CN107603177A - A kind of degradable stalk Polyhydroxyalkanoatecomposite composite material based on montmorillonite enhancing and preparation method thereof - Google Patents
A kind of degradable stalk Polyhydroxyalkanoatecomposite composite material based on montmorillonite enhancing and preparation method thereof Download PDFInfo
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- CN107603177A CN107603177A CN201710870216.7A CN201710870216A CN107603177A CN 107603177 A CN107603177 A CN 107603177A CN 201710870216 A CN201710870216 A CN 201710870216A CN 107603177 A CN107603177 A CN 107603177A
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- montmorillonite
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Abstract
The present invention relates to wood plastic composite field, and in particular to a kind of stalk PHA plastic composite of environment-friendly degradable（Abbreviation straw plastic composite materials in specification）And preparation method thereof.With poly butyric ester（PHB）Plastics and powder of straw are primary raw material, with organo montmorillonite（OMMT）For reinforcing material, in the presence of silane coupler, extruding pelletization, hot pressing cold pressing forming process are passed sequentially through together with other processing aids, realizes the technical process of the preparation of composite.
Description
Technical field
The present invention relates to wood plastic composite field, and in particular to a kind of straw plastic composite of environment-friendly degradable
（Hereinafter referred to as straw plastic composite materials）Preparation method.
Background technology
Natural plant fibre enhancing biodegradable plastic is a kind of new green composite, is had well
Ecological environment compatibility, environmental pollution and human health damage are small, have good development prospect.Natural plant fibre at present
For strengthening biodegradable plastic based on flaxen fiber and wood powder/fiber, bamboo fibre also has been reported that, and can with stalk and biology
The research that degradative plastics prepares composite for raw material is also few, and biodegradable plastic also focuses primarily upon PLA
（PLA）, poly butylene succinate（PBS）.
But traditional wood plastic composite be unable to do without the dependence to wood powder raw material, in face of current China's timber resources supply and demand lance
Under the increasingly serious overall background of shield, how rationally to substitute timber using other natural plant fibres and realize to Biodegradable material
Enhancing become we concern emphasis.
Agricultural crop straw is as in agricultural production, in the byproduct, and nature such as remaining stem, leaf after crop harvesting
A kind of substantial amounts and the renewable biomass resources with extensive use.Compared with the forest reserves are in short supply, China is to pass
The large agricultural country of system, compared with the forest reserves, crops are annual plant mostly, and stalk is relatively rich as its residue resource
It is rich.
Polyhydroxyalkanoate class（PHA）It is a kind of degradable high polymer material by Microbe synthesis, its major product
For poly butyric ester（PHB）, there is good biodegradability and biocompatibility, be widely used in plastic products,
Packaging, the hydrosol, medical embedded material, controlled drug slow-released carrier etc., its hot property, mechanical property and polyethylene, polypropylene
It is similar, it is considered to be a kind of degradation plastic of alternative conventional petroleum chemical plastic, but by production cost height, heat endurance
The restriction for the defects of difference, fragility are big, process window is narrower, limit it and further develop.Therefore, domestic and international expert and scholar utilize
Distinct methods are modified research to PHB, wherein blending is as common physical modification method.By the way that PHB is added with cheap
Thing blending prepares composite, while its original biodegradability is ensured, improves performance, reduces production cost, make up
PHB self-defects.
In addition, although the straw plastic composite materials for replacing wood powder manufacture by stalk can reach requirement, but be difficult to reach compared with
High intensity, the composite manufactured by common stalk and plastics is all slightly inadequate in terms of water resistance, intensity, and cost performance is poor.
Clay is a kind of aluminosilicate mineral with layer structure.The research and development of this aspect was very fast in the last few years
Speed, gradually form an emerging comprehensive branch of learning.Montmorillonite belongs to a kind of natural clay of bentonite, and in China, storage is big,
Price is low.Industrially application is very extensive for it, there is the title of " universal material ".Wherein, with it to polymer/laminated silicic acid
The influence of salt nano composite material is particularly evident, and a small amount of montmorillonite addition can be to the mechanics of composite, calorifics and fire-retardant
Performance is significantly improved, thus turns into domestic and foreign scholars research, the focus of utilization in the last few years.Therefore, use is honest and clean
The montmorillonite of valency becomes our focus as the reinforcing material of the present invention.
