CN105368088A - Method for preparing polyolefin composite from algae - Google Patents
Method for preparing polyolefin composite from algae Download PDFInfo
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- CN105368088A CN105368088A CN201510737734.2A CN201510737734A CN105368088A CN 105368088 A CN105368088 A CN 105368088A CN 201510737734 A CN201510737734 A CN 201510737734A CN 105368088 A CN105368088 A CN 105368088A
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- algae
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- benzoyl peroxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/04—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides
- C08F283/045—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides on to unsaturated polycarbonamides, polyesteramides or polyimides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A method for preparing a polyolefin composite from algae comprises the following steps that firstly, the algae are dried and put into a planetary ball mill for milling, and the ground algae pass through a screen with the mesh number ranging from 500 to 600; secondly, by weight, 50-80 parts of algae powder, 0.5-2 parts of polyesteramide, 4-7 parts of maleic anhydride, 2-5 parts of styrene and 0.01-0.05 part of benzoyl peroxide are added into 15-40 parts of an organic solvent together, and the mixture is heated to 50-80 DEG C under the vacuumizing and stirring conditions to be reacted for 5-7 hours; thirdly, by weight, 20-30 parts of polyolefin, 2-6 parts of a bulking agent and 2-6 parts of lubricant are added into 60-80 parts of pre-reaction liquid, and the mixture is evenly mixed and then extruded through a co-rotating twin screw extruder for granulation. By means of the method, preparation can be carried out through whole algae, and thus the algae utilization rate is greatly increased; the product performance of prepared plastic products can meet the standard, and the method is low in cost, simple in process and suitable for industrial production.
Description
Technical field
The present invention relates to technical field of polymer materials, especially relating to a kind of take algae as composite polyolefine material prepared by main raw material.
Background technology
The application of algae is the previous comparatively popular research topic of order, and one of them direction is using the plastics of algae as the easy degraded of raw material preparation of plastics, thus reduce oil use and can protection of the environment.But algae is applied to plastics and is also in conceptual phase, when its main difficult problem is after algae mixes with softening agent, expanding material, bonding force is inadequate, causes a series of mechanical properties such as the pull resistance of the plastic prod finally obtained, crushing resistance, splitting resistance, torsion fracture resistant cannot be up to standard.Because the conjugation of algae raw material and other raw materials causes small-molecule starting material such as softening agent etc. easily to move not during another problem, thus affect the quality of product.If strengthen the use of the raw material such as softening agent, expanding material, problem above can be overcome, but the consumption of algae can be made to be reduced to very low degree, also just cannot embody and utilize algae to prepare the advantage of the energy-saving and cost-reducing environmental protection of plastics.
Another one problem prepares plastics with algae at present, mainly utilizes the protein inside algae; But the ratio that the protein of algae accounts for algae all wts is not high, this means still have other compositions of a large amount of algae to be rejected, the utilization ratio of algae raw material is too low.
Summary of the invention
For the problems referred to above that prior art exists, the applicant provides a kind of method that algae prepares composite polyolefine material.Adopt present method that full frond can be utilized to be prepared, greatly improve algae utilization ratio; The plastic prod performance prepared is up to standard, and cost is low, technique simple, is applicable to suitability for industrialized production.
Technical scheme of the present invention is as follows:
Algae prepares a method for composite polyolefine material, and concrete steps are as follows:
(1) algae raw material is tentatively cleaned removal impurity post-drying, put into planetary ball mill and grind, cross 500 ~ 600 mesh sieves;
(2) algae powder 50 ~ 80 weight part be sieved and polyesteramide 0.5 ~ 2 weight part, maleic anhydride 4 ~ 7 weight part, vinylbenzene 2 ~ 5 weight part, benzoyl peroxide 0.01 ~ 0.05 weight part are together added in organic solvent 15 ~ 40 weight part, under the condition vacuumizing and stir, be heated to 50 ~ 80 DEG C of reactions 5 ~ 7 hours, obtain pre-reaction liquid;
(3) in pre-reaction liquid 60 ~ 80 weight part, add polyolefine 20 ~ 30 weight part, expanding material 2 ~ 6 weight part and lubricant 2 ~ 6 weight part, by parallel dual-screw extruding machine extruding pelletization after mixing, obtain product.
Water content after the described algae raw material oven dry of step (1) is 7 ~ 12wt%.
The described algae raw material of step (1) dries the particle that rear pre-cut particle diameter is 6 ~ 8mm size.
When grinding in step (1) described planetary ball mill, revolution is 1:1.6 ~ 2 with the rotating ratio of rotation, and the mass ratio of algae raw material and abrading-ball is 1:8.5 ~ 12, and ball radius is 2 ~ 5mm.
Step (2) described benzoyl peroxide can be replaced by the benzoyl peroxide tert-butyl ester or methylethyl ketone peroxide.
Step (2) described organic solvent is toluene, dimethyl phthalate or ethyl acetate.
