CN101942184B - Bamboo powder filling biodegradable compound material and preparation method thereof - Google Patents
Bamboo powder filling biodegradable compound material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a bamboo powder filling biodegradable compound material and a preparation method thereof. The bamboo powder filling biodegradable compound material comprises the following raw materials in part by mass: 30 to 80 parts of biodegradable resin, 20 to 70 parts of bamboo powder, 1 to 19 parts of plasticizer, 0.6 to 6 parts of interface modifier and 4 to 12 parts of aids. The preparation method comprises the following steps of: uniformly mixing the biodegradable resin, bamboo powder, plasticizer, interface modifier and auxiliary agent by using a mixer according to formula proportion; performing melt blending and granulation of the obtained mixture by using a screw extruder to obtain particles; and processing the particles by using an injection molding machine, a sheet extrusion forming machine, a blow molding machine or a film blowing machine, and molding in molds of different shapes to obtain the bamboo powder filling biodegradable compound materials of different shapes. The method has the advantages of high production efficiency and low cost; and the powder filling biodegradable compound material prepared by the method has the advantages of high environmentally-friendly property and economy and excellent usability.
Description
Technical field
The invention belongs to polymeric material field, being specifically related to a kind of is matrix material of main raw material and preparation method thereof with bamboo powder and biodegradable resin.
Background technology
The alternative petroleum base polymer of biodegradable resin and other macromolecular materials that are unfavorable for environment help protecting environment, save the energy, realize Sustainable development.Business-like at present biodegradable resin mainly contains POLYACTIC ACID (PLA), poly butyric ester (PHB), polyhydroxybutyrate-valerate (PHBV), 3-hydroxybutyric acid/4 hydroxybutyric acid multipolymer [P (3HB-co-4HB)], poly butylene succinate (PBS), aliphatics aromatic copolyester (PBAT), carbon dioxide copolymer (PPC) etc.Problems such as in recent years, biodegradable resin development is very fast, but it is higher also to expose cost, and mechanical property, thermotolerance are relatively poor.One of effective way that addresses this problem is with compound preparation biodegradable composite materials such as biodegradable resin and natural biological material such as starch, timber, bamboo woods.
Starch has been widely used in preparing biodegradable composite material.But the rapid increase of the non-grain consumption of starch has caused the worry of people to staple food supply.Therefore, seek the natural biological material that more horn of plenty, cost are more cheap of originating, become that biodegradable composite material is realized Sustainable development and the realistic problem that must face.
Be all the annual output of the Mierocrystalline cellulose that gathers polysaccharide up to 2 * 10 with starch
11Ton is far above 1.8 * 10 of petroleum base macromolecular material
9Ton is that the source is abundant, with low cost.Timber, bamboo wood all belong to cellulose materials.With xylon, wood powder is that the Wood-plastic material of feedstock production has been widely used in fields such as furniture, packing, car and boat interior trim.But the timber cycle of becoming a useful person is grown (about 10～20 years), and China's timber resources relative shortage, to the development formation restriction of Wood-plastic material.
Compare with timber, bamboo wood growth cycle short (about 2～3 years), resource is abundant relatively, and particularly the bamboo secondary industry is flourish, has produced a large amount of industrial wood wastes.In the past, the bamboo industrial wood waste mainly as fuel, greatly reduced the comprehensive utilization ratio of bamboo resource and the added value of bamboo wood.With bamboo wood or bamboo surplus material of processing through processing, modification, carry out compoundly with biodegradable resin again, process biodegradable composite material, become the new technology that latest developments are got up.
Publication number is that the Chinese invention patent of CN101003667 has been reported POLYACTIC ACID/natural-fiber composite material and working method thereof; Employed bamboo fibers is staple fibre or macrofiber; But the information such as size such as order number, diameter, length of bamboo fibers is not provided; The weight content of bamboo fibers only limits to 5～40 parts, and POLYACTIC ACID does not provide information such as molecular weight size, rotational isomerism body burden yet.
Publication number is that the Chinese invention patent of CN101508829 and CN101508830 has been reported a kind of Biodegradable polyester composition; Employed biodegradable resin is the blend of poly butylene succinate and POLYACTIC ACID; But the information such as ratio and arrangement mode of molecular weight, the comonomer of resin is not provided, and employed softening agent only limits to a kind of in dimethyl phthalate, the diethyl phthalate.
Publication number is that the Chinese invention patent of CN101602882 has been reported bamboo powder filled biomass-based resin composite material and preparation method thereof; Employed bamboo powder makes through operations such as classification, boiling, bleaching, cleaning, dryings, and granularity is less than 0.4mm, but the information such as diameter, length of bamboo powder is not provided; Add and do not use any plasticizer or lubricant man-hour; Cause problems such as matrix material processing fluidity deficiency easily, and, the mechanical property and the heat-drawn wire of matrix material do not provided.
Document [Composites:Part A; 2006; 37:80] reported bamboo fibers filling PLA, PBS matrix material, the mean length of employed bamboo fibers and diameter are respectively 500 and 70 microns, use Methionin base coupling agent (LDI) to improve the interface adhesion of matrix material simultaneously.Document [J.Polym.Environ., 2008,16:83; Ind.Eng.Chem.Res., 2010,49:572] reported bamboo fibers filling PHBV matrix material, the mean length of employed bamboo fibers and diameter are respectively 1 centimetre and 16.2 microns, use polymeric isocyanate (pMDI) as coupling agent simultaneously.Above-mentioned document all adopts Banbury mixer to process, and is difficult to realize high-level efficiency, the serialization production of matrix material.
Summary of the invention
First purpose of the present invention is to the above-mentioned state of the art a kind of environmental protection, processing fluidity and well behaved bamboo powder filled biomass degradable composite material to be provided, and it is that main raw material makes with bamboo powder and biodegradable resin that this matrix material utilizes softening agent, interface modifier, auxiliary agent.
Second purpose of the present invention provides a kind of preparation method of bamboo powder filled biomass degradable composite material, and this method production efficiency is high, and preparation cost is cheap, is suitable for producing shape and structure complicacy, thin-walled, large-area goods.
Bamboo powder filled biomass degradable composite material of the present invention, its composition of raw materials comprise following component according to the mass fraction:
30～80 parts of biodegradable resins;
20～70 parts in bamboo powder;
1～19 part in softening agent;
0.6～6 part of interface modifier;
4～12 parts of auxiliary agents;
Described biodegradable resin is a kind of in POLYACTIC ACID (PLA), poly butyric ester (PHB), polyhydroxybutyrate-valerate (PHBV), 3-hydroxybutyric acid/4 hydroxybutyric acid multipolymer [P (3HB-co-4HB)], poly butylene succinate (PBS), aliphatics aromatic copolyester (PBAT), the carbon dioxide copolymer (PPC); Or the poly-blended objects system of above-mentioned resin, each component ratio of co-mixing system be arbitrarily than; The moisture mass content of biodegradable resin is smaller or equal to 5%, and as preferably, the moisture mass content of biodegradable resin can obtain through oven dry smaller or equal to 1%.
To PLA, its weight-average molecular weight is 60,000～160,000, and L optically active isomer molar content is 42%～98%;
To poly butyric ester (PHB), its weight-average molecular weight is 80,000～230,000;
To polyhydroxybutyrate-valerate (PHBV), its weight-average molecular weight is 90,000～500,000, the hydroxyl valerate molar content is 3%～23%;
To 3-hydroxybutyric acid/4 hydroxybutyric acid multipolymer [P (3HB-co-4HB)], its weight-average molecular weight is 70,000～700,000, the 4 hydroxybutyric acid molar content is 4%～20%;
To PBS, its weight-average molecular weight is 70,000～190,000;
To PBAT, its weight-average molecular weight is 30,000～80,000;
To PPC, its weight-average molecular weight is 140,000～420,000.
The mean diameter of described bamboo powder is 75～500 microns, and mean length is 0.1～5 millimeter, and obtaining the order number through the mesh screen classification is 30～200 bamboo powder; The moisture mass content of bamboo powder is smaller or equal to 10%, and as preferably, the moisture mass content of bamboo powder can obtain through oven dry smaller or equal to 2%.
