 302 | 49.88 | 2029 | 75 |
| S3 | 55.46 | 2516 | 118.16 | 70.11 | 3191 | 63 |
| S4 | 33.81 | 1330 | 497.23 | 45.23 | 1781 | 65 |
| S5 | 48.85 | 2034 | 89 | 73.03 | 3335 | 63 |
| S6 | 56.03 | 2830 | 195 | 69.92 | 3515 | 85 |
| DS1 | 15.67 | 920 | ﹥1200 | 20 | 800 | 55 |
| DS2 | 44 | 1800 | 333 | 32 | 1600 | 68 |
Test result by last table 2 can find out that lactic acid composite material of the present invention had both had the favorable mechanical performance, also has higher heat resistance.Relatively can find out from the result of embodiment and Comparative Examples; Various PLA/PBAT co-mixing system of the prior art is difficult to double favorable mechanical property and the resistance toheat of gathering; For example the cantilever beam impact strength of the matrix material of DS1 is higher, promptly has toughness preferably, but its flexural strength and modulus in flexure are lower; And heat-drawn wire is low to moderate 50 ℃, and promptly thermotolerance is relatively poor; Matrix material tensile strength flexural strength and the modulus in flexure of DS2 are lower.And lactic acid composite material of the present invention, the spun glass through adopting silane coupling agent to handle makes lactic acid composite material have higher mechanical properties and resistance toheat simultaneously.
Claims (13)
1. a lactic acid composite material is characterized in that, contains POLYACTIC ACID in the said lactic acid composite material, gathers hexanodioic acid mutual-phenenyl two acid bromide two alcohol ester, compatilizer and spun glass; Wherein said spun glass is process silane coupling agent surface-treated spun glass.
2. lactic acid composite material according to claim 1 is characterized in that, said silane coupling agent is the silane coupling agent that contains amino, carbonyl, carboxyl or epoxy group(ing).
3. lactic acid composite material according to claim 1 and 2 is characterized in that, the diameter of said spun glass is 8-20 μ m, and the length of spun glass is 2-3mm.
4. lactic acid composite material according to claim 1; It is characterized in that said compatilizer is at least a in ethylene-propylene acetoacetic ester-SY-Monomer G terpolymer, ethylene-propylene acid butyl ester-SY-Monomer G terpolymer, the SEBS-g-glycidyl methacrylate copolymer.
5. lactic acid composite material according to claim 1 is characterized in that the weight-average molecular weight of said POLYACTIC ACID is 50000-500000, and the weight-average molecular weight of gathering the hexanodioic acid mutual-phenenyl two acid bromide two alcohol ester is 100000-250000.
6. lactic acid composite material according to claim 1; It is characterized in that; Total mass with lactic acid composite material is a benchmark, and the content of POLYACTIC ACID is 25-60wt%, and the content that gathers the hexanodioic acid mutual-phenenyl two acid bromide two alcohol ester is 15-40wt%; The content of compatilizer is 1-10wt%, and the content of spun glass is 10-30wt%.
7. according to claim 1 or 6 described lactic acid composite materials, it is characterized in that, also contain the nucleator of 1-7wt% in the said lactic acid composite material; Said nucleator is methylene-bis (2,4-di-t-butyl phenoxy) sodium phosphate or an active talcum powder.
8. according to claim 1 or 6 described lactic acid composite materials, it is characterized in that, also contain the oxidation inhibitor of 0.1-0.7wt% in the said lactic acid composite material; Said oxidation inhibitor is four [methyl-β-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, butylated hydroxy anisole, butylated hydroxytoluene, tertiarybutylhydroquinone, phosphorous acid benzene two isodecyl esters, pentaerythritol bis-phosphite, [3-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, tricresyl phosphite (2; 4-di-tert-butyl-phenyl) ester or [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] ten caprylates.
9. the preparation method of the described lactic acid composite material of claim 1 may further comprise the steps:
1) with silane coupling agent spun glass is carried out surface treatment;
2) with POLYACTIC ACID, gather the hexanodioic acid mutual-phenenyl two acid bromide two alcohol ester and compatilizer mixes, obtain pre-composition; With the product of pre-composition and step 1) mix, coextrusion, obtain said lactic acid composite material.
10. preparation method according to claim 9 is characterized in that, in the step 1), silane coupling agent carries out the surface-treated method for spun glass is soaked in silane coupler solution to spun glass, and soak time is 1-3h; The water of pure and mild 5-10wt% that wherein contains silane coupling agent, the 70-80wt% of 15-25wt% in the silane coupler solution.
11. preparation method according to claim 10 is characterized in that, also contains acetic acid in the said silane coupler solution, the content of acetic acid is to make the pH value of silane coupler solution be 4-5.
12. preparation method according to claim 9 is characterized in that step 2) in, POLYACTIC ACID, gather the hexanodioic acid mutual-phenenyl two acid bromide two alcohol ester and compatilizer blended temperature is 30-40 ℃; Pre-composition with 100 weight parts is a benchmark, and wherein the content of POLYACTIC ACID is the 30-80 weight part, and the content that gathers the hexanodioic acid mutual-phenenyl two acid bromide two alcohol ester is the 17-56 weight part, and the content of compatilizer is the 2-14 weight part.
13. preparation method according to claim 9 is characterized in that step 2) in, be benchmark with the pre-composition of 100 weight parts, the consumption of the product of step 1) is the 10-30 weight part; The temperature of the coextrusion of the product of pre-composition and step 1) is 200-230 ℃.
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| US11466151B2 (en) | 2016-10-21 | 2022-10-11 | China Petroleum & Chemical Corporation | Polyester composition, preparation method therefor and application thereof |
| EP3530695A4 (en) * | 2016-10-21 | 2020-06-10 | China Petroleum&Chemical Corporation | Polyester composition and preparation method therefor |
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| US10934391B2 (en) | 2016-10-21 | 2021-03-02 | China Petroleum & Chemical Corporation | Polyester composition and preparation method therefor |
| CN106800756A (en) * | 2017-01-11 | 2017-06-06 | 北京汽车集团有限公司 | Full bio-based degradation material and preparation method thereof and automobile interior and vehicle |
| CN106800756B (en) * | 2017-01-11 | 2019-09-13 | 北京汽车集团有限公司 | Full biology base degradation material and preparation method thereof and automobile interior and vehicle |
| CN106800757A (en) * | 2017-02-10 | 2017-06-06 | 山东永聚医药科技有限公司 | High-toughness polylactic acid film master batch and preparation method thereof |
| CN112898749A (en) * | 2021-01-26 | 2021-06-04 | 苏州塑发生物材料有限公司 | Low-warpage high-toughness glass fiber reinforced polylactic acid composite material and preparation method thereof |
| CN112812526A (en) * | 2021-01-26 | 2021-05-18 | 苏州塑发生物材料有限公司 | Low-warpage low-density glass fiber reinforced polylactic acid composite material and preparation method thereof |
| CN114031907A (en) * | 2021-12-22 | 2022-02-11 | 施塔希(绍兴)新材料有限公司 | Puncture-resistant PBAT composite film and preparation method thereof |
| CN114806120A (en) * | 2022-06-15 | 2022-07-29 | 韩胜 | Preparation method of heat-resistant polylactic acid foaming thermal forming body |
| CN115466491A (en) * | 2022-10-09 | 2022-12-13 | 合肥工业大学 | High-modulus degradable PBAT/PLA compound and preparation method thereof |
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Application publication date: 20120411 |