Step (3) described expanding material is ethene-vinyl acetate copolymer, ethylene-acrylic acid copolymer or ethylene-vinyl alcohol copolymer; Described lubricant is stearic acid, fatty acid ester, stearate calcium or ethylene bis stearic acid amide.
The melt blending temperature of step (3) described granulation is 100 ~ 140 DEG C, and screw speed is 300 ~ 400 revs/min.
The technique effect that the present invention is useful is:
Alga cells entirety is coupling in 3 D stereo network macromolecular structure by present method, the composite polyolefine material compact structure obtained, every excellent in mechanical performance, and the bonding force between raw material is very strong, small molecules migration can not occur, avoid contaminate environment.
Embodiment
Below in conjunction with embodiment, the present invention is specifically described.
Embodiment 1
The invention provides a kind of method that algae prepares composite polyolefine material, concrete steps are as follows:
(1) blue-green algae salvaged from water is tentatively cleaned removal impurity post-drying, the water content after oven dry is 12wt%, and after drying, pre-cut particle diameter is the particle of 8mm size.Then put into planetary ball mill to grind, cross 500 mesh sieves.When grinding in planetary ball mill, revolution is 1:2 with the rotating ratio of rotation, and the mass ratio of algae raw material and abrading-ball is 1:12, and ball radius is 5mm.
(2) algae powder 80 weight part be sieved and polyesteramide 2 weight part, maleic anhydride 7 weight part, vinylbenzene 5 weight part, benzoyl peroxide 0.05 weight part are together added in organic solvent 40 weight part, 80 DEG C of reactions 5 hours are heated under the condition vacuumizing and stir, obtain pre-reaction liquid, organic solvent is toluene.
(3) in pre-reaction liquid 80 weight part, high density polyethylene(HDPE) 30 weight part, expanding material 6 weight part and lubricant 6 weight part is added, by parallel dual-screw extruding machine extruding pelletization after mixing, obtain product, the melt blending temperature of granulation is 140 DEG C, and screw speed is 400 revs/min.Expanding material is ethene-vinyl acetate copolymer, and lubricant is stearic acid.
Embodiment 2
The invention provides a kind of method that algae prepares composite polyolefine material, concrete steps are as follows:
(1) red algae salvaged from water is tentatively cleaned removal impurity post-drying, the water content after oven dry is 10wt%, and after drying, pre-cut particle diameter is the particle of 6mm size.Then put into planetary ball mill to grind, cross 600 mesh sieves.When grinding in planetary ball mill, revolution is 1:1.8 with the rotating ratio of rotation, and the mass ratio of algae raw material and abrading-ball is 1:10, and ball radius is 4mm.
(2) algae powder 60 weight part be sieved and polyesteramide 1 weight part, maleic anhydride 5 weight part, vinylbenzene 3 weight part, benzoyl peroxide 0.03 weight part are together added in organic solvent 25 weight part, under the condition vacuumizing and stir, be heated to 60 DEG C of reactions 6 hours, obtain pre-reaction liquid; Benzoyl peroxide can be replaced by the benzoyl peroxide tert-butyl ester, and organic solvent is dimethyl phthalate.
(3) in pre-reaction liquid 70 weight part, homo-polypropylene 25 weight part, expanding material 4 weight part and lubricant 4 weight part is added, by parallel dual-screw extruding machine extruding pelletization after mixing, obtain product, the melt blending temperature of granulation is 120 DEG C, and screw speed is 300 revs/min.Expanding material is ethylene-acrylic acid copolymer, and lubricant is fatty acid ester.
Embodiment 3
The invention provides a kind of method that algae prepares composite polyolefine material, concrete steps are as follows:
(1) brown alga salvaged from water is tentatively cleaned removal impurity post-drying, the water content after oven dry is 7wt%, and after drying, pre-cut particle diameter is the particle of 6mm size.Then put into planetary ball mill to grind, cross 600 mesh sieves.When grinding in planetary ball mill, revolution is 1:1.6 with the rotating ratio of rotation, and the mass ratio of algae raw material and abrading-ball is 1:8.5, and ball radius is 2mm.
(2) algae powder 50 weight part be sieved and polyesteramide 0.5 weight part, maleic anhydride 4 weight part, vinylbenzene 2 weight part, benzoyl peroxide 0.01 weight part are together added in organic solvent 15 weight part, under the condition vacuumizing and stir, be heated to 50 DEG C of reactions 7 hours, obtain pre-reaction liquid; Benzoyl peroxide can be replaced by methylethyl ketone peroxide, and organic solvent is ethyl acetate.
(3) in pre-reaction liquid 60 weight part, Low Density Polyethylene 20 weight part, expanding material 2 weight part and lubricant 2 weight part is added, by parallel dual-screw extruding machine extruding pelletization after mixing, obtain product, the melt blending temperature of granulation is 100 DEG C, and screw speed is 300 revs/min.Expanding material is ethylene-vinyl alcohol copolymer, and lubricant is stearate calcium.
