CN105694230A - Environment-friendly plastifying biomass composite and preparation method thereof - Google Patents
Environment-friendly plastifying biomass composite and preparation method thereof Download PDFInfo
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- CN105694230A CN105694230A CN201610260716.4A CN201610260716A CN105694230A CN 105694230 A CN105694230 A CN 105694230A CN 201610260716 A CN201610260716 A CN 201610260716A CN 105694230 A CN105694230 A CN 105694230A
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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
- 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
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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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
- C08L97/00—Compositions of lignin-containing materials
- C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
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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
- 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
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
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- Polymers & Plastics (AREA)
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Abstract
The invention relates to an environment-friendly plastifying biomass composite and a preparation method thereof. The composite is prepared from, by weight, 30-70 parts of biomass fibers, 30-70 parts of polyolefin compound, 0.3-14 parts of green ester plasticizer, 2-10 parts of compatilizer, 0.5-2 parts of lubricant and 0.005-0.015 parts of antioxygen. The green ester plasticizer is added for modification while the biomass fibers and the polyolefin compound are plasticized in a torque rheometer, and the suitable composite is obtained, wherein the green ester plasticizer is one or more of epoxidized soybean oil, citrate, acetyl tributyl citrate and cardanol acetate. The biomass composite is good in mechanical performance, the flowing property is improved, the plastifying temperature is reduced, biomass fiber components are increased, and the composite is free of toxins and harm and suitable for industrial production of food packages, disposable tableware and the like.
Description
Technical field
The present invention relates to a kind of environmental protection plasticising biomass composite and preparation method thereof。Belong to natural macromolecular material field。
Background technology
Due to the environmental consciousness quickly increased, the utilization of day by day serious global plastics problem of environmental pollution and reason, sustainable development and the Renewable resource such as the shortage of petroleum resources and price receives original more many attention with exploitation。The biomass fiber being raw material with Plant fiber, has an abundance, and neutral carbon is biodegradable, the advantage such as low cost and low-density so that it is paid close attention to widely in the research and development of biological material。
But due to shortcomings such as biomass fiber poor durability, inflammable, Yi Chao, moth perishable, easy, easy mould growth, therefore polymer and biomass fiber compound is adopted to prepare biomass composite at present, the consistency problem between hydrophilic biomass fiber and oil loving polymer is overcome by adding compatilizer, coupling agent etc., overcome the shortcoming problem that biomass fiber exists so on the one hand, it also avoid the weak points such as simple plastic material yielding aging, high-temerature creep, black brittleness, therefore become the focus of Material Field research。
It is known that plasticizer is to confer to the function additive of polymer product pliability and processing characteristics, if adding suitable plasticizer in the production of biomass composite, it is possible not only to improve toughness of material, it is also possible to improve drawing abillity。Difference according to chemical constitution, plasticizer kind mainly includes the chemical structural type such as phthalic acid ester, aliphatic dibasic acid ester, trimellitate, polyol ester, citrate, phosphate ester, polyester, epoxyfatty acid and ester thereof, wherein the product consumption of phthalic ester plasticizer is maximum, almost accounts for more than the 70% of whole plasticizer total amount。
Li Chunxia etc., in the paper that " plastics package " 24 volume the 3rd phases in 2014 deliver, adopt dioctyl phthalate (DOP) as plasticizer, are prepared for Eucommia shell powder/PVC composite。Research finds, the addition of DOP can significantly improve drawing abillity, and impact strength is also improved significantly。
But, reason based on environment and safe and sanitary, having required in global range since the nineties in 20th century that the cry of restriction use phthalic ester plasticizer is continuous, relevant environmental protection, health, continuable phthalic ester plasticizer succedaneum developmental research report emerge in an endless stream。Therefore, find and select suitable green ester plasticizer to be applied in biomass composite, being one of speedup biomass composite research problem needing solution badly。
Summary of the invention
