CN108484986A - A kind of the low-cost bio plastics and preparation method of heat resistance - Google Patents
A kind of the low-cost bio plastics and preparation method of heat resistance Download PDFInfo
- Publication number
- CN108484986A CN108484986A CN201810221611.7A CN201810221611A CN108484986A CN 108484986 A CN108484986 A CN 108484986A CN 201810221611 A CN201810221611 A CN 201810221611A CN 108484986 A CN108484986 A CN 108484986A
- Authority
- CN
- China
- Prior art keywords
- starch
- liquid
- wax
- barium sulfate
- low
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/02—Starch; Degradation products thereof, e.g. dextrin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B30/00—Preparation of starch, degraded or non-chemically modified starch, amylose, or amylopectin
- C08B30/02—Preparatory treatment, e.g. crushing of raw materials or steeping process
-
- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Mechanical Engineering (AREA)
- Biological Depolymerization Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to biological plastics fields, and in particular to starch-based bio plastics, further to the low-cost bio plastics and preparation method thereof with well processed characteristic, resistance to thermal degradation.The present invention is gelatinized by the way that starch to be crosslinked, and is emulsified, high-pressure spray-drying, rapid condensation, and the particle that starch is coated by wax is formed by curing by wax rapid condensation；It further utilizes barium ions to form the characteristic of barium sulfate precipitate with sulfate ion, saline solution is deposited on and ultimately forms barium sulfate film by the microparticle surfaces of wax cladding starch, obtains the spherex securely coated by barium sulfate；What polymer is kneaded to obtain a kind of low-cost bio plastics of heat resistance with thermoplasticity.Since starch is securely protected by barium sulfate always; the risk of starch thermal degradation is not only avoided, and the starch of barium sulfate package is spherical in shape, has good processing fluidity; especially because starch is protected by barium sulfate shell, the defect of poor water resistance when effectively preventing starch for plastics.
Description
Technical field
The present invention relates to biological plastics fields, and in particular to starch-based bio plastics, further to well processed
The low-cost bio plastics and preparation method thereof of characteristic, resistance to thermal degradation.
Background technology
Degradative plastics played an important role to solving the problem of environmental pollution that disposable plastic packing articles are brought.With
Continuing deeply and putting more effort for environmental protection, single photodegradable plastics, automatic disintegration degradation are difficult to meet people to modeling
Expect the needs of degradation.Sustainable, ecological, environmental protective biological plastics becomes main developing direction.
According to biological plastics industry development, has such as polylactic acid at present（PLA）, poly butylene succinate（PBS）, it is poly-
Carbon dioxide（PPC）, polycaprolactone（PCL）, polyhydroxyalkanoate（PHA）It is moulded completely by the biology that biomass synthesizes etc. a variety of
Material.However just because of these biomass plastics have can degradable property, result in these materials and exist in process
Degradation, and thermoplastic processing stability is very poor, compared with the thermoplastic processing of common plastics, there are melt strengths low, embrittlement etc.
Defect, especially blown film are drawn high when processing puies forward film difficulty, and the biological plastics film frequently resulted in is thicker.
In addition, the system of the biomass plastics such as existing polylactic acid, poly butylene succinate, poly- carbon dioxide, polycaprolactone
Standby there is also many defects, such as raw material to use microbial fermentation or chemically synthesized raw material, it is difficult to continual and steady supply；It prepares
Process stability is poor, it is difficult to which scale is produced in enormous quantities.Therefore cause existing biological plastics of high cost.At present, on the one hand, with
Environmental requirement, market in urgent need biological plastics prepare all kinds of packaging products, and on the other hand, it is difficult to there is low cost, processing can be stablized
Biological plastics supply.
Starch as a kind of low cost can stable mass supply biological material, be that be used to prepare biological plastics preferable
Selection.Existing starch-based bio plastics at present.As Italian Novamont companies produce starch-based degradable plastics, commodity
Name " Mater Bi ", 30,000 tons of annual output, in packaging material, compost bag, amenities, disposable tableware, agricultural mulching etc.
Preferable popularization and application are obtained.Therefore starch is selected to be used to prepare biological plastics, it is not only at low cost, and also raw material can obtain
Continual and steady supply.
It is carbohydrate in view of starch, the crystallinity of starch granules does not have generally between 15% to 45% with modeling
The same thermoplastic processing of material.All the time, in order to which starch is used for biological plastics, the thermoplastification of starch is treated as mainly
Technique direction.Such as：Graft modification is carried out to starch；By carrying out esterification raising to hydroxy functional group reaction on starch structure
The hydrophobic property of starch makes hot-working characteristic of the starch with polymer；It is acted on by being added between plasticizer reduction starch molecule
Power and make starch have thermoplasticity；Fine, which is modified, eliminates crystallization, to weaken the Van der Waals force of starch molecule interchain so that point
Subchain easily moves, and the melting temperature of starch is reduced, with thermoplasticity.But since starch self performance is difficult to thoroughly change,
Therefore existing thermoplastic processing techniques cannot make starch have the thermoplastic processing the same with common plastics at all.To starch with
Starch additive amount is difficult to be promoted when polymer plastic hybrid process, and thermoplastic processing is poor, and water resistance drops starch in the plastic
It is low.
It is limited to the defect of starch thermoplastic processing, causes starch additive amount in starch-based bio plastics limited, and more
When secondary hot-working, there are the risks of thermal degradation for starch, while there is also the defects that water resistance reduces for biological plastics for starch.This
Well known to field technology personnel, the thermostabilization ability of starch is limited, and existing thermoplastic technology processing is difficult to that starch plastic is made to have
Standby preferable resistance high temperature degradation is difficult to have preferable thermoplastic processing mobility, be difficult to the same with common plastics
Water resistance.