Described softening agent is one or more in polyoxyethylene glycol, polyethylene wax, glycerine, DEDB, terephthalate, tetraoctyl 1,2,4,5-benzenetetra-carboxylate, trimellitic acid fat, epoxidized vegetable oil, citrate, the acetyl citrate.
Described interface modifier is one or more in silane coupling agent, titanate coupling agent, aluminate coupling agent, isocyanic ester/tin class catalyzer, polymeric isocyanate, the maleic anhydride/peroxide initiator; Wherein, the tin class catalyzer in isocyanic ester/tin class catalyzer is stannous octoate or dibutyl tin dilaurate, and the add-on of tin class catalyzer is 1%～10% of an isocyanic ester; Peroxide initiator in maleic anhydride/peroxide initiator is Lucidol or Di Cumyl Peroxide 99, and the peroxide initiator add-on is 10%～50% of a maleic anhydride.
Auxiliary packing and nucleator that described auxiliary agent adds for the request for utilization according to goods.Described auxiliary packing is a kind of in starch, talcum powder, silicon-dioxide, titanium oxide, kaolin, lime carbonate, the wollastonite; Described nucleator is sorbyl alcohol, Sodium Benzoate, lactic acid ca, Mierocrystalline cellulose is nanocrystalline, chitin is nanocrystalline, in the SP 1 one or both.
The preparation method of this bamboo powder filled biomass degradable composite material in turn includes the following steps:
Step 1. is even in stirrer for mixing in the composition of raw materials ratio of above-mentioned bamboo powder filled biomass degradable composite material with biodegradable resin, bamboo powder, softening agent, interface modifier, auxiliary agent;
Step 2. is carried out melt blending, granulation with resulting mixture in the step 1 in screw extrusion press, obtain pellet; Described screw extrusion press is single screw extrusion machine or multiple screw extruder;
Step 3. in the different shapes die for molding, obtains difform bamboo powder filled biomass degradable composite material through injection moulding machine, sheet extrusion shaper, blow moulding machine or inflation film manufacturing machine with resulting pellet in the step 2.
The invention has the advantages that: the present invention proposes a kind of bamboo powder filled biomass degradable composite material, its main raw material is biodegradable resin and bamboo powder, and therefore, this matrix material has good green environmental protection and economy; Add softening agent, interface modifier and auxiliary agent in addition; Wherein, Softening agent improves the processing fluidity of matrix material; Interface modifier improves the interface compatibility and the cohesive strength of bamboo powder and biodegradable resin, thereby improves performance of composites, and auxiliary agent improves the outward appearance of matrix material and the crystallinity of biodegradable resin.The invention allows for a kind of method for preparing above-mentioned bamboo powder filled biomass degradable composite material; This method is suitable for preparing even structure, well behaved matrix material; Have advantages such as production efficiency height, preparation cost be cheap simultaneously; Both can process the complicated goods of shape and structure, also can process thin-walled, big area goods through extruding, blowing or film-blowing process through injection molding process.
Embodiment
Below in conjunction with embodiment technical scheme of the present invention is done further to describe.
Embodiment 1
Take by weighing 80 parts of POLYACTIC ACIDs (PLA), 20 parts in bamboo powder, 1 part of polyoxyethylene glycol (PEG), 0.6 part of silane coupling agent (KH-550), 10 parts of starch, 1 part of sorbyl alcohol by mass fraction; Wherein: the weight-average molecular weight of PLA is 160,000; L optically active isomer molar content is 98%; Making the moisture mass content in 12 hours at 80 ℃ of following vacuum dryings is 1%, and the mean diameter of bamboo powder is 80 microns with the microscopy statistics, and mean length is 0.1 millimeter with the microscopy statistics; Be classified as 200 orders through mesh screen, making the moisture mass content in 12 hours at 110 ℃ of following vacuum dryings is 2%.Above-mentioned material rotating speed with 1500 rev/mins in impeller was mixed 6 minutes, inject twin screw extruder then, under the condition of 178 ℃ of die head temperatures, 100 rev/mins of screw speeds, carry out melt blending, granulation; Again with the pellet after the blend in injection moulding machine to carry out injection moulding under 172 ℃ of conditions of nozzle temperature; Obtain standard mechanics test bars, the tensile strength that records matrix material is 40MPa, and modulus is 2.8GPa; Elongation at break is 4.6%, and shock strength is 9.1KJ/m
2, heat-drawn wire (HDT) is 89 ℃, matching die makes Storage jar, writing case, electric appliance casing goods through injection moulding, makes the packing bag goods through blow molding, makes film article through blowfilm shaping.
Embodiment 2
Take by weighing 60 parts of POLYACTIC ACIDs (PLA), 40 parts in bamboo powder, 8 parts of polyethylene waxs, 1.5 parts of titanate coupling agents (NDZ-101), 5 parts of silicon-dioxide, 1 part of Sodium Benzoate by mass fraction; Wherein: the weight-average molecular weight of PLA is 110,000; L optically active isomer molar content is 86%; Making the moisture mass content in 6 hours at 80 ℃ of following vacuum dryings is 2%, and the mean diameter of bamboo powder is 370 microns with the microscopy statistics, and mean length is 2.4 millimeters with the microscopy statistics; Be classified as 40 orders through mesh screen, making the moisture mass content in 12 hours at 120 ℃ of following vacuum dryings is 1%.Above-mentioned material rotating speed with 1500 rev/mins in impeller was mixed 8 minutes, inject twin screw extruder then, under the condition of 178 ℃ of die head temperatures, 100 rev/mins of screw speeds, carry out melt blending, granulation; Again with the pellet after the blend in injection moulding machine to carry out injection moulding under 172 ℃ of conditions of nozzle temperature; Obtain standard mechanics test bars, the tensile strength that records matrix material is 38MPa, and modulus is 3.3GPa; Elongation at break is 3.8%, and shock strength is 8.6KJ/m
2, heat-drawn wire (HDT) is 93 ℃, matching die makes Storage jar, writing case, electric appliance casing goods through injection moulding.
Embodiment 3
Take by weighing 40 parts of POLYACTIC ACIDs (PLA), 60 parts in bamboo powder, 10 parts of dioctyl terephthalates (DOTP), 0.8 part of isocyanic ester (MDI), 0.05 part of stannous octoate, 3 parts of kaolin, 1 part of lactic acid ca by mass fraction; Wherein: the weight-average molecular weight of PLA is 60,000; L optically active isomer molar content is 42%; Making the moisture mass content in 24 hours at 80 ℃ of following vacuum dryings is 0.5%, and the bamboo powder is made up of by 1: 1 mass ratio 40 order bamboo powder and 80 order bamboo powder, and the mean diameter of 40 order bamboo powder is 370 microns with the microscopy statistics; Mean length with the microscopy statistics for being 2.4 millimeters; The mean diameter of 80 order bamboo powder is 180 microns with the microscopy statistics, and for being 0.5 millimeter, it is 1.8% that two kinds of bamboo powder made the moisture mass content in 12 hours at 110 ℃ of following vacuum dryings to mean length with the microscopy statistics.Above-mentioned material rotating speed with 1500 rev/mins in impeller was mixed 8 minutes, inject single screw extrusion machine then, under the condition of 178 ℃ of die head temperatures, 100 rev/mins of screw speeds, carry out melt blending, granulation; Again with the pellet after the blend in injection moulding machine to carry out injection moulding under 172 ℃ of conditions of nozzle temperature; Obtain standard mechanics test bars, the tensile strength that records matrix material is 35MPa, and modulus is 3.7GPa; Elongation at break is 3.5%, and shock strength is 8.2KJ/m
2, heat-drawn wire (HDT) is 96 ℃, matching die makes Storage jar, pen container, electric appliance casing goods through injection moulding, makes sheet material through extrusion molding and is used for guardrail, floor.
