CN109679307A - A kind of biodegradable pearl cotton and preparation method thereof - Google Patents
A kind of biodegradable pearl cotton and preparation method thereof Download PDFInfo
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- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
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Abstract
The invention discloses a kind of biodegradable pearl cottons and preparation method thereof, the pearl cotton is using one of poly (propylene carbonate), plasticizing polylactic acid, poly butylene succinate, thermoplastic starch or their mixture as main material, add wheat stalk powder, nucleating agent, after high-speed mixer and mixing is uniform, squeezed out after twin screw compounder is kneaded, air-cooled stretching and granulation.Crosslinking agent, initiator, antishrinking agent are further added in pellet, it is uniformly mixed, again using supercritical carbon dioxide as foaming agent, pass through two-shipper tandem foam sheet extrusion system, extrusion foaming, the environment-friendly type pearl cotton sheet material for the fully biodegradable that expansion ratio is 30~70 times is obtained, which can substitute existing polyolefin pearl cotton, be used as amortizing packaging material or packaging filler.
Description
Technical field
The invention belongs to field of packaging material, and in particular to one kind can the pearl cotton of natural degradation and its preparation completely
Method.
Background technique
In packaging industry, breakage occurs in order to reduce packaged product due tos by external impacts, vibration etc., uses
A large amount of amortizing packaging material or packaging filler.Common amortizing packaging material mainly has foamed plastic, buffering pneumatic cushion, wood shavings
Paper, Plant Fiber-based Cushion Packaging Materials (such as straw, wood sawdust, luffa).Wherein most commonly used is foamed plastic, foamed plastic
Refer to synthetic resin manufactured a kind of foaming solid material with porous structure after either physically or chemically foaming,
The density of this kind of plastic material is about 0.01~0.50g/cm3, porous structure is also possible to aperture either closed pore,
Hardness and density are adjustable in a certain range, have both had the advantages that all of synthetic resin itself, have also had because of the excellent of imparting that foam
Good resiliency, heat-insulation and heat-preservation etc..
The foamed plastic used as packaging material mainly has PUF (Polyurethane foam, polyurethane foam), EPS
(Expandable Polyethylene, foaminess are poly- by (Expandable Polystyrenes, foamable polystyrene), EPE
Ethylene)), EPP (Expandable Polypropylene, foaminess polypropylene), EPO (Expandable Polyolefin,
Foaminess copolyalkenamer resin) etc..EPS is commonly called as Poly Foam, is that foaming agent is added by polystyrene, makes to set at a certain temperature
Rouge softening, foaming agent vaporization volatilization and foam, then a kind of hard obtained from cooling and shaping has the foamed plastics of hole-closing structure.By
It is small in its high mechanical strength, water imbibition, it is cheap, can also directly by method of molding be made cup of various shapes, disk, box,
Case etc., therefore be widely applied in packaging industry, it is a kind of most padded coaming of current application.But EPS is crisp, no
Resistance to repeat impact, that there are tensile strengths as PUF is low, inflammable, burning when can release a large amount of black smokes and toxic gas etc., one
The packaging industries of a little countries have started to be prohibited from using, and such as America and Europe state in 1998 promulgates a decree times of nonimportation EPS packaging
What product, the mess-tin that China was just done in the departments such as railway disabling EPS in 1999.
EPO, EPE and EPP be commonly called as respectively a Ou Long, according to than dragon and Na Pulong, be to be formed with by polyolefin resin is foamed
The foamed material of countless independent air bubble structures.This type of foam overcomes the disadvantage that EPS is frangible, easily-deformable, recovery is poor；Tool
There is many advantages, such as moisture-proof water proof, shockproof, sound insulation, heat preservation, plasticity is good, toughness is high, crashworthiness power is strong, while also having fine
Resist chemical performance.Noncrosslinking foamed plastics can be with Recycling, it appears relatively environment-friendly.Due to this kind of foamed plastic
Good toughness, be translucent shape mostly, more than pearls of image of bubble of the inside, therefore also referred to as pearl cotton.The product of pearl cotton
Kind has very much, such as ordinary pearl cotton, without wax pearl cotton, special flat pearl cotton, enciphered pearl cotton, encryption stiffened pearl cotton, antistatic
Pearl cotton, lamination pearl cotton, cladded aluminum foil pearl cotton, plates color film fitting pearl cotton, pearl cotton etc. of preventing fires at overlay film pearl cotton.Pearl
Various special sections and component, such as tubular, stick, L shape, U-shaped can also be made in cotton, can also be through overlay film post-processing at various rulers
Very little pearl cotton bag, box.
