CN102888045B - Plant charcoal plastic composite material - Google Patents
Plant charcoal plastic composite material Download PDFInfo
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- CN102888045B CN102888045B CN201210408679.9A CN201210408679A CN102888045B CN 102888045 B CN102888045 B CN 102888045B CN 201210408679 A CN201210408679 A CN 201210408679A CN 102888045 B CN102888045 B CN 102888045B
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Abstract
The invention relates to the field of high polymer, in particular to a plant charcoal plastic composite material which comprises the components in parts by weight: 100 parts of polyethylene with the ultra-high molecular weight of 4-7 million, 30-35 parts of high-density polypropylene with the molecular weight of 1-1.4 million, 8-10 parts of ultralow-density polypropylene, 3-12 parts of fire retardant, 5-10 parts of toughening agent, 2-5 parts of coupling agent, 0.5-1 part of antioxidant and 15-20 parts of plant charcoal. The plant charcoal plastic composite material has excellent toughness as well as higher rigidity, hardness and fire resistance.
Description
Technical field
The present invention relates to field of polymer technology, relate in particular to a kind of plant charcoal plastics composite.
Background technology
Ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE) refers to that relative molecular weight is at more than 1,500,000 polyethylene, be a kind of in current engineering plastics the model engineering plastic of over-all properties the best.Ultrahigh molecular weight polyethylene(UHMWPE) molecular structure is arranged identical with common polythene, and still, because it has very high relative molecular weight, therefore, it has had the not available excellent properties of many common polythene materials.For example: it has the 1. difficult foreign matter that adheres to; 2. resistance to chemical attack; 3. nontoxic, recovery capable of circulation etc.
Although ultrahigh molecular weight polyethylene(UHMWPE) has above-mentioned advantage, but it also has weak point, as poor in temperature tolerance (heat-drawn wire is 80 ℃), poor dimensional stability, hardness low (Rockwell hardness 40-50HRM), rigidity is low, tensile strength is low (34MPa), not antistatic (surface resistivity is 1015 Ω) and without mobility (melt flow rate (MFR) is 0) etc., to machine-shaping, bring great difficulty, the method that generally can only depend on compression molding or plunger extrusion molding is processed, and has limited the application of polyvinyl resin with super-high molecular weight.
Polypropylene (PP) has developed very rapid since nineteen fifty-seven industrialization, is a kind of application plastics very widely.Polyacrylic thermotolerance is better than polyethylene, and its fusing point reaches 164 ℃, can be at 100-120 ℃ life-time service.Polypropylene also has good erosion resistance, electrical insulating property, and its mechanical property comprises that tensile strength, compressive strength, hardness etc. are also fine, and its rigidity and folding resistance are very outstanding.But polypropylene also has its shortcoming urgently overcoming, resemble wear resistance, toughness deficiency etc.
Chinese patent CN02110452 discloses a kind of polypropylene/ultrahigh molecular weight polythene in-situ fibre-formed cocrystallized composite material, yet the mechanical property of this material and flame retardant resistance and static resistance all have much room for improvement.
Summary of the invention
The object of this invention is to provide a kind of plant charcoal plastics composite that there is excellent toughness, possesses again higher rigidity and hardness and flame retardant resistance.
Above-mentioned technical purpose of the present invention is achieved by the following technical programs:
A kind of plant charcoal plastics composite, its weight and consisting of: molecular weight is 100 parts of the ultrahigh molecular weight polyethylene(UHMWPE)s of 400-700 ten thousand, molecular weight is high density poly propylene 30-35 part of 100-140 ten thousand, extremely-low density polypropylene 8-10 part, fire retardant 3-12 part, toughner 5-10 part, coupling agent 2-5 part, oxidation inhibitor 0.5-1 part, plant charcoal 15-20 part.