Invention content
When for existing starch-based bio plastic manufacturing, starch is difficult to thorough thermoplastification, causes in starch-based bio plastics
Middle starch additive amount is few, and the poor fluidity in hot-working, and for starch there are the risk of thermal degradation, plastic products water resistance is bad.
For this purpose, the present invention proposes a kind of low-cost bio plastics of heat resistance, its main feature is that thermoplastification processing is not carried out to starch, but
Using starch microparticles as biological material tight in barium sulfate shell, then adds in the polymer, biology is prepared
Plastics.Its significant advantage, which is starch, to be blended with polymer in processing, and starch is securely protected by barium sulfate always, is not only avoided
The risk of thermal degradation, and the starch of barium sulfate package is spherical in shape, has good mobility, thermoplastic processing mobility
It is good, and since starch is protected by barium sulfate shell, effectively prevent defect of the starch for plastics poor water resistance.The present invention into
One step provides the preparation method of the low-cost bio plastics of the heat resistance.
To achieve the goals above, the present invention uses following specific technical solution：
A kind of preparation method of the low-cost bio plastics of heat resistance, characterized in that specific preparation method is as follows：
（1）The crosslinking agent of the starch of parts by weight 20-30, the water of parts by weight 60-100, parts by weight 1-2 are warming up in a kettle
80-100 DEG C, 20-30min is stirred with the rotating speed of 50-150r/min, makes starch gelatinization, obtains gelatinized corn starch；
（2）By step（1）Obtained gelatinized corn starch is transferred to high speed dispersor with wax, emulsifier, with 800- under the conditions of 80-100 DEG C
The high speed dispersion of 1200r/min emulsifies 5-15min, and the paraffin of gelatinized corn starch and fusing is made to become emulsion；
（3）By step（2）Obtained emulsion is dried through high pressure spray drying machine, and rapid condensation, by rapid condensation, wax
Solidification makes interface shrinkage to form the spherex that spherical shape is coated by wax；
（4）Barium salt is dissolved in water and obtains saturated solution as A liquid；Sal glauberi is dissolved in water and obtains saturated solution as B liquid；
In rotary blender, A liquid, B liquid are passed through by high-pressure atomization, and the spherex coated by wax is passed through by high pressure draught,
Under rotary blender high speed rotation and air blast impact dispersion, A liquid forms liquid level with B liquid on the spherex surface that wax coats
Film, and further growth forms barium sulfate film, it is cleaned, dry, obtain the spherex securely coated by barium sulfate；
（5）By step（4）The obtained spherex securely coated by barium sulfate mixes with thermoplastic polymer, processing aid
After even, it is sent into screw extruder extruding pelletization, obtains the low-cost bio plastics of heat resistance.
Preferably, step（1）Described starch is at least one of cornstarch, tapioca；The kind of starch cost
It is low, it can continue to supply, and quality is stablized relatively.
Preferably, step（1）The crosslinking agent is at least one of epoxychloropropane, borax, sodium tripolyphosphate；It is logical
It crosses and starch is crosslinked, starch is made to be not easy to expand, more stable, water resistance increases, to stablize cladding in the follow-up wax that is more advantageous to,
Further be conducive to barium salt, sulfate stablize microballoon starch surface formed barium sulfate coating film.
Step（2）The emulsifier, it is therefore an objective to make gelatinized starch form drop small one by one with wax, emulsifier prevents
The mutual condensation of fine droplet forms small microballoon to be more advantageous to when follow-up dry.It is micro- in order to make emulsification be formed
Droplet is in Water-In-Oil, it is preferred that the emulsifier selects polyglycerol stearate, Unigly GO 102S, two sweet ester of single oleic acid
In one kind；It can preferably make the paraffin of thawing be coated on the starch microparticles surface of gelatinization.
Preferably, step（2）The wax is selected after condensation in room temperature in solid wax；It is with gelatinized starch in fast quickly cooling
When solidifying, the solidification of wax is so that the spherex that interface shrinkage is coated to formation by wax；More preferably, the wax selects 56#
One kind in semi-refined paraffin wax, 58# semi-refined paraffin waxs.
Preferably, step（2）The gelatinized corn starch, wax, emulsifier are with mass ratio 100:3-5:0.5-1.5 is used cooperatively.
Step（3）The high pressure spray drying machine is that emulsion is spurted into drying in thermal current by high pressure；In order to anti-
Only starch dries coking at an excessive temperature, and in order to make the dry particle drained be quickly cooled down, forms the shallow lake coated by wax
Powder microballoon；It is further preferred that the high pressure spray drying machine uses 0.5-2MPa pressure, the nozzle mist through a diameter of 3-5mm
Change；The thermal current of high pressure spray drying machine uses 80-100 DEG C of unsaturation thermal current.
Step（3）The rapid condensation is to fall into the particle of spray drying in liquid nitrogen bath, by rapid condensation, makes wax
Fast condensation cured makes interface shrinkage to form the spherex of spherical shape coated by wax.
Preferably, step（4）The barium salt selects barium chloride；In mixing arrangement, A liquid, B liquid intake according to
Barium chloride：Sal glauberi molar ratio 1:1；A liquid, B liquid gross mass be wax cladding paste spherex quality 20-
30%。
Step（4）Rotation spiral is set in the rotary blender, and is equipped with oil bath heating chuck, is maintaining device heat
Warm 35-45 DEG C, and with 1000-1500r/min high speed rotations, be conducive to barium salt liquid and sal glauberi saline solution when rotating at high speed
It is uniform in the spherex Dispersion on surface of wax cladding, and growth forms barium sulfate film under the conditions of constant thermal current；High speed is revolved
Material dispersion is fluidization by the spiral turned, to preferably prevent forming bulky grain reunion in barium sulfate growth course.
