CN104031302B - A kind of controllable oxidization biodegradable plastic master batch and preparation method thereof - Google Patents
A kind of controllable oxidization biodegradable plastic master batch and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of controllable oxidization biodegradable plastic master batch, described plastic master batch includes: inorganic filler, carrier, oxidative degradation accelerator, biodegradation promotor and Degradation Control agent；Wherein, described Degradation Control agent is antioxidant.Degradative plastics master batch of the present invention can according to actual environment optimization, linkage oxidative degradation and biodegradable dual variation method system so that it is have the ability of environment specific aim and controlled degradation；The preparation method technique of described degradative plastics master batch is simple, easy and simple to handle, is favorably improved the mixing dispersibility of plastic master batch, provides a kind of effective solution for solving organic and inorganic interface compatibility and dispersed sex chromosome mosaicism.
Description
Technical field
The present invention relates to a kind of biodegradable plastic master batch of controllable oxidization and preparation method thereof, particularly relate to a kind of can under natural environment the preparation method of the plastic master batch of controllable oxidization-bio-degradable and one-step method " self assembly " thereof, belong to containing polymer substance goods or moulding material manufacturing technology field.
Background technology
Plastics industry is fast-developing along with the raising of national economy and people's lives water product, and within 2010, China's plastic industry gross output value reaches 1.42 trillion, accounts for the 10.27% of the light industry gross output value, is the big industry of light industry first.China's plastic total output 54,740,000 tons in 2011, increases by 22.45% on a year-on-year basis；The gross output value 1.61 trillion yuan, increases by 27.45% on a year-on-year basis；Products export volume 56,300,000,000 dollars, increases by 26.74% on a year-on-year basis.Owing to plastic consumption figure constantly increases, waste plastic environmental pollution aggravates year by year.According to China's light industry centre of research and development introduction, nearly 40,000,000 tons of plastic refuse society of China owning amount, plastic refuse recycling amount about 11,000,000 tons after China's consumption in 2010, recovery utilization rate, about 20%, far lags behind the level (more than 50%) of Germany, and the degradation cycle of conventional plastic is more than a century, long-term, serious contaminated environment will be produced, especially packing plastics, accounts for the 1/3 of packaging material total amount, directly abandons after using.The plastic bag that only Hong Kong abandons average every day just has 15,000,000, and the whole year is just more than 5,000,000,000.A large amount of plastic packaging bags long-term adding up in the environment will result in huge, lasting environmental pollution.Although China's " plastic limit " puts into effect so far 4 years, but degradative plastic bag consumption is still less than 5%, and main cause is degraded cost of material and product price height, and degradation property is bad.The degradative plastics packaging bag of domestic production is mainly with the degradation master batch of external import for raw material, more a lot of than conventional plastic price, and product is many based on outlet, and domestic interior use is little.
In existing market, biodegradable plastics has PLA(polylactic acid), PHB(gathers 3-hydroxybutyrate fat), and starch base class plastics.For pure Biodegradable material, such as PLA, PHB, although can be degradable, but its synthesis technique be complicated, and expensive, product is 6～10 times of common plastics price, and needs to put into a large amount of financial resource and material resource more new production equipment, and audient face is little.PHB product degree of crystallinity is high, and fragility is serious, and machine-shaping property is not good, it is also difficult to promote.And for starch base class plastics, due to the superabsorbency of itself, cause moulding processability not good；Secondly, initial starch material rise in price, production cost is higher.
Photodegradable plastics thin film of the prior art, owing to being degraded to certain molecular weight dyschezia to degrade further, the fragment of degraded is difficult to recycle more, in turn results in the pollution problems such as the hardening soil.
CN101402756 adopts cheap calcium carbonate as body material, reduces the consumption of polyethylene, and production technology is simple, and cost is low, and efficiency is high, and degradation time is controlled.But the method adopts that calcium carbonate addition is excessive causes the use time to shorten, mechanical property deviation, and promote without adding biodegradation, degraded can be thorough not.
For simple oxidative degradation plastics (photodegradable plastics), cannot degrade in unglazed situation, cause the problem that the plastics being embedded in soil such as agricultural mulching cannot be degraded；Unstable for environment, or the insufficient place of illumination, the degradation speed of mulch film cannot effectively control.
Therefore, this area needs exploitation a kind of less costly, the controlled and biodegradable plastic master batch of controllable oxidization thoroughly of degrading.
Summary of the invention
For the deficiencies in the prior art, an object of the present invention is in that to provide a kind of controllable oxidization biodegradable plastic master batch, described plastic master batch can controlled degradation, and degraded is comparatively thorough, and the mechanical property of described plastic master batch is better simultaneously, less costly.
The present invention is achieved through the following technical solutions:
A kind of controllable oxidization biodegradable plastic master batch includes: inorganic filler, carrier, oxidative degradation accelerator, biodegradation promotor and Degradation Control agent；Wherein, described Degradation Control agent is antioxidant.
Plastic master batch of the present invention contains oxidative degradation accelerator, biodegradation promotor and Degradation Control agent simultaneously, can according to the ratio of Degradation Control agent and degradation of promoter, obtain the plastic master batch different degradation rates in equivalent environment, and then need to realize the controllable oxidization biodegradation of plastic master batch according to different.The content of degradation of promoter is more many, and the content of Degradation Control agent is more low, then the time degraded is more short.
In different environment (such as illumination, ambient temperature etc.), plastic master batch provided by the invention can also adopt different formula, while meeting instructions for use, can thoroughly be degraded after discarded.As packaging bag is complete in use, discard in environment, under the impact of the environmental factorss such as illumination and degradation of promoter own, Degradation Control agent is constantly consumed, being exhausted, packaging bag, under the combined effect of oxidative degradation accelerator and biodegradation promotor, is degraded rapidly.
Plastic master batch of the present invention has oxidative degradation and biodegradable dual variation method system, and by regulating content and the ratio of oxidative degradation accelerator, Degradation Control agent and biodegradation promotor, Oxidative Degradation Process and biodegradation process are optimized, achieve both linkages, make plastic master batch have the ability of environment specific aim and controlled degradation.