Embodiment 4
Take by weighing 80 parts of poly butyric esters (PHB), 20 parts in bamboo powder, 2 parts of glycerine, 1 part of polymeric isocyanate (pMDI), 10 parts of starch by mass fraction; 1 part of SP 1; Wherein: the weight-average molecular weight of PHB is 230,000; Making the moisture mass content in 12 hours at 70 ℃ of following vacuum dryings is 1.5%, and the mean diameter of bamboo powder is 80 microns with the microscopy statistics, and mean length is 0.1 millimeter with the microscopy statistics; Be classified as 200 orders through mesh screen, making the moisture mass content in 12 hours at 80 ℃ of following vacuum dryings is 8%.Above-mentioned material rotating speed with 1500 rev/mins in impeller was mixed 6 minutes, inject twin screw extruder then, under the condition of 166 ℃ of die head temperatures, 100 rev/mins of screw speeds, carry out melt blending, granulation; Again with the pellet after the blend in injection moulding machine to carry out injection moulding under 162 ℃ of conditions of nozzle temperature; Obtain standard mechanics test bars, the tensile strength that records matrix material is 23MPa, and modulus is 1.0GPa; Elongation at break is 3.3%, and shock strength is 5.7KJ/m
2, heat-drawn wire (HDT) is 90 ℃, matching die makes Storage jar, writing case, electric appliance casing goods through injection moulding, makes the packing bag goods through blow molding, makes film article through blowfilm shaping.
Embodiment 5
Take by weighing 60 parts of poly butyric esters (PHB), 40 parts in bamboo powder, 12 parts of epoxidised soybean oil (ESO), 1 part of maleic anhydride (MA), 0.5 part of Lucidol (BPO), 8 parts of starch by mass fraction; Nanocrystalline 1 part of Mierocrystalline cellulose; Wherein: the weight-average molecular weight of PHB is 140,000; Making the moisture mass content in 12 hours at 60 ℃ of following vacuum dryings is 2%, and the mean diameter of bamboo powder is 250 microns with the microscopy statistics, and mean length is 0.9 millimeter with the microscopy statistics; Be classified as 60 orders through mesh screen, making the moisture mass content in 12 hours at 60 ℃ of following vacuum dryings is 10%.Above-mentioned material rotating speed with 1500 rev/mins in impeller was mixed 8 minutes, inject twin screw extruder then, under the condition of 168 ℃ of die head temperatures, 100 rev/mins of screw speeds, carry out melt blending, granulation; Again with the pellet after the blend in injection moulding machine to carry out injection moulding under 165 ℃ of conditions of nozzle temperature; Obtain standard mechanics test bars, the tensile strength that records matrix material is 20MPa, and modulus is 1.3GPa; Elongation at break is 3.1%, and shock strength is 5.2KJ/m
2, heat-drawn wire (HDT) is 97 ℃, matching die makes Storage jar, writing case, cutlery goods through injection moulding.
Embodiment 6
Take by weighing 30 parts of poly butyric esters (PHB), 70 parts in bamboo powder, 4 parts of epoxidised soybean oil (ESO), 6 parts of tributyl acetylcitrates (ATBC), 1 part of polymeric isocyanate (pMDI), 1 part of maleic anhydride (MA), 0.5 part of Di Cumyl Peroxide 99 (DCP), 3 parts of kaolin, 1 part of SP 1 by mass fraction; Wherein: the weight-average molecular weight of PHB is 80,000; Making the moisture mass content in 12 hours at 50 ℃ of following vacuum dryings is 3%; The bamboo powder is made up of by 1: 1 mass ratio 40 order bamboo powder and 80 order bamboo powder; The mean diameter of 40 order bamboo powder is 370 microns with the microscopy statistics; Mean length with the microscopy statistics for being 2.4 millimeters; The mean diameter of 80 order bamboo powder is 180 microns with the microscopy statistics, and for being 0.5 millimeter, it is 2% that two kinds of bamboo powder made the moisture mass content in 12 hours at 110 ℃ of following vacuum dryings to mean length with the microscopy statistics.Above-mentioned material rotating speed with 1500 rev/mins in impeller was mixed 8 minutes, inject single screw extrusion machine then, under the condition of 170 ℃ of die head temperatures, 100 rev/mins of screw speeds, carry out melt blending, granulation; Again with the pellet after the blend in injection moulding machine to carry out injection moulding under 167 ℃ of conditions of nozzle temperature; Obtain standard mechanics test bars, the tensile strength that records matrix material is 18MPa, and modulus is 1.6GPa; Elongation at break is 2.9%, and shock strength is 5.0KJ/m
2, heat-drawn wire (HDT) is 102 ℃, matching die makes Storage jar, writing case, electric appliance casing goods through injection moulding, makes sheet material through extrusion molding and is used for guardrail, floor.
Embodiment 7
Take by weighing 80 parts of polyhydroxybutyrate-valerates (PHBV), 20 parts in bamboo powder, 6 parts of epoxidised soybean oil (ESO), 1 part of isocyanic ester (MDI), 0.04 part of dibutyl tin dilaurate, 5 parts of kaolin by mass fraction; 1 part of SP 1; Wherein: the weight-average molecular weight of PHBV is 500,000, and the hydroxyl valerate molar content is 23%, and making the moisture mass content in 6 hours at 50 ℃ of following vacuum dryings is 5%; The mean diameter of bamboo powder is 120 microns with the microscopy statistics; Mean length is 0.2 millimeter with the microscopy statistics, is classified as 120 orders through mesh screen, and making the moisture mass content in 12 hours at 110 ℃ of following vacuum dryings is 2%.Above-mentioned material rotating speed with 1500 rev/mins in impeller was mixed 6 minutes, inject twin screw extruder then, under the condition of 169 ℃ of die head temperatures, 100 rev/mins of screw speeds, carry out melt blending, granulation; Again with the pellet after the blend in injection moulding machine to carry out injection moulding under 165 ℃ of conditions of nozzle temperature; Obtain standard mechanics test bars, the tensile strength that records matrix material is 24MPa, and modulus is 1.1GPa; Elongation at break is 4.7%, and shock strength is 7.6KJ/m
2, heat-drawn wire (HDT) is 95 ℃, matching die makes Storage jar, pen container, writing case goods through injection moulding, makes the packing bag goods through blow molding, makes film article through blowfilm shaping.
Embodiment 8
Take by weighing 60 parts of polyhydroxybutyrate-valerates (PHBV), 40 parts in bamboo powder, 8 parts of tributyl acetylcitrates (ATBC), 3 parts of maleic anhydrides (MA), 3 parts of Lucidols (BPO), 8 parts in lime carbonate, nanocrystalline 1 part of Mierocrystalline cellulose by mass fraction; Wherein: the weight-average molecular weight of PHBV is 360,000; The hydroxyl valerate molar content is 3%; Making the moisture mass content in 12 hours at 80 ℃ of following vacuum dryings is 1%, and the mean diameter of bamboo powder is 250 microns with the microscopy statistics, and mean length is 0.9 millimeter with the microscopy statistics; Be classified as 60 orders through mesh screen, making the moisture mass content in 12 hours at 130 ℃ of following vacuum dryings is 1%.Above-mentioned material rotating speed with 1500 rev/mins in impeller was mixed 8 minutes, inject single screw extrusion machine then, under the condition of 170 ℃ of die head temperatures, 100 rev/mins of screw speeds, carry out melt blending, granulation; Again with the pellet after the blend in injection moulding machine to carry out injection moulding under 167 ℃ of conditions of nozzle temperature; Obtain standard mechanics test bars, the tensile strength that records matrix material is 26MPa, and modulus is 1.8GPa; Elongation at break is 4.2%, and shock strength is 6.9KJ/m
2, heat-drawn wire (HDT) is 113 ℃, matching die makes Storage jar, pen container, cutlery goods through injection moulding.