Based on the demand and defect, it is environment-friendly that the present invention proposes that a kind of montmorillonite enhancing stalk is prepared with biological plastics
Type degradable composite material, the composite prepared have intensity higher, and water resistance is more preferable, the wider array of advantage of application.
The content of the invention
It is an object of the invention to provide a kind of straw plastic composite materials；It is another object of the present invention to utilize crops
Residue stalk is main stuffing, and a new way is found for stalk residue higher value application；The present invention also aims to
A kind of preparation method of enhanced environmentally friendly straw plastic composite materials is disclosed.
Technical solution of the present invention is：
The straw plastic composite materials of the present invention, its raw material weight proportioning of soup processed are：50 ~ 70 parts of poly butyric ester PHB, wheat straw powder 30 ~ 50
Part, 1 ~ 3 part of organo montmorillonite, 1 ~ 3 part of KH-550 silane couplers, 0.5 ~ 2.5 part of Tissuemat E, 0.5 ~ 2.5 part of calcium stearate,
2 ~ 5 parts of organo-tin het stabilizer.
The first step, crushing, the screening of stalk：
Stalk is crushed using high speed disintegrator, and the raw material after crushing is passed through into 20 mesh, 40 mesh, 60 purposes respectively
Sieve, the powder of straw that gained particle is located to 40 to 60 mesh deliver to drying process.
Second step, the pretreatment and drying of stalk powder raw material
1 ~ 3 part of silane resin acceptor kh-550 is dissolved in volume ratio 9 using atomized spray processes：In 1 ethanol water, afterwards will
Silane coupler solution is sprayed onto powder of straw surface in sizing applicator, and by the powder of straw after processing under conditions of 103 ± 2 DEG C
24h is dried to moisture content 1 ~ 2%.
3rd step, the mixed at high speed of raw material
Pretreatment and dried wheat straw powder are taken 30 ~ 50 parts, 50 ~ 70 parts of poly butyric ester PHB, organo montmorillonite 1 ~ 3
Part, 0.5 ~ 2.5 part of Tissuemat E, 0.5 ~ 2.5 part of calcium stearate, in 2 ~ 5 parts of input high-speed mixers of organo-tin het stabilizer with
3000r/min mixes certain time.
4th step, extruding pelletization
Mixed at high speed is completed to extrude in raw material input extruder, and crushes and is granulated after cooling down；Extruder each area's reference temperature point
It is not（By taking five area's extruders as an example）：One area：165 DEG C, 2nd area：170 DEG C, 3rd area：175 DEG C, 4th area：175 DEG C, head：165
DEG C, rotating speed 100RPM.
5th step, compression molding
The pellet made is poured into the mould specified, is placed in being preheated in hot press, by certain hot pressing-cold-press process
Shaping can be prepared by dropping straw plastic composite materials based on montmorillonite enhancing.
Embodiment.
Embodiment 1.
Process raw material.
| Material specification | Fundamental property | Source |
| Wheat straw | Moisture content 8 ~ 10% before drying | Wheat straw place of production Henan, provided by ten thousand magnificent ecological board industry Co., Ltds |
| Silane coupler（KH550） | Purity 97% | Coupling agent is provided by Jiangsu Chenguang Coincident Dose Co., Ltd. |
| Poly 3-hydroxy butyrate（PHB） | Model 18J45, density 1.2,4g/cm3,160 DEG C of fusing point, graininess | BASF Aktiengesellschaft produces, and is purchased from Dongguan City camphorwood Tou Huaxin plastic materials business department |
| Organo montmorillonite（OMMT） | 200 mesh, 76 μm of average grain diameter, interlamellar spacing 2.217nm | Huzhou City of Zhejiang Province Feng Hong clays Chemical Co., Ltd. |
Process equipment.
| Instrument and equipment title | Model | Source |
| High-speed mixer | SHR-10A | Yili Machinery Co., Ltd., Zhangjiagang City |
| Parallel dual-screw extruding machine | KESUNKS20 | Kunshan Kesun Rubber ＆ Plastic Machinery Co., Ltd. |
| Hot press | BY 602×2/2 150T | Suzhou Xinxieli Machine Manufacturing Co., Ltd. |
| Cold press | CGYJ-100 | Shijiazhuang Can Gao high frequency machineries Co., Ltd |
As shown in figure 1, the industrial production method bag for dropping straw plastic composite materials that the present embodiment is strengthened based on montmorillonite
Include.
