CN104401078A - Multilayer polylactic acid composite plate and preparation method thereof - Google Patents
Multilayer polylactic acid composite plate and preparation method thereof Download PDFInfo
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- CN104401078A CN104401078A CN201410777731.7A CN201410777731A CN104401078A CN 104401078 A CN104401078 A CN 104401078A CN 201410777731 A CN201410777731 A CN 201410777731A CN 104401078 A CN104401078 A CN 104401078A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/03—3 layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/558—Impact strength, toughness
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/716—Degradable
- B32B2307/7163—Biodegradable
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2605/00—Vehicles
- B32B2605/003—Interior finishings
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- Laminated Bodies (AREA)
Abstract
The invention discloses a multilayer polylactic acid composite plate and a preparation method thereof. The composite plate consists of three layers of structures, wherein the first layer is an anti-impact toughness-enhanced polylactic acid composite layer, the second layer is a high-performance fiber-enhanced polylactic acid composite layer, and the third layer is an anti-impact toughness-enhanced polylactic acid composite layer. The three layers of structures of the composite plate are respectively prepared and are formed after being subjected to hot rolling. The composite plate has the characteristics of high modulus, high intensity and high toughness and biodegradability, and the hardness of the outer layer can be adjusted as required.
Description
Technical field
The present invention relates to a kind of multilayer Polylactic acid composite board and preparation method thereof, refer in particular to a kind of three-decker, intermediate layer has high-strength and high-modulus, that top layer has a high impact resistance and controllable composite board of soft durometer and preparation method thereof.
Background technology
PLA is biodegradable thermoplastic aliphatic's polyester of Prof. Du Yucang, it not only derives from the renewable resource such as corn, cereal, but also there is good biocompatibility, be one of the most promising biodegradable polymer, be widely used in the fields such as bio-medical material, packaging material, daily plastic goods, weaving face fabric, agricultural mulching.But the performance of PLA own has certain defect, and performance is more crisp, modulus and intensity generally, are difficult to reach product requirement after especially making sheet material.
At present, the pertinent literature of PLA sheet material and preparation method thereof, as the preparation method (CN101691054B) of low-interlaminar-spacing polylactic-acid-base linen fiber composite plates, a kind of Polylactic acid composite board and preparation method thereof (CN103538136A), a kind of preparation method (CN103341898A) of flame retardant corn cob clad fiber/polylactic acid fiberboard, utilize the plate of the PLA through being cross-linked and preparation method thereof (CN104169055A), all relate to and carry out polydactyl acid by the method for fiber composite or chemical crosslinking, and be prepared into sheet material.But these patents do not relate to a kind of three-decker, and intermediate layer has high-strength and high-modulus, top layer has high impact resistance and the controllable Polylactic acid composite board of soft durometer.
Summary of the invention
Goal of the invention: in order to solve the deficiencies in the prior art, the invention provides a kind of three-decker that has, intermediate layer has high-strength and high-modulus, that top layer has a high impact resistance and controllable Polylactic acid composite board of soft durometer and preparation method thereof.
Technical scheme: a kind of multilayer Polylactic acid composite board, described Polylactic acid composite board comprises three-layer composite structure, be followed successively by from top to bottom: ground floor is shock-resistant plasticizing polylactic acid composite bed, the second layer is that high-performance fiber strengthens PLA composite bed, and third layer is shock-resistant plasticizing polylactic acid composite bed; The grammes per square metre of described Polylactic acid composite board is 500-3500g/m
2, described ground floor and third layer weight summation account for gross weight than being 40-60%, and second layer weight accounts for gross weight than being 40-60%.
As optimization: the shock-resistant plasticizing polylactic acid composite bed of described ground floor and third layer contains PLA, toughness reinforcing particle, plasticizer and antioxidant.
As optimization: PLA is molecular weight 10-16 ten thousand (mass percent is 40-90%); Toughness reinforcing particle is Biodegradable polyurethane, one or more (mass percent is 10-50%) in polycaprolactone, PLA-trimethylene carbonate, polyoxyethylene; Plasticizer is butyl ricinoleate, one or more (mass percent is 5-20%) in glycerine three-acetylricinoleate carboxylic ester, sucrose stearate, antioxidant (mass percent is 3-5%).
As optimization: it is containing PLA, high-performance fiber, interfacial bonder that the high-performance fiber of the described second layer strengthens PLA composite bed.
As optimization: PLA is molecular weight 10-16 ten thousand (mass percent is 60-90%); High-performance fiber is carbon fiber, one or more (mass percent is 10-40%) in glass fibre, high-strength high-modulus polyethylene, Fanglun l414 long filament, interfacial bonder (5-10%).