Embodiment 9
Take by weighing 40 parts of polyhydroxybutyrate-valerates (PHBV), 60 parts in bamboo powder, 8 parts of epoxidised soybean oil (ESO), 8 parts of tributyl acetylcitrates (ATBC), 1 part of polymeric isocyanate (pMDI), 1 part of maleic anhydride (MA), 0.5 part of Di Cumyl Peroxide 99 (DCP), 7 parts in lime carbonate, 1 part of SP 1 by mass fraction; Wherein: the weight-average molecular weight of PHBV is 90,000; The hydroxyl valerate molar content is 14%; Making the moisture mass content in 6 hours at 75 ℃ of following vacuum dryings is 2%; The bamboo powder is made up of by 1: 1 mass ratio 40 order bamboo powder and 80 order bamboo powder; The mean diameter of 40 order bamboo powder is 370 microns with the microscopy statistics, and for being 2.4 millimeters, the mean diameter of 80 order bamboo powder is 180 microns with the microscopy statistics to mean length with the microscopy statistics; For being 0.5 millimeter, it is 3% that two kinds of bamboo powder made the moisture mass content in 12 hours at 100 ℃ of following vacuum dryings to mean length with the microscopy statistics.Above-mentioned material rotating speed with 1500 rev/mins in impeller was mixed 8 minutes, inject single screw extrusion machine then, under the condition of 170 ℃ of die head temperatures, 100 rev/mins of screw speeds, carry out melt blending, granulation; Again with the pellet after the blend in injection moulding machine to carry out injection moulding under 167 ℃ of conditions of nozzle temperature; Obtain standard mechanics test bars, the tensile strength that records matrix material is 25MPa, and modulus is 2.3GPa; Elongation at break is 3.0%, and shock strength is 6.5KJ/m
2, heat-drawn wire (HDT) is 115 ℃, matching die makes Storage jar, electric appliance casing, flowerpot goods through injection moulding, makes sheet material through extrusion molding and is used for guardrail, floor.
Embodiment 10
Take by weighing 80 parts of 3-hydroxybutyric acid/4 hydroxybutyric acid multipolymers [P (3HB-co-4HB)], 20 parts in bamboo powder, 15 parts of polyoxyethylene glycol (PEG), 1 part of maleic anhydride (MA), 0.5 part of Di Cumyl Peroxide 99 (DCP), 10 parts of starch, nanocrystalline 1 part of chitin by mass fraction; Wherein: the weight-average molecular weight of P (3HB-co-4HB) is 700,000; The 4 hydroxybutyric acid molar content is 7.3%; Making the moisture mass content in 12 hours at 50 ℃ of following vacuum dryings is 3%; The mean diameter of bamboo powder is 120 microns with the microscopy statistics; Mean length is 0.2 millimeter with the microscopy statistics, is classified as 120 orders through mesh screen, and making the moisture mass content in 8 hours at 100 ℃ of following vacuum dryings is 5%.Above-mentioned material rotating speed with 1500 rev/mins in impeller was mixed 6 minutes, inject twin screw extruder then, under the condition of 158 ℃ of die head temperatures, 100 rev/mins of screw speeds, carry out melt blending, granulation; Again with the pellet after the blend in injection moulding machine to carry out injection moulding under 155 ℃ of conditions of nozzle temperature; Obtain standard mechanics test bars, the tensile strength that records matrix material is 21MPa, and modulus is 0.9GPa; Elongation at break is 9.8%, and shock strength is 8.3KJ/m
2, heat-drawn wire (HDT) is 67 ℃, matching die makes Storage jar, pen container, cutlery goods through injection moulding, makes the packing bag goods through blow molding, makes film article through blowfilm shaping.
Embodiment 11
Take by weighing 50 parts of 3-hydroxybutyric acid/4 hydroxybutyric acid multipolymers [P (3HB-co-4HB)], 50 parts in bamboo powder, 5 parts of polyoxyethylene glycol (PEG), 5 parts of glycerine, 1 part of isocyanic ester (MDI), 0.05 part of stannous octoate, 10 parts of titanium oxide, 2 parts of SP 1 by mass fraction; Wherein: the weight-average molecular weight of P (3HB-co-4HB) is 460,000, and the 4 hydroxybutyric acid molar content is 20%, and making the moisture mass content in 12 hours at 50 ℃ of following vacuum dryings is 3%; The mean diameter of bamboo powder is 370 microns with the microscopy statistics; Mean length is 2.4 millimeters with the microscopy statistics, is classified as 40 orders through mesh screen, and making the moisture mass content in 12 hours at 100 ℃ of following vacuum dryings is 3%; It is 1% that titanium oxide made the moisture mass content in 12 hours at 110 ℃ of following vacuum dryings; Above-mentioned material rotating speed with 1500 rev/mins in impeller was mixed 8 minutes, inject single screw extrusion machine then, under the condition of 160 ℃ of die head temperatures, 100 rev/mins of screw speeds, carry out melt blending, granulation; Again with the pellet after the blend in injection moulding machine to carry out injection moulding under 157 ℃ of conditions of nozzle temperature; Obtain standard mechanics test bars, the tensile strength that records matrix material is 20MPa, and modulus is 1.5GPa; Elongation at break is 6.5%, and shock strength is 5.9KJ/m
2, heat-drawn wire (HDT) is 72 ℃, matching die makes Storage jar, electric appliance casing, writing case goods through injection moulding, makes sheet material through extrusion molding and is used for guardrail, floor.
Embodiment 12
Take by weighing 30 parts of 3-hydroxybutyric acid/4 hydroxybutyric acid multipolymers [P (3HB-co-4HB)], 70 parts in bamboo powder, 7 parts of polyoxyethylene glycol (PEG), 6 parts of glycerine, 6 parts of tributyl acetylcitrates (ATBC), 1 part of isocyanic ester (MDI), 0.05 part of stannous octoate, 1 part of maleic anhydride (MA), 0.5 part of Di Cumyl Peroxide 99 (DCP), 3 parts of silicon-dioxide, 1 part of SP 1 by mass fraction; Wherein: the weight-average molecular weight of P (3HB-co-4HB) is 70,000; The 4 hydroxybutyric acid molar content is 4%; Making the moisture mass content in 12 hours at 50 ℃ of following vacuum dryings is 3%; The bamboo powder is made up of by 1: 1 mass ratio 40 order bamboo powder and 80 order bamboo powder; The mean diameter of 40 order bamboo powder is 370 microns with the microscopy statistics, and for being 2.4 millimeters, the mean diameter of 80 order bamboo powder is 180 microns with the microscopy statistics to mean length with the microscopy statistics; For being 0.5 millimeter, it is 2% that two kinds of bamboo powder made the moisture mass content in 12 hours at 110 ℃ of following vacuum dryings to mean length with the microscopy statistics.Above-mentioned material rotating speed with 1500 rev/mins in impeller was mixed 8 minutes, inject single screw extrusion machine then, under the condition of 160 ℃ of die head temperatures, 100 rev/mins of screw speeds, carry out melt blending, granulation; Again with the pellet after the blend in injection moulding machine to carry out injection moulding under 157 ℃ of conditions of nozzle temperature; Obtain standard mechanics test bars, the tensile strength that records matrix material is 17MPa, and modulus is 1.6GPa; Elongation at break is 5.1%, and shock strength is 5.5KJ/m
2, heat-drawn wire (HDT) is 75 ℃, matching die makes Storage jar, electric appliance casing, cutlery goods through injection moulding, makes sheet material through extrusion molding and is used for guardrail, floor.