The spherex that barium sulfate of the present invention securely coats is by barium salt liquid and sal glauberi saline solution in wax packet
The spherex surface covered forms liquid level film, and further growth forms barium sulfate film, due to barium sulfate film be by soluble salt at
It is grown after film, to form the spherex that barium sulfate securely coats；It is a kind of microballoon of micron level, outer layer is sulphur
Sour barium, kernel are starch, very much like with common spherical barium sulfate performance in physical property performance, in plastic collar
The processing application method that common barium sulfate powder filled plastics are fully equivalent to using processing method in domain.
Preferably, step（5）The thermoplastic polymer can select biomass thermal thermoplastic polymer according to specific needs
Such as poly- butyric ester（PHB）, poly- hydroxyl valerate（PHBV）, poly-succinic-butanediol ester（PBS）, polycaprolactone
（PCL）, polylactic acid（PLA）It is one such or a variety of.Or select abiotic matter thermoplastic polymer such as polyethylene（PE）, it is poly-
Propylene（PP）, polyvinyl chloride（PVC）, polystyrene（PS）, ethylene-vinyl acetate copolymer（EVA）, ethylene-acrylic acid copolymer
Object（EAA）, polyethylene terephthalate（PET）, polyamide（PA）In it is one or more.
Preferably, step（5）The processing aid is the conven-tional adjuvants of plastic processing, such as lubricant polyethylene wax or/and
Double ethylene stearmides.
It is further preferred that step（5）The spherex securely coated by barium sulfate, thermoplastic polymer, processing
Auxiliary agent is with mass ratio 3:2:0.1 mixing.
It is further preferred that step（5）It is described by screw extruder be parallel dual-screw extruding machine, screw slenderness ratio is big
In 30:1, screw speed 200-350rpm, rotating speed is excessively high to be caused to shear too strong, and there are the spherex quilts that barium sulfate securely coats
Excessive shear ruptures, and rotating speed is too low, then it is bad to there is shearing dispersion.Screw extruder is related to five temperature controls from charging to discharging
Area processed, temperature setting principle are to be stepped up, and when reaching the thermoplastic polymer melting temperature on basis, then are gradually reduced.One
A typical temperature setting refers to：One 80 DEG C of area；Two 165 DEG C of areas；Three 175 DEG C of areas；Four 185 DEG C of areas；Five 165 DEG C of areas.Due to
The thermoplastic polymer selection on basis is different, and bulk temperature setting will be different.
The present invention also provides the low-cost bio plastics for the heat resistance being prepared by the above method.
The present invention is gelatinized by the way that starch to be crosslinked, and is emulsified, high-pressure spray-drying, rapid condensation, is consolidated by wax rapid condensation
Change the particle for being formed and coating starch by wax；Barium ions is further utilized to form the characteristic of barium sulfate precipitate with sulfate ion, it will
Saline solution is deposited on ultimately forms barium sulfate film by the microparticle surfaces of wax cladding starch, and it is micro- to obtain the starch securely coated by barium sulfate
Ball；The spherex that barium sulfate securely coats is a kind of microballoon of micron level, and outer layer is barium sulfate, and kernel is starch, and
It is fixedly secured, it is very much like with common spherical barium sulfate performance in physical property performance, in the use of plastic applications
Processing method is fully equivalent to the processing application method of common barium sulfate powder filled plastics.Importantly, due to which starch is always
It is securely protected by barium sulfate, not only avoids the risk of starch thermal degradation, and the starch of barium sulfate package is spherical in shape, has good
Good processing fluidity, especially because starch is protected by barium sulfate shell, water resistance when effectively preventing starch for plastics
The defect of difference.Further, the treatment process that starch is coated by barium sulfate is simple, easily-controllable, is suitble to large-scale production, raw materials used
It is easy to get, it is at low cost.
The present invention a kind of the low-cost bio plastics and preparation method of heat resistance, compared with prior art prominent feature and
Beneficial effect is：
1, the present invention does not carry out thermoplasticity processing using traditional to starch, but is coated on what starch was stablized in barium sulfate,
Barium sulfate is that common filler, starch are coated in barium sulfate in plastics, is equally used with common barium sulfate, overcomes shallow lake
Powder be easy thermal degradation, poor water resistance defect, can be applied to the field of plastics processing of wider range.
2, the starch of barium sulfate package is spherical in shape, has good processing fluidity, realizes starch without at thermoplastification
Reason can good hot worked target.
3, preparation process of the present invention is simple, easily-controllable, is suitble to large-scale production, raw materials used to be easy to get, at low cost.
Description of the drawings
Fig. 1 is after the spherex that the barium sulfate that the embodiment of the present invention 1 obtains securely coats is kneaded with thermoplastic polymer
The film scanning electron microscope of obtained biological plastics blowing（SEM）Local map.The spherex of the barium sulfate cladding of spherical shape
Evenly dispersed spherical shape is remained in film, demonstrate again that barium sulfate securely coats starch, effective protection starch.
