CN104163977A - Red lignin/polyolefin composite material and preparation method thereof - Google Patents
Red lignin/polyolefin composite material and preparation method thereof Download PDFInfo
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/066—LDPE (radical process)
Abstract
The invention discloses a red lignin/polyolefin composite material and a preparation method. The red lignin/polyolefin composite material comprises the following raw materials by mass part: 100 parts of alkali lignin in the composite material, 100-400 parts of polyolefin, 2-20 parts of colouring agent, 5-20 parts of plasticizer, and 40-100 parts of lubricant. The preparation method comprises the following steps: adding a colouring agent and a plasticizer in dried alkali lignin powder, uniformly mixing, and drying to obtain the dried alkali lignin pretreated powder; placing the polyolefin material granules under temperature of 120-170 DEG C for melting and milling, physically blending the alkali lignin pretreated powder and molten polyolefin, adding the lubricant, blending and processing to obtain the composite material. The prepared red lignin/polyolefin composite material has the advantages of brilliant appearance color and uniform quality, has comprehensive mechanical properties such as good tensile strength and stretching toughness, has characteristics of no odour, antioxidation and degradable performance, and can be used as the green environmental protection composite material for the package, building material and entertainment fields.
Description
Technical field
The present invention relates to a kind of composite polyolefine material, particularly relate to a kind of red xylogen/composite polyolefine material and preparation method thereof.
Technical background
In general synthetic resins, the output of polyolefin resin is sure to occupy first, wherein take polyethylene, polypropylene as main, and its application is deep into each corner of national economy.Wherein polyvinyl resin content accounts for 38% left and right of global general-use resin total amount, China is also very huge to the requirement of vinyon, output and usage quantity that domestic polyolefin resin is annual all show a rising trend, and the demand of China's polyvinyl resin in 2011 reaches 1846.6 ten thousand tons.The application of visible polyolefin resin more and more receives everybody concern.
Along with the development of human society, people constantly increase the demand of resource, the energy, and meanwhile the problem of the petrochemical industry crisis of resource such as global range oil and environmental pollution day by day becomes the important factor that affects human kind sustainable development.Therefore,, the in the situation that, environmental stress gradually exhausted in petrochemical industry resource increasing the weight of day by day, find reproducible biomass resource, promote the diversification of resource to become world development trends.The raw material sources of biomass resource enrich, reproduction speed is fast, can be used for preparing the energy and chemical raw material, become the important industry that various countries competitively develop, the numerous and confused national strategy of formulating Developing Biomass resource, the energy of the country such as the U.S., Japan, Germany, Sweden.As the U.S. has determined directivity target in 1998: have the 10% renewable resources raw material from plant in the year two thousand twenty chemical fundamentals product at least, bring up to 50% to the year two thousand fifty.
Xylogen is the unique renewable resources that the non-petrochemical industry class of compound aromatic base can be provided of nature, it and Mierocrystalline cellulose, hemicellulose are the main components that forms plant skeleton, its content in land plant is only second to Mierocrystalline cellulose, it is second largest natural organic matter, estimate that the whole world can produce 1,500 hundred million tons of xylogen every year by plant-growth, another China pulp and paper industry can produce about 5,000 ten thousand tons of xylogen byproducts every year.A large amount of use xylogen, as the starting material of Chemicals, can reduce the utilization to Nonrenewable resources such as coal, oil, Sweet natural gases, alleviates the crisis of Nonrenewable resources.It is reported, xylogen can be used for producing concrete admixture, slurries additive agent, dispersion agent, sorbent material etc., is the renewable starting material of a lot of Chemicals.
At present, China is still very limited to the application of xylogen, and most of xylogen byproduct has all passed through burn processing, has not only caused the huge waste of resource, but also has produced the problem of environmental pollution.Based on this, by utilizing blending technology to prepare red xylogen/composite polyolefine material polyolefin resin and alkali lignin, not only can reduce the problem of waste and the environmental pollution of biomass resource, the intensity that can also prepare is high, the matrix material of good toughness, environmental friendliness, novel green, has alleviated the dependence of polyolefin resin to petrochemical industry resource simultaneously.