Embodiment 13
Take by weighing 80 parts of poly butylene succinates (PBS), 20 parts in bamboo powder, 10 parts of glycerine, 1 part of aluminate coupling agent (KL-411-B), 10 parts of starch, 1 part of SP 1 by mass fraction; Wherein: the weight-average molecular weight of PBS is 190,000; Making the moisture mass content in 12 hours at 80 ℃ of following vacuum dryings is 1%; The mean diameter of bamboo powder is 150 microns with the microscopy statistics; Mean length is 0.3 millimeter with the microscopy statistics, is classified as 100 orders through mesh screen, and making the moisture mass content in 24 hours at 90 ℃ of following vacuum dryings is 2.5%.Above-mentioned material rotating speed with 1500 rev/mins in impeller was mixed 6 minutes, inject twin screw extruder then, under the condition of 160 ℃ of die head temperatures, 100 rev/mins of screw speeds, carry out melt blending, granulation; Again with the pellet after the blend in injection moulding machine to carry out injection moulding under 158 ℃ of conditions of nozzle temperature; Obtain standard mechanics test bars, the tensile strength that records matrix material is 32MPa, and modulus is 1.1GPa; Elongation at break is 17.4%, and shock strength is 13.5KJ/m
2, heat-drawn wire (HDT) is 102 ℃, matching die makes writing case, electric appliance casing, cutlery goods through injection moulding, makes the packing bag goods through blow molding, makes film article through blowfilm shaping.
Embodiment 14
Take by weighing 50 parts of poly butylene succinates (PBS), 50 parts in bamboo powder, 5 parts of glycerine, 5 parts of epoxidised soybean oil (ESO), 1 part of maleic anhydride (MA), 0.5 part of Lucidol (BPO), 3 parts of titanium oxide, 1 part of SP 1 by mass fraction; Wherein: the weight-average molecular weight of PBS is 120,000; Making the moisture mass content in 12 hours at 80 ℃ of following vacuum dryings is 1%; The mean diameter of bamboo powder is 250 microns with the microscopy statistics; Mean length is 0.9 millimeter with the microscopy statistics, is classified as 60 orders through mesh screen, and making the moisture mass content in 12 hours at 110 ℃ of following vacuum dryings is 2%.Above-mentioned material rotating speed with 1500 rev/mins in impeller was mixed 8 minutes, inject single screw extrusion machine then, under the condition of 160 ℃ of die head temperatures, 100 rev/mins of screw speeds, carry out melt blending, granulation; Again with the pellet after the blend in injection moulding machine to carry out injection moulding under 158 ℃ of conditions of nozzle temperature; Obtain standard mechanics test bars, the tensile strength that records matrix material is 29MPa, and modulus is 1.6GPa; Elongation at break is 10.7%, and shock strength is 11.0KJ/m
2, heat-drawn wire (HDT) is 105 ℃, matching die makes pen container, Storage jar, electric appliance casing goods through injection moulding, makes sheet material through extrusion molding and is used for guardrail, floor.
Embodiment 15
Take by weighing 30 parts of poly butylene succinates (PBS), 70 parts in bamboo powder, 3 parts of glycerine, 3 parts of epoxidised soybean oil (ESO), 4 parts of tributyl acetylcitrates (ATBC), 1 part of aluminate coupling agent (KL-411-B), 1.5 parts of maleic anhydrides (MA), 0.7 part of Lucidol (BPO), 3 parts of talcum powder, 1 part of SP 1 by mass fraction; Wherein: the weight-average molecular weight of PBS is 70,000; Making the moisture mass content in 24 hours at 80 ℃ of following vacuum dryings is 0.5%; The bamboo powder is made up of by 1: 1 mass ratio 40 order bamboo powder and 80 order bamboo powder; The mean diameter of 40 order bamboo powder is 370 microns with the microscopy statistics; Mean length with the microscopy statistics for being 2.4 millimeters; The mean diameter of 80 order bamboo powder is 180 microns with the microscopy statistics, and for being 0.5 millimeter, it is 2% that two kinds of bamboo powder made the moisture mass content in 12 hours at 110 ℃ of following vacuum dryings to mean length with the microscopy statistics.Above-mentioned material rotating speed with 1500 rev/mins in impeller was mixed 8 minutes, inject single screw extrusion machine then, under the condition of 160 ℃ of die head temperatures, 100 rev/mins of screw speeds, carry out melt blending, granulation; Again with the pellet after the blend in injection moulding machine to carry out injection moulding under 158 ℃ of conditions of nozzle temperature; Obtain standard mechanics test bars, the tensile strength that records matrix material is 27MPa, and modulus is 2.0GPa; Elongation at break is 8.7%, and shock strength is 7.0KJ/m
2, heat-drawn wire (HDT) is 110 ℃, matching die makes writing case, Storage jar, electric appliance casing goods through injection moulding, makes sheet material through extrusion molding and is used for guardrail, floor.
Embodiment 16
Take by weighing 80 parts of aliphatics aromatic copolyesters (PBAT), 20 parts in bamboo powder, 10 parts of polyethylene waxs, 1 part of titanate coupling agent (NDZ-311), 10 parts of starch, 1 part of SP 1 by mass fraction; Wherein: the weight-average molecular weight of PBAT is 80,000; Making the moisture mass content in 16 hours at 80 ℃ of following vacuum dryings is 0.8%; The mean diameter of bamboo powder is 120 microns with the microscopy statistics; Mean length is 0.2 millimeter with the microscopy statistics, is classified as 120 orders through mesh screen, and making the moisture mass content in 12 hours at 110 ℃ of following vacuum dryings is 2%.Above-mentioned material rotating speed with 1500 rev/mins in impeller was mixed 6 minutes, inject twin screw extruder then, under the condition of 157 ℃ of die head temperatures, 100 rev/mins of screw speeds, carry out melt blending, granulation; Again with the pellet after the blend in injection moulding machine to carry out injection moulding under 154 ℃ of conditions of nozzle temperature; Obtain standard mechanics test bars, the tensile strength that records matrix material is 31MPa, and modulus is 1.0GPa; Elongation at break is 18.1%, and shock strength is 14.2KJ/m
2, heat-drawn wire (HDT) is 74 ℃, matching die makes writing case, pen container, cutlery goods through injection moulding, makes the packing bag goods through blow molding, makes film article through blowfilm shaping.
Embodiment 17
Take by weighing 50 parts of aliphatics aromatic copolyesters (PBAT), 50 parts in bamboo powder, 5 parts of polyethylene waxs, 5 parts of polyoxyethylene glycol (PEG), 1.5 parts of aluminate coupling agents (KL-411-B), 10 parts of talcum powder, 1 part of SP 1 by mass fraction; Wherein: the weight-average molecular weight of PBAT is 50,000; Making the moisture mass content in 12 hours at 60 ℃ of following vacuum dryings is 2%; The bamboo powder is made up of by 1: 1 mass ratio 40 order bamboo powder and 80 order bamboo powder; The mean diameter of 40 order bamboo powder is 370 microns with the microscopy statistics, and for being 2.4 millimeters, the mean diameter of 80 order bamboo powder is 180 microns with the microscopy statistics to mean length with the microscopy statistics; For being 0.5 millimeter, it is 2% that two kinds of bamboo powder made the moisture mass content in 12 hours at 110 ℃ of following vacuum dryings to mean length with the microscopy statistics.Above-mentioned material rotating speed with 1500 rev/mins in impeller was mixed 8 minutes, inject single screw extrusion machine then, under the condition of 157 ℃ of die head temperatures, 100 rev/mins of screw speeds, carry out melt blending, granulation; Again with the pellet after the blend in injection moulding machine to carry out injection moulding under 154 ℃ of conditions of nozzle temperature; Obtain standard mechanics test bars, the tensile strength that records matrix material is 28MPa, and modulus is 1.3GPa; Elongation at break is 11.2%, and shock strength is 9.3KJ/m
2, heat-drawn wire (HDT) is 78 ℃, matching die makes writing case, pen container, Storage jar goods through injection moulding, makes sheet material through extrusion molding and is used for guardrail, floor.
