CN101602882A - Bamboo powder filled biomass-based resin composite material and preparation method thereof - Google Patents
Bamboo powder filled biomass-based resin composite material and preparation method thereof Download PDFInfo
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- CN101602882A CN101602882A CNA2008100621980A CN200810062198A CN101602882A CN 101602882 A CN101602882 A CN 101602882A CN A2008100621980 A CNA2008100621980 A CN A2008100621980A CN 200810062198 A CN200810062198 A CN 200810062198A CN 101602882 A CN101602882 A CN 101602882A
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- bamboo powder
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- 235000017166 Bambusa arundinacea Nutrition 0.000 title claims abstract description 106
- 235000017491 Bambusa tulda Nutrition 0.000 title claims abstract description 106
- 241001330002 Bambuseae Species 0.000 title claims abstract description 106
- 235000015334 Phyllostachys viridis Nutrition 0.000 title claims abstract description 106
- 239000011425 bamboo Substances 0.000 title claims abstract description 106
- 239000000843 powder Substances 0.000 title claims abstract description 87
- 239000000463 material Substances 0.000 title claims abstract description 39
- 239000002028 Biomass Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000805 composite resin Substances 0.000 title claims abstract description 10
- 239000007822 coupling agent Substances 0.000 claims abstract description 29
- 239000006096 absorbing agent Substances 0.000 claims abstract description 26
- 229920006025 bioresin Polymers 0.000 claims abstract description 24
- 239000011159 matrix material Substances 0.000 claims abstract description 21
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 11
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 11
- -1 poly butylene succinate Polymers 0.000 claims description 35
- 238000001035 drying Methods 0.000 claims description 25
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 25
- 229920002961 polybutylene succinate Polymers 0.000 claims description 22
- 238000010411 cooking Methods 0.000 claims description 19
- 239000004631 polybutylene succinate Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- 230000001404 mediated effect Effects 0.000 claims description 18
- 238000005469 granulation Methods 0.000 claims description 15
- 230000003179 granulation Effects 0.000 claims description 15
- 238000009835 boiling Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 239000002131 composite material Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 claims description 10
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 239000002023 wood Substances 0.000 claims description 8
- 150000004645 aluminates Chemical class 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 238000011010 flushing procedure Methods 0.000 claims description 4
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 238000010298 pulverizing process Methods 0.000 claims description 4
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
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- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N ethyl butyrate Chemical compound CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- UQGPCEVQKLOLLM-UHFFFAOYSA-N pentaneperoxoic acid Chemical compound CCCCC(=O)OO UQGPCEVQKLOLLM-UHFFFAOYSA-N 0.000 claims description 2
- 229940070710 valerate Drugs 0.000 claims description 2
- 239000004626 polylactic acid Substances 0.000 claims 3
- 229920000520 poly(3-hydroxybutyrate-co-3-hydroxyvalerate) Polymers 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 8
- 235000013305 food Nutrition 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000003755 preservative agent Substances 0.000 abstract description 4
- 230000002335 preservative effect Effects 0.000 abstract description 4
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- 238000010168 coupling process Methods 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- 239000008188 pellet Substances 0.000 description 22
- 239000000047 product Substances 0.000 description 22
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- 229920001155 polypropylene Polymers 0.000 description 4
- 235000013311 vegetables Nutrition 0.000 description 4
- BDIZXIOWAPGQTJ-UHFFFAOYSA-N bis(2-ethylhexyl) phosphono phosphate Chemical compound CCCCC(CC)COP(=O)(OP(O)(O)=O)OCC(CC)CCCC BDIZXIOWAPGQTJ-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
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- 229920001277 pectin Polymers 0.000 description 3
- 235000010987 pectin Nutrition 0.000 description 3
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- 102000004169 proteins and genes Human genes 0.000 description 3
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- 229910002059 quaternary alloy Inorganic materials 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 229940089401 xylon Drugs 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 229920001587 Wood-plastic composite Polymers 0.000 description 1
- WYRGOSDNPFGZFG-UHFFFAOYSA-K [bis(2-ethylhexoxy)-oxidophosphaniumyl] dihydrogen phosphate [bis(2-ethylhexoxy)-oxidophosphaniumyl] hydrogen phosphate [bis(2-ethylhexoxy)-oxidophosphaniumyl] phosphate propan-2-olate titanium(4+) Chemical compound [Ti+4].CC(C)[O-].CCCCC(CC)CO[P+]([O-])(OCC(CC)CCCC)OP(O)(O)=O.CCCCC(CC)CO[P+]([O-])(OCC(CC)CCCC)OP(O)([O-])=O.CCCCC(CC)CO[P+]([O-])(OCC(CC)CCCC)OP([O-])([O-])=O WYRGOSDNPFGZFG-UHFFFAOYSA-K 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
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- IXSZQYVWNJNRAL-UHFFFAOYSA-N etoxazole Chemical compound CCOC1=CC(C(C)(C)C)=CC=C1C1N=C(C=2C(=CC=CC=2F)F)OC1 IXSZQYVWNJNRAL-UHFFFAOYSA-N 0.000 description 1
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Abstract
A kind of bamboo powder filled biomass-based resin composite material comprises the component of following weight proportion: 20～60 parts in bamboo powder, 40～80 parts of bio-based resins, 0.8～5 part of coupling agent, 0.2～0.6 part of antioxidant, 0.1～0.7 part of UV light absorber.The invention also discloses the preparation method of this matrix material.Compared with prior art, advantage of the present invention is: adopting depleted bamboo powder is raw material, by coupling agent the bio-based resin coupling of the bamboo powder of hydrophilic oleophobic and oleophilic drainage is got up, improved the interface compatibility and the cohesive strength of bamboo powder and bio-based resin, this matrix material can be widely used in fields such as automotive upholstery, traffic roadblock, food bag, preservative film, disposable tablecloth, disposable lunch box, flowerpot, knife and fork.