Preferably, the nucleocapsid structure that plastic master batch of the present invention is made up of oxidative degradation accelerator, biodegradation promotor, inorganic filler and Degradation Control agent obtains with carrier is blended；The kernel of described nucleocapsid structure includes inorganic filler and biodegradation agent；The outer layer of described nucleocapsid structure includes oxidative degradation accelerator and Degradation Control agent.
Preferably, the combination of in the oxide of transition metal, halogenide, stearate, laruate, carboxylate, carbaminate or thiophosphate any a kind or at least 2 kinds of oxidative degradation accelerator of the present invention；The combination of described transition metal preferably be selected from titanium, ferrum, manganese, cobalt or rare earth element any a kind or at least 2 kinds.
The example of the oxide of typical but non-limiting transition metal has anatase-type titanium oxide, cerium oxide, lanthana or rear-earth-doped titanium dioxide etc..
The halogenide of described transition metal selected from fluoride, chloride, bromide containing or iodide in the combination of any a kind or at least 2 kinds, the halogenide of typical but non-limiting transition metal can be iron chloride, manganese chloride, cobaltous chloride etc..
The stearate of typical but non-limiting transition metal can be ferric stearate, cobaltous octadecanate, manganese stearate, copper stearate etc..
The moon silicate of typical but non-limiting transition metal can be lauric acid ferrum, lauric acid manganese, lauric acid copper, cobalt laurate etc..
The carbaminate of typical but non-limiting transition metal can be that Methyl disulfide is for iron phosphate, ferric diethyl dithiocarbamate, dibutyl dithiocaarbamate ferrum, diethyldithiocar bamic acid rare earth, dibutyl dithio phosphoric acid rare earth etc..
Preferably, the combination of in ferric stearate, manganese stearate, anatase titanium dioxide, cobalt laurate, iron chloride, lauric acid manganese, carbamic acid ferrum, carbamic acid manganese, cobaltous chloride, the manganese dioxide any a kind or at least 2 kinds of oxidative degradation accelerator of the present invention.
The typical but non-limiting example of combination of described oxidative degradation accelerator includes: the combination etc. of the combination of the combination of anatase-type titanium oxide and ferric stearate, manganese stearate and ferric stearate, anatase-type titanium oxide and manganese stearate.
Preferably, in described plastic master batch, the parts by weight containing oxidative degradation accelerator are 1～10 weight portion, for instance 1.5 weight portions, 1.8 weight portions, 2.4 weight portions, 2.9 weight portions, 3.1 weight portions, 3.6 weight portions, 3.8 weight portions, 4.2 weight portions, 4.7 weight portions, 5.5 weight portions, 6.4 weight portions, 6.8 weight portions, 6.9 weight portions, 7.1 weight portions, 7.6 weight portions, 7.8 weight portions, 8.2 weight portions, 9.7 weight portions, 10 weight portions etc..
Preferably, the combination of in amylomaize, tapioca, chitosan, glycerol and methylcellulose any a kind or at least 2 kinds of described biodegradation promotor, the combination etc. of the combination of described combination such as amylomaize and tapioca, methylcellulose and the combination of the combination of the combination of glycerol, chitosan and tapioca, amylomaize and glycerol, methylcellulose and tapioca.
In conventional corn, amylose content is 22%～27%, and in high straight-chain maize, amylose content is more than 40%.
Preferably, in described plastic master batch, the parts by weight containing biodegradation promotor are 1～70 weight portion, for instance 1.5 weight portions, 3.8 weight portions, 8.4 weight portions, 13.9 weight portions, 18.1 weight portions, 22.6 weight portions, 29.8 weight portions, 32.2 weight portions, 39.7 weight portions, 41.5 weight portions, 45.8 weight portions, 48.4 weight portions, 52.9 weight portions, 59.1 weight portions, 63.6 weight portions, 68.8 weight portions, 69.2 weight portions, 69.8 weight portions etc..
Preferably, the combination of in amine antioxidants and/or phenolic antioxidant any a kind or at least 2 kinds of antioxidant of the present invention.
Preferably, described amine antioxidants selected from N-isopropyl-N '-diphenyl-para-phenylene diamine (also known as: age resistor IPPD), N, the combination of any a kind or at least 2 kinds in N '-diphenyl-para-phenylene diamine (also known as antioxidant DPPD) or N-phenyl-a-naphthylamine (also known as antioxidant PA), the combination of described combination such as age resistor IPPD and antioxidant DPPD, the combination of age resistor IPPD and antioxidant PA, the combination etc. of age resistor IPPD, antioxidant DPPD and antioxidant PA.
Preferably, described phenolic antioxidant is selected from 2, 6-di-t-butyl-PAP, 2, 6-ditertbutylparacresol, 2, 6-di-t-butyl paranitrophenol, 2, 6-di-t-butyl-4 (dimethyl aminomethyl) phenol, β-(3, 5-di-tert-butyl-hydroxy phenyl) propanoic acid octadecanol ester (also known as antioxidant: 1076) or four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propanoic acid] combination of in pentaerythritol ester (also known as antioxidant 1010) any a kind or at least 2 kinds, described combination such as 2, the combination of 6-ditertbutylparacresol and antioxidant 1010, 2, 6-di-t-butyl-PAP and 2, the combination etc. of 6-di-t-butyl-4 (dimethyl aminomethyl) phenol.
Preferably, the parts by weight containing antioxidant in described plastic master batch are 1～2 weight portion, for instance 1.1 weight portions, 1.3 weight portions, 1.6 weight portions, 1.7 weight portions, 1.8 weight portions, 1.9 weight portions etc..
According to local natural conditions, add plastic master batch provided by the invention in plastic substrate reshaping in proportion, it is possible to ensure the controlled degradation of plastic.
The present invention selects inorganic filler and biodegradation promotor as the innermost layer of masterbatch and masterbatch core, is requisite component in masterbatch, its character determining masterbatch and purposes.