Embodiment 18
Take by weighing 30 parts of aliphatics aromatic copolyesters (PBAT), 70 parts in bamboo powder, 3 parts of polyethylene waxs, 4 parts of polyoxyethylene glycol (PEG), 3 parts of epoxidised soybean oil (ESO), 1 part of aluminate coupling agent (KL-411-B), 1 part of titanate coupling agent (NDZ-311), 3 parts of kaolin, 1 part of Sodium Benzoate by mass fraction; Wherein: the weight-average molecular weight of PBAT is 30,000; Making the moisture mass content in 12 hours at 80 ℃ of following vacuum dryings is 1%; The bamboo powder is made up of by 1: 1 mass ratio 40 order bamboo powder and 80 order bamboo powder; The mean diameter of 40 order bamboo powder is 370 microns with the microscopy statistics; Mean length with the microscopy statistics for being 2.4 millimeters; The mean diameter of 80 order bamboo powder is 180 microns with the microscopy statistics, and for being 0.5 millimeter, it is 2% that two kinds of bamboo powder made the moisture mass content in 12 hours at 110 ℃ of following vacuum dryings to mean length with the microscopy statistics.Above-mentioned material rotating speed with 1500 rev/mins in impeller was mixed 8 minutes, inject single screw extrusion machine then, under the condition of 157 ℃ of die head temperatures, 100 rev/mins of screw speeds, carry out melt blending, granulation; Again with the pellet after the blend in injection moulding machine to carry out injection moulding under 154 ℃ of conditions of nozzle temperature; Obtain standard mechanics test bars, the tensile strength that records matrix material is 25MPa, and modulus is 1.4GPa; Elongation at break is 10.5%, and shock strength is 9.0KJ/m
2, heat-drawn wire (HDT) is 80 ℃, matching die makes writing case, pen container, electric appliance casing goods through injection moulding, makes sheet material through extrusion molding and is used for guardrail, floor.
Embodiment 19
Take by weighing 80 parts of carbon dioxide copolymers (PPC), 20 parts in bamboo powder, 10 parts of polyoxyethylene glycol (PEG), 1 part of silane coupling agent (KH-570), 10 parts of starch, 1 part of Sodium Benzoate by mass fraction; Wherein: the weight-average molecular weight of PPC is 420,000; Making the moisture mass content in 12 hours at 30 ℃ of following vacuum dryings is 5%; The mean diameter of bamboo powder is 150 microns with the microscopy statistics; Mean length is 0.3 millimeter with the microscopy statistics, is classified as 100 orders through mesh screen, and making the moisture mass content in 15 hours at 120 ℃ of following vacuum dryings is 1.5%.Above-mentioned material rotating speed with 1500 rev/mins in impeller was mixed 6 minutes, inject twin screw extruder then, under the condition of 155 ℃ of die head temperatures, 100 rev/mins of screw speeds, carry out melt blending, granulation; Again with the pellet after the blend in injection moulding machine to carry out injection moulding under 152 ℃ of conditions of nozzle temperature; Obtain standard mechanics test bars, the tensile strength that records matrix material is 30MPa, and modulus is 0.8GPa; Elongation at break is 11.6%, and shock strength is 9.5KJ/m
2, heat-drawn wire (HDT) is 68 ℃, matching die makes writing case, Storage jar, cutlery goods through injection moulding, makes the packing bag goods through blow molding, makes film article through blowfilm shaping.
Embodiment 20
Take by weighing 50 parts of carbon dioxide copolymers (PPC), 50 parts in bamboo powder, 10 parts of diethylene glycol dibenzoates (DEDB), 1.5 parts of titanate coupling agents (NDZ-311w), 10 parts of wollastonites, 1 part of Sodium Benzoate by mass fraction; Wherein: the weight-average molecular weight of PPC is 300,000; Making the moisture mass content in 16 hours at 30 ℃ of following vacuum dryings is 4.5%; The mean diameter of bamboo powder is 370 microns with the microscopy statistics; Mean length is 2.4 millimeters with the microscopy statistics, is classified as 40 orders through mesh screen, and making the moisture mass content in 12 hours at 110 ℃ of following vacuum dryings is 2%.Above-mentioned material rotating speed with 1500 rev/mins in impeller was mixed 8 minutes, inject single screw extrusion machine then, under the condition of 155 ℃ of die head temperatures, 100 rev/mins of screw speeds, carry out melt blending, granulation; Again with the pellet after the blend in injection moulding machine to carry out injection moulding under 152 ℃ of conditions of nozzle temperature; Obtain standard mechanics test bars, the tensile strength that records matrix material is 30MPa, and modulus is 1.2GPa; Elongation at break is 10.4%, and shock strength is 9.1KJ/m
2, heat-drawn wire (HDT) is 70 ℃, matching die makes writing case, pen container, Storage jar goods through injection moulding, makes sheet material through extrusion molding and is used for guardrail, floor.
Embodiment 21
Take by weighing 40 parts of carbon dioxide copolymers (PPC), 60 parts in bamboo powder, 3 parts of polyoxyethylene glycol (PEG), 4 parts of diethylene glycol dibenzoates (DEDB), 3 parts of dipropylene glycol dibenzoates (DPGDB), 1 part of aluminate coupling agent (KL-411-B), 1 part of titanate coupling agent (NDZ-311w), 5 parts of silicon-dioxide, 2 parts in lime carbonate by mass fraction; Wherein: the weight-average molecular weight of PPC is 140,000; Making the moisture mass content in 12 hours at 30 ℃ of following vacuum dryings is 5%; The bamboo powder is made up of by 1: 1 mass ratio 40 order bamboo powder and 80 order bamboo powder; The mean diameter of 40 order bamboo powder is 370 microns with the microscopy statistics; Mean length with the microscopy statistics for being 2.4 millimeters; The mean diameter of 80 order bamboo powder is 180 microns with the microscopy statistics, and for being 0.5 millimeter, it is 2% that two kinds of bamboo powder made the moisture mass content in 12 hours at 110 ℃ of following vacuum dryings to mean length with the microscopy statistics.Above-mentioned material rotating speed with 1500 rev/mins in impeller was mixed 8 minutes, inject single screw extrusion machine then, under the condition of 155 ℃ of die head temperatures, 100 rev/mins of screw speeds, carry out melt blending, granulation; Again with the pellet after the blend in injection moulding machine to carry out injection moulding under 152 ℃ of conditions of nozzle temperature; Obtain standard mechanics test bars, the tensile strength that records matrix material is 25MPa, and modulus is 1.4GPa; Elongation at break is 8.3%, and shock strength is 8.9KJ/m
2, heat-drawn wire (HDT) is 73 ℃, matching die makes writing case, Storage jar, electric appliance casing goods through injection moulding, makes sheet material through extrusion molding and is used for guardrail, floor.
Embodiment 22
Take by weighing 20 parts of POLYACTIC ACIDs (PLA), 20 parts of poly butylene succinates (PBS), 60 parts in bamboo powder, 10 parts of tributyl citrates (TBC), 1 part of silane coupling agent (KH-560), 1 part of maleic anhydride (MA), 0.5 part of Lucidol (BPO), 3 parts of kaolin, 1 part of Sodium Benzoate by mass fraction; Wherein: the weight-average molecular weight of PLA is 90,000; L optically active isomer molar content is 96%; The weight-average molecular weight of PBS is 100,000; It is 1% that PLA and PBS made the moisture mass content in 12 hours at 80 ℃ of following vacuum dryings, and the mean diameter of bamboo powder is 370 microns with the microscopy statistics, and mean length is 2.4 millimeters with the microscopy statistics; Be classified as 40 orders through mesh screen, making the moisture mass content in 12 hours at 110 ℃ of following vacuum dryings is 2%.Above-mentioned material rotating speed with 1500 rev/mins in impeller was mixed 8 minutes, inject twin screw extruder then, under the condition of 175 ℃ of die head temperatures, 100 rev/mins of screw speeds, carry out melt blending, granulation; Again with the pellet after the blend in injection moulding machine to carry out injection moulding under 172 ℃ of conditions of nozzle temperature; Obtain standard mechanics test bars, the tensile strength that records matrix material is 33MPa, and modulus is 2.6GPa; Elongation at break is 6.5%, and shock strength is 8.7KJ/m
2, heat-drawn wire (HDT) is 90 ℃, matching die makes writing case, pen container, electric appliance casing, cutlery goods through injection moulding, makes sheet material through extrusion molding and is used for guardrail, floor.
