CN102276848A - Method for modifying and pretreating bacterium mushroom stick used for preparing wood-plastic composite material - Google Patents
Method for modifying and pretreating bacterium mushroom stick used for preparing wood-plastic composite material Download PDFInfo
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- CN102276848A CN102276848A CN 201110211935 CN201110211935A CN102276848A CN 102276848 A CN102276848 A CN 102276848A CN 201110211935 CN201110211935 CN 201110211935 CN 201110211935 A CN201110211935 A CN 201110211935A CN 102276848 A CN102276848 A CN 102276848A
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- bacterium mushroom
- mushroom rod
- coupling agent
- plastic composite
- oven dry
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Abstract
The invention relates to a method for modifying and pretreating a bacterium mushroom stick used for preparing a wood-plastic composite material, and the method comprises the following steps of: (1) firstly crushing, stoving and screening the bacterium mushroom stick; and (2) then carrying out chemical graft modification: stirring the bacterium mushroom stick subjected to the crushing, stoving and screening at high speed; when the temperature reaches 105-115 DEG C, adding a chemical initiator monomer, then adding a coupling agent, and continuing stirring at high speed; and when the temperature reaches 120-125 DEG C, stopping the stirring, wherein the following raw materials are adopted in parts by weight: 90-120 parts of the bacterium mushroom stick subjected to the crushing, stoving and screening, 0.1-1 part of the chemical initiator monomer and 0.5-4 parts of the coupling agent. According to the invention, waste material can be changed into things of value, the bacterium mushroom stick can be well combined with PVC (poly vinyl chloride) resin to prepare a wood fiber raw material of the wood-plastic composite material, thus environmental pollution problem caused by the bacterium mushroom stick is solved and production cost is reduced.
Description
Technical field
The present invention relates to the modification pretreatment process that a kind of bacterium mushroom rod is used for the wood plastic composite preparation.
Background technology
Bacterium mushroom rod is that agricultural planting is produced the left next waste of becteriums product.A large amount of bacterium mushroom rods are deposited in around the mushroom plantation, rural area, are difficult to dispose, and the time has been grown and also can send a kind of septic taste, contaminate environment.Need to use a large amount of lignocellulose raw materials in the preparation process of wood plastic composite, but find by the mass analysis that the sample of bacterium mushroom rod is done: the main component of bacterium mushroom rod differs very big with the main component of making the needed lignocellulose raw material of wood plastic composite: the lignocellulose molecular weight in the bacterium mushroom rod raw material significantly reduces, the content of other organic composition also reduces in a large number, molecular weight reduces.Therefore, if bacterium mushroom rod directly uses, adds in PVC wood plastic composite and the goods, will directly reduce the physical and mechanical properties of wood plastic composite.
Summary of the invention
In order to solve existing in prior technology the problems referred to above, the invention provides the modification pretreatment process that a kind of bacterium mushroom rod is used for the wood plastic composite preparation, it can be turned waste into wealth, make bacterium mushroom rod become can with the polyvinyl chloride resin good combination with the preparation wood plastic composite lignocellulose raw material, both solve the problem of environmental pollution that bacterium mushroom rod is caused, reduced production cost again.
Technical solution of the present invention is to constitute like this, and a kind of bacterium mushroom rod is used for the modification pretreatment process of wood plastic composite preparation, and it is characterized in that: it may further comprise the steps:
1. carry out fragmentation, oven dry and the Screening Treatment of bacterium mushroom rod earlier, the moisture content of bacterium mushroom rod is remained in 8%, remove impurity by screening by oven dry;
2. then carrying out grafting modification handles: earlier will be through the bacterium mushroom rod high-speed stirring of fragmentation, oven dry and Screening Treatment; When temperature reaches 105-115 ℃, add the chemical initiator monomer, make its molecule chain end form active group at bacterium mushroom rod wood fibre; Then add coupling agent, continue high-speed stirring; When reaching 120-125 ℃, temperature stops to stir; In this step, the weight proportion of each raw material is as follows:
Bacterium mushroom rod 90-120 part through fragmentation, oven dry and Screening Treatment;
1 part of chemical initiator monomer 0.1-;
4 parts of coupling agent 0.5-.