Description
Technical field
The present invention relates to a kind of environment-friendly composite material, relating in particular to a kind of is the matrix material of raw material with bamboo powder and bio-based resin, the invention still further relates to the preparation method of bamboo powder filled biomass-based resin composite material.
Background technology
In recent years, with the originate matrix material of the compound preparation of plastics of natural plant fibres such as timber, bamboo wood and multiple oil such as polypropylene, polyethylene, polyvinyl chloride, fields such as automotive trim, building structure, fitting-up have been widely used in.For wooden material, xylon, wood powder all have research fully and use, and have obtained certain economic benefits and social benefit.But timber is become a useful person the cycle long (about 20～30 years), and China is the abundant country of a timber resources, and reserves are little, and output does not satisfy the needs in market, this application that is restricting wood plastic composite and development more or less.Comparatively speaking, bamboo wood is a kind of growth cycle fast (about 2～3 years), and is very abundant at China's bamboo timber resource, and the renewable very widely plant of purposes is to advantages such as environment and ecological damage are few.Therefore, along with the fast development of bamboo processing industry, bamboo-plastic composite material will be faster, is applied in people's all respects such as clothing, food, lodging and transportion--basic necessities of life widely.
The utilization of bamboo wood, great majority are earlier bamboo processing to be become bamboo fibers, after a series of processing and modification, carry out compoundly with resin and plastic again, make related compound material and goods.This type of document is more, as: publication number is the Chinese invention patent application of CN101003667A, a kind of " poly(lactic acid)/natural-fiber composite material and production method thereof " disclosed, and for example: Chinese invention patent ZL200410060809.X discloses a kind of " complete processing of bamboo fibers " (Granted publication number for CN1263922C), the former the undeclared concrete source of described natural fiber mode, poly(lactic acid) does not provide the molecular weight size yet, left-handed or dextrorotation structure is (hereinafter to be referred as L or D, specifically shown in Figure 1 as follows) information such as content, and, such as materials such as bamboo fiberss, (do not remove pectin through handling early stage, polysaccharide, protein etc.), can go up the over-all properties that influences matrix material largely; The described complete processing of the latter is to carry out postorder after the finished product bamboo wood will being broken apart by chopping, pulverizes again to handle, and wastes resource and has brought certain environment negative effect.
And for a long time, a large amount of bamboo powder waste materials all is to adopt burning, landfill or mode such as abandon is handled after the bamboo processing, is not effectively utilized.
For this reason, the patent No. is that to disclose a kind of be the matrix material of main raw material with bamboo fibers, bamboo powder, xylon resin base to the Chinese invention patent " bamboo fibers, bamboo powder, xylon polymer matrix composites " (Granted publication number for CN1284831C) of ZL200410061464.X, and interpolation tackiness agent (as Resins, epoxy, urea-formaldehyde resin or resol), solidifying agent and thinner, compression moulding under certain temperature and pressure condition, its finished product outward appearance is coarse, but the material cutting is relatively poor and be difficult to be pressed into sample than complicated shape.
In addition, research (the Li Zhenghong of document bamboo fibers reinforced polypropylene compound material, Fujian Forestry Inst.'s journal, 2005,25 (3): 179-201) provided a kind of method for preparing the bamboo fibers reinforced polypropylene compound material, though this method is matrix with plastics, and employing number average length is that the bamboo powder of 0.33mm is a weighting agent, can improve because bamboo powder length-to-diameter ratio is too big, the mobile difference of material compound tense causes being difficult to extruding or the shortcoming of injection moulding processing, but the characteristic that polypropylene is degraded hardly makes it in the difficult advantage that shows of the current society that advocates " recycling economy, green economy ".
As improvement, publication number is the Chinese invention patent application of CN1827700A, " a kind of bamboo powder-high density polyethylene composite materials and preparation method thereof " disclosed, similarly also having publication number is the Chinese invention patent application of CN1827699A, CN1865339A, and these patents provide bamboo powder new application scheme in matrix material.