Inorganic filler can cause stress to concentrate in plastic, absorbs ultraviolet light and causes surrounding molecular photooxidation, and then produces be full of cracks, accelerated degradation；Increase OTR oxygen transmission rate, and then increase plastic oxygen uptake value, promote oxidative degradation.Inorganic filler can accelerate goods air slaking under air and water effect, increases micropore, promotes degraded.
Biodegradation promotor can not only cause stress to concentrate, and increases OTR oxygen transmission rate, and is the bait attracting to digest the microorganism of plastic.A part for microorganism food food chain can be become when oxidative degradation makes plastic molecular weight and molecular weight to short carbon chain.Inorganic filler lays particular emphasis on accelerated degradation when auxiliary is exposed to the plastic oxidative degradation of air and water, and biodegradation promotor lays particular emphasis on the accelerated degradation after the oxidative degradation accepting buried plastic.
The different adding proportions of inorganic filler and biodegradation promotor determine the difference degraded scheme of plastic.
Preferably, the combination of in technical grade calcium carbonate powder, dolomite powder, Pulvis Talci powder, kaolin powder or bentonite powder any a kind or at least 2 kinds of inorganic filler of the present invention, the combination etc. of described combination such as technical grade calcium carbonate powder and the combination of dolomite powder, Pulvis Talci powder and the combination of kaolin powder, bentonite powder and technical grade ground calcium carbonate powder.
Preferably, the granularity of described inorganic filler is more than 800 orders, such as 830 orders, 880 orders, 930 orders, 970 orders, 1270 orders, 1360 orders, 1490 orders, 1585 orders, 1670 orders, 1850 orders, 1945 orders, 2035 orders, 2040 orders, 2235 orders, 2500 orders etc., preferably 1250～2000 order, it is preferred that 1250 orders.
Preferably, in described plastic master batch, the parts by weight containing inorganic filler are 40～70 weight portions, for instance 40.7 weight portions, 41.5 weight portions, 45.8 weight portions, 48.4 weight portions, 52.9 weight portions, 55.1 weight portions, 58.6 weight portions, 62.8 weight portions, 65.2 weight portions, 68.7 weight portions etc..
Preferably, described carrier is selected from polyethylene；The combination of described polyethylene preferably be selected from Low Density Polyethylene (LDPE), linear low density polyethylene (LLDPE) or high density polyethylene (HDPE) (HDPE) any a kind or at least 2 kinds, the combination of described combination such as LDPE and LLDPE, the combination of HDPE and LLDPE, LDPE, LLDPE and HDPE combination etc..
Preferably, the parts by weight containing carrier in described plastic master batch are 30～50 weight portions, for instance 30.7 weight portions, 31.5 weight portions, 35.8 weight portions, 38.4 weight portions, 42.9 weight portions, 45.1 weight portions, 48.6 weight portions etc..
Carrier of the present invention all can pass through commercially available, and the model of typical but non-limiting carrier has: the 2426K of industrial group of Li Ande Basel；18D and the 18D0 of Daqing petrochemical；The 2426F of Maoming Petrochemical；The 7050 of middle petrochemical industry good fortune refining；Raise 2426H and the 2426K of sub-BASF；DFDA-2001 and the DFDA-7042 in middle petrochemical industry Guangzhou；Taiwan mould 3224；The 218W of Saudi Arabia SABIC；The HD5301AA of Shanghai match section；Raise the 5000S etc. of sub-petrochemical industry.
When plastic uses, the Degradation Control agent in master batch controls plastics and keeps due life-span and function in use；After plastic abandoned, when, after Degradation Control agent approach exhaustion, in master batch, oxidative degradation accelerator (mainly some nontoxic metal ions) reduces molecular weight by oxidation reaction so that polymer becomes fragile, it is easier to microbial decomposition；And biodegradation promotes that material (mainly some natural plant celluloses) promotes microbial growth, a large amount of microorganism phagocytosis is promoted to be degraded to the polyethylene molecule of microorganism decomposable asymmetric choice net rank；It addition, the high amount of inorganic filler filled in plastics, weakening the active force between polymer segment, after the free radical chain-breaking reaction generation that the weakening of secondary bond power makes light degradation cause, the mechanical properties decrease of plastics is particularly evident.
Better in order to what each component of plastic master batch can be bonded, evenly, described plastic master batch also includes modifying agent, dispersant and binding agent in dispersion.
The effect of modifying agent is the compatibility between increase masterbatch core (inorganic filler and biodegradation promotor) same to carrier (such as polyethylene) and affinity, makes masterbatch core organically combine with carrier.
Preferably, the combination of in titanate coupling agent, aluminate coupling agent or silane coupler any a kind or at least 2 kinds of described modifying agent.
Containing different two groups of chemical property in coupling agent molecule structure, one is the group of parent's inorganic matter, easily and mineral surfaces chemically reactive；Another is organophilic group, can with synthetic resin or other polymer generation chemical reaction or generate hydrogen bond and be dissolved in wherein, and therefore coupling agent is referred to as " molecular bridge ".The present invention selects coupling agent as the modifying agent of plastic master batch, it is therefore an objective to the inorganic filler in masterbatch core can be combined preferably with the carrier of outer layer.
Modifying agent of the present invention all can pass through commercially available, the example of typical but non-limiting modifying agent has: single alcoxyl fatty acid ester type titanate coupling agent is (such as NDZ-131, or the KR-TTS of Kenrich oil company of the U.S.), single alcoxyl phosphate type titanate coupling agent is (such as NDZ-102, or the KR-12 of Kenrich petrochemistry company of the U.S.), single alcoxyl Pyrophosphate Type Yitanate Coupling Agent is (such as NDZ-201, or the KR-38S of Kenrich petrochemistry company of the U.S.), fluoroacetic acid chelating titanate coupling agent, ethylene glycol chelating titanate coupling agent etc..
Preferably, the parts by weight containing modifying agent in described plastic master batch are 1～5 weight portion, for instance 1.1 weight portions, 1.3 weight portions, 1.6 weight portions, 2.2 weight portions, 2.8 weight portions, 3.3 weight portions, 3.6 weight portions, 4.2 weight portions, 4.8 weight portions etc..