A preparation method for multilayer Polylactic acid composite board, comprises the steps:
1), one or more pre-preg in carbon fiber, glass fibre, high-strength high-modulus polyethylene, Fanglun l414 long filament in interfacial bonder, then parallel or intersection sprawls into 2-5 layer, and spread prefabricated 1mm polylactic acid film between every layer, form high-performance fiber through hot pressing and strengthen PLA composite bed;
2), by PLA, toughness reinforcing particle, plasticizer drying, premix, then become the shock-resistant plasticizing polylactic acid roller lifting hanging arm guiding mechanism for intaglio press of 2-5mm by double screw extruder blended melting extrusion calendaring;
3), using shock-resistant plasticizing polylactic acid composite bed as first and third layer, high-performance fiber strengthens PLA composite bed as the second layer, dries, form composite board finally by hot rolling through precompressed, heat.
As optimization: in described step 1), hot pressing temperature is 170-230 DEG C, and hot pressing pressure is 2-7MPa, and hot pressing time is 30-90s.
As optimization: described step 2) in, melt temperature is 170-230 DEG C, screw diameter 55mm, and screw speed is 30-60r/min.
As optimization: in described step 3), hot-rolled temperature is 170-230 DEG C, and hot rolling pressure is 2-7MPa.
As optimization: in described step 3), the composite board of formation is while high strength, high-modulus, and surperficial soft durometer controls in the scope of shore hardness 90D-42D.
Beneficial effect: the composite board that the present invention prepares has the feature of high-modulus, high strength, high tenacity and biodegradability, and its skin can adjust soft durometer as required.The intermediate layer of this sheet material can provide rigidity and the intensity of sheet material entirety, and skin can provide good toughness thus the impulsive force of opposing foreign object, and the soft durometer on its top layer can regulate through row as required.This composite board can be applicable to the products such as vehicle inside decoration plate, electric appliance casing, has both had the performance providing product structure intensity, and can provide again good outer comfort.
Accompanying drawing explanation
Fig. 1 is structural representation of the present invention.
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further described.For those skilled in the art, under the premise without departing from the principles of the invention, can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Specific embodiment 1
As shown in Figure 1, a kind of multilayer Polylactic acid composite board, described Polylactic acid composite board comprises three-layer composite structure, be followed successively by from top to bottom: ground floor is shock-resistant plasticizing polylactic acid composite bed 1, the second layer is that high-performance fiber strengthens PLA composite bed 2, and third layer is shock-resistant plasticizing polylactic acid composite bed 3; The grammes per square metre of described Polylactic acid composite board is 500g/m
2, it is 40% that described ground floor and third layer weight summation account for gross weight ratio, and it is 60% that second layer weight accounts for gross weight ratio.
The shock-resistant plasticizing polylactic acid composite bed of described ground floor and third layer contains PLA, toughness reinforcing particle, plasticizer and antioxidant.
PLA is molecular weight 100,000; Toughness reinforcing particle is Biodegradable polyurethane; Plasticizer is butyl ricinoleate, antioxidant.
It is containing PLA, high-performance fiber, interfacial bonder that the high-performance fiber of the described second layer strengthens PLA composite bed.
PLA is molecular weight 100,000; High-performance fiber is carbon fiber, interfacial bonder.
A preparation method for multilayer Polylactic acid composite board, comprises the steps:
1), carbon fibre initial rinse stain in interfacial bonder, then parallel laid generate 2 layers, and between every layer, spread prefabricated 1mm polylactic acid film, form high-performance fiber through hot pressing and strengthen PLA composite bed;
2), by PLA, toughness reinforcing particle, plasticizer drying, premix, then become the shock-resistant plasticizing polylactic acid roller lifting hanging arm guiding mechanism for intaglio press of 2mm by double screw extruder blended melting extrusion calendaring;
3), using shock-resistant plasticizing polylactic acid composite bed as first and third layer, high-performance fiber strengthens PLA composite bed as the second layer, dries, form composite board finally by hot rolling through precompressed, heat.
In described step 1), hot pressing temperature is 170 DEG C, and hot pressing pressure is 2MPa, and hot pressing time is 30s.
Described step 2) in, melt temperature is 170 DEG C, screw diameter 55mm, and screw speed is 30r/min.
In described step 3), hot-rolled temperature is 170 DEG C, and hot rolling pressure is 2MPa.
In described step 3), the composite board of formation is while high strength, high-modulus, and surperficial soft durometer controls in the scope of shore hardness 42D.
Specific embodiment 2
As shown in Figure 1, a kind of multilayer Polylactic acid composite board, described Polylactic acid composite board comprises three-layer composite structure, be followed successively by from top to bottom: ground floor is shock-resistant plasticizing polylactic acid composite bed 1, the second layer is that high-performance fiber strengthens PLA composite bed 2, and third layer is shock-resistant plasticizing polylactic acid composite bed 3; The grammes per square metre of described Polylactic acid composite board is 3500g/m
2, it is 60% that described ground floor and third layer weight summation account for gross weight ratio, and it is 40% that second layer weight accounts for gross weight ratio.