As preferably, described plant charcoal makes through following methods:
(1) raw material pre-treatment: plant material is sent in microwave vacuum tank, be evacuated to vacuum tightness for-0.02MPa～-0.001MPa, then carry out microwave treatment, microwave frequency is 300MHz～950MHz, and microwave treatment time is 1～3min;
(2) plant charcoal preparation: the plant material through pre-treatment gained is experienced to dry, pre-charing, charing, calcining and cooling successively, control combustion is warming up to 700-750 ℃ or 900-1000 ℃ and is incubated 40-80min with the speed of 5-15 ℃/min, and then with the speed of 5-15 ℃/min, is warming up to 1000-1500 ℃ or 1600-1800 ℃ and is incubated 2-8h and obtain plant charcoal.
As preferably, described plant material is corn cob, bamboo or pine tree.
More preferably, for corn cob or bamboo, control combustion is warming up to 700-750 ℃ and be incubated 40-80min with the speed of 5-15 ℃/min, and then is warming up to 1000-1500 ℃ and be incubated 2-8h with the speed of 5-15 ℃/min, obtains plant charcoal.
More preferably, for pine tree, control combustion is warming up to 900-1000 ℃ and be incubated 40-80min with the speed of 5-15 ℃/min, and then is warming up to 1600-1800 ℃ and be incubated 2-8h with the speed of 5-15 ℃/min, obtains plant charcoal.
As preferably, described fire retardant is counted composed of the following components by weight: 20～50 parts of ammonium low polyphosphates, 10～25 parts, ammonium phosphate, 6～12 parts of ammonium pyrophosphates, 5～20 parts, ammonium sulfate, 5～10 parts of boric acid, 10～25 parts, water.
The present invention's fire retardant used, environmentally safe, has also guaranteed workman's health safety in production process, and can recycle.
As preferably, described toughner is terpolymer EP rubber EPDM or second the third glue.
As preferably, described coupling agent is silane coupling agent, aluminate coupling agent or aluminium titanium composite coupler.
As preferably, described oxidation inhibitor is phosphorous acid ester or irgasfos 168.
A production method for plant charcoal plastics composite, it comprises the following steps successively:
(1) raw material pre-treatment: plant material is sent in microwave vacuum tank, be evacuated to vacuum tightness for-0.02MPa～-0.001MPa, then carry out microwave treatment, microwave frequency is 300MHz～950MHz, and microwave treatment time is 1～3min;
(2) plant charcoal preparation: the plant material through pre-treatment gained is experienced to dry, pre-charing, charing, calcining and cooling successively, control combustion is warming up to 700-750 ℃ or 900-1000 ℃ and is incubated 40-80min with the speed of 5-15 ℃/min, and then with the speed of 5-15 ℃/min, is warming up to 1000-1500 ℃ or 1600-1800 ℃ and is incubated 2-8h and obtain plant charcoal;
(3) modifying plastics: adopting molecular weight is that the ultrahigh molecular weight polyethylene(UHMWPE) of 400-700 ten thousand and high density poly propylene that molecular weight is 100-140 ten thousand are base-material blending and modifying, in the course of processing, add fire retardant, toughner, coupling agent, oxidation inhibitor and step (1) gained plant charcoal;
Wherein the weight ratio of each component is:
100 parts of ultrahigh molecular weight polyethylene(UHMWPE)s;
High density poly propylene 30-35 part;
Extremely-low density polypropylene 8-10 part,
Fire retardant 3-12 part;
Toughner 5-10 part;
Coupling agent 2-5 part;
Oxidation inhibitor 0.5-1 part;
Plant charcoal 15-20 part.
The present invention can control moisture and the perforate of plant material by pre-treatment, contributes to the preparation of follow-up plant charcoal, and the plant charcoal of preparation and have good conduction and de-taste function can be removed the smell of plastics; Static resistance to plastics performance has promoter action; Between ultrahigh molecular weight polyethylene(UHMWPE) and the molecular chain of high density poly propylene, be mutually wound around simultaneously, by extremely-low density polypropylene, toughner, coupling agent and oxidation inhibitor, regulate its consistency and antioxidant, improved the processing characteristics of ultra-high molecular weight, the plant charcoal plastics composite that makes to prepare gained has excellent toughness, possesses higher rigidity and hardness and flame retardant resistance again.