The present invention selects coupling agent as modifying agent, changes the compatibility at organic and inorganic interface.
Dispersant can promote that oleophylic state masterbatch core and oxidation accelerator, Biostimulation agent ground are dispersed, it is prevented that it forms fritter, improves masterbatch ground processing fluidity, gloss and feel thereof simultaneously.
Preferably, the combination of in stearic acid or stearate any a kind or at least 2 kinds of described dispersant, preferred stearic acid, barium stearate, zinc stearate, calcium stearate, magnesium stearate, in the combination of any a kind or at least 2 kinds, it is preferred that stearic acid and/or zinc stearate.
The typical but non-limiting example that combines of described dispersant has the combination of stearic acid and magnesium stearate, the combination of zinc stearate and magnesium stearate, the combination etc. of stearic acid, barium stearate and calcium stearate.
Preferably, the parts by weight containing dispersant in described plastic master batch are 1～5 weight portion, for instance 1.1 weight portions, 1.3 weight portions, 1.6 weight portions, 2.2 weight portions, 2.8 weight portions, 3.3 weight portions, 3.6 weight portions, 4.2 weight portions, 4.8 weight portions etc..
In the present invention, dispersant serves the effect of dispersed each component, improves the uniformly dispersed of each component.
Preferably, described binding agent is selected from paraffin, Tissuemat E, OPE, ethylene bis stearamide, the combination of any a kind or at least 2 kinds of white oil, the combination of described combination such as paraffin and Tissuemat E, the combination of ethylene bis stearamide and white oil, the combination etc. of the combination of Tissuemat E, paraffin and ethylene bis stearamide, paraffin and OPE.
nullPreferably，In described plastic master batch, the parts by weight containing binding agent are 1～20 weight portion，Such as 1.1 weight portion、1.7 weight portions、2.6 weight portions、3.2 weight portions、3.8 weight portions、4.3 weight portions、4.6 weight portions、5.2 weight portions、5.8 weight portions、6.7 weight portions、7.2 weight portions、7.7 weight portions、8.3 weight portions、8.5 weight portions、9.1 weight portions、9.6 weight portions、9.8 weight portions、10.2 weight portion、10.6 weight portion、11.2 weight portion、12.6 weight portion、13.3 weight portion、13.6 weight portion、14.2 weight portion、15.2 weight portion、15.8 weight portion、16.7 weight portion、17.2 weight portion、17.7 weight portion、18.3 weight portion、18.5 weight portion、19.1 weight portion、19.6 weight portion、19.8 weight portion etc..
As optimal technical scheme, controllable oxidization biodegradable plastic master batch of the present invention includes following component by weight:
As optional technical scheme, controllable oxidization biodegradable plastic master batch of the present invention includes following component by weight:
Preferably, described controllable oxidization biodegradable plastic master batch includes following component by weight:
Alternatively, described controllable oxidization biodegradable plastic master batch includes following component by weight:
The two of the purpose of the present invention are in that the preparation method providing a kind of controllable oxidization biodegradable plastic master batch as described in one of the object of the invention, and described method is a step " self-assembly method ".
The preparation method of controllable oxidization biodegradable plastic master batch of the present invention comprises the steps:
(1) inorganic filler and biodegradation promotor dried and mix, preparing masterbatch core；
(2) it is dividedly in some parts modifying agent, makes coupling layer self assembly graft to masterbatch core periphery；
(3) oxidative degradation accelerator and Degradation Control agent are added, mixing；
(4) dispersant is added, mixing；
(5) carrier is added, mixing；
(6) add binding agent, mix balling-up, obtain ball material；
Alternatively, after step (6), following steps are carried out:
(7) ball material extrusion is obtained degradative plastics master batch.
Can being that modifying agent is divided into 3～7 deciles described in step (2), gradation adds in reactor in batches, and add needs interval 2～4min every time.
Preferably, described mixing apparatus is selected from any a kind in V-Mixer, high-speed mixer；
Preferably, in step (1)～(7), the incorporation time in high-speed mixer is totally not less than 40min；
Preferably, the temperature of described mixing is 100～140 DEG C, such as 103 DEG C, 118 DEG C, 126 DEG C, 137 DEG C, 139 DEG C etc., rotating speed is 400～800rpm, for instance 410rpm, 450rpm, 505rpm, 560rpm, 685rpm, 750rpm, 770rpm, 790rpm etc..
Preferably, the temperature of step (1) described mixing is 110～140 DEG C, such as 113 DEG C, 118 DEG C, 126 DEG C, 137 DEG C, 139 DEG C etc., rotating speed is 400～600rpm, such as 410rpm, 450rpm, 505rpm, 560rpm, 585rpm etc., time is 10～20min, for instance 11min, 14min, 16min, 18min, 19min etc..
Preferably, the temperature of step (2) described mixing is 100～130 DEG C, such as 103 DEG C, 108 DEG C, 116 DEG C, 122 DEG C, 129 DEG C etc., rotating speed is 600～800rpm, such as 610rpm, 650rpm, 705rpm, 760rpm, 785rpm, 790rpm etc., time is 18～20min, for instance 18.5min, 19min, 19.5min etc..
Preferably, the temperature of step (3) and step (4) described mixing is 100～130 DEG C, for instance 103 DEG C, 108 DEG C, 116 DEG C, 122 DEG C, 129 DEG C etc., rotating speed is 600～800rpm, such as 610rpm, 650rpm, 705rpm, 760rpm, 785rpm, 790rpm etc., the time is 5min.
Preferably, the temperature of step (5) described mixing is 100～110 DEG C, such as 101 DEG C, 103 DEG C, 106 DEG C, 107 DEG C, 109 DEG C etc., rotating speed is 600～800rpm, such as 610rpm, 650rpm, 705rpm, 760rpm, 785rpm, 790rpm etc., time is 3～5min, for instance 3.3min, 3.8min, 4.0min, 4.2min, 4.7min, 4.9min etc..