Summary of the invention
First technical problem to be solved by this invention is to provide a kind of environmental protection, handling ease and well behaved bamboo powder filled biomass-based resin composite material at the above-mentioned state of the art, and it is that main raw material makes with bamboo powder and bio-based resin that this matrix material utilizes coupling agent.
Second technical problem to be solved by this invention provides a kind of bamboo powder filled biomass-based resin composite material preparation method, this method handling ease, and preparation cost is cheap.
The present invention solves the technical scheme that above-mentioned first technical problem adopts: this bamboo powder filled biomass-based tree matrix material comprises the component of following weight proportion:
20～60 parts in bamboo powder;
40～80 parts of bio-based resins;
0.8～5 part of coupling agent;
0.2～0.6 part of antioxidant;
0.1～0.7 part of UV light absorber.
Described bamboo powder preferably makes successively as follows:
A, classification operation are that mesh screen is crossed as 40～200 purposes in the bamboo wood material pulverizing back that will collect, obtain the bamboo powder of granularity less than 0.4mm, obtain former bamboo powder;
B, cooking process are that boiling temperature is 85～100 ℃ with the former bamboo powder boiling in cooking liquor after the classification, and cooking time is 2～3 hours, and the mass ratio of cooking liquor and bamboo powder is 5: 1～7: 1, and boiling finishes post-flush, dries;
In c, bleaching process, the bamboo powder after will drying are put into volume ratio 1: 1～2.5: 1 the water-reducible hydrogen peroxide, stir bleaching in 2～3 hours;
D, matting, water flushing, pH is between 7.0～7.5 to the system;
E, drying process, vacuum-drying in 70～95 ℃ of scopes, the standby bamboo powder water content in dry back is less than 12%.
Described bio-based resin is to be the polymkeric substance of one or more resin alloys of forming of feedstock conversion with the renewable resources.The renewable resources here can be cereal, pulse family, cotton, straw and vegetables oil, lignocellulose etc.Further, described polymkeric substance be in poly(lactic acid) (PLA), polyhydroxyalkanoate (PHA) or the poly butylene succinate (PBS) any one, or any binary blend system of the two among the three, or three's tertiary blending system, each component ratio of co-mixing system be any than.
To PLA, its weight-average molecular weight is 60,000～160,000, and the L molar content is 42%～98%;
To PHA (the following Fig. 2 of structural formula), can be considered the polymkeric substance of fat hydroxyl acid, equal poly structure that both can Fig. 2 (A) exists, and copolymerization structure formation that also can Fig. 2 (B) exists.To Fig. 2 (A), R is positive alkyl group side chain, and to nonyl, m is 1,2 or 3 to scope from methyl, but in most cases m is 1, and especially, when R was methyl, PHA was poly butyric ester (PHB), and its weight-average molecular weight is 90,000～230,000; To Fig. 2 (B), R
1, R
2Be positive alkyl group side chain, to nonyl, x, m are 1,2 or 3 to scope from methyl, but most applications is 1, especially, works as R
1Be methyl, R
2Be ethyl, or R
1Be ethyl, R
2During for methyl and x=m=1, PHA is polyhydroxybutyrate-valerate (PHBV), and its weight-average molecular weight is 110,000～180,000, and hydroxyl valerate molar content (hereinafter to be referred as HV%) is 3%～23%;
To PBS, its weight-average molecular weight is 80,000～190,000.
Described coupling agent can be one or more of silane coupling agent, titanate coupling agent and aluminate coupling agent.Described antioxidant can be one or both of antioxidant 168 or antioxidant 1010.Described UV light absorber can be one or more of UV-531, UV-571, UV-284.
The present invention solves above-mentioned second technical scheme that technical problem adopted: a kind of preparation method of bamboo powder filled biomass-based resin composite material in turn includes the following steps:
A, bamboo powder and coupling agent are stirred;
B, again the product among the above-mentioned steps a and bio-based resin, antioxidant and UV light absorber are mediated;
C, the product among the above-mentioned steps b is carried out granulation in twin screw extruder, oven dry.
Wherein, each composition weight proportioning is as follows:
20～60 parts in bamboo powder;
40～80 parts of bio-based resins;
0.8～5 part of coupling agent;
0.2～0.6 part of antioxidant;
0.1～0.7 part of UV light absorber.
The drying-granulating material is through injection moulding machine, sheet forming machine, blow moulding machine or inflation film manufacturing machine, in the different shapes die for molding, obtain difform bamboo powder-biomass-based resin composite material finished product, both can make baroque goods by Shooting Technique, also can make articles for daily use by plastic uptake technology, more can make sheet material or sheet material by melt extruding, end product flexibly, extensively can be practical.
Bio-based resin (PLA, PHB, PHBV, PBS etc.) can be a raw material with biomass such as renewable resources such as cereal, pulse family, cotton, straw and vegetables oil, lignocelluloses, change into certain chemical earlier, but be converted into the polymkeric substance of thermoplastic processing again by biological, chemical process.In recent years because technology improves and the decline of production cost, make bio-based resin more and more be subjected to people's attention and the parent looks at.Though the plastics in fossil resource source have superior cost performance, a series of problems such as its extremely urgent resource scarcity, white pollution and scrap handling, but bring powerful historic opportunities for the development of fast degraded biologically bio-based resin.
