CN102391626B - Non-petroleum base complete degradation master batch and preparation method thereof - Google Patents
Non-petroleum base complete degradation master batch and preparation method thereof Download PDFInfo
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- CN102391626B CN102391626B CN 201110214966 CN201110214966A CN102391626B CN 102391626 B CN102391626 B CN 102391626B CN 201110214966 CN201110214966 CN 201110214966 CN 201110214966 A CN201110214966 A CN 201110214966A CN 102391626 B CN102391626 B CN 102391626B
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Abstract
The embodiment of the invention discloses a non-petroleum base complete degradation master batch which comprises the following components in percentage by weight: 30%-50% of carrier, 20%-70% of pigment and 0-60% of stuffing, wherein the carrier is a biological base complete degradation polymer; the biological base complete degradation polymer comprises one or two of hydroxy fatty acid ester PHA series, polylactic acid PLA and polydiethylene glycol sebacate PBS. The master batch prepared by the invention contains no petroleum base and no degradable addition agent; and the needed carrier is derived from renewable resources, thereby realizing the complete degradation in the true sense and more effectively promoting the application of a degradable material and the protection of environments.
Description
Technical field
The invention belongs to chemical field and relate to a kind of Masterbatch and preparation method thereof, relate in particular to a kind of non-petroleum base degradable Masterbatch and preparation method thereof
Background technology
In in the past nearly 100 years, macromolecular material industry has obtained the development of advancing by leaps and bounds.The application of synthesized polymer material and development are very easy to people's life, and still, a large amount of uses of disposable non-degradable goods have but brought the serious environmental pollution problem." white pollution " problem has caused global concern; Various countries drop into manpower one after another, financial resources are carried out the research and development of full-biodegradable material; Through the development of recent two decades, the research and development of Wholly-degradable material have nowadays been made significant headway, and the degradable material goods are accepted by people because of its degradation property, the feature of environmental protection gradually fully; Get their way into people's lives, certain function has been played in the solution of " white pollution " problem.The complete biodegradable performance is the characteristic of this based article; With the prior resin in petroleum base source is that the Masterbatch of carrier can not satisfy this based article in the requirement of processing coloring process to degradation property, and therefore exploitation is that the colour batch of carrier has good using value with degradable material fully.And the patent of this respect is very few, and this patent is to realize that really Wholly-degradable material still possesses the important invention of degradation characteristic fully behind the painted formation goods of processing.
Patent CN1368516, used carrier is non-degradable materials such as Vilaterm or ethylene-vinyl acetate in Masterbatch that CN101392078, CN101319068 etc. provide and preparation method thereof; Patent CN101475695 provides a kind of Wholly-degradable primary color master batch and preparation method thereof, and in the non-degradable analog assistants such as polyethylene wax, OPE, paraffin, white oil one or more are arranged in this Masterbatch formula system.This Masterbatch formula system is too complicated, and small molecules auxiliary agent kind is many and accounting is many, can influence the Wholly-degradable material processing products, and there is certain risk in problem such as cause that small molecules is separated out easily.CN102040814A provides a kind of black agglomerate that is exclusively used in polylactic acid based degradable plastics; Formula system contains petroleum base non-degradable auxiliary agents such as polyethylene wax, ethene-vinyl acetate wax and EBS equally, can't realize Masterbatch degraded fully truly.
Degradable material has experienced the development from " degradable " to " high-fall separating "; Part degradation material such as starch filled Vestolen PP 7052 or polythene material; Just the starch part can be degraded; The Masterbatch of therefore traditional with the Vilaterm is carrier can use in this type degradation material goods; But nowadays degradable material has developed into the degradable material stage fully, and the color master-batch of these degradable material goods of will demanding perfection also should possess fully the performance of degraded, however now on the market and above-mentioned disclosed several patents all do not realize Masterbatch can degrade fully on moity.
Summary of the invention
Embodiment of the invention technical problem to be solved is; A kind of non-petroleum base Masterbatch and preparation method thereof of can degrading fully is provided; Employing degradable material fully is a carrier, does not add any petroleum base and non-degradable auxiliary agent, relies on advanced production technique and equipment to make the Masterbatch of can degrading fully; Really make the Wholly-degradable material goods after painted, still keep its characteristic of degrading fully, comprise the recipe ingredient of following weight percent:
Carrier 30 as one kind % ~ 50%
Pigment 20% ~ 70%
Stopping composition 0 ~ 60%,
Wherein, said carrier is a bio-based degradation polymer fully, and said bio-based degradation polymer fully comprises among polyhydroxyalkanoate PHA series, polylactic acid PLA and the poly butylene succinate PBS one or both.