Embodiment 23
Take by weighing 20 parts of POLYACTIC ACIDs (PLA), 20 parts of aliphatics aromatic copolyesters (PBAT), 60 parts in bamboo powder, 10 parts of dipropylene glycol dibenzoates (DPGDB), titanate coupling agent (NDZ-201), 1 part of maleic anhydride (MA), 0.5 part of Lucidol (BPO), 3 parts of silicon-dioxide, 1 part of lactic acid ca by mass fraction; Wherein: the weight-average molecular weight of PLA is 90,000; L optically active isomer molar content is 96%; The weight-average molecular weight of PBAT is 30,000; It is 1% that PLA and PBAT made the moisture mass content in 12 hours at 80 ℃ of following vacuum dryings, and the mean diameter of bamboo powder is 370 microns with the microscopy statistics, and mean length is 2.4 millimeters with the microscopy statistics; Be classified as 40 orders through mesh screen, making the moisture mass content in 12 hours at 110 ℃ of following vacuum dryings is 2%.Above-mentioned material rotating speed with 1500 rev/mins in impeller was mixed 8 minutes, inject twin screw extruder then, under the condition of 175 ℃ of die head temperatures, 100 rev/mins of screw speeds, carry out melt blending, granulation; Again with the pellet after the blend in injection moulding machine to carry out injection moulding under 172 ℃ of conditions of nozzle temperature; Obtain standard mechanics test bars, the tensile strength that records matrix material is 35MPa, and modulus is 2.2GPa; Elongation at break is 8.6%, and shock strength is 9.5KJ/m
2, heat-drawn wire (HDT) is 87 ℃, matching die makes writing case, electric appliance casing goods through injection moulding, makes sheet material through extrusion molding and is used for guardrail, floor.
Embodiment 24
Take by weighing 20 parts of polyhydroxybutyrate-valerates (PHBV), 20 parts of poly butyric esters (PHB), 60 parts in bamboo powder, 10 parts of tetraoctyl 1,2,4,5-benzenetetra-carboxylates (TOPM), 1 part of silane coupling agent (KH-550), 1 part of isocyanic ester (MDI), 0.04 part of dibutyl tin dilaurate, 5 parts in lime carbonate, 1 part of SP 1 by mass fraction; Wherein: the weight-average molecular weight of PHBV is 120,000; The hydroxyl valerate molar content is 5%; The weight-average molecular weight of PHB is 150,000; It is 1.2% that PHBV and PHB made the moisture mass content in 12 hours at 70 ℃ of following vacuum dryings, and the bamboo powder is made up of by 1: 1 mass ratio 40 order bamboo powder and 80 order bamboo powder, and the mean diameter of 40 order bamboo powder is 370 microns with the microscopy statistics; Mean length with the microscopy statistics for being 2.4 millimeters; The mean diameter of 80 order bamboo powder is 180 microns with the microscopy statistics, and for being 0.5 millimeter, it is 2% that two kinds of bamboo powder made the moisture mass content in 12 hours at 80 ℃ of following vacuum dryings to mean length with the microscopy statistics.Above-mentioned material rotating speed with 1500 rev/mins in impeller was mixed 8 minutes, inject single screw extrusion machine then, under the condition of 168 ℃ of die head temperatures, 100 rev/mins of screw speeds, carry out melt blending, granulation; Again with the pellet after the blend in injection moulding machine to carry out injection moulding under 165 ℃ of conditions of nozzle temperature; Obtain standard mechanics test bars, the tensile strength that records matrix material is 21MPa, and modulus is 2.0GPa; Elongation at break is 5.1%, and shock strength is 6.2KJ/m
2, heat-drawn wire (HDT) is 92 ℃, matching die makes electric appliance casing, Storage jar, writing case goods through injection moulding, makes sheet material through extrusion molding and is used for guardrail, floor.
Embodiment 25
Take by weighing 20 parts of polyhydroxybutyrate-valerates (PHBV), 20 parts of 3-hydroxybutyric acids/4 hydroxybutyric acid multipolymer [P (3HB-co-4HB)], 60 parts in bamboo powder, 1 part of tributyl acetylcitrate (ATBC), 1 part of polymeric isocyanate (pMDI), 1 part of maleic anhydride (MA), 0.5 part of Lucidol (BPO), 10 parts of starch, 1 part of SP 1, nanocrystalline 1 part of chitin by mass fraction; Wherein: the weight-average molecular weight of PHBV is 220,000; The hydroxyl valerate molar content is 3%; Making the moisture mass content in 12 hours at 80 ℃ of following vacuum dryings is 1%; The weight-average molecular weight of P (3HB-co-4HB) is 400,000, and the 4 hydroxybutyric acid molar content is 11%, and making the moisture mass content in 12 hours at 60 ℃ of following vacuum dryings is 2%; The mean diameter of bamboo powder is 370 microns with the microscopy statistics; Mean length is 2.4 millimeters with the microscopy statistics, is classified as 40 orders through mesh screen, and making the moisture mass content in 12 hours at 110 ℃ of following vacuum dryings is 2%.Above-mentioned material rotating speed with 1500 rev/mins in impeller was mixed 8 minutes, inject single screw extrusion machine then, under the condition of 160 ℃ of die head temperatures, 100 rev/mins of screw speeds, carry out melt blending, granulation; Again with the pellet after the blend in injection moulding machine to carry out injection moulding under 156 ℃ of conditions of nozzle temperature; Obtain standard mechanics test bars, the tensile strength that records matrix material is 25MPa, and modulus is 1.4GPa; Elongation at break is 6.2%, and shock strength is 6.0KJ/m
2, heat-drawn wire (HDT) is 90 ℃, matching die makes electric appliance casing, Storage jar, writing case goods through injection moulding, makes sheet material through extrusion molding and is used for guardrail, floor.
Embodiment 26
Take by weighing 15 parts of POLYACTIC ACIDs (PLA), 15 parts of polyhydroxybutyrate-valerates (PHBV), 10 parts of aliphatics aromatic copolyesters (PBAT), 60 parts in bamboo powder, 2 parts of polyethylene waxs, 4 parts of epoxidised soybean oil (ESO), 4 parts of triethyl citrates (TEC), 1 part of aluminate coupling agent (KL-411-B), 1 part of titanate coupling agent (NDZ-311), 1 part of maleic anhydride (MA), 0.5 part of Lucidol (BPO), 3 parts of silicon-dioxide, 1 part of sorbyl alcohol, nanocrystalline 1 part of Mierocrystalline cellulose by mass fraction; Wherein: the weight-average molecular weight of PLA is 90,000; L optically active isomer molar content is 97%; The weight-average molecular weight of PHBV is 320,000; The hydroxyl valerate molar content is 8%; The weight-average molecular weight of PBAT is 30,000; It is 2% that PLA, PHBV and PBAT made the moisture mass content in 12 hours at 70 ℃ of following vacuum dryings, and the mean diameter of bamboo powder is 370 microns with the microscopy statistics, mean length with the microscopy statistics for being 2.4 millimeters; Be classified as 40 orders through mesh screen, making the moisture mass content in 12 hours at 110 ℃ of following vacuum dryings is 2%.Above-mentioned material rotating speed with 1500 rev/mins in impeller was mixed 8 minutes, inject twin screw extruder then, under the condition of 172 ℃ of die head temperatures, 100 rev/mins of screw speeds, carry out melt blending, granulation; Again with the pellet after the blend in injection moulding machine to carry out injection moulding under 167 ℃ of conditions of nozzle temperature; Obtain standard mechanics test bars, the tensile strength that records matrix material is 30MPa, and modulus is 2.5GPa; Elongation at break is 6.8%, and shock strength is 7.7KJ/m
2, heat-drawn wire (HDT) is 97 ℃, matching die makes Storage jar, writing case, cutlery goods through injection moulding, makes sheet material through extrusion molding and is used for guardrail, floor.