Preferably, the temperature of step (6) described mixing is 100～110 DEG C, such as 101 DEG C, 103 DEG C, 106 DEG C, 107 DEG C, 109 DEG C etc., rotating speed is 600～800rpm, such as 610rpm, 650rpm, 705rpm, 760rpm, 785rpm, 790rpm etc., time is 5～10min, for instance 5.3min, 5.8min, 6.0min, 6.2min, 7.7min, 7.9min, 8.3min, 8.8min, 9.4min, 9.7min etc..
The three of the purpose of the present invention are in that to provide the using method of a kind of controllable oxidization biodegradable plastic master batch as described in one of the object of the invention, described method is add in plastic substrate by the degradative plastics master batch that step (7) prepares, any a kind of molding mode in injection mo(u)lding, extrusion molding or blowfilm shaping, makes degradable plastic product；
Preferably, in described plastic, the addition of degradative plastics master batch accounts for 1～30wt% of plastic degradation goods gross mass, for instance 1.1wt%, 1.4wt%, 2.0wt%, 2.8wt%, 6.8wt%, 10.4wt%, 11.5wt%, 13.7wt%, 18.6wt%, 21wt%, 23.5wt%, 27.8wt%, 28.7wt%, 29.4wt% etc..
The preparation method of controllable oxidization biodegradable plastic master batch of the present invention, under the effect of modifying agent, coupling agent is formed outside masterbatch core, carrier (polyethylene) and masterbatch core are organically combined, and under the effect of modifying agent, all the other components of described plastic master batch are wrapped in outside masterbatch core by self assembly, obtain ball material, obtain ball material through extruding after.
Compared with prior art, there is advantages that
(1) the Homogeneous phase mixing compositions such as the oxidative degradation accelerator of different compositions and content, biodegradation promotor in the structure of degradative plastics master batch of the present invention, and according to actual environment optimization, linkage oxidative degradation and biodegradable dual variation method system so that it is there is the ability of environment specific aim and controlled degradation；
(2) preparation method of degradative plastics master batch of the present invention is a step " self assembly " method, have only to raw material blended, balling-up in proportion, pelletize, technique is simple, easy and simple to handle, it is favorably improved the mixing dispersibility of plastic master batch, provides a kind of effective solution for solving organic and inorganic interface compatibility and dispersed sex chromosome mosaicism.
Accompanying drawing explanation
Fig. 1 is the ball material photo that embodiment 1 step (6) self assembly mixing balling-up obtains；
Fig. 2 is the ball material photo that embodiment 2 step (6) self assembly mixing balling-up obtains；
Fig. 3 is the degradation master batch photo that embodiment 1 prepares；
Fig. 4 is the degradation master batch photo that embodiment 2 prepares；
Fig. 5 is the infrared figure that degradable film prepared by embodiment 1 changes with ageing time；
Fig. 6 is the carbonyl index figure that degradable film prepared by embodiment 1 changes with ageing time with comparative example 1～3；
Fig. 7 is the elongation at break figure that degradable film prepared by embodiment 1 changes with ageing time with comparative example 1～3；
Fig. 8 is comparison diagram before and after the aging 254h of degradable film of embodiment 1 preparation；
Fig. 9 is the infrared figure that degradable film prepared by embodiment 2 changes with ageing time；
Figure 10 is the carbonyl index figure that degradable film prepared by embodiment 1 changes with ageing time with comparative example 1～3；
Figure 11 is the elongation at break figure that degradable film prepared by embodiment 2 changes with ageing time with comparative example 1～3；
Figure 12 is comparison diagram before and after the aging 254h of degradable film of embodiment 1 preparation.
Detailed description of the invention
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art understand the present invention it will be clearly understood that described embodiment is only help, are not construed as the concrete restriction to the present invention.
The preparation method of a kind of controllable oxidization biodegradable plastic master batch, comprises the steps:
(1) putting in high-speed mixer by inorganic filler powder 40～70 parts and biodegradation promotor 1～70 part, control temperature at 110～140 DEG C, rotating speed controls at 400～600rpm, mix and blend 10～20min；
(2) modifying agent 1～5 part is divided into five equal portions, is dividedly in some parts in high-speed mixer, every minor tick 3min；Temperature controls at 100～130 DEG C, and rotating speed controls at 600～800rpm, mix and blend 18～20min；
(3) by oxidative degradation accelerator 1～10 part and 1～2 part of addition high-speed mixer of Degradation Control agent, temperature controls at 100～130 DEG C, and rotating speed controls at 600～800rpm, mix and blend 5min；
(4) by 1～5 part of addition high-speed mixer of dispersant, temperature controls at 100～130 DEG C, and rotating speed controls at 600～800rpm, mix and blend 5min；
(5) by carrier 30 as one kind～50 part addition high-speed mixer, temperature controls at 100～110 DEG C, and rotating speed controls at 600～800rpm, mix and blend 3～5min；
(6) by 1～20 part of addition high-speed mixer of binding agent, temperature controls at 100～110 DEG C, and rotating speed controls at 600～800rpm, mix and blend 5～10min, and balling-up discharging obtains ball material；
(7) ball material being proceeded to double screw extruder, temperature controls to extrude at 150～180 DEG C, and the material of extrusion is water cooled, pelletizing prepares degradative plastics master batch.
A kind of using method of controllable oxidization biodegradable plastic master batch:
(8) the degradative plastics master batch that will obtain, adds according to the addition of 1～30wt% and enters plastic substrate LDPE, and any a kind of molding mode in injection mo(u)lding, extrusion molding or blowfilm shaping, makes degradable plastic product.