As preferably, described step (3) is first mediated 40-50min by described fire retardant, toughner, coupling agent, oxidation inhibitor and step (1) gained plant charcoal in Banbury mixer at 90-100 ℃, and then adds in described base-material.
The present invention's kneading of first will be first fire retardant, toughner, coupling agent, oxidation inhibitor and step (1) gained plant charcoal pressurize in Banbury mixer contributes to fully mixing of plant charcoal and fire retardant, toughner, coupling agent, oxidation inhibitor, prevents the migration of fire retardant, oxidation inhibitor.
Accompanying drawing explanation
Fig. 1 is the temperature controlling system schematic diagram of the vertical moving-bed of plant charcoal charing of the present invention;
In figure, A-drying zone; The pre-char zone of B-; C-char zone; D-calcining zone; E-cooling zone; F-is with the temperature sensing device of CPU; D1/d2/d3-oxidizer entrance hole; T1/t2/t3-point for measuring temperature.
Embodiment
As shown in Figure 1, the vertical moving-bed that plant charcoal preparation is used is divided into drying zone A, pre-char zone B, char zone C, calcining zone D and cooling zone E.D mono-side in calcining zone is distributed with many oxidizer entrance holes that can regulate closure or openness, as d1, d2, d3 etc., opposite side is to having the point for measuring temperature at each aperture place as t1, t2, t3 etc., and each aperture place temperature shows by the temperature sensing device F being connected with this point for measuring temperature.
Embodiment mono-
The plant material that the present embodiment adopts is corn cob.
Plant material is sent in microwave vacuum tank, be evacuated to vacuum tightness for-0.02MPa, then carry out microwave treatment, microwave frequency is 300MHzMHz, and microwave treatment time is 1min;
Plant material through pre-treatment gained is experienced dry successively, pre-charing, charing, calcining and cooling, the temperature of each point for measuring temperature, drying zone A is 150 ℃, pre-char zone B is 275 ℃, char zone C is 450 ℃, during intensification, observe the temperature of the district of D shown in Fig. 1 combustion zone different positions, when somewhere, combustion zone is as too low in the temperature of d2, open the aperture at this place, importing air locally burns, this place's temperature is raise, control the combustion zone temperature experiencing in bamboo folding process, control combustion is warming up to 700 ℃ and be incubated 40min with the speed of 5 ℃/min, and then be warming up to 1600 ℃ and be incubated 2h and obtain plant charcoal with the speed of 5 ℃/min,
Modifying plastics: first 3 parts of fire retardants, 5 parts of terpolymer EP rubber EPDM toughner, 2 parts of silane coupling agents, 0.5 part of phosphorous acid ester and 15 parts of plant charcoal are mediated to 40min in Banbury mixer at 90 ℃, and then add in the base-material that high density poly propylene that ultrahigh molecular weight polyethylene(UHMWPE) that 100 parts of molecular weight are 400-500 ten thousand, 8 parts of extremely-low density polypropylene and 30 parts of molecular weight are 100-110 ten thousand forms, high-speed mixing is by twin screw extruder extruding pelletization, and extrusion temperature is 210 ℃.
The fire retardant using is counted composed of the following components by weight: 20 parts of ammonium low polyphosphates, 10 parts, ammonium phosphate, 6 parts of ammonium pyrophosphates, 5 parts, ammonium sulfate, 5 parts of boric acid, 10 parts, water.
Product performance index is in Table 1.
Embodiment bis-
The plant material that the present embodiment adopts is bamboo chip (being about 40cm).
