CN106674728A - Easily-degradable anti-shrinkage polypropylene master batch and preparation method thereof - Google Patents
Easily-degradable anti-shrinkage polypropylene master batch and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an easily-degradable anti-shrinkage polypropylene master batch, wherein polypropylene serves as a base material, the types and the formula of the master batch are optimized, and a production process is improved. A complex antioxidant which contains a biologic antioxidant, modified nanocarbon which can obviously improve high temperature resistance, shrinkage resistance, relative tensile load, strength and toughness and elasticity modulus of the polypropylene master batch, calcium fruit fibers which can obviously improve shock resistance of the polypropylene master batch, are easily biodegradable and lower production cost, polyethylene/winter rye peptide complexes which can greatly improve low temperature resistance of the polypropylene master batch and bitter almond oil which can effectively improve lubricating property and oxidation resistance of the polypropylene master batch are scientifically compounded; the obtained compound has a synergistic effect with other processing aids; finally, the environment-friendly easily-degradable anti-shrinkage polypropylene master batch with good physical property is obtained.
Description
Technical field
The present invention relates to polypropylene masterbatch, and in particular to a kind of degradable, anti-shrink polypropylene masterbatch and preparation method thereof.
Background technology
Polypropylene is a kind of good general-purpose plastics of combination property, and its total output alreadys exceed polyvinyl chloride and turns into and is only second to
The second largest general-purpose plastics of polyethylene.Main feature：Nontoxic, tasteless, density is small, and intensity, rigidity, hardness heat resistance are superior to low
Pressure polyethylene, there is counter-bending fatigue strength higher, can have good electrical property and high-frequency insulation using at 100 degree or so
Property do not influenceed by humidity, but become fragile during low temperature, it is not wear-resisting, easily it is aging.Because it has a notch sensitivity, and heat distortion temperature it is low,
Molding shrinkage is big, hardness and wear no resistance, and limits its answering in fields such as product packaging, automobile, household electrical appliance, buildings
With in particular with the continuous expansion that PP is applied in fields such as household electrical appliance, tableware, packagings for foodstuff.
Polypropylene belongs to semicrystalline resin, and its molding shrinkage is generally 1.4-2.6%, with acrylonitrile-butadiene-benzene
(molding shrinkage is 0.4- to the amorphous materialses such as ethylene-dien terpolymer (ABS), polystyrene (PS), makrolon (PC)
0.8%) compared to much greater.Molding shrinkage herein, also known as secondary shrinkage factor, refers to that material is molded system after moulding
Size difference between product and mold cavity.Plastic is fetched into from mould to be stablized in this period of time, and size still occurs small
Change, one kind change be to continue with shrink, this shrink be referred to as after-contraction.Another kind change is some hydroscopic plastics because of moisture absorption
There is expansion.The control of polyacrylic shrinkage factor is applied to that range effects are larger, during the injection, storage and use in product
Shrinkage behavior often occurs, causes product to produce warpage, it is local to produce internal stress and product size unstable.Therefore, reduce
The shrinkage factor of PP turns into the important research direction for improving PP performances.
At present, disclosed anti-shrink polypropylene material is more:The A of Chinese patent CN 104140590 disclose one
Polypropylene film material that kind of heat resistanceheat resistant is shunk and preparation method thereof, the polypropylene film material that heat resistanceheat resistant is shunk by following component according to
Weight is than composition：Polipropene 25~30 part, 15~18 parts of polyimides, 8~14 parts of poly terephthalic acid dipropyl, propylidene two
3~4 parts of alcohol, isophthalic acid are 2~5 parts, dicyclopentadiene is 6~7 parts, styrene is 2~3 parts.Poly- the third of heat resistanceheat resistant contraction
The preparation method of alkene thin-film material is to mix, melting, extrude, roll, film forming.The polypropylene film material for preparing overcomes
The heating of conventional polypropylene films material is susceptible to the problem shunk.The A of Chinese patent CN 105218951 disclose a kind of low receipts
Shrinkage modified polypropylene material, is prepared from by the following raw material counted by weight：Acrylic resin 40-80 parts, four feet
ZnOw 2-5 parts, inorganic particle 10-20 parts, 0.05-1.2 parts of α nucleators, antioxidant 1-5 parts, high density polyethylene (HDPE) 5-
30 parts；The acrylic resin is COPP K9026, and the COPP K9026 is in 230 DEG C × 2.16kg test-strips
Melt flow rate (MFR) under part is 30g/10min.The invention utilizes the collaboration of whisker, high density polyethylene (HDPE) and inorganic particle three
Effect, the particularly addition of four-leg crystal whisker of zinc oxide not only greatly reduces polyacrylic molding shrinkage, the mechanics of material
Performance is also greatly improved.The A of Chinese patent CN 105745269 disclose a kind of mechanicalness with the shrinkage factor for reducing and balance
The polypropene composition of energy, the polypropene composition is common comprising Noblen, two kinds of heterophasic propylene copolymers, rubbery ethylenes
Polymers and inorganic filler.The A of Chinese patent CN 105273301 disclose a kind of low-shrinkage PP composite material.By such as
The raw material of lower mass fraction is made：Acrylic resin 59.5-89.95 parts, metallocene linear-low density polyethylene 10-35 parts, increase
Tough dose 1-5 parts and talcum powder 0.05-0.5 parts.The invention utilizes metallocene linear-low density polyethylene, toughener and talcum powder
Mixture prepared with the polypropylene blending modified of low-shrinkage, solve the problems, such as that polypropylene shrinkage factor is big, operation letter
Just, can be widely applied to the direct injection production of the high-grade part higher to shrinkage factor requirement and for basic tree modified once again
Fat.