The first step, Wheat Straw raw material is crushed, and filter out mesh number and continue to employ for the wheat straw powder of 60 mesh or so.
Described breaking method is：Refinement crushing is carried out to Wheat Straw wood shavings particle using high speed disintegrator, and according to thing
Expect fineness D90 standards, being located at 60 mesh or so using industrial screen reservation mesh number continues to employ.
Second step, the pretreatment of wheat straw powder, 2 parts of silane resin acceptor kh-550s are dissolved in by volume using atomizing spraying mode
Than 9：In 1 ethanol water, silane coupler solution is sprayed onto to powder of straw surface in sizing applicator afterwards, and by after processing
Powder of straw 24h is dried under conditions of 103 ± 2 DEG C to moisture content 1 ~ 2%.
The atomizing spraying method is:By the way of drum-type glue mixer atomizing spraying coupling agent, it is aided with ring type glue mixing
Rubs mutually is acted on so that coupling agent is scattered more uniform in Wheat straw between machine causes Wheat Straw.
3rd step, the mixed at high speed of raw material take 40 parts of dried wheat straw powder, and 60 parts of poly butyric ester plastics are organic
1 part of montmorillonite, 2 parts of Tissuemat E, 1 part of calcium stearate, 5 parts of organo-tin het stabilizer TF-500B, put into high-speed mixer
Mixed 5 minutes with 3000r/min.
4th step, extruding pelletization, mixed at high speed is completed to extrude in raw material input extruder, and crushes and be granulated after cooling down,
Extruder temperature is set as an area：165 DEG C, 2nd area：170 DEG C, 3rd area：175 DEG C, 4th area：175 DEG C, head：165 DEG C, screw rod turns
Fast 100RPM.
5th step, compression molding, pouring into 270mm × 270mm × 3mm appointed product moulds for particle, juxtaposition have been granulated it
In preheating 3min on hot press, through hot pressing-cold moudling, 170 DEG C, hot pressing pressure 4MPa of hot pressing temperature, hot pressing time 6min is cold
Press room temperature is cold-pressed, cold pressing pressure 4MPa, is cold-pressed time 12min, you can is made a kind of and is dropped straw modeling based on montmorillonite enhancing
Composite.
Brief description of the drawings：Fig. 1 is the theme schematic flow sheet of the embodiment of the present invention.
Claims (5)
1. a kind of degradable stalk Polyhydroxyalkanoatecomposite composite material based on montmorillonite enhancing and preparation method thereof, it includes institute
The processing and manufacturing step of the montmorillonite type and the methods of enhancing used, the species of PHA, and composite
Suddenly.
2. it is according to claim 1 it is a kind of based on montmorillonite enhancing degradable stalk Polyhydroxyalkanoatecomposite composite material and
Montmorillonite type in its preparation method, it is characterised in that：Montmorillonite type is the organo montmorillonite Jing Guo organically-modified processing,
Interlamellar spacing is more unmodified, and montmorillonite is bigger, is 200 mesh with reference to mesh number, with reference to 76 μm of average grain diameter, with reference to interlamellar spacing 2.217nm.
3. according to claim 1 it is a kind of based on montmorillonite enhancing degradable stalk Polyhydroxyalkanoatecomposite composite material and its
The methods of montmorillonite enhancing in preparation method, it is characterised in that：Using high-temperature fusion blending method, and in lubricating auxiliary agent
Under the effect such as Tissuemat E so that montmorillonite is uniformly interspersed among stalk and plastic substrate, plays humidification.