The P3/4HB of said polyhydroxyalkanoate PHA series for having better mechanical property, wherein, said 4HB component concentration is 10% ~ 20%.
Preferably, said polyhydroxyalkanoate PHA series is synthetic through biological fermentation process, and said poly butylene succinate PBS obtains bio-based Succinic Acid and butyleneglycol monomer through fermentation, and is synthetic through biological process again.
Preferable, the pigment dyestuff that said pigment comprises white titanium pigment, carbon black and comprises P.B., P.Y. and P.R. different colours series.
Said stopping composition comprises one or both in starch, lime carbonate, talcum powder and the permanent white, and fineness is 800 ~ 2500 orders.
Preferable, said starch comprises W-Gum, yam starch or tapioca(flour).
In order to solve the problems of the technologies described above, the embodiment of the invention provides a kind of preparation method of the Masterbatch of can degrading fully, cooperates single screw extrusion machine to realize that its preparation method is following through continuous Banbury mixer:
1. metering
According to the prescription composition requirement, each component materials constantly is transferred to continuous Banbury mixer material mouth through WT-MSR respectively.Rate of feeding: 200 ~ 1000kg/hr.
2. banburying
After each component materials gets into continuous Banbury mixer material mouth, by two rotors drive to get into that the Banbury mixer chamber is sheared, kneading, banburying become the melt shape, gets into the single screw extrusion machine spout through the Banbury mixer front opening.Two rotors or be divided into four parts: feeding screw channel section, the spirane structure section of advancing, pusher spirane structure section and melt span line.Each zone temperatures is provided with as follows: 40 ~ 60 ℃ of feeding screw channel sections, 150 ~ 160 ℃ of the spirane structure sections of advancing, 170 ~ 180 ℃ of pusher spirane structure sections, 150-180 ℃ of melt span line.The Banbury mixer rotating speed is at 200 ~ 500 rev/mins, Banbury mixer front opening 10 ~ 100%.
3. extruding pelletization
The melt piece gets into single-screw machine feeding section from the Banbury mixer opening; Can get into further fusion plastification in the single screw extrusion machine by the auxiliary feeding of pusher; The single screw extrusion machine rotating speed is controlled at 20 ~ 50 rev/mins; Temperature is controlled at 130 ~ 180 degree, and material is extruded through die orifice after through 100 or 200 purpose screen clothes, cuts granulation under water, water ring cuts granulation or tie rod is cut granulation.
4. dry
Entering into drying machine through transmission after the granulation carries out drying, removes moisture.
5. screening
Particle is sent to after drying and sieves processing in the vibratory screening apparatus, obtains uniform Masterbatch.
Embodiment of the present invention embodiment has following beneficial effect:
The invention provides a kind of Masterbatch that can degrade fully, its preparation material is made up of the non-petroleum base material fully, has avoided the use of nondegradable auxiliary agent; Adopt material to be renewable resources; And can realize degrading fully, be applicable to the painted of degradation material, positive effect arranged for environment protection; Utilize mechanical technology to break away from dependence, in the protection environment, practiced thrift production cost auxiliary agent.
Embodiment
Better clear for technical problem, technical scheme and beneficial effect that the present invention will be solved, below in conjunction with embodiment, the present invention is explained further details.
Embodiment 1:
Prescription: (unit is KG)
Poly butylene succinate PBS:30
White titanium pigment: 70
The preparation method is following:
Each component materials is transferred in the continuous Banbury mixer hopper through WT-MSR respectively according to the prescription consumption; Rate of feeding is 200kg/hr; By two rotors drive to get into that the banburying chamber is sheared, kneading, banburying become the melt shape, the Banbury mixer rotating speed is at 200 rev/mins, 40 ℃ of feeding screw channel sections, 150 ℃ of the spirane structure sections of advancing, 170 ℃ of pusher spirane structure sections, 150 ℃ of melt span lines; Banbury mixer front opening 10%; Melt gets in the single screw extrusion machine, and the single screw extrusion machine rotating speed is 30 rev/mins, and temperature range is set to 130 ℃-140 ℃-150 ℃-150 ℃-160 ℃-155 ℃-150 ℃; Material is extruded through die orifice after through 200 purpose screen clothes, cuts granulation and transmission under water and enters into drying machine and carry out drying, remove moisture.Particle is sent to after drying and sieves processing in the vibratory screening apparatus, obtains big or small homogeneous, and water ratio is 0.15% white degradation master batch.