In molecular structure due to xylogen, contain the chromophoric groups such as phenolic hydroxyl group, carbonyl, easy oxidized and aobvious black in the process with the mixing of polyolefine high temperature, the xylogen/composite polyolefine material color preparing is black; Because the black of xylogen/composite polyolefine material is limit, be unfavorable for the application that it is multi-field.As Chinese invention patent application 201310150272.5 has been prepared polyolefine/enzymolysis xylogen matrix material, but its to the color of matrix material is attractive in appearance, do not improve, limited to the application of matrix material on people's daily life field.Chinese invention patent application 102051002A prepared Mei separate Mu Zhi Su ?Mu matter Xian Wei ?polyolefine hybrid composite, it is not also stressed the color of matrix material.Therefore, the present invention proposes to prepare the preparation method of red xylogen/composite polyolefine material.
In molecular structure due to xylogen, contain the groups such as hydroxyl, methoxyl group, polarity is strong, and polyolefine belongs to apolar substance, and both polarity difference are larger, and consistency is poor.Xylogen and polyolefine are easily reunited when blend in polyene hydrocarbon phase, thereby make the composite materials property variation of preparation, cannot realize further industrial application.Therefore, in matrix material, add mechanical property that softening agent, lubricant improve red xylogen/composite polyolefine material to reach industrial application requirement.
Summary of the invention
The object of the present invention is to provide that a kind of environmental friendliness, material color are attractive in appearance, quality homogeneous, there is the comprehensive mechanical properties such as good tensile strength and tensile toughness, have the novel red xylogen/composite polyolefine material of the advantages such as odorless, anti-oxidant, degradable simultaneously concurrently.
Another object of the present invention is also to provide the preparation method of described red xylogen/composite polyolefine material.
In lignin molecule, contain the chromophoric groups such as a large amount of phenolic hydroxyl groups, carbonyl, with polyolefin plastics high temperature mixing process in easy oxidized and aobvious black; In the molecular structure of xylogen, contain the groups such as hydroxyl, methoxyl group, polarity is strong simultaneously, and polyolefine belongs to apolar substance, and both polarity difference are larger, and consistency is poor.In the cut-and-try work in early stage, find, adopt Disperse Blue-79, Acid Blue A, acid fluorescent blue AX, acid bright red AXJ, Methylene Blue BB, alkaline royal blue AL, cationic yellow X ?2RL, reactive brilliant yellow X ?the emerald green pigment such as blue of the dye well 4402 such as 6G be the aterrimus that tinting material all fails to change xylogen/composite polyolefine material.But find that ferric oxide can the overwhelming majority hide because of the oxidized and aobvious black of xylogen, show the redness of ferric oxide itself simultaneously, therefore, the present invention carries out ferric oxide tinting material and xylogen Combined Processing and prepares red xylogen/composite polyolefine material; For the red xylogen/composite polyolefine material that makes to prepare is applicable to wider Application Areas, further adding softening agent improves, the polar group of plasticizer molecule and the polar group of xylogen connect by hydrogen bond, and the hydrophobic part of plasticizer molecule is inserted into the hydrophobic position of xylogen particle, therefore softening agent adds the agglomeration power between the polar functional group that has shielded xylogen, break the aggregate structure of xylogen in polyolefine, improved the consistency between xylogen particle and polyene hydrocarbon phase; Meanwhile, adding of lubricant makes, between xylogen particle and polyene hydrocarbon phase, ball effect occurs, and improved toughness and the Young's modulus of matrix material.
The object of the invention is to realize by the following method:
A preparation method for red xylogen/composite polyolefine material, comprises the following steps and processing condition:
(1) the alkali lignin raw material through super-dry is carried out to physical pulverization, obtain alkali lignin powder, then in alkali lignin powder, add tinting material, softening agent, mix, dry, obtain dry alkali lignin pre-treatment powder;
(2) polyolefine material grain is placed in and at 120～170 ℃, carries out melting refining glue, subsequently the polyolefine of described alkali lignin pre-treatment powder and melting is carried out to physical blending, in the technological process of blend, add lubricant, blend is processed, and the material cake obtaining can obtain red xylogen/composite polyolefine material through overmolding;
In mass fraction, the consumption of alkali lignin, polyolefin plastics, tinting material, softening agent and lubricant is respectively 100 parts, 100～400 parts, 2～20 parts, 5～20 parts and 40～100 parts;
Described polyolefin plastics is one or more in high density polyethylene(HDPE), Low Density Polyethylene, injection moulding class polypropylene;
Described tinting material is ferric oxide;
Described softening agent is one or more in methacryloxypropyl trimethoxy silane, vinyltrimethoxy silane, dioctyl phthalate (DOP), dibutyl phthalate, epoxy soybean oil, clorafin, maleic anhydride grafted polyethylene, palm wax and polyethylene wax;
Described lubricant is one or more in stearic acid, aluminum stearate, calcium stearate, Zinic stearas, nano-calcium carbonate and Nano carbon white.
