CN105001603A - Fully biodegradable material with polylactic acid/polyterephthalic dibutyl adipate used as base materials and preparation method thereof - Google Patents
Fully biodegradable material with polylactic acid/polyterephthalic dibutyl adipate used as base materials and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a fully biodegradable material with polylactic acid/polyterephthalic dibutyl adipate used as base materials and a preparation method thereof. The material provided by the invention is composed of polylactic acid, polyterephthalic dibutyl adipate, a bio-based filler, an inorganic filler and a few amount of auxiliaries. The material has been certified by American ASTMD6400, European EN13432 and Australian AS4736 and is a fully biodegradable material. The fully biodegradable material contains the following ingredients, by weight, 5-60 parts of polylactic acid (PLA), 5-60 parts of polyterephthalic dibutyl adipate, 5-40 parts of the bio-based filler, 5-45 parts of the inorganic filler and 0.3-10 parts of the auxiliaries. The above ingredients are fully mixed, and the mixture undergoes melt plastification by a screw and then is directly extruded to obtain a board of 0.2-2mm thick. The board can undergo embossed work to obtain fruit trays, vegetable trays, disposable knives and forks and the like.
Description
Technical field
The invention belongs to technical field of polymer materials, particularly relating to a kind of take PLA/PBAT as full-biodegradable material of base-material and preparation method thereof.
Background technology
The application of current biodegradable material is more and more extensive, also more and more higher to the requirement of degradable material, not only has certain requirement to the performance of material, requires also very high, especially in food use and disposable product to its degraded security aspect.
Poly(lactic acid) (PLA) material is Wholly-degradable biomaterial, and it comprises PLA and PDLA, and it has superior physical property, can be divided into injection grade according to its purposes, film-grade and fibre-grade.This material is hard, and tensile strength is comparatively large, but shock strength is limited, directly can not be used for moulding plate etc.Poly terephthalic acid hexanodioic acid fourth diester (PBAT) belongs to thermoplastic biodegradable's plastics, it is the multipolymer of tetramethylene adipate and mutual-phenenyl two acid bromide two alcohol ester, have the characteristic of PBA and PBT concurrently, existing good ductility and elongation at break, also have good thermotolerance and impact property; In addition, also there is excellent biological degradability.But the tensile strength of PBAT material is inadequate, directly can not be used for sheet material etc.; Their respective advantages is got up by we, and their Application Areas can be made to expand.
Summary of the invention
The present invention is in conjunction with prior art, and developing a kind of take PLA/PBAT as the full-biodegradable material of base-material.According to mass fraction meter, this material is made up of following component:
Poly(lactic acid) (PLA) 5-60
Poly terephthalic acid hexanodioic acid fourth diester (PBAT) 5-60
Bio-based filler 5-40
Mineral filler 5-45
Auxiliary agent 0.3-10
According to mass fraction meter, be preferably made up of following component:
Poly(lactic acid) (PLA) 37
Poly terephthalic acid hexanodioic acid fourth diester (PBAT) 42.5
Bio-based filler 10
Mineral filler 10
Compatilizer 0.3
Softening agent 0.2
Wherein, described poly(lactic acid) comprises at least one in PDLA, PLLA, and its weight-average molecular weight is 120000-180000, and melting index is 4-10g/10min;
The weight-average molecular weight of described poly terephthalic acid hexanodioic acid fourth diester is 80000-160000;
Described bio-based filler is at least one in W-Gum, thermoplastic starch, 400-600 order wood powder, 400-500 order bamboo fibers, 300-500 order powdered rice hulls, 300-400 order Mierocrystalline cellulose;
Described is at least one in 650-1000 order talcum powder, 500-1000 order calcium carbonate, 800 order mica powders, 600 order potter's clay, the polynite of 600-1000 order without based filler;
Described auxiliary agent mainly comprises: compatilizer, oxidation inhibitor, softening agent, thermo-stabilizer, toughener, toughner; Compatilizer selects maleic anhydride graft compatilizer; Food grade antioxygen 1010 selected by oxidation inhibitor; Epoxy soybean oil series selected by softening agent, and oxirane value is greater than 6.0%, adds requirement and meet European EN13432 standard.
Take PLA/PBAT as a preparation method for the full-biodegradable material of base-material, comprise the following steps:
1) by polylactic resin and the process of poly terephthalic acid hexanodioic acid fourth diester resin drying, its water content≤200PPM is made;
2) accurately take the raw materials such as poly(lactic acid), poly terephthalic acid hexanodioic acid fourth diester, bio-based filler, mineral filler, auxiliary agent, added in high mixer and fully mix;
3) material mixed is extruded through twin screw extruder obtain full-biodegradable material.