Embodiment 2:
Prescription: (unit is KG)
Poly butylene succinate PBS:30
White titanium pigment: 60
Permanent white: 10
The preparation method is following:
Each component materials is transferred in the continuous Banbury mixer hopper through WT-MSR respectively according to the prescription consumption; Rate of feeding is 300kg/hr; By two rotors drive to get into that the banburying chamber is sheared, kneading, banburying become the melt shape, the Banbury mixer rotating speed is at 250 rev/mins, 40 ℃ of feeding screw channel sections, 150 ℃ of the spirane structure sections of advancing, 170 ℃ of pusher spirane structure sections, 160 ℃ of melt span lines; Banbury mixer front opening 30%; Melt gets in the single screw extrusion machine, and the single screw extrusion machine rotating speed is 35 rev/mins, and temperature range is set to 130 ℃-140 ℃-145 ℃-150 ℃-155 ℃-145 ℃-140 ℃; Material is extruded through die orifice after through 100 purpose screen clothes, cuts granulation and transmission under water and enters into drying machine and carry out drying, remove moisture.Particle is sent to after drying and sieves processing in the vibratory screening apparatus, obtains big or small homogeneous, and water ratio is 0.09% white degradation master batch.
Embodiment 3:
Prescription: (unit is KG)
Polyhydroxyalkanoate P3/4HB (4HB content: 15%): 40
Poly butylene succinate PBS:10
Carbon black: 50
The preparation method is following:
Each component materials is transferred in the continuous Banbury mixer hopper through WT-MSR respectively according to the prescription consumption, and rate of feeding is 1000kg/hr, by two rotors drive to get into that the banburying chamber is sheared, kneading, banburying become the melt shape; The Banbury mixer rotating speed is at 500 rev/mins, 60 ℃ of feeding screw channel sections, 155 ℃ of the spirane structure sections of advancing, 180 ℃ of pusher spirane structure sections, 170 ℃ of melt span lines, Banbury mixer front opening 50%; Melt gets in the single screw extrusion machine;, the single screw extrusion machine rotating speed is 50 rev/mins, temperature range is set to 130 ℃-140 ℃-150 ℃-160 ℃-170 ℃-160 ℃-150 ℃; Material is extruded through die orifice after through 100 purpose screen clothes; Carry out water ring and cut granulation, cross in the vibratory screening apparatus and sieve processing, be transferred to then and carry out drying in the drying machine, remove moisture; Obtain big or small homogeneous, water ratio be 0.10% black agglomerate.
Embodiment 4:
Prescription: (unit is KG)
Polyhydroxyalkanoate P3/4HB (4HB content: 20%): 40
Lime carbonate (1250 order): 10
W-Gum: 10
Yellow P.Y.180:40
The preparation method is following:
Each component materials is transferred in the continuous Banbury mixer hopper through WT-MSR respectively according to the prescription consumption, and rate of feeding is 500kg/hr, by two rotors drive to get into that the banburying chamber is sheared, kneading, banburying become the melt shape; The Banbury mixer rotating speed is at 350 rev/mins; 50 ℃ of feeding screw channel sections, 160 ℃ of the spirane structure sections of advancing, 180 ℃ of pusher spirane structure sections, 180 ℃ of melt span lines, Banbury mixer front opening 100%, melt get in the single screw extrusion machine; The single screw extrusion machine rotating speed is 50 rev/mins; Temperature range is set to 140 ℃-150 ℃-160 ℃-165 ℃-175 ℃-180 ℃-170 ℃, and material is extruded through die orifice after through 100 purpose screen clothes, carries out water ring and cuts granulation; Cross and sieve processing in the vibratory screening apparatus; Obtain uniform Masterbatch, be transferred to then and carry out drying in the drying machine, remove moisture, final water ratio is 0.2%.