The shock-resistant plasticizing polylactic acid composite bed of described ground floor and third layer contains PLA, toughness reinforcing particle, plasticizer and antioxidant.
PLA is molecular weight 160,000; Toughness reinforcing particle is polycaprolactone; Plasticizer is glycerine three-acetylricinoleate carboxylic ester, antioxidant.
It is containing PLA, high-performance fiber, interfacial bonder that the high-performance fiber of the described second layer strengthens PLA composite bed.
PLA is molecular weight 160,000; High-performance fiber is glass fibre, interfacial bonder.
A preparation method for multilayer Polylactic acid composite board, comprises the steps:
1), fiberglass prepreg in interfacial bonder, then intersect and sprawl into 5 layers, and between every layer, spread prefabricated 1mm polylactic acid film, form high-performance fiber through hot pressing and strengthen PLA composite bed;
2), by PLA, toughness reinforcing particle, plasticizer drying, premix, then become the shock-resistant plasticizing polylactic acid roller lifting hanging arm guiding mechanism for intaglio press of 5mm by double screw extruder blended melting extrusion calendaring;
3), using shock-resistant plasticizing polylactic acid composite bed as first and third layer, high-performance fiber strengthens PLA composite bed as the second layer, dries, form composite board finally by hot rolling through precompressed, heat.
In described step 1), hot pressing temperature is 230 DEG C, and hot pressing pressure is 7MPa, and hot pressing time is 90s.
Described step 2) in, melt temperature is 230 DEG C, screw diameter 55mm, and screw speed is 60r/min.
In described step 3), hot-rolled temperature is 230 DEG C, and hot rolling pressure is 7MPa.
In described step 3), the composite board of formation is while high strength, high-modulus, and surperficial soft durometer controls in the scope of shore hardness 90D.
Specific embodiment 3
As shown in Figure 1, a kind of multilayer Polylactic acid composite board, described Polylactic acid composite board comprises three-layer composite structure, be followed successively by from top to bottom: ground floor is shock-resistant plasticizing polylactic acid composite bed 1, the second layer is that high-performance fiber strengthens PLA composite bed 2, and third layer is shock-resistant plasticizing polylactic acid composite bed 3; The grammes per square metre of described Polylactic acid composite board is 1500g/m
2, it is 50% that described ground floor and third layer weight summation account for gross weight ratio, and it is 50% that second layer weight accounts for gross weight ratio.
The shock-resistant plasticizing polylactic acid composite bed of described ground floor and third layer contains PLA, toughness reinforcing particle, plasticizer and antioxidant.
PLA is molecular weight 130,000; Toughness reinforcing particle is PLA-trimethylene carbonate; Plasticizer is sucrose stearate, antioxidant.
It is containing PLA, high-performance fiber, interfacial bonder that the high-performance fiber of the described second layer strengthens PLA composite bed.
PLA is molecular weight 140,000; High-performance fiber is high-strength high-modulus polyethylene, interfacial bonder.
A preparation method for multilayer Polylactic acid composite board, comprises the steps:
1), high-strength high-modulus polyethylene pre-preg in interfacial bonder, then intersect and sprawl into 4 layers, and between every layer, spread prefabricated 1mm polylactic acid film, form high-performance fiber through hot pressing and strengthen PLA composite bed;
2), by PLA, toughness reinforcing particle, plasticizer drying, premix, then become the shock-resistant plasticizing polylactic acid roller lifting hanging arm guiding mechanism for intaglio press of 3mm by double screw extruder blended melting extrusion calendaring;
3), using shock-resistant plasticizing polylactic acid composite bed as first and third layer, high-performance fiber strengthens PLA composite bed as the second layer, dries, form composite board finally by hot rolling through precompressed, heat.
In described step 1), hot pressing temperature is 210 DEG C, and hot pressing pressure is 5MPa, and hot pressing time is 68s.
Described step 2) in, melt temperature is 190 DEG C, screw diameter 55mm, and screw speed is 48r/min.
In described step 3), hot-rolled temperature is 185 DEG C, and hot rolling pressure is 5MPa.
In described step 3), the composite board of formation is while high strength, high-modulus, and surperficial soft durometer controls in the scope of shore hardness 75D.