Wherein, extruder screw rotating speed controls at 100-300r/min;
Extruder screw each warm area temperature arranges as follows:
| One district's (DEG C) | Two districts' (DEG C) | Three districts' (DEG C) | Four districts' (DEG C) | Five districts' (DEG C) | Six districts' (DEG C) | Seven districts' (DEG C) | Eight districts' (DEG C) | Nine districts' (DEG C) | Die head (DEG C) |
| 70-170 | 70- 170 | 80-170 | 90-170 | 100-180 | 100-190 | 100-170 | 100-170 | 100-180 | 120-200 |
When food sanitation condition is permitted, this material can be processed into fruit tray through mold pressing, vegetable dish pallet, and disposable knife and fork etc.
Material of the present invention can 100% complete biodegradable, and its degradation speed controlled at 4-8 month, and its working strength and traditional PP, PE material are close.
Embodiment
Below by specific embodiment technical scheme of the present invention done and further illustrate, but the present invention is not limited to these examples.
A kind of take PLA/PBAT as full-biodegradable material of base-material and preparation method thereof, described twin screw extruder, and refer to the twin screw extruder that polymer modification industry is conventional, its screw combinations and length-to-diameter ratio can require according to material modification.
example one
Poly(lactic acid) (PLA) 25 parts, poly terephthalic acid hexanodioic acid fourth diester (PBAT) 54 parts, W-Gum 10 parts, talcum powder 10 parts, phase solvent 0.3 part, 0.7 part, softening agent, polylactic resin and poly terephthalic acid hexanodioic acid fourth diester resin vacuum drying treatment, make its water content≤200PPM, above-mentioned raw materials is added 700r/min in high mixer to mix 9 minutes and make it even, 0.2-0.5mm heavy-gauge sheeting is extruded again, the disintegration degree by plastics under GB GBT19811-2005(composting conditions through twin screw 180r/min) to test its disintegration be 100% after 20 weeks.
example two
Poly(lactic acid) (PLA) 30 parts, poly terephthalic acid hexanodioic acid fourth diester (PBAT) 49 parts, W-Gum 10 parts, talcum powder 10 parts, compatilizer 0.3 part, 0.7 part, softening agent, polylactic resin and the process of poly terephthalic acid hexanodioic acid fourth diester resin drying, make its water content≤200PPM, above-mentioned raw materials is added 700r/min in high mixer to mix 9 minutes and make it even, 0.2-0.5mm heavy-gauge sheeting is extruded again, the disintegration degree by plastics under GB GBT19811-2005(composting conditions through twin screw 180r/min) to test its disintegration be 100% after 20 weeks.
example three
Poly(lactic acid) (PLA) 33 parts, poly terephthalic acid hexanodioic acid fourth diester (PBAT) 46 parts, W-Gum 10 parts, talcum powder 10 parts, compatilizer 0.3 part, 0.7 part, softening agent, polylactic resin and the process of poly terephthalic acid hexanodioic acid fourth diester resin drying, make its water content≤200PPM, above-mentioned raw materials is added 700r/min in high mixer to mix 9 minutes and make it even, 0.2-0.5mm heavy-gauge sheeting is extruded again, the disintegration degree by plastics under GB GBT19811-2005(composting conditions through twin screw 180r/min) to test its disintegration be 100% after 20 weeks.
example four
Poly(lactic acid) (PLA) 40 parts, poly terephthalic acid hexanodioic acid fourth diester (PBAT) 39 parts, W-Gum 10 parts, talcum powder 10 parts, compatilizer 0.3 part, 0.7 part, softening agent, polylactic resin and the process of poly terephthalic acid hexanodioic acid fourth diester resin drying, make its water content≤200PPM, above-mentioned raw materials is added 700r/min in high mixer to mix 9 minutes and make it even, 0.2-0.5mm heavy-gauge sheeting is extruded again, the disintegration degree by plastics under GB GBT19811-2005(composting conditions through twin screw 180r/min) to test its disintegration be 100% after 20 weeks.
example five
Poly(lactic acid) (PLA) 45 parts, poly terephthalic acid hexanodioic acid fourth diester (PBAT) 34 parts, W-Gum 10 parts, talcum powder 10 parts, compatilizer 0.3 part, 0.7 part, softening agent, polylactic resin and the process of poly terephthalic acid hexanodioic acid fourth diester resin drying, make its water content≤200PPM, above-mentioned raw materials is added 700r/min in high mixer to mix 9 minutes and make it even, 0.2-0.5mm heavy-gauge sheeting is extruded again, the disintegration degree by plastics under GB GBT19811-2005(composting conditions through twin screw 180r/min) to test its disintegration be 100% after 20 weeks.
example six
Poly(lactic acid) (PLA) 50 parts, poly terephthalic acid hexanodioic acid fourth diester (PBAT) 29 parts, W-Gum 10 parts, talcum powder 10 parts, compatilizer 0.3 part, 0.7 part, softening agent.Polylactic resin and the process of poly terephthalic acid hexanodioic acid fourth diester resin drying, make its water content≤200PPM, above-mentioned raw materials is added 700r/min in high mixer to mix 9 minutes and make it even, 0.2-0.5mm heavy-gauge sheeting is extruded again, the disintegration degree by plastics under GB GBT19811-2005(composting conditions through twin screw 180r/min) to test its disintegration be 100% after 20 weeks.