Thus, it is compound to utilize plant powder and bio-based resin to carry out effective blend, can give full play to the advantage separately of resin and vegetable fibre, avoid the problems of fossil resource source plastics, being to expand the effective way that bio-based resin is used chain, also is the new model of plant resources high-value-use, bio-based resin industrialized development.
Compared with prior art, the invention has the advantages that: by coupling agent the bio-based resin coupling of the bamboo powder of hydrophilic oleophobic and oleophilic drainage, improve the interface compatibility and the cohesive strength of bamboo powder and bio-based resin, can give full play to the advantage separately of resin and vegetable fibre, avoid the problems of fossil resource source plastics, expand the approach of bio-based resin application chain, reached the purpose of the over-all properties of improving matrix material.Full biomass source based on matrix material, dissolving property of environment is superior, and the matrix material outward appearance that obtains is good, warpage not, have certain stretching-resisting bending-resisting intensity, therefore can be used as automotive upholstery, traffic roadblock instrument, sports goods, knife and fork, disposable lunch-box, tablecloth, outdoor flowerpot, cup and hotel's daily necessities etc.This matrix material integral body can turn waste into wealth, and environmental friendliness, and resource is fully used.
Description of drawings
Fig. 1 is L, the D structure explanatory view of poly(lactic acid);
Fig. 2 is the PHA skeleton symbol.
Embodiment
Embodiment describes in further detail the present invention below in conjunction with accompanying drawing.
The former bamboo powder other to the bamboo processing machine, except that existing certain impurity, size differ, some minor component of own intrinsic (as protein, fat, pectin etc.) needs to remove before compound blend, so, need after the pulverizing through following a few step treatment process: classification, boiling, bleaching, cleaning, drying.Through after the above processing, obtain standby bamboo powder.
Described classification operation is the former bamboo powder of collecting to be pulverized the back cross 40-200 order mesh screen, tentatively obtains the bamboo powder of granularity less than 0.4mm;
Described cooking process is with the former bamboo powder boiling some time in cooking liquor after the classification, and its purpose is to dissolve materials such as the pectin that contains in the former bamboo powder, protein.Wherein said cooking liquor is the aqueous solution of caustic soda (NaOH), the add-on of caustic soda is that the pH of cooking liquor is remained on more than 12, described boiling temperature is 85～100 ℃, cooking time is 2～3h, the mass ratio of cooking liquor and bamboo powder is 5: 1～7: 1, the intact back of boiling flushing with clean water 2～3 times is dried naturally;
Described bleaching process is that natural air dried bamboo powder after the above-mentioned boiling is bleached processing.Be specially: the bamboo powder after will drying is put in water be diluted to volume ratio 1: 1～2.5: 1 the hydrogen peroxide, stirs fully bleaching in 2～3 hours;
Described cleaning, drying process adopt technology well known in the art to get final product, and still, want in the guarantee system pH after the cleaning about 7.3, obtain water content after the drying less than 12% standby bamboo powder.
Then bamboo powder and coupling agent are stirred;
Again the product in the above-mentioned steps and bio-based resin, antioxidant and UV light absorber are mediated;
At last product is carried out granulation at twin screw extruder with under 167 ℃～210 ℃, 80rpm～120rpm condition, on equipment such as forcing machine, injection moulding machine, inflation film manufacturing machine, sheet-forming machine, make the product of different shapes, different size, different purposes then.
Wherein, each composition weight proportioning is as follows:
20～60 parts in bamboo powder;
40～80 parts of bio-based resins;
0.8～5 part of coupling agent;
0.2～0.6 part of antioxidant;
0.1～0.7 part of UV light absorber.
Embodiment 1:
With 20 parts of (mass fractions of standby bamboo powder, down together), titanate coupling agent (NDZ-311) stirs for 0.8 part, again with drying treatment after 80 parts of poly(lactic acid) (PLA), the Mw=11 ten thousand of this poly(lactic acid), L content 67%, mass ratio is 1: 1 0.4 part in a mixing oxidation inhibitor at 1010: 168, after 0.2 part of high speed of UV-571 UV light absorber is fully mediated 18 minutes, pour in the twin screw extruder while hot, extruding pelletization under 180 ℃ of die head temperatures, screw speed 80rpm condition, pellet is uniformly mixed.Next step, will mix pellet in injection moulding machine to carry out injection moulding under 175 ℃ of temperature process of nozzle temperature, supporting knife and fork mould obtains disposable knife and fork goods.