Technical problem solved by the invention is based on safety and environmental grounds, a kind of environmental protection plasticising biomass composite and preparation method thereof is provided, and it is excessively poor to overcome mobility in common biomass composite preparation process so that the defects such as its mechanical performance reduction。Adopt environmental protection plasticising biomass composite prepared by the present invention, good mechanical property, and the whole preparation course of processing is simple to operate, have employed the green ester plasticizer of environmental protection, environmental friendliness, nontoxic, it is more suitable for the commercial production such as packaging for foodstuff, disposable tableware。
The purpose of the present invention is realized by techniques below scheme:
A kind of environmental protection plasticising biomass composite, it is characterised in that component and parts by weight that described composite includes are as follows:
Described biomass fiber is one or more in straw fine powder, bamboo powder, wood powder, paper pulp fiber；
Described TPO compound is one or more in polyethylene (PE), polypropylene (PP), polystyrene (PS)；
Described green ester plasticizer is one or more in epoxy soybean oil, citrate, tributyl 2-acetylcitrate, Cardanol yl acetate；
Described compatilizer is preferably selected from one or more of maleic anhydride inoculated polypropylene, glycidyl methacrylate graft polypropylene and glycidyl methacrylate graft polyformaldehyde；
Described lubricant is one or more in ethylene bis stearic acid amide, Tissuemat E and stearic acid；
Described antioxidant is the one in antioxidant 1010, antioxidant 1076 or antioxidant 164。
The preparation method that present invention also offers a kind of above-mentioned environmental protection plasticising biomass composite, it is characterised in that described method comprises the steps:
(1) by 60～80 DEG C of biomass fibers dried, TPO compound and compatilizer, lubricant, that high-speed mixer and mixing put into by antioxidant is uniform, obtains compound A；
(2) compound A obtained for step (1) added torque rheometer and adds green ester plasticizer, being mixed to get Homogeneous phase mixing material B in 130 DEG C～170 DEG C, add pulverizer after cooling, obtain pellet；
(3) 60～80 DEG C of dried pellets are added in injection machine, injection moulding at 130 DEG C～170 DEG C, obtain described environmental protection plasticising biomass composite。
In step (1), water content≤2% of each raw material after drying, (described percentage ratio refers to that the quality of water accounts for the ratio of each raw materials quality)。
Mixture described in step (1) is 5～8 minutes in the time of high-speed mixer and mixing；
In step (1), the order of addition of mixture should be processing aid and adds after other raw material premixs。
Mixing time mixing in torque rheometer described in step (2) is 5～30min, and torque rheometer rotating speed is 20～100r/min；
The particle diameter < 3mm of the pellet obtained after the pulverizing described in step (2)。
The mold temperature in injection mo(u)lding described in step (3) is at 30 DEG C～80 DEG C, it is preferred that be 30 DEG C～50 DEG C。
The described injection pressure in injection mo(u)lding is 3.5MPa。
The present invention compared with prior art has the following advantages and beneficial effect:
(1) in speedup biomass composite, the content of biomass fiber, much larger than the content of biomass fiber in existing wood plastic composite, greatly reduces the cost of material。
(2) application of green ester plasticizer, completes the replacement to phthalic ester plasticizer, under the premise of environmental protection, improves the toughness of composite, improve the processing characteristics of composite。
(3) product prepared by the green ester plasticizer in the present invention, environmental friendliness, nontoxic, can be used for packaging for foodstuff, disposable tableware etc. and relate to field of food safety。
Detailed description of the invention
Mode by the examples below further illustrates the present invention, but does not therefore limit the present invention among described scope of embodiments。The experimental technique of unreceipted actual conditions in the following example, conventionally and condition, or selects according to catalogue。
Embodiment 1
Being raw material with paper pulp fiber and polypropylene, adopting epoxy soybean oil is that disposable tableware prepared by plasticizer, and its production stage is as follows:
(1) by 60～80 DEG C of paper pulp fibers dried 30 parts, 70 parts and 3 parts polypropylene grafted maleic anhydrides of polypropylene, 1 part of Tissuemat E and 0.1 part antioxidant 1010 to put into high-speed mixer and mixing uniform, obtain compound A；
(2) obtained compound A being added torque rheometer, add epoxy soybean oil (EOS) 1 part, under 170 DEG C and 40r/min rotating speed, mixing 10min is uniformly mixed and expects B；Add pulverizer after cooling, obtain pellet；
(3) being added in injection machine by 60～80 DEG C of dried pellets, barrel temperature is 170 DEG C, and mold temperature is 30 DEG C, and injection pressure is 3.5MPa, cooling and demolding, obtains environmental protection plasticising biomass composite disposable tableware。