Described chemical initiator monomer is made of dicumyl peroxide or maleic anhydride, and described coupling agent is made of titanate coupling agent or silane coupling agent or aluminate coupling agent.
Coupling agent is multi-functional organic compound, an end solubilized or be diffused in the polyvinyl chloride resin of interface region, and the other end can form bond with hydrophilic radical in the wood fibre and close, and improves the interfacial adhesion between filler and matrix.As a result, one side direct graft polymerization between the part molecule of bacterium mushroom rod raw material forms crosslinked; On the other hand, the polyfunctional group of coupling agent can make wood fibre and polyvinyl chloride resin merge well, forms an organic whole, thereby improves the physical and mechanical properties of wood plastic composite.
Compared to prior art, the present invention has following remarkable advantage: the present invention handles by the modification preplasticizing to bacterium mushroom rod, the refuse of this agriculture production of bacterium mushroom rod is turned waste into wealth, make bacterium mushroom rod become can with the polyvinyl chloride resin good combination with the preparation wood plastic composite lignocellulose raw material, both solve the problem of environmental pollution that bacterium mushroom rod is caused, reduced production cost again.In addition,, therefore both enlarged raw-material optional scope, also played the effect of saving timber resources because lignocellulose raw materials such as the alternative after treatment wood powder that generally uses at present of bacterium mushroom rod, bamboo powder are produced qualified Wood Plastics Composite Product.
Embodiment
Below in conjunction with embodiment and embodiment content of the present invention is elaborated:
The specific embodiment of the invention relates to the modification pretreatment process that a kind of bacterium mushroom rod is used for the wood plastic composite preparation, and it is characterized in that: it may further comprise the steps:
1. carry out fragmentation, oven dry and the Screening Treatment of bacterium mushroom rod earlier, the moisture content of bacterium mushroom rod is remained in 8%, remove impurity by screening by oven dry;
2. then carrying out grafting modification handles: earlier will be through the bacterium mushroom rod high-speed stirring of fragmentation, oven dry and Screening Treatment; When temperature reaches 105-115 ℃, add chemical initiator monomer (can constitute) by dicumyl peroxide or maleic anhydride, make its molecule chain end form active group at bacterium mushroom rod wood fibre; Then add coupling agent (can constitute), continue high-speed stirring by titanate coupling agent or silane coupling agent; When reaching 120-125 ℃, temperature stops to stir; In this step, the weight proportion of each raw material is as follows:
Bacterium mushroom rod 90-120 part through fragmentation, oven dry and Screening Treatment;
1 part of chemical initiator monomer 0.1-;
4 parts of coupling agent 0.5-.
Above step is removed moisture too much in the wood fibre mainly by the frictional heat of high-speed stirring; And finish by the high-shear that height stirs wood fibre is carried out sufficient chemical modification, eliminate the polarity of wood fibre as much as possible.
In addition, also provide will be as follows with the preparation method that polyvinyl chloride resin and various auxiliary agent are mixed with wood plastic composite through the pretreated bacterium mushroom rod of modification in the present invention:
(1) high speed blend: polyvinyl chloride resin, pretreated wood fibre and the various auxiliary agent of modification are carried out preplasticizing by the high-speed stirring blend; Described auxiliary agent comprises lubricant, thermo-stabilizer, anti-impact modifier and whipping agent, and the concrete grammar of high speed blend is as follows:
1. earlier with polyvinyl chloride resin and thermo-stabilizer high-speed stirring mixing together;
2. when temperature reaches 75-90 ℃, Yi Bian add lubricant, anti-impact modifier and through the pretreated wood fibre of modification, Yi Bian continue high-speed stirring;
3. when temperature reaches 110-116 ℃, Yi Bian add whipping agent, Yi Bian continue high-speed stirring;
4. when temperature reaches 118-125 ℃, stop to stir, material is transferred to cooling vessel is cooled to below 60 ℃, stand-by.