These types of foamed plastic (pearl cotton) is widely used in all trades and professions, all deposits although haveing excellent performance, being quality-high and inexpensive
Inflammable after foaming, resistance to ag(e)ing is excellent and is difficult to natural degradation, and the foaming agent used is mostly low-boiling alkane or easy heat
The organic compound of decomposition, when foaming, escape inflammable or easy leakage and generate a large amount of VOC emissions, simultaneously because its density is low, value
It is small and cause its cost recovery high, it is arbitrarily abandoned mostly after use, causes a large amount of white pollution.Therefore, in order to alleviate or
Solve traditional foamed plastic packaging waste pressure caused by environment, development and production green can the foamed plastic of natural degradation make
Seem extremely urgent for package buffer material, it may have very high Social benefit and economic benefit.
2004, ZL200310110045.6 disclosed a kind of using 80% or more starch as substrate, micronized polyethylene
Alcohol is aided with nucleating agent and flow ability modifying agent as foaming agent as film forming reinforcing agent, water, is prepared for double screw extruder extrusion
A kind of foam amortizing packaging material of fully biodegradable, to replace amorphism to require the expanded polystyrene (EPS) of filling.
But the water imbibition of the foam is strong, resilience is poor, and service performance can not show a candle to pearl cotton, and price is higher.
2010, ZL201010235181.8 disclosed a kind of flaxen fiber filling polylactic acid, and azodicarbonamide is sent out
Infusion, zinc oxide make blowing promotor, and moulded from foam forms in 168~190 DEG C of baking oven, and this foamed plastics biological can drop
Solution, no pollution to the environment, mechanical property is good, can be used for the fields such as various packagings, shockproof, heat-insulated.But it is numb in this production technology
Fiber need to be handled with buck, and complex procedures are at high cost, moulded from foam low efficiency, and expansion ratio is unstable.
2017, ZL201710267423.3, which is disclosed, a kind of made toughening with polyadipate-mutual-phenenyl two acid bromide two alcohol ester
Agent polydactyl acid makees reaction compatilizer with epoxies chain extender, and organic modification montmonrillonite makees nucleating agent, is mixed into through mixing
Supercritical carbon dioxide is passed through in autoclave, after pressure maintaining 3~6 hours, rapid pressure release obtains the biodegradable of high foamability
Foamed material.This production efficiency is low, at high cost, and expansion ratio is unstable, poor product quality.
2018, ZL201711196120.3 disclosed one kind with polyadipate-mutual-phenenyl two acid bromide two alcohol ester and Ke Sheng
Object degradation polymer (one of polylactic acid, carbon dioxide-epoxy propane copolymer, poly butylene succinate or a variety of) is
Major ingredient, azodicarbonamide etc. make foaming agent, and zinc oxide, stearic acid etc. make blowing promotor, room temperature after sheet material are extruded into after mixing
Lower use60Co or electron accelerator crosslinking with radiation are first handled 2~48 hours in 50~80 DEG C of hot bath, then 190~250
It is handled 1~20 minute at DEG C, obtains the biodegradable foam material of crosslinking with radiation.Although the foamed material that this mode obtains
Mechanical property greatly improves, and equally exists complex process, high production cost, and the foaming agents such as azodicarbonamide have residual etc. to ask
Topic.
Summary of the invention
The technical problems to be solved by the invention are as follows: how to provide a kind of energy continuous production, and production cost is low, Diamond Search
Discharge, reactive blowing agent residual, expansion ratio it is high can natural degradation completely pearl cotton and preparation method thereof.
The technical solution of the present invention is as follows: a kind of biodegradable pearl cotton, by weight, its composition are as follows: can biology
85~100 parts of degraded macromolecular major ingredient, 10~15 parts of straw powder filler material, 3.5~7 parts of nucleating agent, 2~3 parts of crosslinking agent, cause
0.15~0.22 part of agent, 0.34~1.2 part of antishrinking agent.
Further, the Biodegradable high-molecular major ingredient is poly (propylene carbonate), plasticizing polylactic acid, poly-succinic fourth
One of diol ester, thermoplastic starch or their mixture.
Further, the straw powder filler material is 70 microns of wheat stalk powders below of partial size.
Further, the nucleating agent is hydrophobically modified nanometer calcium carbonate, hydrophobically modified nano silica or hydrophobic changes
One kind or their mixture of property montmorillonite.
Further, the crosslinking agent is vinyl silanes.Preferably, crosslinking agent is vinyltriethoxysilane.
Further, the initiator is one of benzoyl peroxide, azodiisobutyronitrile or their mixture.
Further, the antishrinking agent is glycerin monostearate.