The performance detection of the plasticising biomass composite that embodiment 1 prepares is: hot strength is 43.6MPa, and elongation at break is 12.8%, and bending strength is 80.5MPa, and bending modulus is 4340.1MPa, and notch impact strength is 2.7KJ/m2。
Embodiment 2
Being raw material with wood powder and polypropylene, adopting epoxy soybean oil is that indoor floor prepared by plasticizer, and its production stage is as follows:
(1) by 60～80 DEG C of wood powders dried 30 parts, 70 parts and 3 parts polypropylene grafted maleic anhydrides of polypropylene, 1 part of Tissuemat E and 0.1 part antioxidant 1010 to put into high-speed mixer and mixing uniform, obtain compound A；
(2) obtained compound A being added torque rheometer, add epoxy soybean oil 2 parts, under 170 DEG C and 40r/min rotating speed, mixing 10min is uniformly mixed and expects B；Add pulverizer after cooling, obtain pellet；
(3) being added in injection machine by 60～80 DEG C of dried pellets, barrel temperature is 170 DEG C, and mold temperature is 30 DEG C, and injection pressure is 3.5MPa, cooling and demolding, obtains plasticising biomass composite indoor floor sheet material。
The performance detection of the plasticising biomass composite that embodiment 2 prepares is: hot strength is 42.3MPa, and elongation at break is 13.4%, and bending strength is 65.7MPa, and bending modulus is 4500.9MPa, and notch impact strength is 3.7KJ/m2。
Embodiment 3
Being raw material with bamboo powder and polypropylene, tributyl 2-acetylcitrate is plasticizer, produces door-plate material, and its production stage is as follows:
(1) by 60～80 DEG C of bamboo powder dried 50 parts, 50 parts and 3 parts polypropylene grafted maleic anhydrides of polypropylene, 1 part of Tissuemat E and 0.1 part antioxidant 1010 to put into high-speed mixer and mixing uniform, obtain compound A；
(2) obtained compound A being added torque rheometer, add tributyl 2-acetylcitrate 2 parts, under 170 DEG C and 40r/min rotating speed, mixing 10min is uniformly mixed and expects B；Add pulverizer after cooling, obtain pellet；
(3) being added in injection machine by 60～80 DEG C of dried pellets, barrel temperature is 170 DEG C, and mold temperature is 30 DEG C, and injection pressure is 3.5MPa, cooling and demolding, obtains plasticising biomass composite sheet material。
The performance detection of the plasticising biomass composite that embodiment 3 prepares is: hot strength is 40.2MPa, and elongation at break is 8.8%, and bending strength is 72.1MPa, and bending modulus is 4231.7MPa, and notch impact strength is 4.1KJ/m2。
Comparative example 1
Being raw material with paper pulp fiber and polypropylene, prepare disposable tableware, its production stage is as follows:
(1) by 60～80 DEG C of paper pulp fibers dried 30 parts, 70 parts, 3 parts polypropylene grafted maleic anhydrides of polypropylene, 1 part of Tissuemat E and 0.1 part antioxidant 1010 to put into high-speed mixer and mixing uniform, obtain compound A；
(2) obtained compound A being added torque rheometer, under 195 DEG C and 40r/min rotating speed, mixing 10min is uniformly mixed and expects B；Add pulverizer after cooling, obtain pellet；
(3) being added in injection machine by 60～80 DEG C of dried pellets, barrel temperature is 195 DEG C, and mold temperature is 30 DEG C, and injection pressure is 3.5MPa, cooling and demolding, obtains environmental protection plasticising biomass composite disposable tableware。
The performance detection of the biomass composite that comparative example 1 prepares is: hot strength is 38.3MPa, and elongation at break is 9.1%, and bending strength is 56.2MPa, and bending modulus is 4075.8MPa, and notch impact strength is 2.2KJ/m2。
Comparative example 2
Being raw material with straw and polypropylene, adopting dioctyl phthalate (DOP) is plasticizer, prepares composite board, and its production stage is as follows:
(1) by 60～80 DEG C of straws dried 30 parts, polypropylene 70 parts, 2 parts and 1 part Tissuemat E of dioctyl phthalate and 0.1 part antioxidant 1010 to put into high-speed mixer and mixing uniform, obtain compound A；
(2) obtained compound A is added extruder, be uniformly mixed at 185 DEG C of mixing 10min and expect B；Pellet is obtained by comminutor；
(3) being added in injection machine by 60～80 DEG C of dried pellets, barrel temperature is 185 DEG C, and mold temperature is 30 DEG C, and injection pressure is 2.5MPa, obtains composite board。
The performance detection of the composite board that comparative example 2 prepares is: hot strength is 39.3MPa, and elongation at break is 8.7%, and bending strength is 59.4MPa, and bending modulus is 4128.2MPa, and notch impact strength is 2.6KJ/m2。
Although the present invention being described in detail and having quoted some instantiations as proof, as long as but it will be understood by those skilled in the art that without departing from the spirit and scope of the present invention, it is obvious for making various changes or revising。
The contrast of example sample prepared by table one present invention and comparative example