As can be seen from Table 1, along with poly terephthalic acid hexanodioic acid fourth diester per-cent in the material increases, the tensile strength of material is on a declining curve, and elongation at break is increase trend, and the proportioning of each component in material can be regulated in actual use to meet the service requirements of each based article.
Table 1
| Component | Example one | Example two | Example three | Example four | Example five | Example six |
| PLA（%） | 25 | 30 | 33 | 40 | 45 | 50 |
| PBAT（%） | 54 | 49 | 46 | 39 | 34 | 29 |
| W-Gum (%) | 10 | 10 | 10 | 10 | 10 | 10 |
| Talcum powder (%) | 10 | 10 | 10 | 10 | 10 | 10 |
| Auxiliary agent (%) | 1 | 1 | 1 | 1 | 1 | 1 |
| Tensile strength (MPa) | 6.3 | 9.4 | 11.2 | 12.1 | 15.8 | 21.3 |
| Shock strength (MPa) | 19.1 | 16.3 | 14.2 | 13.5 | 12.7 | 8.4 |
Claims (10)
1. be a full-biodegradable material for base-material with PLA/PBAT, it is characterized in that, according to mass fraction meter, be made up of following component:
Poly(lactic acid) (PLA) 5-60
Poly terephthalic acid hexanodioic acid fourth diester (PBAT) 5-60
Bio-based filler 5-40
Mineral filler 5-45
Auxiliary agent 0.3-10.
2. according to claim 1 a kind of take PLA/PBAT as the full-biodegradable material of base-material, it is characterized in that, according to mass fraction meter, be preferably made up of following component:
Poly(lactic acid) (PLA) 37
Poly terephthalic acid hexanodioic acid fourth diester (PBAT) 42.5
Bio-based filler 10
Mineral filler 10
Compatilizer 0.3
Softening agent 0.2.
3. according to claim 1 a kind of take PLA/PBAT as the full-biodegradable material of base-material, it is characterized in that, described poly(lactic acid) comprises at least one in PDLA, PLLA, and its weight-average molecular weight is 120000-180000, and melting index is 4-10g/10min.
4. according to claim 1 a kind of take PLA/PBAT as the full-biodegradable material of base-material, it is characterized in that, the weight-average molecular weight of described poly terephthalic acid hexanodioic acid fourth diester is 80000-160000.
5. according to claim 1 a kind of take PLA/PBAT as the full-biodegradable material of base-material, it is characterized in that, described bio-based filler is at least one in W-Gum, thermoplastic starch, 400-600 order wood powder, 400-500 order bamboo fibers, 300-500 order powdered rice hulls, 300-400 order Mierocrystalline cellulose.
6. according to claim 1 a kind of take PLA/PBAT as the full-biodegradable material of base-material, it is characterized in that, described is at least one in 650-1000 order talcum powder, 500-1000 order calcium carbonate, 800 order mica powders, 600 order potter's clay, the polynite of 600-1000 order without based filler.
7. according to claim 1 a kind of take PLA/PBAT as the full-biodegradable material of base-material, it is characterized in that, described auxiliary agent mainly comprises: compatilizer, oxidation inhibitor, softening agent, thermo-stabilizer, toughener, toughner; Compatilizer selects maleic anhydride graft compatilizer; Food grade antioxygen 1010 selected by oxidation inhibitor; Epoxy soybean oil series selected by softening agent, and oxirane value is greater than 6.0%, adds requirement and meet European EN13432 standard.
8. be a preparation method for the full-biodegradable material of base-material with PLA/PBAT, it is characterized in that, comprise the following steps:
1) by polylactic resin and the process of poly terephthalic acid hexanodioic acid fourth diester resin drying, its water content≤200PPM is made;
2) accurately take the raw materials such as poly(lactic acid), poly terephthalic acid hexanodioic acid fourth diester, bio-based filler, mineral filler, auxiliary agent, added in high mixer and fully mix;
3) material mixed is extruded through twin screw extruder obtain full-biodegradable material.
9. according to claim 8 a kind of take PLA/PBAT as the preparation method of the full-biodegradable material of base-material, it is characterized in that, in step 3), extruder screw rotating speed controls at 100-300r/min.
10. according to claim 8 a kind of take PLA/PBAT as the preparation method of the full-biodegradable material of base-material, it is characterized in that, extruder screw each warm area temperature arranges as follows:
。
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Application publication date: 20151028 |