Claims (10)
1. a multilayer Polylactic acid composite board, it is characterized in that: described Polylactic acid composite board comprises three-layer composite structure, be followed successively by from top to bottom: ground floor is shock-resistant plasticizing polylactic acid composite bed, the second layer is that high-performance fiber strengthens PLA composite bed, and third layer is shock-resistant plasticizing polylactic acid composite bed; The grammes per square metre of described Polylactic acid composite board is 500-3500g/m
2, described ground floor and third layer weight summation account for gross weight than being 40-60%, and second layer weight accounts for gross weight than being 40-60%.
2. multilayer Polylactic acid composite board according to claim 1, is characterized in that: the shock-resistant plasticizing polylactic acid composite bed of described ground floor and third layer contains PLA, toughness reinforcing particle, plasticizer and antioxidant.
3. multilayer Polylactic acid composite board according to claim 2, is characterized in that: PLA is molecular weight 10-16 ten thousand; Toughness reinforcing particle is one or more in Biodegradable polyurethane, polycaprolactone, PLA-trimethylene carbonate, polyoxyethylene; Plasticizer is one or more in butyl ricinoleate, glycerine three-acetylricinoleate carboxylic ester, sucrose stearate.
4. multilayer Polylactic acid composite board according to claim 1, is characterized in that: it is containing PLA, high-performance fiber, interfacial adhesion 1 dose that the high-performance fiber of the described second layer strengthens PLA composite bed.
5. multilayer Polylactic acid composite board according to claim 4, is characterized in that: PLA is molecular weight 10-16 ten thousand; High-performance fiber is one or more in carbon fiber, glass fibre, high-strength high-modulus polyethylene, Fanglun l414 long filament.
6. the preparation method of multilayer Polylactic acid composite board according to claim 1, is characterized in that: comprise the steps:
1), one or more pre-preg in carbon fiber, glass fibre, high-strength high-modulus polyethylene, Fanglun l414 long filament in interfacial bonder, then parallel or intersection sprawls into 2-5 layer, and spread prefabricated 1mm polylactic acid film between every layer, form high-performance fiber through hot pressing and strengthen PLA composite bed;
2), by PLA, toughness reinforcing particle, plasticizer drying, premix, then become the shock-resistant plasticizing polylactic acid roller lifting hanging arm guiding mechanism for intaglio press of 2-5mm by double screw extruder blended melting extrusion calendaring;
3), using shock-resistant plasticizing polylactic acid composite bed as first and third layer, high-performance fiber strengthens PLA composite bed as the second layer, dries, form composite board finally by hot rolling through precompressed, heat.
7. the preparation method of multilayer Polylactic acid composite board according to claim 6, it is characterized in that: in described step 1), hot pressing temperature is 170-230 DEG C, hot pressing pressure is 2-7MPa, and hot pressing time is 30-90s.
8. the preparation method of multilayer Polylactic acid composite board according to claim 6, is characterized in that: described step 2) in, melt temperature is 170-230 DEG C, screw diameter 55mm, and screw speed is 30-60r/min.
9. the preparation method of multilayer Polylactic acid composite board according to claim 6, it is characterized in that: in described step 3), hot-rolled temperature is 170-230 DEG C, hot rolling pressure is 2-7MPa.
10. the preparation method of multilayer Polylactic acid composite board according to claim 6, is characterized in that: in described step 3), and the composite board of formation is while high strength, high-modulus, and surperficial soft durometer controls in the scope of shore hardness 90D-42D.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105860469A (en) * | 2016-04-29 | 2016-08-17 | 太仓龙益塑业有限公司 | High-thermal-conductivity bioplastic |
| CN106928673A (en) * | 2017-03-22 | 2017-07-07 | 嘉兴学院 | A kind of antibiotic carbon fiber/lactic acid composite material and its production and use |
| CN108624016A (en) * | 2018-04-24 | 2018-10-09 | 上海交通大学 | Aramid fiber modified carbon fiber enhances polylactic acid thermoplastic composite and preparation method |
| CN110861327A (en) * | 2019-11-12 | 2020-03-06 | 苏州淼昇电子有限公司 | Preparation method of high-toughness impact-resistant PET (polyethylene terephthalate) protective film |
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Effective date of registration: 20191202 Address after: 215614 new materials, floor 3, building D, Fenghuang science and Technology Pioneer Park, Fenghuang Town, Zhangjiagang City, Suzhou City, Jiangsu Province Patentee after: Suzhou Duoban New Material Technology Co., Ltd. Address before: 226000 Jiangsu city of Nantong province sik Road No. 9 Patentee before: Nantong University |
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Denomination of invention: A multilayer polylactic acid composite plate and its preparation method Effective date of registration: 20220614 Granted publication date: 20170322 Pledgee: Bank of Suzhou Co.,Ltd. Zhangjiagang sub branch Pledgor: SUZHOU DUOROU NEW MATERIAL TECHNOLOGY Co.,Ltd. Registration number: Y2022320010232 |