Embodiment 5:
Prescription: (unit is KG)
Polyhydroxyalkanoate P3/4HB (4HB content: 10%): 35
Poly butylene succinate PBS:10
Talcum powder (2500 order): 15
Yam starch: 10
Red P.R.254:30
The preparation method is following:
Each component materials is transferred in the continuous Banbury mixer hopper through WT-MSR respectively according to the prescription consumption, and rate of feeding is 750kg/hr, by two rotors drive to get into that the banburying chamber is sheared, kneading, banburying become the melt shape; The Banbury mixer rotating speed is at 400 rev/mins; 50 ℃ of feeding screw channel sections, 120 ℃ of the spirane structure sections of advancing, 150 ℃ of pusher spirane structure sections, 160 ℃ of melt span lines, Banbury mixer front opening 60%, melt get in the single screw extrusion machine; The single screw extrusion machine rotating speed is 35 rev/mins; Temperature range is set to 130 ℃-150 ℃-155 ℃-160 ℃-170 ℃-170 ℃-160 ℃, and material is extruded through die orifice after through 200 purpose screen clothes, carries out water ring and cuts granulation; Cross and sieve processing in the vibratory screening apparatus; Obtain uniform Masterbatch, be transferred to then and carry out drying in the drying machine, remove moisture, the final water ratio of red master batch is 0.15%.
Embodiment 6:
Prescription: (unit is KG)
Poly butylene succinate PBS:40
Polylactic acid PLA: 20
Blue P.B.15:3:40
The preparation method is following:
Each component materials is transferred in the continuous Banbury mixer hopper through WT-MSR respectively according to the prescription consumption, and rate of feeding is 400kg/hr, by two rotors drive to get into that the banburying chamber is sheared, kneading, banburying become the melt shape; The Banbury mixer rotating speed is at 300 rev/mins, 40 ℃ of feeding screw channel sections, 160 ℃ of the spirane structure sections of advancing, 175 ℃ of pusher spirane structure sections, 165 ℃ of melt span lines, Banbury mixer front opening 45%; Melt gets in the single screw extrusion machine; The single screw extrusion machine rotating speed is 35 rev/mins, and temperature range is set to 130 ℃-140 ℃-155 ℃-160 ℃-170 ℃-180 ℃-175 ℃, and material is extruded through die orifice after through 200 purpose screen clothes; Carry out tie rod and cut granulation; Cross and sieve processing in the vibratory screening apparatus, obtain uniform Masterbatch, be transferred to then and carry out drying in the drying machine, remove moisture.The final water ratio of blue master batch is 0.12%.
Above disclosedly be merely preferred embodiment of the present invention, can not limit the present invention's interest field certainly with this, the equivalent variations of therefore doing according to claim of the present invention still belongs to the scope that the present invention is contained.
Claims (1)
1. non-petroleum base Masterbatch of can degrading fully is characterized in that the said Masterbatch of can degrading fully comprises the recipe ingredient of following weight percent: carrier 30 as one kind % ~ 50%, pigment 20% ~ 70%, stopping composition 0 ~ 60%, more than each component concentration summation be 100%; Said carrier is a bio-based degradation polymer fully, and said bio-based degradation polymer fully comprises among polyhydroxyalkanoate PHA series, polylactic acid PLA and the poly butylene succinate PBS one or both; The P3/4HB of said polyhydroxyalkanoate PHA series for having better mechanical property, wherein, said 4HB component concentration is 10% ~ 20%; Said polyhydroxyalkanoate PHA series and polylactic acid PLA, all synthetic through biological fermentation process; Said poly butylene succinate PBS obtains bio-based Succinic Acid and butyleneglycol through fermentation, and the regrowth method is synthetic; Said pigment comprises white titanium pigment, carbon black and comprises P.B., P.Y. and P.R. different colours series; The fineness of said stopping composition is that 800 ~ 2500 orders are selected from one or both in starch, lime carbonate, talcum powder and the permanent white, and said starch comprises W-Gum, yam starch or tapioca(flour);
The non-petroleum base Masterbatch of can degrading fully cooperates single screw extrusion machine to realize through continuous Banbury mixer:
(1) metering:
By weight percentage 30% ~ 50% carrier, 20% ~ 70% pigment and 0 ~ 60% stopping composition constantly are transferred to continuous Banbury mixer material mouth through WT-MSR respectively; Rate of feeding: 200 ~ 1000kg/hr;
(2) banburying:
After each component materials gets into continuous Banbury mixer material mouth, by two rotors drive to get into that the Banbury mixer chamber is sheared, kneading, banburying become the melt shape, gets into the single screw extrusion machine spout through the Banbury mixer front opening; Two rotors or be divided into four parts: feeding screw channel section, the spirane structure section of advancing, pusher spirane structure section and melt span line; Each zone temperatures is provided with as follows: 40 ~ 60 ℃ of feeding screw channel sections, 150 ~ 160 ℃ of the spirane structure sections of advancing, 170 ~ 180 ℃ of pusher spirane structure sections, 150-180 ℃ of melt span line, Banbury mixer rotating speed be at 200 ~ 500 rev/mins, Banbury mixer front opening 10 ~ 100%;
(3) extruding pelletization:
The melt piece gets into single-screw machine feeding section from the Banbury mixer opening; Get into further fusion plastification in the single screw extrusion machine by the auxiliary feeding of pusher; The single screw extrusion machine rotating speed is controlled at 20 ~ 50 rev/mins; Temperature is controlled at 130 ~ 180 degree, and material is extruded through die orifice after through 100 or 200 purpose screen clothes, cuts granulation under water, water ring cuts granulation or tie rod is cut granulation;
(4) drying:
Entering into drying machine through transmission after the granulation carries out drying, removes moisture;
(5) screening:
Particle is sent to after drying and sieves processing in the vibratory screening apparatus, obtains uniform Masterbatch.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104151800A (en) * | 2014-08-19 | 2014-11-19 | 东莞市普凯塑料科技有限公司 | Biodegradable plastic color master batch and making method thereof |
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| CN104494261B (en) * | 2014-12-11 | 2016-08-17 | 昆山市张浦彩印厂 | Degradable EVOH high-barrier composite film |
| CN104650549A (en) * | 2015-02-10 | 2015-05-27 | 利丰新材料科技（深圳）有限公司 | PLA (polylactic acid) degradable color master batch and preparation method thereof |
| CN105400154A (en) * | 2015-12-04 | 2016-03-16 | 河南天仁生物材料研究所有限公司 | Biodegradable plastic color masterbatch and preparation method thereof |
| CN108070225B (en) * | 2016-11-17 | 2022-02-08 | 普立万聚合体（上海）有限公司 | Polyester articles having a simulated metallic or pearlescent appearance |
| CN107955348A (en) * | 2017-11-14 | 2018-04-24 | 青岛卓森纳生物工程有限公司 | A kind of environmentally-friendly plastic Masterbatch and its manufacture method |
| CN110922613A (en) * | 2019-11-29 | 2020-03-27 | 安徽丰原福泰来聚乳酸有限公司 | Colored polylactic acid particles and preparation method thereof |
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| CN101475695A (en) * | 2008-12-29 | 2009-07-08 | 王文广 | Wholly-degradable primary color master batch and preparation thereof |
| CN102040814A (en) * | 2010-12-29 | 2011-05-04 | 深圳市科聚新材料有限公司 | Special black master batch for polylactic acid based degradable plastics and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475695A (en) * | 2008-12-29 | 2009-07-08 | 王文广 | Wholly-degradable primary color master batch and preparation thereof |
| CN102040814A (en) * | 2010-12-29 | 2011-05-04 | 深圳市科聚新材料有限公司 | Special black master batch for polylactic acid based degradable plastics and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104151800A (en) * | 2014-08-19 | 2014-11-19 | 东莞市普凯塑料科技有限公司 | Biodegradable plastic color master batch and making method thereof |
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Application publication date: 20120328 Assignee: CHENGDU FEISITE NEW MATERIAL Co.,Ltd. Assignor: MALION NEW MATERIALS Co.,Ltd. Contract record no.: X2021510000003 Denomination of invention: Non petroleum based completely degradable masterbatch and its preparation method Granted publication date: 20121212 License type: Common License Record date: 20210208 |
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