The invention also discloses a kind of preparation methods of biodegradable pearl cotton, include the following steps:
(1) Biodegradable high-molecular major ingredient, straw powder filler material and nucleating agent are weighed in proportion, are added to the mixer,
It is uniformly mixed, obtains premix；
(2) it selects screw slenderness ratio for the parallel double-screw extruding granulator of 35:1~45:1, step (1) is obtained pre-
Mixing is added in the loading hopper of double-screw extruding pelletizing machine, and the barrel temperature of setting double-screw extruding pelletizing machine is 160~190
DEG C, the temperature for exporting die head is 170~185 DEG C, and screw speed is 100~260 revs/min, after temperature is increased to preset value
Start to squeeze out, then by the air-cooled pelletizing of tie rod, obtains resin granular material；
(3) crosslinking agent, initiator and antishrinking agent are weighed in proportion, is placed in container, and absolute ethyl alcohol and stirring dissolution is added
And be uniformly mixed, obtain liquid processing aid；
(4) resin granular material for taking step (2) to obtain is added in mixing machine, sprays the liquid that step (3) obtain while stirring
Body processing aid, is thoroughly mixed, and obtains secondary premix；
(5) the secondary premix for obtaining step (4) puts into foam sheet extrusion system, and injects supercritical carbon dioxide
Extrusion foaming is carried out, biodegradable pearl cotton sheet material is obtained.
Further, the straw powder filler material is prepared by the following method: wheat stalk harvest after by natural drying,
Air-dry, its moisture content made to drop to 15% hereinafter, then by preliminary sorting, must not have go rotten it is rotten, be mingled with silt, stone or its
Its sundries；Then stalk is further used into hot-air seasoning, be crushed to 70 microns of partial size with rotary cutter type plant straw crusher hereinafter,
Drying to moisture content is lower than 2%.
Further, in step (5), the foam sheet extrusion system is the TJ120/ of Shandong Tong Jia Machinery Co., Ltd.
150 systems.
Compared with prior art, the invention has the following advantages:
1, a large amount of by-products for the generating when present invention is using agricultural production --- wheat stalk powder is as main filler, general
It is directly used after wheat stalk drying and crushing, not only raw material sources are extensive, sufficient, and no longer generate other in use
Waste will not generate any problem of environmental pollution.
2, crosslinking agent is made by the way that vinyl silanes are added, makees initiator with benzoyl peroxide or azodiisobutyronitrile,
Cross-linked structure appropriate is formed in system, increases the intensity and resilience of pearl cotton.
3, system uses supercritical carbon dioxide foaming as foaming agent, is foamed by physics mode, in process of production both
There is no the discharge of VOC, will not may generate residual, the pearl produced in this way in pearl cotton product as chemical foaming agent
Cotton can be used for the buffering package of food, drug class commodity.
4, the production technology of pearl cotton uses the TJ120/150 system of Shandong Tong Jia Machinery Co., Ltd., can continuously certainly
Dynamic metaplasia produces, high production efficiency, and expansion ratio is controllable.It can both recycle after pearl cotton product use and utilize again, can also abandon
It sets and gives free rein to degradation recurrence soil in the environment, do not cause any pollution to environment.
Specific embodiment
Embodiment
After wheat stalk harvest by natural drying, air-dry, so that its moisture content is dropped to 15% hereinafter, then by preliminary point
Choosing must not have to go rotten and go bad, be mingled with silt, stone or other sundries；Then stalk is further used into hot-air seasoning, uses rotary cutter type
Plant straw crusher is crushed to 70 microns of partial size hereinafter, drying to moisture content lower than 2%, obtains straw powder filler material.
According to the formula rate in table 1:
(1) Biodegradable high-molecular major ingredient, straw powder filler material and nucleating agent are weighed, is added to the mixer, stirring is mixed
It closes uniformly, obtains premix；
(2) it selects screw slenderness ratio for the parallel double-screw extruding granulator of 35:1~45:1, step (1) is obtained pre-
Mixing is added in the loading hopper of double-screw extruding pelletizing machine, and the barrel temperature of setting double-screw extruding pelletizing machine is 160~190
DEG C, the temperature for exporting die head is 170~185 DEG C, and screw speed is 100~260 revs/min, after temperature is increased to preset value
Start to squeeze out, then by the air-cooled pelletizing of tie rod, obtains the resin granular material that partial size is 2~5mm；
(3) crosslinking agent, initiator and antishrinking agent are weighed in proportion, is placed in container, and absolute ethyl alcohol and stirring dissolution is added
And be uniformly mixed, obtain liquid processing aid；
(4) resin granular material for taking step (2) to obtain is added in mixing machine, sprays the liquid that step (3) obtain while stirring
Body processing aid, is thoroughly mixed, and obtains secondary premix；
(5) the secondary premix that step (4) obtains is added to the TJ120/150 system of Shandong Tong Jia Machinery Co., Ltd.
Hopper in, by two-shipper tandem foam sheet extrusion system, marginal not enters supercritical carbon dioxide side extrusion, then cooling fixed
Type batches, just obtain expansion ratio be 30~70 times, 600~1200mm of width, 0.5~8.0mm of thickness can completely biology drop
The environment-friendly type pearl cotton sheet material of solution.