Embodiment 2:
With 30 parts of (mass fractions of standby bamboo powder, down together), silane coupling agent (KH-550) stirs for 1.2 parts, again with drying treatment after 70 parts of polyhydroxybutyrate-valerates (PHBV), the Mw=12 ten thousand of this PHBV, HV% is 4%, 0.3 part in 168 oxidation inhibitor, mass ratio UV-531: UV-284 is that 1: 2 mixing UV light absorber is fully mediated after 25 minutes in homogenizer for 0.3 part together, pour granulation under 169 ℃ of die head temperatures, screw speed 110rpm condition in the twin screw extruder while hot into, pellet is uniformly mixed.Next step, to mix pellet melt extrudes under 170 ℃ of temperature, on the sheet forming machine with 170 ℃, 11MPa hot pressing, by regulating roller space (0.6～3mm), obtain the different sheet material of thickness, under malleation or condition of negative pressure, sheet material is made the product commonly used of life cycles weak points such as difform disposable lunch box, plate, flowerpot while hot.
Embodiment 3:
With 20 parts of (mass fractions of standby bamboo powder, down together), silane coupling agent (KH-570) stirs for 0.8 part, again with drying treatment after 80 parts of poly butyric esters (PHB), the Mw=15 ten thousand of this PHB, 0.4 part in 1010 oxidation inhibitor, mass ratio UV-531: UV-284 is that 1: 4 mixing UV light absorber is fully mediated after 28 minutes in homogenizer for 0.4 part together, pour granulation under 175 ℃ of die head temperatures, screw speed 90rpm condition in the twin screw extruder while hot into, pellet is uniformly mixed.Next step introduces injection moulding in the injection moulding machine with mangcorn, 180 ℃ of nozzle temperatures, and moulds such as supporting flowerpot, knife and fork obtain products such as disposable flowerpot, knife and fork.
Embodiment 4:
With 30 parts of (mass fractions of standby bamboo powder, down together), titanate coupling agent (NDZ-311) stirs for 1.5 parts, again with drying treatment after 70 parts of polyhydroxybutyrate-valerates (PHBV), the Mw=11 ten thousand of this PHBV, HV% is 8%, be at 1010: 168 1: 1 0.6 part in oxidation inhibitor, the UV-531 UV light absorber is fully mediated after 22 minutes in homogenizer for 0.4 part together, pour granulation under 172 ℃ of die head temperatures, screw speed 110rpm condition in the twin screw extruder while hot into, pellet is uniformly mixed.Next step, to mix pellet melt extrudes under 170 ℃ of temperature, on the sheet forming machine with 170 ℃, 10MPa hot pressing, by regulating roller space (0.6～3mm), obtain the different sheet material of thickness, under malleation or condition of negative pressure, sheet material made products such as difform disposable lunch box, plate, flowerpot while hot.
Embodiment 5:
With 50 parts of (mass fractions of standby bamboo powder, down together), aluminate coupling agent (KL-411-B) stirs for 2.0 parts, again with drying treatment after 50 parts of polyhydroxybutyrate-valerates (PHBV), the Mw=18 ten thousand of this PHBV, HV% is 3%, 0.5 part in 1010 oxidation inhibitor, the UV-571 UV light absorber is fully mediated after 30 minutes in homogenizer for 0.6 part together, pour granulation under 175 ℃ of die head temperatures, screw speed 80rpm condition in the twin screw extruder while hot into, pellet is uniformly mixed.Next step, to mix pellet melt extrudes under 172 ℃ of temperature, on the sheet forming machine with 170 ℃, 15MPa hot pressing, by regulating roller space (0.6～5mm), obtain the different sheet material of thickness, after sheet material carried out reasonable cutting and assembly unit, can make products such as the traffic roadblock of certain purposes and guardrail.
Embodiment 6:
With 20 parts of (mass fractions of standby bamboo powder, down together), (mass ratio NDZ-311: NDZ-311w=1: 1) 1.2 parts stir composite titanium acid esters coupling agent, again with drying treatment after 80 parts of PBS (Mw=17 ten thousand), 0.5 part in 1010 oxidation inhibitor, UV light absorber is fully mediated after 30 minutes in homogenizer for 0.2 part together, pour granulation under 180 ℃ of die head temperatures, screw speed 80rpm condition in the twin screw extruder while hot into, pellet is uniformly mixed.Next step, to mix pellet melt extrudes under 185 ℃ of temperature, in inflation film manufacturing machine, carry out blown film by certain technology, regulate pulling speed and adjust thickness (0.05～0.1mm), can obtain the membrane product of different thickness, again through making hotel's articles for use such as eco-friendly food bag, preservative film, refuse bag and disposable tablecloth after printing, the cutting processing.
Embodiment 7:
With 30 parts of (mass fractions of standby bamboo powder, down together), titanate coupling agent (NDZ-311w) stirs for 1.2 parts, again with drying treatment after 70 parts of poly(lactic acid) (PLA), the Mw=15 ten thousand of this poly(lactic acid), L content 55%, mass ratio is 3: 1 0.4 part in a mixing oxidation inhibitor at 1010: 168, after 0.2 part of high speed of UV-531 UV light absorber is fully mediated 18 minutes, pour in the twin screw extruder while hot, extruding pelletization under 200 ℃ of die head temperatures, screw speed 90rpm condition, pellet is uniformly mixed.Next step, to mix pellet melt extrudes under 195 ℃ of temperature, on the sheet forming machine with 200 ℃, 15MPa hot pressing, by regulating roller space (0.6～5mm), obtain the different sheet material of thickness, after sheet material carried out reasonable cutting and assembly unit, can make products such as the traffic roadblock of certain purposes and guardrail.