Embodiment 1～6
The formula that table 1 is controllable oxidization biodegradable plastic master batch described in the embodiment of the present invention 1～6 forms:
The formula composition of controllable oxidization biodegradable plastic master batch described in table 1 embodiment 1～6
Described in embodiment 1～6, the preparation method of controllable oxidization biodegradable plastic master batch comprises the steps:
(1) putting in high-speed mixer by the inorganic filler powder of formula ratio and biodegradation promotor, control temperature at 110～140 DEG C, rotating speed controls at 400～600rpm, mix and blend 10～20min；
(2) modifying agent of formula ratio is divided into five equal portions, is dividedly in some parts in high-speed mixer, every minor tick 3min；Temperature controls at 100～130 DEG C, and rotating speed controls at 600～800rpm, mix and blend 18～20min；
(3) the oxidative degradation accelerator of formula ratio and degradation of promoter being added in high-speed mixer, temperature controls at 100～130 DEG C, and rotating speed controls at 600～800rpm, mix and blend 5min；
(4) being added in high-speed mixer by the dispersant of formula ratio, temperature controls at 100～130 DEG C, and rotating speed controls at 600～800rpm, mix and blend 5min；
(5) being added in high-speed mixer by the carrier of formula ratio, temperature controls at 100～110 DEG C, and rotating speed controls at 600～800rpm, mix and blend 3～5min；
(6) being added in high-speed mixer by the binding agent of formula ratio, temperature controls at 100～110 DEG C, and rotating speed controls at 600～800rpm, mix and blend 5～10min, and balling-up discharging obtains ball material；(Fig. 1 is the ball material photo that embodiment 1 step (6) self assembly mixing balling-up obtains to the ball material that embodiment 1 and embodiment 2 obtain as depicted in figs. 1 and 2；Fig. 2 is the ball material photo that embodiment 2 step (6) self assembly mixing balling-up obtains)；
(7) ball material being proceeded to double screw extruder, temperature controls to extrude at 150～180 DEG C, and the material of extrusion is water cooled, pelletizing prepares degradative plastics master batch；(Fig. 3 is the degradation master batch photo that embodiment 1 prepares to the degradation master batch that embodiment 1 and embodiment 2 obtain as shown in Figure 3 and Figure 4；Fig. 4 is the degradation master batch photo that embodiment 2 prepares).
The degradative plastics master batch that will obtain, adds according to the addition of 10wt% and enters plastic substrate good fortune refining LDPE7050, and through inflation film manufacturing machine blowfilm shaping, temperature controls, at 130～180 DEG C, to make degradable plastic film.Film thickness is 10～30 μm.
Embodiment 7
The preparation method of a kind of controllable oxidization biodegradable plastic master batch comprises the steps:
(1) putting in high-speed mixer by 40 parts of the Pulvis Talci powder of 800 orders, methylcellulose 30 parts and chitosan 40 parts, control temperature at 110～140 DEG C, rotating speed controls at 400～600rpm, mix and blend 10～20min；
(2) titanate coupling agent 5 parts is divided into five equal portions, is dividedly in some parts in high-speed mixer, every minor tick 3min；Temperature controls at 100～130 DEG C, and rotating speed controls at 600～800rpm, mix and blend 18～20min；
(3) by cobalt laurate 7 parts, 3 parts of iron chloride, age resistor IPPD1 part and 1 part of addition high-speed mixer of antioxidant DPPD, temperature controls at 100～130 DEG C, and rotating speed controls at 600～800rpm, mix and blend 5min；
(4) by magnesium stearate 4 parts and 1 part of addition high-speed mixer of stearic acid, temperature controls at 100～130 DEG C, and rotating speed controls at 600～800rpm, mix and blend 5min；
(5) LLDPE50 part being added in high-speed mixer, temperature controls at 100～110 DEG C, and rotating speed controls at 600～800rpm, mix and blend 3～5min；
(6) by 20 parts of addition high-speed mixers of ethylene bis stearamide, temperature controls at 100～110 DEG C, and rotating speed controls at 600～800rpm, mix and blend 5～10min, and balling-up discharging obtains ball material；
(7) ball material being proceeded to double screw extruder, temperature controls to extrude at 150～180 DEG C, and the material of extrusion is water cooled, pelletizing prepares degradative plastics master batch.
The degradative plastics master batch that will obtain, adds according to the addition of 1wt% and enters plastic substrate LDPE, and through blowfilm shaping mode, make degradation plastic packaging bag.
Embodiment 8
The preparation method of a kind of controllable oxidization biodegradable plastic master batch comprises the steps:
(1) putting in high-speed mixer by 10 parts of the dolomite powder of 2500 orders, 40 parts of the bentonite powder of 2300 orders and tapioca 1 part, control temperature at 110～140 DEG C, rotating speed controls at 400～600rpm, mix and blend 10～20min；
(2) silane coupler 1 part is divided into five equal portions, is dividedly in some parts in high-speed mixer, every minor tick 3min；Temperature controls at 100～130 DEG C, and rotating speed controls at 600～800rpm, mix and blend 18～20min；
(3) by carbamic acid ferrum 0.5 part, cobaltous chloride 0.5 part, antioxidant 1010 0.5 part and 0.5 part of addition high-speed mixer of antioxidant PA, temperature controls at 100～130 DEG C, and rotating speed controls at 600～800rpm, mix and blend 5min；
(4) by copper stearate 0.1 part and 0.9 part of addition high-speed mixer of barium stearate, temperature controls at 100～130 DEG C, and rotating speed controls at 600～800rpm, mix and blend 5min；
(5) HDPE30 part being added in high-speed mixer, temperature controls at 100～110 DEG C, and rotating speed controls at 600～800rpm, mix and blend 3～5min；
(6) by 1 part of addition high-speed mixer of paraffin, temperature controls at 100～110 DEG C, and rotating speed controls at 600～800rpm, mix and blend 5～10min, and balling-up discharging obtains ball material；
(7) ball material being proceeded to double screw extruder, temperature controls to extrude at 150～180 DEG C, and the material of extrusion is water cooled, pelletizing prepares degradative plastics master batch.
The degradative plastics master batch that will obtain, adds according to the addition of 30wt% and enters plastic substrate HDPE, and through injection molding, make degradation plastic mess-tin.
Comparative example
Select in the good fortune refining LDPE7050 1(figure as a comparison case not adding degradative plastics master batch as LDPE)；
Select commercial products NewQuantumHoudings(U.S. quantum Pty Ltd) Oxium1010 2(figure as a comparison case in be business-1)；
Select commercial products NewQuantumHoudings(U.S. quantum Pty Ltd) Ecoplas 3(figure as a comparison case in be business-2).