Compared with comparative example 1 (not adding plasticizer), it is possible to finding that the hot strength of environmental protection plasticising biomass composite, elongation at break, bending strength and the notch impact strength prepared by the present invention are obviously improved, processing temperature substantially reduces；With comparative example 2 (addition Conventional plasticizers) contrast it can be seen that in biomass composite, green esters environment-friendlyplasticizer plasticizer replaces traditional phthalic ester plasticizer, and performance and the processing temperature of composite are greatly improved。Illustrate that the present invention is effective。
Claims (7)
1. an environmental protection plasticising biomass composite, it is characterised in that component and parts by weight that described composite includes are as follows:
Described biomass fiber is one or more in straw fine powder, bamboo powder, wood powder, paper pulp fiber；
Described TPO compound is one or more in polyethylene (PE), polypropylene (PP), polystyrene (PS)；
Described green ester plasticizer is one or more in epoxy soybean oil, citrate, tributyl 2-acetylcitrate, Cardanol yl acetate；
Described compatilizer is preferably selected from one or more of maleic anhydride inoculated polypropylene, glycidyl methacrylate graft polypropylene and glycidyl methacrylate graft polyformaldehyde；
Described lubricant is one or more in ethylene bis stearic acid amide, Tissuemat E and stearic acid；
Described antioxidant is the one in antioxidant 1010, antioxidant 1076 or antioxidant 164。
2. the preparation method of environmental protection plasticising biomass composite as claimed in claim 1, it is characterised in that described method comprises the steps:
(1) by 60～80 DEG C of biomass fibers dried, TPO compound and compatilizer, lubricant, that high-speed mixer and mixing put into by antioxidant is uniform, obtains compound A；
(2) compound A obtained for step (1) added torque rheometer and adds green ester plasticizer, being mixed to get Homogeneous phase mixing material B in 130 DEG C～170 DEG C, add pulverizer after cooling, obtain pellet；
(3) 60～80 DEG C of dried pellets are added in injection machine, injection moulding at 130 DEG C～170 DEG C, obtain described environmental protection plasticising biomass composite。
3. the preparation method of environmental protection plasticising biomass composite as claimed in claim 2, it is characterised in that in described step (1), water content≤2% of each raw material after drying。
4. the preparation method of environmental protection plasticising biomass composite as claimed in claim 2, it is characterised in that the described mixture described in step (1) is 5～8 minutes in the time of high-speed mixer and mixing；The order of addition of mixture is that processing aid adds after other raw material premixs。
5. the preparation method of environmental protection plasticising biomass composite as claimed in claim 2, it is characterised in that the mixing time described in step (2) is 5～30min, and torque rheometer rotating speed is 20～100r/min；The particle diameter < 3mm of described pellet。
6. the preparation method of environmental protection plasticising biomass composite as claimed in claim 2, it is characterised in that the mold temperature in injection mo(u)lding described in step (3) is 30 DEG C～80 DEG C, and the described injection pressure in injection mo(u)lding is 3.5MPa。
7. the preparation method of environmental protection plasticising biomass composite as claimed in claim 6, it is characterised in that。The mold temperature in injection mo(u)lding described in step (3) is 30 DEG C～50 DEG C。
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| CN106221000A (en) * | 2016-07-28 | 2016-12-14 | 陈林美 | A kind of high intensity tear-resistant polypropylene film formula |
| CN107474394A (en) * | 2017-09-30 | 2017-12-15 | 中国科学院过程工程研究所 | A kind of high-performance bio-based composite material and preparation method thereof |
| WO2018090117A1 (en) * | 2016-11-17 | 2018-05-24 | Fibria Celulose S.A. | Process for obtaining thermoplastic composite pellets reinforced with cellulose pulp and additive cellulose pulp |
| CN109401020A (en) * | 2018-11-07 | 2019-03-01 | 上海昶法新材料有限公司 | A kind of papermaking waste/composite polyethylene material and preparation method thereof |
| CN106046830B (en) * | 2016-07-04 | 2019-06-21 | 沈阳化工大学 | A kind of preparation method of natural Cortex Eucommiae wood plastic composite |
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| CN104497429A (en) * | 2014-12-10 | 2015-04-08 | 淄博龙沙高分子材料科技有限公司 | Ecological pollution-free wood-plastic pencil body material as well as preparation method and special mold thereof |
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Inventor after: Guo Weihong Inventor after: Li Zhuang Inventor after: Xu Ting Inventor after: Wu Genhua Inventor after: Wang Jikui Inventor after: Li Qiuying Inventor after: Wang Yuming Inventor after: Liu Biye Inventor before: Guo Weihong Inventor before: Li Zhuang Inventor before: Xu Ting Inventor before: Wu Genhua Inventor before: Wang Jikui Inventor before: Li Qiuying Inventor before: Wang Yuming Inventor before: Liu Biye |
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Application publication date: 20160622 |