Embodiment 8:
With 45 parts of (mass fractions of standby bamboo powder, down together), titanate coupling agent (NDZ-201) stirs for 1.5 parts, again with drying treatment after PHBV (Mw=16 ten thousand, HV% is 12%) 55 parts, 0.4 part in 1010 oxidation inhibitor, mass ratio UV-531: UV-571 is that 1: 1 mixing UV light absorber is fully mediated after 25 minutes in homogenizer for 0.4 part together, pour in the twin screw extruder while hot, under 168 ℃ of die head temperatures, screw speed 90rpm condition, carry out granulation, obtain uniform bamboo powder/PHBV binary system composite granule.Next step, to mix pellet melt extrudes under 170 ℃ of temperature, on sheet-forming machine with 170 ℃, 2MPa precompressed 3 minutes, again with 170 ℃, 13MPa hot pressing 8 minutes, the 5min moulding of colding pressing under the 11MPa condition at last is by mold exchange more or regulate mold interval (3mm～11mm), obtain the different sheet material of thickness, this product is because light weight, environmental protection, characteristics such as energy-conservation can be applicable to fields such as automotive upholstery, traffic roadblock instrument, sports goods.
Embodiment 9:
With 50 parts of (mass fractions of standby bamboo powder, down together), titanate coupling agent (NDZ-101) stirs for 1.2 parts, again with drying treatment after PHBV (Mw=16 ten thousand, HV% is 12%) 30 parts, 0.2 part in 20 parts of PBS (Mw=15 ten thousand) and 168 oxidation inhibitor, mass ratio UV-531: UV-571 is that 1: 3 mixing UV light absorber is fully mediated after 22 minutes in homogenizer for 0.4 part together, pour in the twin screw extruder while hot, 169 ℃ of die head temperatures, carry out granulation under the screw speed 100rpm condition, obtain the composite granule of uniform bamboo powder/PHBV/PBS ternary system.Next step, to mix pellet melt extrudes under 172 ℃ of temperature, on sheet-forming machine with 175 ℃, 2MPa precompressed 3 minutes, again with 175 ℃, 13MPa hot pressing 8 minutes, the 5min moulding of colding pressing under the 11MPa condition at last is by mold exchange more or regulate mold interval (3mm～11mm), obtain the different sheet material of thickness, this product is because light weight, environmental protection, characteristics such as energy-conservation can be applicable to fields such as automotive upholstery, traffic roadblock instrument, sports goods.
Embodiment 10:
With 32 parts of (mass fractions of standby bamboo powder, down together), aluminate coupling agent (DL-2411-C) stirs for 1.2 parts, again with drying treatment after PHBV (Mw=13 ten thousand, HV% is 12%) 28 parts, 25 parts of PBS (Mw=15 ten thousand), (Mw=15 ten thousand for PLA, L content is 85%) 0.6 part in 15 parts and 1010 oxidation inhibitor, mass ratio UV-531: UV-284 is that 4: 1 mixing UV light absorber are fully mediated after 25 minutes in homogenizer for 0.5 part together, pour in the twin screw extruder while hot, 172 ℃ of die head temperatures, carry out granulation by certain technology under the screw speed 105rpm condition, obtain the composite granule of uniform bamboo powder/PHBV/PBS/PLA quaternary system.Next step, to mix pellet melt extrudes under 170 ℃ of temperature, on sheet-forming machine with 170 ℃, 2MPa precompressed 2min, again with 165 ℃, 14MPa hot pressing 8 minutes, the moulding in 5 minutes of colding pressing under the 12MPa condition at last is by mold exchange more or regulate mold interval (3mm～11mm), obtain the different sheet material of thickness, this product is because light weight, environmental protection, characteristics such as energy-conservation can be applicable to fields such as automotive upholstery, traffic roadblock instrument, sports goods.
Embodiment 11:
With 20 parts of (mass fractions of standby bamboo powder, down together), silane coupling agent (KH-560) stirs for 0.8 part, again with drying treatment after PHBV (Mw=19 ten thousand, HV% is 12%) 10 parts, 0.3 part in 70 parts of poly butylene succinates (PBS) (Mw=17 ten thousand) and 168 oxidation inhibitor, the UV-531 UV light absorber is fully mediated after 27 minutes in homogenizer for 0.3 part together, pour in the twin screw extruder while hot, 172 ℃ of die head temperatures, carry out granulation under the screw speed 110rpm condition, obtain the composite granule of uniform bamboo powder/PHBV/PBS ternary system.Next step, to mix pellet melt extrudes under 175 ℃ of temperature, in inflation film manufacturing machine, carry out blown film by certain technology, regulate pulling speed and adjust thickness (0.05～0.1mm), can obtain the membrane product of different thickness, again through making hotel's articles for use such as eco-friendly food bag, preservative film, refuse bag and disposable tablecloth after printing, the cutting processing.