Embodiment 27
Take by weighing 15 parts of carbon dioxide copolymers (PPC), 15 parts of polyhydroxybutyrate-valerates (PHBV), 10 parts of poly butylene succinates (PBS), 60 parts in bamboo powder, 2 parts of glycerine, 3 parts of epoxidised soybean oil (ESO), 5 parts of tributyl acetylcitrates (ATBC), 1 part of silane coupling agent (KH-550), 1 part of polymeric isocyanate (pMDI), 1 part of maleic anhydride (MA), 0.5 part of Lucidol (BPO), 10 parts of starch, 1 part of SP 1, nanocrystalline 1 part of chitin by mass fraction; Wherein: the weight-average molecular weight of PPC is 300,000; The weight-average molecular weight of PHBV is 120,000; The hydroxyl valerate molar content is 12%; The weight-average molecular weight of PBS is 140,000; It is 5% that PPC made the moisture mass content in 12 hours at 30 ℃ of following vacuum dryings; It is 1.2% that PHBV and PBS made the moisture mass content in 12 hours at 70 ℃ of following vacuum dryings, and the bamboo powder is made up of by 1: 1: 1 mass ratio 40 order bamboo powder, 60 order bamboo powder, 120 order bamboo powder, and the mean diameter of 40 order bamboo powder is 370 microns with the microscopy statistics; Mean length with the microscopy statistics for being 2.4 millimeters; The mean diameter of 80 order bamboo powder is 180 microns with the microscopy statistics, and for being 0.5 millimeter, the mean diameter of 120 order bamboo powder is 120 microns with the microscopy statistics to mean length with the microscopy statistics; For being 0.2 millimeter, it is 2% that three kinds of bamboo powder made the moisture mass content in 12 hours at 110 ℃ of following vacuum dryings to mean length with the microscopy statistics.Above-mentioned material rotating speed with 1500 rev/mins in impeller was mixed 8 minutes, inject twin screw extruder then, under the condition of 165 ℃ of die head temperatures, 100 rev/mins of screw speeds, carry out melt blending, granulation; Again with the pellet after the blend in injection moulding machine to carry out injection moulding under 162 ℃ of conditions of nozzle temperature; Obtain standard mechanics test bars, the tensile strength that records matrix material is 24MPa, and modulus is 1.8GPa; Elongation at break is 8.1%, and shock strength is 9.5KJ/m
2, heat-drawn wire (HDT) is 91 ℃, matching die makes electric appliance casing, writing case, pen container goods through injection moulding, makes sheet material through extrusion molding and is used for guardrail, floor.
Claims (7)
1. bamboo powder filled biomass degradable composite material is characterized in that the component of this matrix material and the mass fraction of each component are:
30～80 parts of biodegradable resins;
20～70 parts in bamboo powder;
1～19 part in softening agent;
0.6～6 part of interface modifier;
4～12 parts of auxiliary agents;
Described biodegradable resin is the poly-blended objects system of one or more formations in poly butyric ester, polyhydroxybutyrate-valerate, 3-hydroxybutyric acid/4 hydroxybutyric acid multipolymer, poly butylene succinate, aliphatics aromatic copolyester, the carbon dioxide copolymer; The moisture mass content is smaller or equal to 5% in the biodegradable resin;
The weight-average molecular weight of described poly butyric ester is 80,000～230,000;
The weight-average molecular weight of described polyhydroxybutyrate-valerate is 90,000～500,000, the hydroxyl valerate molar content is 3%～23%;
The weight-average molecular weight of described 3-hydroxybutyric acid/4 hydroxybutyric acid multipolymer is 70,000～700,000, the 4 hydroxybutyric acid molar content is 4%～20%;
The weight-average molecular weight of described poly butylene succinate is 70,000～190,000;
The weight-average molecular weight of described aliphatics aromatic copolyester is 30,000～80,000;
The weight-average molecular weight of described carbon dioxide copolymer is 140,000～420,000;
The mean diameter of described bamboo powder is 75～500 microns, and mean length is 0.1～5 millimeter, and obtaining the order number through the mesh screen classification is 30～200 bamboo powder; The moisture mass content is smaller or equal to 10% in the bamboo powder.
2. a kind of bamboo powder filled biomass degradable composite material as claimed in claim 1 is characterized in that:
Described softening agent is one or more in polyoxyethylene glycol, polyethylene wax, glycerine, DEDB, terephthalate, tetraoctyl 1,2,4,5-benzenetetra-carboxylate, trimellitic acid fat, epoxidized vegetable oil, citrate, the acetyl citrate.
3. a kind of bamboo powder filled biomass degradable composite material as claimed in claim 1 is characterized in that:
Described interface modifier is one or more in silane coupling agent, titanate coupling agent, aluminate coupling agent, isocyanic ester/tin class catalyzer, polymeric isocyanate, the maleic anhydride/peroxide initiator; Wherein, the tin class catalyzer in isocyanic ester/tin class catalyzer is stannous octoate or dibutyl tin dilaurate, and the add-on of tin class catalyzer is 1%～10% of an isocyanic ester; Peroxide initiator in maleic anhydride/peroxide initiator is Lucidol or Di Cumyl Peroxide 99, and the peroxide initiator add-on is 10%～50% of a maleic anhydride.
4. a kind of bamboo powder filled biomass degradable composite material as claimed in claim 1 is characterized in that:
Described auxiliary agent comprises auxiliary packing and nucleator, and wherein said auxiliary packing is a kind of in starch, talcum powder, silicon-dioxide, titanium oxide, kaolin, lime carbonate, the wollastonite;
Described nucleator is that Mierocrystalline cellulose is nanocrystalline, chitin is nanocrystalline, in the SP 1 one or both.
5. a kind of bamboo powder filled biomass degradable composite material as claimed in claim 1 is characterized in that: the moisture mass content of described biodegradable resin is smaller or equal to 1%.
6. a kind of bamboo powder filled biomass degradable composite material as claimed in claim 1 is characterized in that: the moisture mass content is smaller or equal to 2% in the described bamboo powder.
7. the preparation method of bamboo powder filled biomass degradable composite material is characterized in that the concrete steps of this method are:
Step 1. is even in stirrer for mixing by following mass fraction with biodegradable resin, bamboo powder, softening agent, interface modifier, auxiliary agent;
30～80 parts of biodegradable resins;
20～70 parts in bamboo powder;
1～19 part in softening agent;
0.6～6 part of interface modifier;
4～12 parts of auxiliary agents;
Described biodegradable resin is the poly-blended objects system of one or more formations in poly butyric ester, polyhydroxybutyrate-valerate, 3-hydroxybutyric acid/4 hydroxybutyric acid multipolymer, poly butylene succinate, aliphatics aromatic copolyester, the carbon dioxide copolymer; The moisture mass content is smaller or equal to 5% in the biodegradable resin;
The weight-average molecular weight of described poly butyric ester is 80,000～230,000;
The weight-average molecular weight of described polyhydroxybutyrate-valerate is 90,000～500,000, the hydroxyl valerate molar content is 3%～23%;
The weight-average molecular weight of described 3-hydroxybutyric acid/4 hydroxybutyric acid multipolymer is 70,000～700,000, the 4 hydroxybutyric acid molar content is 4%～20%;
The weight-average molecular weight of described poly butylene succinate is 70,000～190,000;
The weight-average molecular weight of described aliphatics aromatic copolyester is 30,000～80,000;
The weight-average molecular weight of described carbon dioxide copolymer is 140,000～420,000;
The mean diameter of described bamboo powder is 75～500 microns, and mean length is 0.1～5 millimeter, and obtaining the order number through the mesh screen classification is 30～200 bamboo powder; The moisture mass content is smaller or equal to 10% in the bamboo powder;
Step 2. is carried out melt blending, granulation with resulting mixture in the step 1 in screw extrusion press, obtain pellet; Described screw extrusion press is single screw extrusion machine or multiple screw extruder;
Step 3. in the different shapes die for molding, obtains difform bamboo powder filled biomass degradable composite material through injection moulding machine, sheet extrusion shaper, blow moulding machine or inflation film manufacturing machine with resulting pellet in the step 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102887261A CN101942184B (en) | 2010-09-21 | 2010-09-21 | Bamboo powder filling biodegradable compound material and preparation method thereof |
Applications Claiming Priority (1)
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