For further real the object of the invention, preferably, described alkali lignin is that bamboo, poplar, Eucalyptus, birch, Pinus massoniana Lamb alkali paper-making black liquor obtain through acid out; The solids content mass percent of described alkali lignin is 95%～99%.The particle diameter of alkali lignin pre-treatment powder is 5～100 microns.The time of described refining glue is 1～5 minute.Described being dried as putting into the baking oven of 50～80 ℃ processed 12～36 hours.The time that described blend is processed is 10～30 minutes.
Red xylogen/composite polyolefine material, is made by above-mentioned preparation method, and the color of this matrix material is old red, adjusts tinting material deal and obtains different dark ruddy products, and tensile strength is 23～26MPa, and fracture extensibility is 80～120%.
The present invention except alkali lignin all by pure content meter.
The present invention compares and has following outstanding advantages and effect with xylogen/composite polyolefine material and polyolefin plastics:
1, with respect to xylogen/composite polyolefine material, xylogen/composite polyolefine material of the present invention be old red, color is attractive in appearance, quality homogeneous and odorless, has widened its Application Areas, can go deep into the plastic prod field in people's daily life.
2, than polyolefin plastics, red xylogen/composite polyolefine material of the present invention has better tensile strength, and biodegradable, belongs to a kind of environmental friendliness, novel " green " matrix material.
3, because xylogen comes from industrial by-products, raw materials cost is extremely low, and therefore than pure polyolefin plastics, red xylogen/composite polyolefine material of the present invention has lower cost.
4, owing to containing a large amount of phenolic hydroxyl groups in lignin molecule structure, be natural antioxidant, therefore red xylogen/composite polyolefine material of the present invention has good uvioresistant and weathering resistance.
The polyolefin plastics of 5, filling than existing pearl filler, red xylogen/composite polyolefine material of the present invention has better tensile toughness and impact resistance, can be for injection moulding and blow molding process, purposes is wider.
Accompanying drawing explanation
Fig. 1 is the mechanical property correlation curve figure of the red xylogen/composite polyethylene material of embodiment 3 gained, high density polyethylene(HDPE), calcium carbonate/composite polyethylene material.
Fig. 2 is the section SEM figure of the red xylogen/composite polyethylene material of embodiment 3 gained.
Fig. 3 is the section SEM figure of high-density polyethylene material.
Fig. 4 is the section SEM figure of calcium carbonate/composite polyethylene material.
Embodiment
For understanding better the present invention, below in conjunction with specific embodiments and the drawings, the invention will be further described, but embodiment does not form the restriction to the claimed scope of the present invention.
Embodiment 1
(1) 100 grams of dry alkali lignins (are mainly carried out to acid out with Eucalyptus and pine by alkali paper-making black liquor again and process the alkali lignin preparing, as follows) through pulverizing, obtain the alkali lignin powder that particle diameter is approximately 5 microns, in alkali lignin powder, add again 2 grams of ferric oxide tinting materials and 5 grams of polyethylene wax softening agent, three is mixed, then be placed in baking oven, at 50 ℃, process 36 hours, obtain dry alkali lignin pre-treatment powder.
(2) the 100 grams of alkali lignin powder and 100 grams of injection moulding class polypropylene material grain (the PP K1008 that pre-treatment are obtained, Yanshan Petrochemical, as follows) and 150 grams of high density polyethylene(HDPE) material grain (HDPE5200B, Yanshan Petrochemical, as follows) mix, then at 170 ℃, carry out physical blending, in the technological process of blend, add respectively 10 grams of stearic acid and 30 grams of nano-calcium carbonate lubricants, after blend is processed 10 minutes, material cake can obtain red xylogen/composite polyolefine material through overmolding.
Embodiment 2
(1) 100 grams of dry alkali lignins are obtained to the alkali lignin powder that particle diameter is approximately 100 microns through pulverizing, in alkali lignin powder, add again 10 grams of ferric oxide tinting materials, 15 grams of maleic anhydride grafted polyethylenes and 5 grams of palm wax softening agent, make four to mix, then be placed in baking oven, at 60 ℃, process 20 hours, obtain dry alkali lignin pre-treatment powder.