Embodiment 12:
With 30 parts of (mass fractions of standby bamboo powder, down together), aluminate coupling agent (TL-411-A) stirs for 1.2 parts, again with drying treatment after 30 parts of poly(lactic acid) (PLA), the Mw=12 ten thousand of this poly(lactic acid), L content 75%, 40 parts of poly butylene succinates (PBS) (Mw=17 ten thousand), mass ratio is 1: 1 0.2 part in a mixing oxidation inhibitor at 1010: 168, after 0.2 part of high speed of UV-571 UV light absorber is fully mediated 20 minutes, pour in the twin screw extruder while hot, 200 ℃ of die head temperatures, extruding pelletization under the screw speed 100rpm condition, pellet is uniformly mixed.Next step, to mix pellet melt extrudes under 205 ℃ of temperature, on the sheet forming machine with 210 ℃, 15MPa hot pressing, by regulating roller space (0.6～5mm), obtain the different sheet material of thickness, after sheet material carried out reasonable cutting and assembly unit, can make the products such as automotive upholstery, traffic roadblock and guardrail of certain purposes.
Embodiment 13:
With 20 parts of (mass fractions of standby bamboo powder, down together), silane coupling agent (KH-560) stirs for 0.8 part, again with drying treatment after 15 parts of PHB (Mw=11 ten thousand), 0.3 part in 65 parts of poly butylene succinates (PBS) (Mw=12 ten thousand) and 1010 oxidation inhibitor, the UV-284 UV light absorber is fully mediated after 27 minutes in homogenizer for 0.3 part together, pour in the twin screw extruder while hot, under 173 ℃ of die head temperatures, screw speed 80rpm condition, carry out granulation, obtain the composite granule of uniform bamboo powder/PHB/PBS ternary system.Next step, to mix pellet melt extrudes under 175 ℃ of temperature, in inflation film manufacturing machine, carry out blown film by certain technology, regulate pulling speed and adjust thickness (0.05～0.1mm), can obtain the membrane product of different thickness, again through making hotel's articles for use such as eco-friendly food bag, preservative film, refuse bag and disposable tablecloth after printing, the cutting processing.
Embodiment 14:
With 25 parts of (mass fractions of standby bamboo powder, down together), aluminate coupling agent (DL-2411-B) stirs for 1.2 parts, again with drying treatment after 10 parts of PHB (Mw=13 ten thousand), 40 parts of PBS (Mw=15 ten thousand), (Mw=15 ten thousand for PLA, L content is 85%) 0.6 part in 25 parts and 168 oxidation inhibitor, mass ratio UV-571: UV-284 is that 2: 1 mixing UV light absorber are fully mediated after 28 minutes in homogenizer for 0.5 part together, pour in the twin screw extruder while hot, 175 ℃ of die head temperatures, carry out granulation by certain technology under the screw speed 120rpm condition, obtain the composite granule of uniform bamboo powder/PHB/PBS/PLA quaternary system.Next step, to mix pellet melt extrudes under 178 ℃ of temperature, on sheet-forming machine with 178 ℃, 2MPa precompressed 2min, again with 165 ℃, 16MPa hot pressing 7 minutes, the moulding in 5 minutes of colding pressing under the 12MPa condition at last is by mold exchange more or regulate mold interval (3mm～11mm), obtain the different sheet material of thickness, this product is because light weight, environmental protection, characteristics such as energy-conservation can be applicable to fields such as automotive upholstery, traffic roadblock instrument, sports goods.
Embodiment 15:
With 60 parts of (mass fractions of standby bamboo powder, down together), aluminate coupling agent (DL-2411-B) stirs for 4 parts, again with drying treatment after 10 parts of PHB (Mw=13 ten thousand), 10 parts of PBS (Mw=15 ten thousand), (Mw=15 ten thousand for PLA, L content is 85%) 0.3 part in 20 parts and 168 oxidation inhibitor, mass ratio UV-571: UV-284 is that 2: 1 mixing UV light absorber are fully mediated after 28 minutes in homogenizer for 0.7 part together, pour in the twin screw extruder while hot, 175 ℃ of die head temperatures, carry out granulation by certain technology under the screw speed 120rpm condition, obtain the composite granule of uniform bamboo powder/PHB/PBS/PLA quaternary system.Next step, to mix pellet melt extrudes under 178 ℃ of temperature, on sheet-forming machine with 178 ℃, 2MPa precompressed 2min, again with 175 ℃, 16MPa hot pressing 7 minutes, the moulding in 5 minutes of under the 12MPa condition, colding pressing at last, by mold exchange more or regulate mold interval (3mm～11mm), obtain the different sheet material of thickness.This product is because light weight, environmental protection, characteristics such as energy-conservation can be applicable to fields such as automotive upholstery, traffic roadblock instrument, sports goods.