The material formula ratio of the pearl cotton of 1 different ratio of table and the physical property of the pearl cotton as made from the formula.
Claims (10)
1. a kind of biodegradable pearl cotton, which is characterized in that by weight, its composition are as follows: Biodegradable high-molecular
85~100 parts of major ingredient, 10~15 parts of straw powder filler material, 3.5~7 parts of nucleating agent, 2~3 parts of crosslinking agent, initiator 0.15~
0.22 part, 0.34~1.2 part of antishrinking agent.
2. the biodegradable pearl cotton of one kind according to claim 1, which is characterized in that the biodegradable high score
Sub- major ingredient is one of poly (propylene carbonate), plasticizing polylactic acid, poly butylene succinate, thermoplastic starch or theirs is mixed
Close object.
3. the biodegradable pearl cotton of one kind according to claim 1, which is characterized in that the straw powder filler material is
70 microns of wheat stalk powders below of partial size.
4. the biodegradable pearl cotton of one kind according to claim 1, which is characterized in that the nucleating agent is hydrophobic changes
Property nanometer calcium carbonate, one kind of hydrophobically modified nano silica or hydrophobically modified montmorillonite or their mixture.
5. the biodegradable pearl cotton of one kind according to claim 1, which is characterized in that crosslinking agent is three second of vinyl
Oxysilane.
6. the biodegradable pearl cotton of one kind according to claim 1, which is characterized in that the initiator is peroxidating
One of benzoyl, azodiisobutyronitrile or their mixture.
7. the biodegradable pearl cotton of one kind according to claim 1, which is characterized in that the antishrinking agent is single hard
Glycerol.
8. the preparation method of the biodegradable pearl cotton of any one of -7 described one kind according to claim 1, which is characterized in that packet
Include following steps:
(1) Biodegradable high-molecular major ingredient, straw powder filler material and nucleating agent are weighed in proportion, is added to the mixer, and are stirred
It is uniformly mixed, obtains premix；
(2) select screw slenderness ratio for the parallel double-screw extruding granulator of 35:1~45:1, the premix that step (1) is obtained
It being added in the loading hopper of double-screw extruding pelletizing machine, the barrel temperature of setting double-screw extruding pelletizing machine is 160~190 DEG C,
The temperature for exporting die head is 170~185 DEG C, and screw speed is 100~260 revs/min, is started after temperature is increased to preset value
It squeezes out, then by the air-cooled pelletizing of tie rod, obtains resin granular material；
(3) crosslinking agent, initiator and antishrinking agent are weighed in proportion, is placed in container, and absolute ethyl alcohol and stirring is added and dissolves and mixes
It closes uniformly, obtains liquid processing aid；
(4) resin granular material for taking step (2) to obtain is added in mixing machine, is sprayed the liquid that step (3) obtain while stirring and is added
Work auxiliary agent, is thoroughly mixed, and obtains secondary premix；
(5) the secondary premix for obtaining step (4) puts into foam sheet extrusion system, and injects supercritical carbon dioxide progress
Extrusion foaming obtains biodegradable pearl cotton sheet material.
9. a kind of preparation method of biodegradable pearl cotton according to claim 8, which is characterized in that the straw powder
Filler material is prepared by the following method: wheat stalk harvest after by natural drying, air-dry, make its moisture content drop to 15% with
Under, then by preliminary sorting, must not have to go rotten and go bad, be mingled with silt, stone or other sundries；Then stalk is further used
Hot-air seasoning is crushed to 70 microns of partial size with rotary cutter type plant straw crusher hereinafter, drying to moisture content is lower than 2%.
10. a kind of preparation method of biodegradable pearl cotton according to claim 8, which is characterized in that step (5)
In, the foam sheet extrusion system is the TJ120/150 system of Shandong Tong Jia Machinery Co., Ltd..
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811607248.9A CN109679307A (en) | 2018-12-27 | 2018-12-27 | A kind of biodegradable pearl cotton and preparation method thereof |
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| CN201811607248.9A CN109679307A (en) | 2018-12-27 | 2018-12-27 | A kind of biodegradable pearl cotton and preparation method thereof |
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| CN113071172A (en) * | 2021-03-24 | 2021-07-06 | 力斯特(无锡)包装科技有限公司 | High-strength degradable EPE heat-insulation pearl wool board and processing method |
| CN114957944A (en) * | 2022-05-31 | 2022-08-30 | 武汉嘉诚塑胶有限公司 | Preparation method of environment-friendly EPE pearl wool material |
| CN116496542A (en) * | 2023-06-13 | 2023-07-28 | 山东联欣环保科技有限公司 | Preparation method of carbon dioxide-based biodegradable foaming material |
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