Plant material is sent in microwave vacuum tank, be evacuated to vacuum tightness for-0.001MPa, then carry out microwave treatment, microwave frequency is 950MHz, and microwave treatment time is 3min;
Plant material through pre-treatment gained is experienced dry successively, pre-charing, charing, calcining and cooling, the temperature of each point for measuring temperature, drying zone A is 150 ℃, pre-char zone B is 275 ℃, char zone C is 450 ℃, during intensification, observe the temperature of the district of D shown in Fig. 1 combustion zone different positions, when somewhere, combustion zone is as too low in the temperature of d2, open the aperture at this place, importing air locally burns, this place's temperature is raise, control the combustion zone temperature experiencing in bamboo folding process, control combustion is warming up to 750 ℃ and be incubated 80min with the speed of 15 ℃/min, and then heat up 1500 ℃ and be incubated 8h and obtain plant charcoal with the speed of 15 ℃/min,
Modifying plastics: first 12 parts of fire retardants, 10 parts of second the third glue toughner, 2-5 part aluminate coupling agent, 1 part of irgasfos 168 and 20 parts of plant charcoal are mediated to 50min in Banbury mixer at 100 ℃, and then add in the base-material that high density poly propylene that ultrahigh molecular weight polyethylene(UHMWPE) that 100 parts of molecular weight are 600-700 ten thousand, 10 parts of extremely-low density polypropylene and 35 parts of molecular weight are 130-140 ten thousand forms, high-speed mixing is by twin screw extruder extruding pelletization, and extrusion temperature is 220 ℃.
The fire retardant using is counted composed of the following components by weight: 50 parts of ammonium low polyphosphates, 25 parts, ammonium phosphate, 12 parts of ammonium pyrophosphates, 20 parts, ammonium sulfate, 10 parts of boric acid, 25 parts, water.
Embodiment tri-
The plant material that the present embodiment adopts is pine tree, ingresses after pine tree is removed to epidermis impurity, and length is controlled and is no more than 15cm.
Plant material is sent in microwave vacuum tank, be evacuated to vacuum tightness for-0.01MPa, then carry out microwave treatment, microwave frequency is 550MHz, and microwave treatment time is 2min;
Plant material through pre-treatment gained is experienced dry successively, pre-charing, charing, calcining and cooling, the temperature of each point for measuring temperature, drying zone A is 180 ℃, pre-char zone B is 325 ℃, char zone C is 530 ℃, during intensification, observe the temperature of the district of D shown in Fig. 1 combustion zone different positions, when somewhere, combustion zone is as too low in the temperature of d2, open the aperture at this place, importing air locally burns, this place's temperature is raise, control the combustion zone temperature experiencing in bamboo folding process, control combustion is warming up to 900 ℃ and be incubated 50min with the speed of 10 ℃/min, and then be warming up to 1600 ℃ and be incubated 5h and obtain plant charcoal with the speed of 10 ℃/min,
Modifying plastics: first 8 parts of fire retardants, 6 parts of terpolymer EP rubber EPDM toughner, 4 parts of aluminium titanium composite couplers, 0.7 part of phosphorous acid ester and 18 parts of plant charcoal are mediated to 45min in Banbury mixer at 95 ℃, and then add in the base-material that high density poly propylene that ultrahigh molecular weight polyethylene(UHMWPE) that 100 parts of molecular weight are 500-600 ten thousand, 9 parts of extremely-low density polypropylene and 33 parts of molecular weight are 120-130 ten thousand forms, high-speed mixing is by twin screw extruder extruding pelletization, and extrusion temperature is 230 ℃.
The fire retardant using is counted composed of the following components by weight: 30 parts of ammonium low polyphosphates, 15 parts, ammonium phosphate, 8 parts of ammonium pyrophosphates, 15 parts, ammonium sulfate, 8 parts of boric acid, 15 parts, water.
Embodiment tetra-
With embodiment tri-, different is that the raw material using is beech; Control combustion is warming up to 1000 ℃ and be incubated 50min with the speed of 10 ℃/min, and then is warming up to 1800 ℃ and be incubated 5h and obtain plant charcoal with the speed of 10 ℃/min.
Embodiment five
With embodiment tri-, different is that fire retardant is decabromodiphynly oxide, antimonous oxide and expansibility flame-proof agent ammonium polyphosphate APP, and three's ratio is 10:5:1.
Comparative example one
With embodiment mono-, different is that plant material does not pass through microwave vacuum pre-treatment, but carries out modifying plastics after being directly prepared into plant charcoal.
Comparative example two
With embodiment bis-, different is that plant material is sent in microwave vacuum tank, is evacuated to vacuum tightness to be-0.4MPa, then carries out microwave treatment, and microwave frequency is 1200MHz, and microwave treatment time is 5min, and the plant charcoal weight of adding when modifying plastics is 5 parts.