Specific implementation mode
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
（1）The epoxychloropropane of the cornstarch of 20kg, the water of 60kg, 1kg are warming up to 80-100 DEG C in a kettle, with
The rotating speed of 50r/min stirs 20min, makes starch gelatinization, obtains gelatinized corn starch；
（2）By step（1）Obtained gelatinized corn starch 100kg and 3kg 56# semi-refined paraffin waxs, 1kg emulsifier polyglycerol stearates
It is transferred to high speed dispersor, 15min is emulsified with the high speed dispersion of 800r/min under the conditions of 80-100 DEG C, makes gelatinized corn starch and fusing
Paraffin becomes the emulsion of Water-In-Oil phase；
（3）By step（2）Obtained emulsion is through high pressure spray drying machine, the nozzle through a diameter of 3mm under 0.5MPa pressure
Atomization is dried into 100 DEG C of unsaturation thermal currents, and the dry particle of draining is fallen into liquid nitrogen bath, by rapid condensation,
The fast condensation cured of wax is set to make interface shrinkage to form the spherex of spherical shape coated by wax；
（4）Barium chloride is dissolved in water and obtains saturated solution as A liquid；Using sal glauberi be dissolved in water obtain saturated solution as
B liquid；In mixing arrangement, A liquid, B liquid are passed through by high-pressure atomization, and the spherex coated by wax is passed through by high pressure draught；
In rotary blender, A liquid, B liquid intake according to barium chloride：Sal glauberi molar ratio 1:1；A liquid, B liquid
Gross mass is the 20% of the spherex quality of wax cladding paste；Rotation spiral is set in rotary blender, and is equipped with oil bath heating
Chuck maintains 35 DEG C of device heat temperature, and with 1000r/min high speed rotations, when rotating at high speed barium salt liquid and sal glauberi salt
Liquid is uniform in the spherex Dispersion on surface that wax coats, and growth forms barium sulfate film under the conditions of constant thermal current；Through water
Cleaning, drying, obtain the spherex securely coated by barium sulfate；
（5）By step（4）The polyethylene 7042 of obtained spherex 40kg, 25kg for securely being coated by barium sulfate, 0.5kg
Polyethylene wax mixes, and is squeezed out through parallel dual-screw extruding machine, screw slenderness ratio 35:1, screw speed 200rpm, each area's temperature
Control exists：One 80 DEG C of area；Two 165 DEG C of areas；Three 175 DEG C of areas；Four 185 DEG C of areas；Five 165 DEG C of areas, the low cost for obtaining heat resistance are raw
Object plastics.
The film drawing for the biological plastics blowing that embodiment 1 obtains is as thin as 0.008mm, it is local by scanning electron microscopic observation,
Such as attached drawing 1, the spherex that the barium sulfate of spherical shape coats remains evenly dispersed spherical shape in film, therefore starch is firm
Solid be coated in barium sulfate.
Embodiment 2
（1）The borax of the tapioca of 25kg, the water of 65kg, 1.5kg are warming up to 80-100 DEG C in a kettle, with 150r/
The rotating speed of min stirs 25min, makes starch gelatinization, obtains gelatinized corn starch；
（2）By step（1）Obtained gelatinized corn starch 100kg and 3.5kg 58# semi-refined paraffin waxs, 1kg emulsifier polyglycerol oleates
It is transferred to high speed dispersor, 15min is emulsified with the high speed dispersion of 1000r/min under the conditions of 80-100 DEG C, makes gelatinized corn starch and fusing
Paraffin become the emulsion of Water-In-Oil phase；
（3）By step（2）Obtained emulsion is through high pressure spray drying machine, the nozzle mist through a diameter of 5mm under 1MPa pressure
Change, dried into 80-100 DEG C of unsaturation thermal current, and the dry particle of draining is fallen into liquid nitrogen bath, passes through fast quickly cooling
It is solidifying, so that the fast condensation cured of wax is made interface shrinkage to form the spherex of spherical shape coated by wax；
（4）Barium chloride is dissolved in water and obtains saturated solution as A liquid；Using sal glauberi be dissolved in water obtain saturated solution as
B liquid；In rotary blender, A liquid, B liquid are passed through by high-pressure atomization, and the spherex coated by wax is circulated by high pressure gas
Enter；In rotary blender, A liquid, B liquid intake according to barium chloride：Sal glauberi molar ratio 1:1；A liquid, B liquid
Gross mass be wax cladding paste spherex quality 25%；Rotation spiral is set in the rotary blender, and equipped with oil
Heating jacket is bathed, is maintaining 45 DEG C of device heat temperature, and with 1500r/min high speed rotations, when rotating at high speed barium salt liquid and ten water
Sodium sulphate saline solution is uniform in the spherex Dispersion on surface that wax coats, and growth forms barium sulfate under the conditions of constant thermal current
Film；Material dispersion is fluidization by high-speed rotating spiral, to preferably prevent from forming bulky grain in barium sulfate growth course
Reunite.It is cleaned, dry, obtain the spherex securely coated by barium sulfate；
（5）By step（4）The polypropylene of obtained spherex 45kg, 30kg for securely being coated by barium sulfate, double second of 0.5kg
Stearmide mixing is supportted, is squeezed out through parallel dual-screw extruding machine, screw slenderness ratio 40:1, screw speed 300rpm, each area's temperature
Degree control exists：One 100 DEG C of area；Two 170 DEG C of areas；Three 180 DEG C of areas；Four 195 DEG C of areas；Five 175 DEG C of areas, obtain the low of heat resistance
Cost, biological plastics.