(2) the 100 grams of alkali lignin powder and the 400 grams of Low Density Polyethylene material grain (LDPE1I50A that pre-treatment are obtained, Yanshan Petrochemical, as follows) mix, then at 120 ℃, carry out physical blending, in the technological process of blend, add respectively 20 grams of Zinic stearass and 30 grams of nano-calcium carbonate powder lubricants, after blend is processed 15 minutes, material cake can obtain red xylogen/composite polyolefine material through overmolding.
Embodiment 3
(1) 100 grams of dry alkali lignins are obtained to the alkali lignin powder that particle diameter is approximately 20 microns through pulverizing, in alkali lignin powder, add again 5 grams of ferric oxide tinting materials, 5 grams of dibutyl phthalates and 10 grams of Plasticizer Epoxidized Soybean Oil, make four to mix, then be placed in baking oven, at 80 ℃, process 18 hours, obtain dry alkali lignin pre-treatment powder.
(2) 100 grams of alkali lignin powder that pre-treatment obtained mix with 200 grams of high density polyethylene(HDPE) material grains; then at 150 ℃, carry out physical blending; in the technological process of blend; add respectively 15 grams of aluminum stearates and 45 grams of stearic acid lubricants; after blend is processed 20 minutes, material cake can obtain red xylogen/composite polyolefine material through overmolding.
Embodiment 4
(1) 100 grams of dry alkali lignins are obtained to the alkali lignin powder that particle diameter is approximately 40 microns through pulverizing, in alkali lignin powder, add again 20 grams of ferric oxide tinting materials, 10 grams of dibutyl phthalates and 10 grams of clorafin softening agent, make four to mix, then be placed in baking oven, at 75 ℃, process 12 hours, obtain dry alkali lignin pre-treatment powder.
(2) 100 grams of alkali lignin powder that pre-treatment obtained mix with 300 grams of Low Density Polyethylene material grains; then at 140 ℃, carry out physical blending; in the technological process of blend; add respectively 20 grams of calcium stearates and 60 grams of talcum powder lubricants; after blend is processed 30 minutes, material cake can obtain red xylogen/composite polyolefine material through overmolding.
Embodiment 5
(1) 100 grams of dry alkali lignins are obtained to the alkali lignin powder that particle diameter is approximately 60 microns through pulverizing, in alkali lignin powder, add again 15 grams of ferric oxide tinting materials, 12 grams of dioctyl phthalate (DOP) softening agent, three is mixed, then be placed in baking oven, at 80 ℃, process 24 hours, obtain dry alkali lignin pre-treatment powder.
(2) 100 grams of alkali lignin powder that pre-treatment obtained mix with 200 grams of injection moulding class polypropylene material grains and 200 grams of Low Density Polyethylene material grains; then at 120 ℃, carry out physical blending; in the technological process of blend; add respectively 20 grams of stearic acid and 80 grams of Nano carbon white lubricants; after blend is processed 25 minutes, material cake can obtain red xylogen/composite polyolefine material through overmolding.
Dye product and pigment product
(1) 100 grams of dry alkali lignins are obtained to the alkali lignin powder that particle diameter is approximately 20 microns through pulverizing, in alkali lignin powder, add again 5 grams of dyestuffs (or pigment), 5 grams of dibutyl phthalates and 10 grams of Plasticizer Epoxidized Soybean Oil, make four to mix, then be placed in baking oven, at 80 ℃, process 18 hours, obtain dry alkali lignin pre-treatment powder.
(2) 100 grams of alkali lignin powder that pre-treatment obtained mix with 200 grams of high density polyethylene(HDPE) material grains; then at 150 ℃, carry out physical blending; in the technological process of blend; add respectively 15 grams of aluminum stearates and 45 grams of stearic acid lubricants; after blend is processed 20 minutes, material cake can obtain black xylogen/composite polyolefine material through overmolding.