4. according to claim 1 it is a kind of based on montmorillonite enhancing degradable stalk Polyhydroxyalkanoatecomposite composite material and its
The species of PHA in preparation method, it is characterised in that：It includes poly 3-hydroxy butyrate（PHB）, it is poly-（3- hydroxyls
Butyrate -3- hydroxyl valerates）（PHBV）, it is poly-（3-hydroxybutyrate ester -4 hydroxybutyric acid ester）（P3/4HB）, it is poly-（3- hydroxyl fourths
The hydroxycaproic ester of acid esters -3）（PHBH）.
5. according to claim 1 it is a kind of based on montmorillonite enhancing degradable stalk Polyhydroxyalkanoatecomposite composite material and its
The processing of composite in preparation method and manufacturing step, it is characterised in that：Using PHA as adhesive, by with
It is underlying in certain temperature and pressure by the pretreated powder of straw of silane coupler, reinforcing material montmorillonite and other processing aids
Melt blending and granulation in extruder, and the process being molded in corresponding product mould by hot pressing-cold-press process.
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| CN201710870216.7A CN107603177A (en) | 2017-09-23 | 2017-09-23 | A kind of degradable stalk Polyhydroxyalkanoatecomposite composite material based on montmorillonite enhancing and preparation method thereof |
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| CN201710870216.7A CN107603177A (en) | 2017-09-23 | 2017-09-23 | A kind of degradable stalk Polyhydroxyalkanoatecomposite composite material based on montmorillonite enhancing and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109096586A (en) * | 2018-09-06 | 2018-12-28 | 安徽英美达新材料科技有限公司 | A kind of preparation method of environmental type EPE pearl wool |
| CN111500029A (en) * | 2020-05-08 | 2020-08-07 | 深圳国至新材料科技有限公司 | Bio-based degradable knife and fork material and preparation method thereof |
| CN116574390A (en) * | 2023-06-14 | 2023-08-11 | 东北林业大学 | Inorganic hybridization reinforced straw-based biomass composite material and preparation method thereof |
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| CN102181165A (en) * | 2011-04-13 | 2011-09-14 | 北京中诺德瑞工业科技有限公司 | Production method of straw wood-like material and product thereof |
| CN103242631A (en) * | 2012-02-14 | 2013-08-14 | 上海杰事杰新材料(集团)股份有限公司 | Biodegradable composite material and preparation method thereof |
| CN103374213A (en) * | 2012-04-26 | 2013-10-30 | 苏州达同新材料有限公司 | Preparation method of polylactic acid/montmorillonite nano composite material |
| CN107097322A (en) * | 2017-05-17 | 2017-08-29 | 北京林业大学 | A kind of string adhering technique based on PHA film |
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2017
- 2017-09-23 CN CN201710870216.7A patent/CN107603177A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102181165A (en) * | 2011-04-13 | 2011-09-14 | 北京中诺德瑞工业科技有限公司 | Production method of straw wood-like material and product thereof |
| CN103242631A (en) * | 2012-02-14 | 2013-08-14 | 上海杰事杰新材料(集团)股份有限公司 | Biodegradable composite material and preparation method thereof |
| CN103374213A (en) * | 2012-04-26 | 2013-10-30 | 苏州达同新材料有限公司 | Preparation method of polylactic acid/montmorillonite nano composite material |
| CN107097322A (en) * | 2017-05-17 | 2017-08-29 | 北京林业大学 | A kind of string adhering technique based on PHA film |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109096586A (en) * | 2018-09-06 | 2018-12-28 | 安徽英美达新材料科技有限公司 | A kind of preparation method of environmental type EPE pearl wool |
| CN111500029A (en) * | 2020-05-08 | 2020-08-07 | 深圳国至新材料科技有限公司 | Bio-based degradable knife and fork material and preparation method thereof |
| CN116574390A (en) * | 2023-06-14 | 2023-08-11 | 东北林业大学 | Inorganic hybridization reinforced straw-based biomass composite material and preparation method thereof |
| CN116574390B (en) * | 2023-06-14 | 2024-05-03 | 东北林业大学 | Inorganic hybridization reinforced straw-based biomass composite material and preparation method thereof |
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Application publication date: 20180119 |