The low-cost bio plastics for the heat resistance that embodiment 2 obtains are measured into melt index (MI) under the conditions of 165 DEG C, 2.16kg
For 5.9g/10min；Under the conditions of 160 DEG C, mixing 20min in mixer does not occur incipient scorch and degradation, has good heat-resisting
Thermal stability.Then by blowing inflation film manufacturing machine blown film under 45 types, film tensile strength is up to 29MPa；Elongation at break 310%.
Embodiment 3
（1）The sodium tripolyphosphate of the cornstarch of 30kg, the water of 100kg, 2kg are warming up to 80-100 DEG C in a kettle, with
The rotating speed of 100r/min stirs 30min, makes starch gelatinization, obtains gelatinized corn starch；
（2）By step（1）Obtained gelatinized corn starch 100kg and 5kg 58# semi-refined paraffin waxs, two sweet ester of 1.5kg emulsifier lists oleic acid
It is transferred to high speed dispersor, 5min is emulsified with the high speed dispersion of 1200r/min under the conditions of 80-100 DEG C, makes gelatinized corn starch and fusing
Paraffin becomes the emulsion of Water-In-Oil phase；（3）By step
（2）Obtained emulsion is through high pressure spray drying machine, the nozzle atomization through a diameter of 5mm under 2MPa pressure, into 80-
100 DEG C of unsaturation thermal current drying, and the dry particle of draining is fallen into liquid nitrogen bath, by rapid condensation, make wax rapid cooling
Cure makes interface shrinkage to form the spherex of spherical shape coated by wax；
（4）Barium chloride is dissolved in water and obtains saturated solution as A liquid；Using sal glauberi be dissolved in water obtain saturated solution as
B liquid；In rotary blender, A liquid, B liquid are passed through by high-pressure atomization, and the spherex coated by wax is circulated by high pressure gas
Enter；In rotary blender, A liquid, B liquid intake according to barium chloride：Sal glauberi molar ratio 1:1；A liquid, B liquid
Gross mass be wax cladding paste spherex quality 30%；Rotation spiral is set in the rotary blender, and equipped with oil
Heating jacket is bathed, is maintaining 35 DEG C of device heat temperature, and with 1500r/min high speed rotations, be conducive to barium salt liquid when rotating at high speed
The spherex Dispersion on surface coated in wax with sal glauberi saline solution is uniform, and grows and formed under the conditions of constant thermal current
Barium sulfate film；Material dispersion is fluidization by high-speed rotating spiral, to preferably prevent from being formed in barium sulfate growth course
Bulky grain is reunited.It is cleaned, dry, obtain the spherex securely coated by barium sulfate；
（5）By step（4）The polylactic acid of obtained spherex 60kg, 30kg for securely being coated by barium sulfate, double second of 0.5kg
Stearmide mixing is supportted, is squeezed out through parallel dual-screw extruding machine, screw slenderness ratio 35:1, screw speed 200rpm, each area's temperature
Degree control exists：One 110 DEG C of area；Two 145 DEG C of areas；Three 165 DEG C of areas；Four 175 DEG C of areas；Five 160 DEG C of areas, obtain the low of heat resistance
Cost, biological plastics.
The low-cost bio plastic testing hot-working mobility for the heat resistance that embodiment 3 is obtained, in 145 DEG C, 2.16kg
Under the conditions of measure melt index (MI) be 3.8g/10min；It is prepared into complete biodegradable sheet material, tensile strength 39MPa through calendering；It is disconnected
Schizogenesis elongation 110%；Notch impact strength 3.15KJ/m2.Show good thermal fluidity, resistance to hot-workability.
Comparative example 1
（1）The borax of the tapioca of 25kg, the water of 65kg, 1.5kg are warming up to 80-100 DEG C in a kettle, with 150r/
The rotating speed of min stirs 25min, makes starch gelatinization, obtains gelatinized corn starch；
（2）By step（1）Obtained gelatinized corn starch is through high pressure spray drying machine, the nozzle mist through a diameter of 5mm under 1MPa pressure
Change, is dried into 80-100 DEG C of unsaturation thermal current, obtain gelatinized starch particle；
（3）Barium chloride is dissolved in water and obtains saturated solution as A liquid；Using sal glauberi be dissolved in water obtain saturated solution as
B liquid；In rotary blender, A liquid, B liquid are passed through by high-pressure atomization, and gelatinized starch particle is passed through by high pressure draught；
In rotary blender, A liquid, B liquid intake according to barium chloride：Sal glauberi molar ratio 1:1；A liquid, B liquid it is total
Quality is the 25% of gelatinized starch particle mass；Rotation spiral is set in the rotary blender, and is pressed from both sides equipped with oil bath heating
Set is maintaining 45 DEG C of device heat temperature, and with 1500r/min high speed rotations, and growth forms sulphur under the conditions of constant thermal current
Sour barium film；It is cleaned, dry, obtain the gelatinized starch particle coated by barium sulfate；
（4）By step（3）The polypropylene of obtained gelatinized starch particle 45kg, 30kg for being coated by barium sulfate, double second of 0.5kg
Stearmide mixing is supportted, is squeezed out through parallel dual-screw extruding machine, screw slenderness ratio 40:1, screw speed 300rpm, each area's temperature
Degree control exists：One 100 DEG C of area；Two 170 DEG C of areas；Three 180 DEG C of areas；Four 195 DEG C of areas；Five 175 DEG C of areas, obtain the low of heat resistance
Cost, biological plastics.
Comparative example 1 compared with Example 2, does not use paraffin pre-coated starch, 2 complete phase of remaining technique and embodiment
Together；Due to there is no to use paraffin pre-coated starch so that gelatinized starch particle is dissolved in salt when subsequent sulphuric acid barium coats, it is difficult to shape
At complete barium sulfate coating, non-can completely obtains the spherical starch of barium sulfate cladding.Under the conditions of 160 DEG C, in mixer
Mixing occurs serious incipient scorch and degradation in 7min since starch fails to obtain the complete protection of barium sulfate.