In addition, as required, in the 3. stage in above-mentioned steps, when adding whipping agent, also can add an amount of mould inhibitor and/or ultra-violet stabilizer.If wood plastic composite is used for the open air, then preferably add ultra-violet stabilizer, add if be used for indoor then do not need.The interpolation of mould inhibitor is mainly decided according to the degree of drying of environment for use.
(time and temperature requirement) is most important the order of addition(of ingredients) of each raw material and reinforced opportunity in this step, directly has influence on the quality of product.Described polyvinyl chloride resin, lubricant, thermo-stabilizer, anti-impact modifier, whipping agent, mould inhibitor, ultra-violet stabilizer and as follows through the weight proportion between the bacterium mushroom rod of fragmentation, oven dry and Screening Treatment:
Polyvinyl chloride resin: 100 parts,
Bacterium mushroom rod through fragmentation, oven dry and Screening Treatment: 90-120 part,
Lubricant: 2-4 part,
Thermo-stabilizer: 6-10 part,
Anti-impact modifier: 8-12 part,
Whipping agent: 1-3 part,
Mould inhibitor: 0.5-1 part,
Ultra-violet stabilizer: 0.5-1 part.
Available starting material are as follows in the wood plastic composite:
Described polyvinyl chloride resin comprises SG5 or SG7;
Described lubricant comprises at least a in paraffin or the stearate; Because the mobile extreme difference of wood fibre adds the flowability that lubricant can strengthen wood fibre, increases the flowability of polyvinyl chloride resin simultaneously, keeps any surface finish of wood plastic product.
Described thermo-stabilizer comprises calcium-zinc composite stabilizing agent, organotin stabilizer, rare-earth stabilizer or lead salt one package stabilizer;
Described anti-impact modifier comprises thermoplastic elastic body C PE(chlorinatedpolyethylene) or the ACR(acrylate) at least a; Anti-impact modifier can strengthen wood plastic composite shock resistance, improve material snappiness, improve the resistance to low temperature of material;
Described whipping agent comprises heat release type whipping agent and endothermic blowing agent;
Described mould inhibitor comprises nano composite antibiotic material, and described nano composite antibiotic material comprises at least a in nano titanium oxide or the sterilant; The purpose that adds mould inhibitor is to prevent that wood plastic composite from going mouldy, and it can prevent the growth of flavus, aspergillus niger etc. effectively;
Described ultra-violet stabilizer comprises the UV-531 one package stabilizer.Ultra-violet stabilizer can reduce and prevent and treat the destruction of ultraviolet ray to wood plastic composite effectively, prolongs the duration of service and the life-span of product.
(2) extrusion moulding: the mass transport that preplasticizing is good fully plastifies material to forcing machine under the proper temperature condition, will plastify good material afterwards and clamp-on in the forming mould, makes the material extrusion moulding under the effect of squeeze; Making material carry out abundant plastifying proper temperature condition is 170-200 ℃;
(3) cooling and shaping: with the parison cools typing of extrusion moulding.The method of described cooling and shaping is that parison with extrusion moulding is successively by cooling die and cooling bath cooling and shaping.
In addition, in the preprocessing process of bacterium mushroom rod, as required, also an amount of mineral filler can be added in the bacterium mushroom rod, make bacterium mushroom rod with an amount of mineral filler high-speed stirring; Perhaps step (1) the 2. described adding lubricant of stage, anti-impact modifier and through the pretreated bacterium mushroom of modification rod in, add an amount of mineral filler high-speed stirring together; Described mineral filler comprises CaCO
3Or at least a in the talcum powder; Described mineral filler with the weight proportion of the bacterium mushroom rod of process fragmentation, oven dry and Screening Treatment is: mineral filler 0-20 part, and through bacterium mushroom rod 90-120 part of fragmentation, oven dry and Screening Treatment.Certainly, in the actual production process, the interpolation of mineral filler is not essential.