The comparative sample of Fig. 5-Fig. 7, Fig. 9-Figure 11 is pure ldpe film, the commercial product-1 of equal master batch addition 10wt% and commercial product-2.
Performance test:
Plastic sheeting prepared by embodiment 1～6 and comparative example 1～3 is carried out aging, ageing process carries out aging according to national standard mark " plastics laboratory light source exposes experimental technique " (GB/T16422.1-2006), and selection equipment is CLM--SN-500A ultraviolet xenon lamp aging case.
Product for aging front and back carries out test as follows:
Tensile property: utilize LDS-500 electronic tensile machine to measure the tensile property of plastics according to national standard " stretched plastic film test method " (GB13022-91)；
Carbonyl index: the plastic sheeting of aging front and back is carried out infrared test, and calculates carbonyl index.
2020cm-1For C-H functional group, invariant position in ageing process；With 2020cm-1It is defined as carbonyl index as benchmark；1717cm-1Locating as carbonyl peak is produce in ageing of plastics process, and aging more serious carbonyl peak is more strong；Described carbonyl index is calculated according to equation below:
CI is carbonyl index, and A is peak area.
The performance test results of embodiment 1～6 and comparative example 1～3 is as shown in table 2:
Table 2 is the performance test results of embodiment 1～6 and comparative example 1～3
| Test examples | Elongation at break (%) after 254h | Carbonyl index after 254h |
| Embodiment 1 | 0 | 23.4 |
| Embodiment 2 | 0 | 18.3 |
| Embodiment 3 | 0 | 19.4 |
| Embodiment 4 | 0 | 17.9 |
| Embodiment 5 | 0 | 26.5 |
| Embodiment 6 | 0 | 22.8 |
| Comparative example 1 | 312 | 4.2 |
| Comparative example 2 | 0 | 10.8 |
| Comparative example 3 | 0 | 9.5 |
As can be seen from Table 2, degradative plastics master batch provided by the invention has good degradation property, and after 254h, namely carbonyl index can reach about 20, and elongation at break almost reduces to 0.
Shown in the performance test results such as Fig. 5～7 and Fig. 9～11 of embodiment 1, embodiment 2 and comparative example 1～3, (Fig. 6 is the carbonyl index figure that degradable film prepared by embodiment 1 changes with ageing time with comparative example 1～3；Fig. 7 is the elongation at break figure that degradable film prepared by embodiment 1 changes with ageing time with comparative example 1～3；Figure 10 is the carbonyl index figure that degradable film prepared by embodiment 1 changes with ageing time with comparative example 1～3；Figure 11 is the elongation at break figure that degradable film prepared by embodiment 2 changes with ageing time with comparative example 1～3；)；
(Fig. 5 is the infrared figure that degradable film prepared by embodiment 1 changes with ageing time to the infrared figure that Fig. 5 and Fig. 9 respectively embodiment 1 and 2 changes with ageing time；Fig. 9 is the infrared figure that degradable film prepared by embodiment 2 changes with ageing time)；
Fig. 8 and Figure 12 is that (Fig. 8 is comparison diagram before and after the aging 254h of degradable film of embodiment 1 preparation to the embodiment 1 and 2 contrast photo before and after aging 254h respectively；Figure 12 is comparison diagram before and after the aging 254h of degradable film of embodiment 1 preparation).
Applicant states, the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment, but the invention is not limited in above-mentioned detailed process equipment and technological process, namely do not mean that the present invention has to rely on above-mentioned detailed process equipment and technological process could be implemented.The equivalence of each raw material of product of the present invention, it will be clearly understood that any improvement in the present invention, is replaced and the interpolation of auxiliary element, concrete way choice etc. by person of ordinary skill in the field, all falls within protection scope of the present invention and open scope.
Claims (39)
1. a controllable oxidization biodegradable plastic master batch, it is characterised in that described plastic master batch includes: inorganic filler, carrier, oxidative degradation accelerator, biodegradation promotor and Degradation Control agent；
Wherein, described Degradation Control agent is antioxidant；
The nucleocapsid structure that described plastic master batch is made up of oxidative degradation accelerator, biodegradation promotor, inorganic filler and Degradation Control agent obtains with carrier is blended；The kernel of described nucleocapsid structure includes inorganic filler and biodegradation agent；The outer layer of described nucleocapsid structure includes oxidative degradation accelerator and Degradation Control agent；
The combination of in the oxide of transition metal, halogenide, stearate, laruate, carbaminate or sulfate-phosphate any a kind or at least 2 kinds of described oxidative degradation accelerator；The combination of in titanium, ferrum, manganese, cobalt or rare earth element any a kind or at least 2 kinds of described transition metal.
2. plastic master batch as claimed in claim 1, it is characterized in that, the combination of in ferric stearate, manganese stearate, anatase titanium dioxide, cobalt laurate, iron chloride, lauric acid manganese, carbamic acid ferrum, carbamic acid manganese, cobaltous chloride, the manganese dioxide any a kind or at least 2 kinds of described oxidative degradation accelerator.
3. plastic master batch as claimed in claim 1, it is characterised in that in described plastic master batch, the parts by weight containing oxidative degradation accelerator are 1～10 weight portion.
4. plastic master batch as claimed in claim 1, it is characterised in that the combination of in amylomaize, tapioca, chitosan, glycerol and methylcellulose any a kind or at least 2 kinds of described biodegradation promotor.
5. plastic master batch as claimed in claim 1, it is characterised in that in described plastic master batch, the parts by weight containing biodegradation promotor are 1～70 weight portion.
6. plastic master batch as claimed in claim 1, it is characterised in that the combination of in amine antioxidants and/or phenolic antioxidant any a kind or at least 2 kinds of described antioxidant.
7. plastic master batch as claimed in claim 6, it is characterised in that described amine antioxidants is selected from N-isopropyl-N '-diphenyl-para-phenylene diamine, N, N ' combination of in-diphenyl-para-phenylene diamine or N-phenyl-a-naphthylamine any a kind or at least 2 kinds.