Comparative example 2
（1）The borax of the tapioca of 25kg, the water of 65kg, 1.5kg are warming up to 80-100 DEG C in a kettle, with 150r/
The rotating speed of min stirs 25min, makes starch gelatinization, obtains gelatinized corn starch；
（2）By step（1）Obtained gelatinized corn starch 100kg and 3.5kg 58# semi-refined paraffin waxs, 1kg emulsifier polyglycerol oleates
It is transferred to high speed dispersor, 15min is emulsified with the high speed dispersion of 1000r/min under the conditions of 80-100 DEG C, makes gelatinized corn starch and fusing
Paraffin become the emulsion of Water-In-Oil phase；
（3）By step（2）Obtained emulsion is through high pressure spray drying machine, the nozzle mist through a diameter of 5mm under 1MPa pressure
Change, dried into 80-100 DEG C of unsaturation thermal current, and the dry particle of draining is fallen into liquid nitrogen bath, passes through fast quickly cooling
It is solidifying, so that the fast condensation cured of wax is made interface shrinkage to form the spherex of spherical shape coated by wax；
（4）Barium chloride is dissolved in water and obtains saturated solution as A liquid；Using sal glauberi be dissolved in water obtain saturated solution as
B liquid；In rotary blender, A liquid, B liquid are passed through by high-pressure atomization, and the spherex coated by wax is circulated by high pressure gas
Enter；In rotary blender, A liquid, B liquid intake according to barium chloride：Sal glauberi molar ratio 1:1；A liquid, B liquid
Gross mass be wax cladding paste spherex quality 25%；Rotation spiral is set in the rotary blender, and equipped with oil
Heating jacket is bathed, is maintaining 65 DEG C of device heat temperature, and with 100r/min high speed rotations, barium salt liquid is with sal glauberi saline solution in wax
The spherex Dispersion on surface of cladding, and growth forms barium sulfate film under the conditions of constant thermal current；It is cleaned, dry, it obtains
To the spherex securely coated by barium sulfate；
（5）By step（4）The polypropylene of obtained spherex 45kg, 30kg for securely being coated by barium sulfate, double second of 0.5kg
Stearmide mixing is supportted, is squeezed out through parallel dual-screw extruding machine, screw slenderness ratio 40:1, screw speed 300rpm, each area's temperature
Degree control exists：One 100 DEG C of area；Two 170 DEG C of areas；Three 180 DEG C of areas；Four 195 DEG C of areas；Five 175 DEG C of areas, obtain the low of heat resistance
Cost, biological plastics.
Compared with Example 2, rotary blender heating temperature reaches 65 DEG C to comparative example 2, and revolution speed of screw only has 100r/
Min, remaining technique are identical with embodiment 2；The barium sulfate coating uniformity is caused to be deteriorated as a result, and temperature is excessively high causes
Further growth is accumulated after barium sulfate coating, and under the conditions of 160 DEG C, mixing 20min in mixer does not occur incipient scorch and degradation,
Barium sulfate is preferable to the protective value of starch, but due to barium sulfate accumulated growth, spherical unobvious, hot-working mobility compared with
Difference, it is 2.6g/10min that melt index (MI) is measured under the conditions of 165 DEG C, 2.16kg；Then thin by blowing inflation film manufacturing machine blowing under 45 types
Film, film tensile strength is up to 21MPa；Elongation at break 280%.
Comparative example 3
（1）The borax of the tapioca of 25kg, the water of 65kg, 1.5kg are warming up to 80-100 DEG C in a kettle, with 150r/
The rotating speed of min stirs 25min, makes starch gelatinization, obtains gelatinized corn starch；
（2）By step（1）Obtained gelatinized corn starch 100kg and 3.5kg 58# semi-refined paraffin waxs, 1kg emulsifier polyglycerol oleates
It is transferred to high speed dispersor, 15min is emulsified with the high speed dispersion of 1000r/min under the conditions of 80-100 DEG C, makes gelatinized corn starch and fusing
Paraffin become the emulsion of Water-In-Oil phase；
（3）By step（2）Obtained emulsion is through high pressure spray drying machine, the nozzle mist through a diameter of 5mm under 1MPa pressure
Change, dried into 80-100 DEG C of unsaturation thermal current, and the dry particle of draining is fallen into liquid nitrogen bath, passes through fast quickly cooling
It is solidifying, so that the fast condensation cured of wax is made interface shrinkage to form the spherex of spherical shape coated by wax；
（4）Barium chloride is dissolved in water and obtains saturated solution as A liquid；Using sal glauberi be dissolved in water obtain saturated solution as
B liquid；In rotary blender, A liquid, B liquid are passed through by high-pressure atomization, and the spherex coated by wax is circulated by high pressure gas
Enter；In rotary blender, A liquid, B liquid intake according to barium chloride：Sal glauberi molar ratio 1:1；A liquid, B liquid
Gross mass be wax cladding paste spherex quality 25%；Rotation spiral is set in the rotary blender, and equipped with oil
Heating jacket is bathed, is maintaining 45 DEG C of device heat temperature, and with 1500r/min high speed rotations, when rotating at high speed barium salt liquid and ten water
Sodium sulphate saline solution is uniform in the spherex Dispersion on surface that wax coats, and growth forms barium sulfate under the conditions of constant thermal current
Film；Material dispersion is fluidization by high-speed rotating spiral, to preferably prevent from forming bulky grain in barium sulfate growth course
Reunite.It is cleaned, dry, obtain the spherex securely coated by barium sulfate；
（5）By step（4）The polypropylene of obtained spherex 45kg, 30kg for securely being coated by barium sulfate, double second of 0.5kg
Stearmide mixing is supportted, is squeezed out through parallel dual-screw extruding machine, screw slenderness ratio 40:1, screw speed 380rpm, each area's temperature
Degree control exists：One 100 DEG C of area；Two 170 DEG C of areas；Three 180 DEG C of areas；Four 195 DEG C of areas；Five 175 DEG C of areas, obtain the low of heat resistance
Cost, biological plastics.