Test case:
Embodiment 1 ~ 3 is obtained plastic grain detect according to national standard, performance is as shown in table 1.
Table 1
The present invention prepares the density of composite polyolefine material, and comparatively conventional polyolefin elastomerics is slightly high, and water absorbing properties is height compared with common polyolefine material; The present invention prepares composite polyolefine material mechanical property and greatly improves, and snappiness also strengthens greatly, and shock resistance is not lost, and hardness declines; Heat-drawn wire is slightly low, and mobility during melting improves.
Claims (8)
1. algae prepares a method for composite polyolefine material, it is characterized in that concrete steps are as follows:
(1) algae raw material is tentatively cleaned removal impurity post-drying, put into planetary ball mill and grind, cross 500 ~ 600 mesh sieves;
(2) algae powder 50 ~ 80 weight part be sieved and polyesteramide 0.5 ~ 2 weight part, maleic anhydride 4 ~ 7 weight part, vinylbenzene 2 ~ 5 weight part, benzoyl peroxide 0.01 ~ 0.05 weight part are together added in organic solvent 15 ~ 40 weight part, under the condition vacuumizing and stir, be heated to 50 ~ 80 DEG C of reactions 5 ~ 7 hours, obtain pre-reaction liquid;
(3) in pre-reaction liquid 60 ~ 80 weight part, add polyolefine 20 ~ 30 weight part, expanding material 2 ~ 6 weight part and lubricant 2 ~ 6 weight part, by parallel dual-screw extruding machine extruding pelletization after mixing, obtain product.
2. method according to claim 1, is characterized in that the water content after the described algae raw material oven dry of step (1) is 7 ~ 12wt%.
3. method according to claim 1, is characterized in that the described algae raw material of step (1) dries the particle that rear pre-cut particle diameter is 6 ~ 8mm size.
4. method according to claim 1, when it is characterized in that grinding in step (1) described planetary ball mill, revolution is 1:1.6 ~ 2 with the rotating ratio of rotation, and the mass ratio of algae raw material and abrading-ball is 1:8.5 ~ 12, and ball radius is 2 ~ 5mm.
5. method according to claim 1, is characterized in that step (2) described benzoyl peroxide can be replaced by the benzoyl peroxide tert-butyl ester or methylethyl ketone peroxide.
6. method according to claim 1, is characterized in that step (2) described organic solvent is toluene, dimethyl phthalate or ethyl acetate.
7. method according to claim 1, is characterized in that step (3) described expanding material is ethene-vinyl acetate copolymer, ethylene-acrylic acid copolymer or ethylene-vinyl alcohol copolymer; Described lubricant is stearic acid, fatty acid ester, stearate calcium or ethylene bis stearic acid amide.
8. method according to claim 1, it is characterized in that the melt blending temperature of step (3) described granulation is 100 ~ 140 DEG C, screw speed is 300 ~ 400 revs/min.
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CN201510737734.2A CN105368088A (en) | 2015-11-03 | 2015-11-03 | Method for preparing polyolefin composite from algae |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116218044A (en) * | 2018-04-27 | 2023-06-06 | 阿尔吉斯有限责任公司 | Elastomer composite comprising algae biomass filler |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102115576A (en) * | 2009-12-31 | 2011-07-06 | 金伯利-克拉克环球有限公司 | Natural biological polymer thermoplastic film |
CN102918097A (en) * | 2010-03-25 | 2013-02-06 | 罗盖特兄弟公司 | Plant material compositions and method for preparing same |
CN104144984A (en) * | 2011-08-24 | 2014-11-12 | 阿尔吉斯有限责任公司 | Macrophyte-based bioplastic |
CN105001489A (en) * | 2015-07-10 | 2015-10-28 | 无锡太湖蓝藻资源应用技术研究院有限公司 | Bio-based polyolefin composite material and preparation method therefor |
-
2015
- 2015-11-03 CN CN201510737734.2A patent/CN105368088A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102115576A (en) * | 2009-12-31 | 2011-07-06 | 金伯利-克拉克环球有限公司 | Natural biological polymer thermoplastic film |
CN102918097A (en) * | 2010-03-25 | 2013-02-06 | 罗盖特兄弟公司 | Plant material compositions and method for preparing same |
CN104144984A (en) * | 2011-08-24 | 2014-11-12 | 阿尔吉斯有限责任公司 | Macrophyte-based bioplastic |
CN105001489A (en) * | 2015-07-10 | 2015-10-28 | 无锡太湖蓝藻资源应用技术研究院有限公司 | Bio-based polyolefin composite material and preparation method therefor |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116218044A (en) * | 2018-04-27 | 2023-06-06 | 阿尔吉斯有限责任公司 | Elastomer composite comprising algae biomass filler |
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Application publication date: 20160302 |