The described auxiliary agent of step (1) also can comprise auxiliary addition agent; Described auxiliary addition agent comprises at least a in epoxy soybean oil, dioctyl phthalate (DOP), static inhibitor or the pigment; The interpolation time of described auxiliary addition agent is the 2. stage in step (1), adds high-speed stirring with lubricant, anti-impact modifier with through pretreated bacterium mushroom rod; The weight proportion of described polyvinyl chloride resin and auxiliary addition agent is as follows: 100 parts of polyvinyl chloride resins: auxiliary addition agent 5-8 part.The interpolation of auxiliary addition agent also is dispensable, mainly decides according to the actual performance needs of the wood plastic composite of producing.
Embodiment 1
1. carry out fragmentation, oven dry and the Screening Treatment of bacterium mushroom rod earlier, the moisture content of bacterium mushroom rod is remained in 8%, remove impurity by screening by oven dry;
2. then carrying out grafting modification handles: earlier will be through the bacterium mushroom rod 90kg high-speed stirring of fragmentation, oven dry and Screening Treatment; When temperature reaches 105 ℃, add dicumyl peroxide 0.1kg, make its molecule chain end form active group at bacterium mushroom rod wood fibre; Then add titanate coupling agent 0.5kg, continue high-speed stirring; When reaching about 120 ℃, temperature stops to stir, and stand-by.
Embodiment 2
1. carry out fragmentation, oven dry and the Screening Treatment of bacterium mushroom rod earlier, the moisture content of bacterium mushroom rod is remained in 8%, remove impurity by screening by oven dry;
2. then carrying out grafting modification handles: earlier will be through the bacterium mushroom rod 105kg high-speed stirring of fragmentation, oven dry and Screening Treatment; When temperature reaches 110 ℃, add dicumyl peroxide 0.5kg, make its molecule chain end form active group at bacterium mushroom rod wood fibre; Then add titanate coupling agent 2kg, continue high-speed stirring; When reaching about 122 ℃, temperature stops to stir, and stand-by.
Embodiment 3
1. carry out fragmentation, oven dry and the Screening Treatment of bacterium mushroom rod earlier, the moisture content of bacterium mushroom rod is remained in 8%, remove impurity by screening by oven dry;
2. then carrying out grafting modification handles: earlier will be through the bacterium mushroom rod 120kg high-speed stirring of fragmentation, oven dry and Screening Treatment; When temperature reaches 115 ℃, add dicumyl peroxide 1kg, make its molecule chain end form active group at bacterium mushroom rod wood fibre; Then add titanate coupling agent 4kg, continue high-speed stirring; When reaching about 125 ℃, temperature stops to stir, and stand-by.
Embodiment 4
To be mixed with acquisition three groups of wood plastic composites (routine 4-1, routine 4-2, routine 4-3) according to following steps through the pretreated bacterium mushroom rod of embodiment 1-3 modification and 100kg polyvinyl chloride resin, 3kg lubricant (employing paraffin), 8kg thermo-stabilizer (employing calcium-zinc composite stabilizing agent), 10kg anti-impact modifier (adopting CPE), 2kg whipping agent, 0.8kg mould inhibitor (employing nano titanium oxide) and 0.8kg ultra-violet stabilizer.
(1) high speed blend:
1. earlier with polyvinyl chloride resin and thermo-stabilizer high-speed stirring mixing together;
2. when temperature reaches 82 ℃, Yi Bian add lubricant, anti-impact modifier and through pretreated wood fibre, Yi Bian continue high-speed stirring;
3. when temperature reaches 112 ℃, Yi Bian add whipping agent, mould inhibitor and ultra-violet stabilizer, Yi Bian continue high-speed stirring;
4. when temperature reaches 120 ℃, stop to stir, material is transferred to cooling vessel is cooled to below 60 ℃, stand-by.
(3) extrusion moulding: the mass transport that preplasticizing is good fully plastifies material to forcing machine under 185 ℃ temperature condition, will plastify good material afterwards and clamp-on in the forming mould, makes the material extrusion moulding under the effect of squeeze;
(4) cooling and shaping: with the parison of extrusion moulding successively by cooling die and cooling bath cooling and shaping.