Comparative example 3 compared with Example 2, in the spherex that securely coats barium sulfate and polypropylene by screw mixing
When, using screw speed 380rpm, since rotating speed is too fast, barium sulfate encasement excessive shear is easily caused, there are the risks of rupture.
For the low-cost bio plastics for the heat resistance that comparative example 3 is obtained under the conditions of at 160 DEG C, there is portion in mixing 16min in mixer
The phenomenon that dividing incipient scorch.
Claims (10)
1. a kind of preparation method of the low-cost bio plastics of heat resistance, characterized in that specific preparation method is as follows：
（1）The crosslinking agent of the starch of parts by weight 20-30, the water of parts by weight 60-100, parts by weight 1-2 are warming up in a kettle
80-100 DEG C, 20-30min is stirred with the rotating speed of 50-150r/min, makes starch gelatinization, obtains gelatinized corn starch；
（2）By step（1）Obtained gelatinized corn starch is transferred to high speed dispersor with wax, emulsifier, with 800- under the conditions of 80-100 DEG C
The high speed dispersion of 1200r/min emulsifies 5-15min, and the paraffin of gelatinized corn starch and fusing is made to become emulsion；
（3）By step（2）Obtained emulsion is dried through high pressure spray drying machine, and is fallen into liquid nitrogen bath, by rapid condensation,
The fast condensation cured of wax is set to make interface shrinkage to form the spherex of spherical shape coated by wax；
（4）Barium salt is dissolved in water and obtains saturated solution as A liquid；Sal glauberi is dissolved in water and obtains saturated solution as B liquid；
In rotary blender, A liquid, B liquid are passed through by high-pressure atomization, and the spherex coated by wax is passed through by high pressure draught；Institute
Rotation spiral is set in the rotary blender stated, and is equipped with oil bath heating chuck, is maintaining device heat 35-45 DEG C warm, and with
1000-1500r/min high speed rotations, under rotary blender high speed rotation and air blast impact dispersion, A liquid is with B liquid in wax
The spherex surface of cladding forms liquid level film, and further growth forms barium sulfate film, cleaned, dry, obtains by sulfuric acid
The spherex that barium securely coats；
（5）By step（4）The obtained spherex securely coated by barium sulfate mixes with thermoplastic polymer, processing aid
After even, it is sent into screw extruder extruding pelletization, obtains the low-cost bio plastics of heat resistance.
2. the preparation method of the low-cost bio plastics of a kind of heat resistance according to claim 1, it is characterized in that：Step（1）
Described starch is at least one of cornstarch, tapioca；The crosslinking agent is epoxychloropropane, borax, trimerization
At least one of sodium phosphate.
3. the preparation method of the low-cost bio plastics of a kind of heat resistance according to claim 1, it is characterized in that：Step（2）
The wax selects one kind in 56# semi-refined paraffin waxs, 58# semi-refined paraffin waxs；The emulsifier selection polyglycerol stearate,
One kind in Unigly GO 102S, two sweet ester of single oleic acid.
4. the preparation method of the low-cost bio plastics of a kind of heat resistance according to claim 1, it is characterized in that：Step（2）
The gelatinized corn starch, wax, emulsifier are with mass ratio 100:3-5:0.5-1.5 is used cooperatively.
5. the preparation method of the low-cost bio plastics of a kind of heat resistance according to claim 1, it is characterized in that：Step（3）
The high pressure spray drying machine uses 0.5-2MPa pressure, the nozzle atomization through a diameter of 3-5mm；The heat of high pressure spray drying machine
Air-flow uses 80-100 DEG C of unsaturation thermal current.
6. the preparation method of the low-cost bio plastics of a kind of heat resistance according to claim 1, it is characterized in that：Step（4）
The barium salt selects barium chloride；In mixing arrangement, A liquid, B liquid intake according to barium chloride：Sal glauberi
Molar ratio 1:1；A liquid, B liquid gross mass be wax cladding paste spherex quality 20-30%.
7. the preparation method of the low-cost bio plastics of a kind of heat resistance according to claim 1, it is characterized in that：Step（5）
The thermoplastic polymer is selected poly- butyric ester, poly- hydroxyl valerate, poly-succinic-butanediol ester, polycaprolactone, is gathered
Lactic acid is one such or a variety of；Or select polyethylene, polypropylene, polyvinyl chloride, polystyrene, ethene-vinyl acetate total
Polymers, ethylene-acrylic acid copolymer（EAA）, it is polyethylene terephthalate, one or more in polyamide.
8. the preparation method of the low-cost bio plastics of a kind of heat resistance according to claim 1, it is characterized in that：Step（5）
The processing aid is polyethylene wax or/and double ethylene stearmides；The spherex securely coated by barium sulfate, thermoplastic
Property polymer, processing aid are with mass ratio 3:2:0.1 mixing.