8. plastic master batch as claimed in claim 6, it is characterized in that, described phenolic antioxidant is selected from 2,6-di-t-butyl-PAP, 2,6-ditertbutylparacresol, 2,6-di-t-butyl paranitrophenol, 2,6-di-t-butyl-4 (dimethyl aminomethyl) phenol, β-(3,5-di-tert-butyl-hydroxy phenyl) combination of in propanoic acid octadecanol ester or four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester any a kind or at least 2 kinds.
9. plastic master batch as claimed in claim 1, it is characterised in that in described plastic master batch, the parts by weight containing antioxidant are 1～2 weight portion.
10. plastic master batch as claimed in claim 1, it is characterised in that the combination of in ground calcium carbonate powder, dolomite powder, Pulvis Talci powder, kaolin powder or bentonite powder any a kind or at least 2 kinds of described inorganic filler.
11. plastic master batch as claimed in claim 1, it is characterised in that the granularity of described inorganic filler is more than 800 orders.
12. plastic master batch as claimed in claim 11, it is characterised in that the granularity of described inorganic filler is 1250～2000 orders.
13. plastic master batch as claimed in claim 12, it is characterised in that the granularity of described inorganic filler is 1250 orders.
14. plastic master batch as claimed in claim 1, it is characterised in that in described plastic master batch, the parts by weight containing inorganic filler are 40～70 weight portions.
15. plastic master batch as claimed in claim 1, it is characterised in that described carrier is selected from polyethylene.
16. plastic master batch as claimed in claim 15, it is characterised in that the combination of in Low Density Polyethylene, linear low density polyethylene or high density polyethylene (HDPE) any a kind or at least 2 kinds of described polyethylene.
17. plastic master batch as claimed in claim 1, it is characterised in that in described plastic master batch, the parts by weight containing carrier are 30～50 weight portions.
18. plastic master batch as claimed in claim 1, it is characterised in that described plastic master batch also includes modifying agent, dispersant and binding agent.
19. plastic master batch as claimed in claim 18, it is characterised in that the combination of in titanate coupling agent, aluminate coupling agent or silane coupler any a kind or at least 2 kinds of described modifying agent.
20. plastic master batch as claimed in claim 18, it is characterised in that in described plastic master batch, the parts by weight containing modifying agent are 1～5 weight portion.
21. plastic master batch as claimed in claim 18, it is characterised in that the combination of in stearic acid or stearate any a kind or at least 2 kinds of described dispersant.
22. plastic master batch as claimed in claim 21, it is characterised in that the combination of in stearic acid, barium stearate, zinc stearate, calcium stearate, magnesium stearate any a kind or at least 2 kinds of described dispersant.
23. plastic master batch as claimed in claim 22, it is characterised in that described dispersant is selected from stearic acid and/or zinc stearate.
24. plastic master batch as claimed in claim 18, it is characterised in that in described plastic master batch, the parts by weight containing dispersant are 1～5 weight portion.
25. plastic master batch as claimed in claim 18, it is characterised in that described binding agent is selected from paraffin, OPE, Tissuemat E, ethylene bis stearamide, the combination of any a kind or at least 2 kinds of white oil.
26. plastic master batch as claimed in claim 18, it is characterised in that in described plastic master batch, the parts by weight containing binding agent are 1～20 weight portion.
27. the plastic master batch as described in one of claim 1～26, it is characterised in that described plastic master batch includes following component by weight:
28. the plastic master batch as described in one of claim 1～26, it is characterised in that described plastic master batch includes following component by weight:
29. the preparation method of the controllable oxidization biodegradable plastic master batch as described in one of claim 1～28, it is characterised in that described method comprises the steps:
(1) inorganic filler and biodegradation promotor dried and mix, preparing masterbatch core；
(2) it is dividedly in some parts modifying agent, makes coupling layer self assembly graft to masterbatch core periphery；
(3) oxidative degradation accelerator and Degradation Control agent are added, mixing；
(4) dispersant is added, mixing；
(5) carrier is added, mixing；
(6) add binding agent, mix balling-up, obtain ball material；
(7) ball material extrusion is obtained degradative plastics master batch.
30. preparation method as claimed in claim 29, it is characterised in that mixing apparatus is selected from any a kind in V-Mixer, high-speed mixer.
31. preparation method as claimed in claim 29, it is characterised in that the temperature of described mixing is 100～140 DEG C, and rotating speed is 400～800rpm.
32. preparation method as claimed in claim 29, it is characterised in that in step (1)～(7), the incorporation time in high-speed mixer is totally not less than 40min.
33. preparation method as claimed in claim 29, it is characterised in that the temperature of step (1) described mixing is 110～140 DEG C, and rotating speed is 400～600rpm, and the time is 10～20min.
34. preparation method as claimed in claim 29, it is characterised in that the temperature of step (2) described mixing is 100～130 DEG C, and rotating speed is 600～800rpm, and the time is 18～20min.
35. preparation method as claimed in claim 29, it is characterised in that the temperature of step (3) and step (4) described mixing is 100～130 DEG C, and rotating speed is 600～800rpm, and the time is 5min.
36. preparation method as claimed in claim 29, it is characterised in that the temperature of step (5) described mixing is 100～110 DEG C, and rotating speed is 600～800rpm, and the time is 3～5min.
37. preparation method as claimed in claim 29, it is characterised in that the temperature of step (6) described mixing is 100～110 DEG C, and rotating speed is 600～800rpm, and the time is 5～10min.
38. the using method of controllable oxidization biodegradable plastic master batch as described in one of claim 1～28, it is characterized in that, described method is for add in plastic substrate by described controllable oxidization biodegradable plastic master batch, any a kind of molding mode in injection mo(u)lding, extrusion molding or blowfilm shaping, makes degradable plastic product.
39. using method as claimed in claim 38, it is characterised in that in described plastic, the addition of degradative plastics master batch is 1～30wt%.
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