Comparative example three
With embodiment tri-, different is when modifying plastics, not add fire retardant.
Each embodiment of table 1 and comparative example's product performance index
As can be seen from Table 1,
(1) tensile strength of the embodiment of the present invention one-embodiment three products and tensile modulus are large, and its shock resistance is described, elasticity and hardness are large; Melting index is high, and its good fluidity is described; Socle girder notched Izod impact strength is large, illustrates that its toughness is large; Surface resistivity is large, illustrates that its antistatic property is strong; The flaming combustion time is long and the internally fired nonflame time is short, illustrates that its flame retardant resistance is strong; The plant material that embodiment tetra-adopts is beech, and its various aspects of performance is slightly poor;
(2) fire retardant that embodiment five adopts is different from embodiment mono--embodiment tetra-, and its flame retardant properties is slightly poor;
(3) comparative example one plant material does not pass through microwave vacuum pre-treatment, and the various aspects of performance of its product is poor; Plant charcoal weight and microwave vacuum treatment process parameter that comparative example two adds are different, and the various aspects of performance of its product especially static resistance is poor.
This specific embodiment is only explanation of the invention; it is not limitation of the present invention; those skilled in the art can make to the present embodiment the modification that there is no creative contribution as required after reading this specification sheets, but as long as within the scope of claim of the present invention, are all subject to the protection of patent law.
Claims (9)
1. a plant charcoal plastics composite, it is characterized in that weight and consisting of: molecular weight is 100 parts of the ultrahigh molecular weight polyethylene(UHMWPE)s of 400-700 ten thousand, molecular weight is high density poly propylene 30-35 part of 100-140 ten thousand, extremely-low density polypropylene 8-10 part, fire retardant 3-12 part, toughner 5-10 part, coupling agent 2-5 part, oxidation inhibitor 0.5-1 part, plant charcoal 15-20 part;
Described plant charcoal makes through following methods:
(1) raw material pre-treatment: plant material is sent in microwave vacuum tank, be evacuated to vacuum tightness for-0.02MPa～-0.001MPa, then carry out microwave treatment, microwave frequency is 300MHz～950MHz, and microwave treatment time is 1～3min;
(2) plant charcoal preparation: the plant material through pre-treatment gained is experienced to dry, pre-charing, charing, calcining and cooling successively, control combustion is warming up to 700-750 ℃ or 900-1000 ℃ and is incubated 40-80min with the speed of 5-15 ℃/min, and then with the speed of 5-15 ℃/min, is warming up to 1000-1500 ℃ or 1600-1800 ℃ and is incubated 2-8h and obtain plant charcoal.
2. a kind of plant charcoal plastics composite according to claim 1, is characterized in that: described plant material is corn cob, bamboo or pine tree.
3. a kind of plant charcoal plastics composite according to claim 2, is characterized in that: described fire retardant is counted composed of the following components by weight: 20～50 parts of ammonium low polyphosphates, 10～25 parts, ammonium phosphate, 6～12 parts of ammonium pyrophosphates, 5～20 parts, ammonium sulfate, 5～10 parts of boric acid, 10～25 parts, water.
4. a kind of plant charcoal plastics composite according to claim 3, is characterized in that: described toughner is terpolymer EP rubber EPDM.
5. a kind of plant charcoal plastics composite according to claim 4, is characterized in that: described coupling agent is silane coupling agent, aluminate coupling agent or aluminium titanium composite coupler.
6. a kind of plant charcoal plastics composite according to claim 5, is characterized in that: described oxidation inhibitor is irgasfos 168.