9. the preparation method of the low-cost bio plastics of a kind of heat resistance according to claim 1, it is characterized in that：Step（5）
It is described by screw extruder be parallel dual-screw extruding machine, screw slenderness ratio be more than 30:1, screw speed 200-350rpm.
10. a kind of low-cost bio plastics for heat resistance that any one of claim 1-9 the methods are prepared.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810221611.7A CN108484986A (en) | 2018-03-17 | 2018-03-17 | A kind of the low-cost bio plastics and preparation method of heat resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810221611.7A CN108484986A (en) | 2018-03-17 | 2018-03-17 | A kind of the low-cost bio plastics and preparation method of heat resistance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108484986A true CN108484986A (en) | 2018-09-04 |
Family
ID=63339687
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810221611.7A Pending CN108484986A (en) | 2018-03-17 | 2018-03-17 | A kind of the low-cost bio plastics and preparation method of heat resistance |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108484986A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110283338A (en) * | 2019-06-04 | 2019-09-27 | 北京化工大学 | A kind of method of the dry preparation powder nitrile rubber of synchronous spraying |
| CN112063042A (en) * | 2020-08-17 | 2020-12-11 | 余姚市宏邦包装有限公司 | Degradable polypropylene plastic and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101250296A (en) * | 2008-03-14 | 2008-08-27 | 珠海天威飞马打印耗材有限公司 | Degradable polyethylene composition and method of making the same |
| CN101760037A (en) * | 2008-12-23 | 2010-06-30 | 金发科技股份有限公司 | Completely degraded plant powder modified thermoplastics composite material and preparation method thereof |
| CN107266782A (en) * | 2016-04-06 | 2017-10-20 | 黑龙江鑫达企业集团有限公司 | A kind of starch-based degradable biological plastics PP and preparation method thereof |
-
2018
- 2018-03-17 CN CN201810221611.7A patent/CN108484986A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101250296A (en) * | 2008-03-14 | 2008-08-27 | 珠海天威飞马打印耗材有限公司 | Degradable polyethylene composition and method of making the same |
| CN101760037A (en) * | 2008-12-23 | 2010-06-30 | 金发科技股份有限公司 | Completely degraded plant powder modified thermoplastics composite material and preparation method thereof |
| CN107266782A (en) * | 2016-04-06 | 2017-10-20 | 黑龙江鑫达企业集团有限公司 | A kind of starch-based degradable biological plastics PP and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110283338A (en) * | 2019-06-04 | 2019-09-27 | 北京化工大学 | A kind of method of the dry preparation powder nitrile rubber of synchronous spraying |
| CN110283338B (en) * | 2019-06-04 | 2020-05-19 | 北京化工大学 | Method for preparing powdered nitrile rubber through synchronous spray drying |
| CN112063042A (en) * | 2020-08-17 | 2020-12-11 | 余姚市宏邦包装有限公司 | Degradable polypropylene plastic and preparation method and application thereof |
| CN112063042B (en) * | 2020-08-17 | 2022-08-30 | 余姚市宏邦包装有限公司 | Degradable polypropylene plastic and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6763619B1 (en) | How to prepare highly biodegradable materials | |
| Reis et al. | Biodegradable trays of thermoplastic starch/poly (lactic acid) coated with beeswax | |
| CN103384702B (en) | Polylactic acid-based film | |
| Li et al. | Comparative study on the blends of PBS/thermoplastic starch prepared from waxy and normal corn starches | |
| AU2010337977B2 (en) | Natural biopolymer thermoplastic films | |
| Zhang et al. | Thermoplastic starch | |
| CN112940474B (en) | Antibacterial puncture-resistant biodegradable packaging bag and preparation method thereof | |
| WO2020134850A1 (en) | Degradable bio-based masterbatch and preparation method therefor and application thereof, | |
| KR20100046206A (en) | Biodegradable water-sensitive films | |
| WO2008028356A1 (en) | Inorganic material combination reinforced, heat-resistant biodegradable masterbatch pellets and its preparation | |
| Castaño et al. | Physical, chemical and mechanical properties of pehuen cellulosic husk and its pehuen-starch based composites | |
| WO2022000465A1 (en) | Multi-stage modified thermoplastic starch masterbatch and application thereof in preparing starch-based biodegradable film | |
| CN108192303A (en) | A kind of preparation method of biodegradable equipment for prepn. of yoghurt material and product | |
| CN110835417A (en) | Barrier degradable antibacterial food preservative film and preparation method and application thereof | |
| CN110294923A (en) | Fretting map complete biodegradable polymer sheet and preparation method thereof | |
| CN113185809B (en) | Heat-resistant full-biodegradable composite material for thin-wall injection molding product and preparation method thereof | |
| WO2019003077A1 (en) | Resin composition and method for producing same | |
| CN108484986A (en) | A kind of the low-cost bio plastics and preparation method of heat resistance | |
| CN111205604A (en) | Ultrathin high-strength high-toughness biodegradable mulching film material and film, and preparation method and application thereof | |
| Haque et al. | Processing, compatibilization and properties of ternary composites of Mater-Bi with polyolefins and hemp fibres | |
| CN108239324A (en) | A kind of biology base stalk composite plastic and preparation method thereof | |
| WO2020088214A1 (en) | Pha-modified tps/pbat biodegradable resin and preparation method therefor | |
| CN107936486B (en) | Biodegradable polyester composition for shopping bags | |
| EP0781807B1 (en) | Biodegradable composition, a process and equipment for preparing the same | |
| CN109401239A (en) | A kind of biodegradable material for crisper, crisper and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20180904 |