Embodiment 5(control group)
To not pass through other raw material that pretreated bacterium mushroom rod 100kg of modification and embodiment 4 enumerate, and be prepared according to embodiment 4 listed steps.
The preparation effect comparison
It is as follows that one group of wood plastic composite that three groups of wood plastic composites that prepare by embodiment 4 and embodiment 5 prepare detects contrast
In addition, change the dicumyl peroxide among routine 4-1, routine 4-2, the routine 4-3 into maleic anhydride, change titanate coupling agent into silane coupling agent, all the other proportioning raw materials are identical with processing step, the detected result basically identical of detected result and routine 4-1, routine 4-2, routine 4-3, positive and negative deviation is within 5%.
Claims (2)
1. a bacterium mushroom rod is used for the modification pretreatment process that wood plastic composite prepares, and it is characterized in that: it may further comprise the steps:
1. carry out fragmentation, oven dry and the Screening Treatment of bacterium mushroom rod earlier, the moisture content of bacterium mushroom rod is remained in 8%, remove impurity by screening by oven dry;
2. then carrying out grafting modification handles: earlier will be through the bacterium mushroom rod high-speed stirring of fragmentation, oven dry and Screening Treatment; When temperature reaches 105-115 ℃, add the chemical initiator monomer, make its molecule chain end form active group at bacterium mushroom rod wood fibre; Then add coupling agent, continue high-speed stirring; When reaching 120-125 ℃, temperature stops to stir; In this step, the weight proportion of each raw material is as follows:
Bacterium mushroom rod 90-120 part through fragmentation, oven dry and Screening Treatment;
Chemical initiator monomer 0.1-1 part;
Coupling agent 0.5-4 part.
2. bacterium mushroom rod according to claim 1 is used for the modification pretreatment process of wood plastic composite preparation, it is characterized in that: described chemical initiator monomer is made of dicumyl peroxide or maleic anhydride, and described coupling agent is made of titanate coupling agent or silane coupling agent or aluminate coupling agent.
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| CN201110211935A CN102276848B (en) | 2011-07-27 | 2011-07-27 | Method for modifying and pretreating bacterium mushroom stick used for preparing wood-plastic composite material |
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| CN201110211935A CN102276848B (en) | 2011-07-27 | 2011-07-27 | Method for modifying and pretreating bacterium mushroom stick used for preparing wood-plastic composite material |
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| CN102276848A true CN102276848A (en) | 2011-12-14 |
| CN102276848B CN102276848B (en) | 2012-09-26 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103214751A (en) * | 2012-09-21 | 2013-07-24 | 上海工程技术大学 | PVC/agricultural waste composite material, and preparation method and application thereof |
| CN105985658A (en) * | 2015-02-15 | 2016-10-05 | 承德华鑫实业有限公司 | Composite material prepared from mushroom stick wastes and used for degradable flower pots, and molding method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100999093A (en) * | 2007-01-01 | 2007-07-18 | 梁占傲 | Board |
| CN101864130A (en) * | 2010-07-26 | 2010-10-20 | 南京皇家聚锋建筑材料有限公司 | PVC plastic-wood material |
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- 2011-07-27 CN CN201110211935A patent/CN102276848B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100999093A (en) * | 2007-01-01 | 2007-07-18 | 梁占傲 | Board |
| CN101864130A (en) * | 2010-07-26 | 2010-10-20 | 南京皇家聚锋建筑材料有限公司 | PVC plastic-wood material |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103214751A (en) * | 2012-09-21 | 2013-07-24 | 上海工程技术大学 | PVC/agricultural waste composite material, and preparation method and application thereof |
| CN103214751B (en) * | 2012-09-21 | 2015-06-17 | 上海工程技术大学 | PVC/agricultural waste composite material, and preparation method and application thereof |
| CN105985658A (en) * | 2015-02-15 | 2016-10-05 | 承德华鑫实业有限公司 | Composite material prepared from mushroom stick wastes and used for degradable flower pots, and molding method thereof |
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| CN102276848B (en) | 2012-09-26 |
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Granted publication date: 20120926 Termination date: 20180727 |