7. a production method for plant charcoal plastics composite according to claim 1, is characterized in that: comprise the following steps successively:
(1) raw material pre-treatment: plant material is sent in microwave vacuum tank, be evacuated to vacuum tightness for-0.02MPa～-0.001MPa, then carry out microwave treatment, microwave frequency is 300MHz～950MHz, and microwave treatment time is 1～3min;
(2) plant charcoal preparation: the plant material through pre-treatment gained is experienced to dry, pre-charing, charing, calcining and cooling successively, control combustion is warming up to 700-750 ℃ or 900-1000 ℃ and is incubated 40-80min with the speed of 5-15 ℃/min, and then with the speed of 5-15 ℃/min, is warming up to 1000-1500 ℃ or 1600-1800 ℃ and is incubated 2-8h and obtain plant charcoal;
(3) modifying plastics: adopting molecular weight is that the ultrahigh molecular weight polyethylene(UHMWPE) of 400-700 ten thousand, high density poly propylene and the extremely-low density polypropylene that molecular weight is 100-140 ten thousand are base-material blending and modifying, in the course of processing, add fire retardant, toughner, coupling agent, oxidation inhibitor and step (2) gained plant charcoal;
Wherein the weight ratio of each component is:
100 parts of ultrahigh molecular weight polyethylene(UHMWPE)s;
High density poly propylene 30-35 part;
Extremely-low density polypropylene 8-10 part,
Fire retardant 3-12 part;
Toughner 5-10 part;
Coupling agent 2-5 part;
Oxidation inhibitor 0.5-1 part;
Plant charcoal 15-20 part.
8. the production method of a plant charcoal plastics composite according to claim 7, it is characterized in that: described step (3) is first mediated 40-50min by described fire retardant, toughner, coupling agent, oxidation inhibitor and step (2) gained plant charcoal in Banbury mixer at 90-100 ℃, and then adds in described base-material.
9. the production method of a plant charcoal plastics composite according to claim 8, it is characterized in that: for corn cob or bamboo plant material, control combustion is warming up to 700-750 ℃ and be incubated 40-80min with the speed of 5-15 ℃/min, and then be warming up to 1000-1500 ℃ and be incubated 2-8h with the speed of 5-15 ℃/min, obtain plant charcoal.
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| CN104292610B (en) * | 2013-07-17 | 2017-09-05 | 博富科技股份有限公司 | Load the preparation method of PA6 plant charcoal modified polypropene |
| CN104327360A (en) * | 2014-11-25 | 2015-02-04 | 侨健新能源科技（苏州）有限公司 | Efficient degradable modified plastic material |
| CN104327361A (en) * | 2014-11-25 | 2015-02-04 | 侨健新能源科技（苏州）有限公司 | High-performance degradable modified plastic material |
| CN113652030A (en) * | 2021-08-25 | 2021-11-16 | 瑞安市嘉润新材料科技有限公司 | Elastic tray net material and preparation method thereof |
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| CN101323688A (en) * | 2008-07-28 | 2008-12-17 | 广东电缆厂有限公司 | Highly effective flame-retardant environment-protective thermoplastic plastic and making process thereof |
| CN101757891A (en) * | 2010-01-13 | 2010-06-30 | 云南瑞升烟草技术（集团）有限公司 | Preparation method of natural plant carbonated material and application thereof to cigarette filter rod |
| CN101921428A (en) * | 2010-08-17 | 2010-12-22 | 丁宏广 | Monofilament applied to bamboo charcoal air strainer and preparation process and application thereof |
| CN102659723A (en) * | 2012-04-27 | 2012-09-12 | 广州博能能源科技有限公司 | Process for preparing furfural by using agricultural by-products of high and crude fiber plants |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101323688A (en) * | 2008-07-28 | 2008-12-17 | 广东电缆厂有限公司 | Highly effective flame-retardant environment-protective thermoplastic plastic and making process thereof |
| CN101757891A (en) * | 2010-01-13 | 2010-06-30 | 云南瑞升烟草技术（集团）有限公司 | Preparation method of natural plant carbonated material and application thereof to cigarette filter rod |
| CN101921428A (en) * | 2010-08-17 | 2010-12-22 | 丁宏广 | Monofilament applied to bamboo charcoal air strainer and preparation process and application thereof |
| CN102659723A (en) * | 2012-04-27 | 2012-09-12 | 广州博能能源科技有限公司 | Process for preparing furfural by using agricultural by-products of high and crude fiber plants |
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