Comparative example
Embodiment 3 products are carried out to sample preparation, adopt MTS universal testing machine test tensile strength, fracture extensibility, Ying Li ?the mechanical performance data such as strain curve; To the section of composite sample, adopt SEM to carry out microscopic analysis, disclose the mechanism of action of phase in matrix material.Table 1 is the mechanical property observed value of the red xylogen/composite polyethylene material of embodiment 3 gained, contrasts with high density polyethylene(HDPE), calcium carbonate/composite polyethylene material, dye product and pigment product simultaneously; Fig. 1 is the tensile stress-strain curve figure of the red xylogen/composite polyethylene material of embodiment 3 gained, contrasts with high density polyethylene(HDPE) and calcium carbonate/composite polyethylene material simultaneously; Fig. 2 is the sample section SEM figure of the red xylogen/composite polyethylene material of embodiment 3 gained, contrasts with high density polyethylene(HDPE) and calcium carbonate/composite polyethylene material simultaneously.
Table 1
As shown in table 1, the appearance color of dye product 1, dye product 2 and pigment product 1 is black, simultaneously corresponding mechanical property is poor, and the appearance color of embodiment 3 products is old red, and this illustrates the appearance color that can improve xylogen/composite polyethylene material that adds of ferric oxide.The fracture extensibility of embodiment 3 products, high density polyethylene(HDPE), calcium carbonate/composite polyethylene material is respectively 108.37%, 269.10%, 66.20%, and the calcium carbonate that experiment adopts is the modified calcium carbonate that industrial blowing is used.Can find out, the fracture extensibility of embodiment 3 products is lower than former high density polyethylene(HDPE), but the polythene material higher than calcium carbonate reinforcement, this explanation embodiment 3 products have good toughness, its toughness has surpassed the polythene material of industrial conventional calcium carbonate reinforcement at present, and its mechanical property can meet the requirement of industrial blowing to plastics toughness.The tensile strength of embodiment 3 products is 24.97Mpa, slightly be better than the 24.41Mpa of the polythene material of calcium carbonate reinforcement, and the 22.33Mpa of high density polyethylene(HDPE), this explanation embodiment 3 products are compared with the plastics of calcium carbonate reinforcement with former plastics, tensile strength is loss not, and has increase more by a small margin.Embodiment 3 products have good appearance color, and this characteristic makes its application in a lot of fields have stronger competitive power, and cost also slightly reduces.
As shown in Figure 1, the tensile stress-strain curve contrast of embodiment 3 products and high density polyethylene(HDPE), calcium carbonate/composite polyethylene material can be found out, prolongation along with stretching displacement, after first increasing, the tensile stress of the polythene material of embodiment 3 products and calcium carbonate reinforcement sharply reduces, and the tensile stress of high density polyethylene(HDPE) reduces after first increasing gently, the fracture deformation behavior of three kinds of materials of this explanation all shows as the toughness deformation behavior with yielding stress; The breaking strain of embodiment 3 products is less than high density polyethylene(HDPE), but higher than the polythene material of calcium carbonate reinforcement, and deformability of this explanation embodiment 3 products is not as former high density polyethylene(HDPE), but is better than the polythene material of calcium carbonate reinforcement.The yielding stress of embodiment 3 products is 24.97Mpa, higher than the 24.41Mpa of calcium carbonate reinforcement polythene material and the 22.33Mpa of high density polyethylene(HDPE), this explanation embodiment 3 products are a kind of good toughness materials, alkali lignin add the toughness deformation character that does not change high density polyethylene(HDPE), than the polythene material of high density polyethylene(HDPE) and calcium carbonate reinforcement, there is higher working strength.
The appearance color of embodiment 3 products is aobvious red, and color is attractive in appearance, quality homogeneous.The color of this product is vulnerable to people's acceptance than black.
As shown in Figure 2,3, 4, embodiment 3 products, high density polyethylene(HDPE), calcium carbonate/composite polyethylene material are quenched through liquid nitrogen disconnected, the SEM of section schemes (amplifying 3000 times) and can find out, the section of high density polyethylene(HDPE) is coarse, and reticulated structure is clear; The section of embodiment 3 products is more coarse, and reticulated structure is complicated and very thin, presents particulate state projection; And the section of the polythene material of calcium carbonate reinforcement is comparatively smooth.From cross-section morphology, can judge that embodiment 3 products belong to ductile rupture, so toughness is better than the polythene material of calcium carbonate reinforcement.In addition as can be seen from Figure 2, in embodiment 3 products alkali lignin particle at polyolefin resin the dispersion in mutually comparatively even, do not occur assembling, can obviously improve the adding of this explanation softening agent and lubricant xylogen particle at polyethylene the dispersion situation in mutually, effectively stoped the reunion of xylogen particle.