Claims (10)
1, a kind of bamboo powder filled biomass-based resin composite material is characterized in that comprising the component of following weight proportion:
20～60 parts in bamboo powder;
40～80 parts of bio-based resins;
0.8～5 part of coupling agent;
0.2～0.6 part of antioxidant;
0.1～0.7 part of UV light absorber.
2, matrix material according to claim 1 is characterized in that described bamboo powder makes successively as follows:
A, classification operation are that mesh screen is crossed in the bamboo wood material pulverizing back that will collect, obtain the bamboo powder of granularity less than 0.4mm, obtain former bamboo powder;
B, cooking process are that boiling temperature is 85～100 ℃ with the former bamboo powder boiling in cooking liquor after the classification, and cooking time is 2～3 hours, and the mass ratio of cooking liquor and bamboo powder is 5: 1～7: 1, and boiling finishes post-flush, dries;
C, bleaching process, the bamboo powder after will drying are put in water be diluted to volume ratio 1: 1～2.5: 1 the hydrogen peroxide, stir bleaching in 2～3 hours;
D, matting, water flushing, pH is between 7.0～7.5 to the system;
E, drying process, vacuum-drying in 70～95 ℃ of scopes, the standby bamboo powder water content in dry back is less than 12%.
3, matrix material according to claim 2 is characterized in that described cooking liquor is that pH is at the caustic soda soln more than 12.
4, matrix material according to claim 1 is characterized in that described bio-based resin is for being the polymkeric substance of one or more resin alloys of forming of feedstock conversion from renewable resources.
5, matrix material according to claim 4, it is characterized in that described polymkeric substance be among polylactic acid PLA, polyhydroxyalkanoate PHA or the poly butylene succinate PBS any one, or any binary blend system of the two among the three, or three's tertiary blending system, each component ratio of co-mixing system be arbitrarily than;
To PLA, its weight-average molecular weight is 60,000～160,000, and the L molar content is 42%～98%;
To PHA, can be considered the polymkeric substance of fat hydroxyl acid, it both can structure A equal poly structure exist, copolymerization structure formation that also can structure B exists, for structure A, R is positive alkyl group side chain, to nonyl, m is 1,2 or 3 to scope, when R is methyl from methyl, PHA is poly butyric ester PHB, and its weight-average molecular weight is 90,000～230,000; For structure B, R
1, R
2Be positive alkyl group side chain, to nonyl, x, m are 1,2 or 3 to scope, work as R from methyl
1Be methyl, R
2Be ethyl, or R
1Be ethyl, R
2Be methyl, and during x=m=1, PHA is polyhydroxybutyrate-valerate PHBV, its weight-average molecular weight is 110,000～180,000, and the hydroxyl valerate molar content hereinafter to be referred as HV%, is 3%～23%;
To PBS, its weight-average molecular weight is 80,000～190,000.
6, matrix material according to claim 1 is characterized in that described coupling agent is all types of silane coupling agent, titanate coupling agent and aluminate coupling agent, in the trade mark one or more.
7, matrix material according to claim 1 is characterized in that described antioxidant is one or both of antioxidant 168 or antioxidant 1010.
8, matrix material according to claim 1 is characterized in that described UV light absorber is one or more of UV-531, UV-571, UV-284.
9, a kind of bamboo powder filled biomass-based resin composite material preparation method in turn includes the following steps:
A, bamboo powder and coupling agent are stirred,
B, again the product among the above-mentioned steps a and bio-based resin, antioxidant and UV light absorber are mediated;
C, the product among the above-mentioned steps b is carried out granulation in twin screw extruder, oven dry,
Wherein, each composition weight proportioning is as follows:
20～60 parts in bamboo powder;
40～80 parts of bio-based resins;
0.8～5 part of coupling agent;
0.2～0.6 part of antioxidant;
0.1～0.7 part of UV light absorber.
10, composite material and preparation method thereof according to claim 9 is characterized in that the bamboo powder described in the step a makes successively as follows:
A, classification operation are that mesh screen is crossed in the bamboo wood material pulverizing back that will collect, obtain the bamboo powder of granularity less than 0.4mm, obtain former bamboo powder;
B, cooking process are that boiling temperature is 85～100 ℃ with the former bamboo powder boiling in cooking liquor after the classification, and cooking time is 2～3 hours, and the mass ratio of cooking liquor and bamboo powder is 5: 1～7: 1, and boiling finishes post-flush, dries;
C, bleaching process, the bamboo powder after will drying are put in water be diluted to volume ratio 1: 1～2.5: 1 the hydrogen peroxide, stir bleaching in 2～3 hours;
D, matting, water flushing, pH is between 7.0～7.5 to the system;
E, drying process, vacuum-drying in 70～95 ℃ of scopes, the standby bamboo powder water content in dry back is less than 12%.
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