The raw material and the blending technology that due to other embodiment, adopt all have similar feature with embodiment 3, and after tested, the performance of other embodiment products obtained therefrom is also substantially similar to embodiment 3, therefore do not repeat one by one.
Claims (8)
1. a preparation method for red xylogen/composite polyolefine material, is characterized in that comprising the following steps and processing condition:
(1) the alkali lignin raw material through super-dry is carried out to physical pulverization, obtain alkali lignin powder, then in alkali lignin powder, add tinting material, softening agent, mix, dry, obtain dry alkali lignin pre-treatment powder;
(2) polyolefine material grain is placed in and at 120～170 ℃, carries out melting refining glue, subsequently the polyolefine of described alkali lignin pre-treatment powder and melting is carried out to physical blending, in the technological process of blend, add lubricant, blend is processed, and the material cake obtaining can obtain red xylogen/composite polyolefine material through overmolding;
In mass fraction, the consumption of alkali lignin, polyolefin plastics, tinting material, softening agent and lubricant is respectively 100 parts, 100～400 parts, 2～20 parts, 5～20 parts and 40～100 parts;
Described polyolefin plastics is one or more in high density polyethylene(HDPE), Low Density Polyethylene, injection moulding class polypropylene;
Described tinting material is ferric oxide;
Described softening agent is one or more in methacryloxypropyl trimethoxy silane, vinyltrimethoxy silane, dioctyl phthalate (DOP), dibutyl phthalate, epoxy soybean oil, clorafin, maleic anhydride grafted polyethylene, palm wax and polyethylene wax;
Described lubricant is one or more in stearic acid, aluminum stearate, calcium stearate, Zinic stearas, nano-calcium carbonate and Nano carbon white.
2. the preparation method of red xylogen/composite polyolefine material according to claim 1, is characterized in that: described alkali lignin is that bamboo, poplar, Eucalyptus, birch, Pinus massoniana Lamb alkali paper-making black liquor obtain through acid out.
3. the preparation method of red xylogen/composite polyolefine material according to claim 1 and 2, is characterized in that: the solids content mass percent of described alkali lignin is 95%～99%.
4. the preparation method of red xylogen/composite polyolefine material according to claim 1, is characterized in that: the particle diameter of described alkali lignin pre-treatment powder is 5～100 microns.
5. the preparation method of red xylogen/composite polyolefine material according to claim 1, is characterized in that: the time of described refining glue is 1～5 minute.
6. the preparation method of red xylogen/composite polyolefine material according to claim 1, is characterized in that: described being dried as putting into the baking oven of 50～80 ℃ processed 12～36 hours.
7. the preparation method of red xylogen/composite polyolefine material according to claim 1, is characterized in that: the time that described blend is processed is 10～30 minutes.
8. a red xylogen/composite polyolefine material, it is characterized in that: by method described in claim 1, prepared, the color of matrix material is old red, adjusts tinting material deal and obtains different dark ruddy products, tensile strength is 23～26MPa, and fracture extensibility is 80～120%.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106349534A (en) * | 2016-08-22 | 2017-01-25 | 华南理工大学 | Enzymatic hydrolysis lignin/polyolefin composite material as well as preparation method and application thereof |
| CN106432909A (en) * | 2016-09-28 | 2017-02-22 | 武汉纺织大学 | Lignin based antioxidant for polyolefin, preparation method and application |
| CN106432909B (en) * | 2016-09-28 | 2019-03-29 | 武汉纺织大学 | A kind of lignin-base antioxidant and preparation method and application for polyolefin |
| CN106832981A (en) * | 2017-02-16 | 2017-06-13 | 深圳市博富隆新材料科技有限公司 | A kind of method that utilization black liquid prepares bio-based reinforced filling |
| CN107446219A (en) * | 2017-09-25 | 2017-12-08 | 安徽依采妮纤维材料科技有限公司 | A kind of preparation method of lignin plastic composite |
| CN107513203A (en) * | 2017-09-25 | 2017-12-26 | 安徽依采妮纤维材料科技有限公司 | A kind of preparation method of the silica-filled plastic composite of Grafted Nano-scale |
| CN108219151A (en) * | 2018-01-12 | 2018-06-29 | 山东科技大学 | A kind of method in lignin surface grafting polymerization object |
| CN108219151B (en) * | 2018-01-12 | 2020-07-21 | 山东科技大学 | Method for grafting polymer on surface of lignin |
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