The antishrinking agent feature lists such as talcum powder, the ZnOw that related polypropylene plastics material disclosed above is used
One, other physical properties such as elongation at break, opposing tensile forces, impact strength and performance can be caused to decline.Anti-shrink
Effect is also not ideal；Simultaneously the inserts mostly inorganic salt filler such as silicate and calcium carbonate that is used not easily biological-degradable,
Easily make alkalization of soils, severe environmental pollution can be caused.
Carbon fiber is in traditional use in addition to as heat-insulating material.It is many as reinforcing material be added to resin, metal,
In the materials such as ceramics, concrete, composite is constituted.Carbon fiber has turned into the most important reinforcing material of advanced composite material.By
In carbon fibre composite have it is light and it is strong, light and just, high temperature resistant, corrosion-resistant, endurance, physical dimension good stability and set
Meter property it is good, can large area global formation the features such as, the every field in Aero-Space, defence and military and civilian industry is obtained extensively
General application.Carbon fiber can be processed into fabric, felt, seat, band, paper and other materials.High-performance carbon fibre is manufacture advanced composite material
Expect most important reinforcing material.
CNT has high intensity, toughness and elastic modelling quantity in terms of mechanics.Its elasticity is up to 1TPa, about steel
5 times, the elastic modelling quantity with diamond is almost identical, and its elastic strain is about 5%, reaches as high as 12%.No matter is CNT
It is that intensity or toughness are all far superior to any fibrous material.Using CNT as composite material reinforcement body, can show good
Good intensity, elasticity, fatigue resistance.CNT not only has excellent mechanical property, also with excellent electricity, optical
Energy.Many experiments show, compared with other reinforcements (such as carbon black, carbon fiber or metal charge), CNT is to polymerization
The improvement of thing based composites electric conductivity is more notable, and because CNT has nano-grade size, addition is few, its
Polymer composites can also strengthen its mechanical performance and other performance while good electric conductivity is obtained, while also
Be conducive to the design of macromolecular material other performance, therefore suffer from extensive concern.
But the active group of carbon fiber, carbon nano tube surface is considerably less, the interaction with macromolecular material group is very
It is weak, and the draw ratio and specific surface area of CNT are big, divide in the polymer for be prepared be difficult to during polymer composite
Dissipate uniform, agglomeration easily occur, it is impossible to embody its excellent properties.Therefore it is modified to the surface of CNT to seem extremely
It is important.
To sum up, with polypropylene as base-material, masterbatch raw material type and formula are optimized, science compounds modified carbon fiber and carbon
Nanotube, calcium carbonate and silicate are replaced with organic degradable filler, improve production technology, are prepared a kind of physical property and are used
Degradable, anti-shrink polypropylene masterbatch of good performance is necessary.
The content of the invention
Technical problem solved by the invention is the defect for overcoming existing polypropylene masterbatch and preparation method thereof, with polypropylene
It is base-material, optimizes masterbatch raw material type and formula, improves production technology, science composite antioxidant of the compounding containing biologic antioxidants；
It is remarkably improved polypropylene masterbatch high temperature resistant and anti-contracility energy, tensile load, intensity, toughness and elastic modelling quantity is modified relatively
Nano-sized carbon；It is remarkably improved polypropylene masterbatch shock resistance and easily biological-degradable, the calcium fruit fiber of reduction production cost；Can be big
Big polyethylene/winter rye the peptide complexes for improving polypropylene masterbatch resistance to low temperature, can effectively improve polypropylene masterbatch lubricity
And the almond oil of inoxidizability；With other processing aids synergy, a kind of good environment-friendly type of physical property is finally obtained
Degradable, anti-shrink polypropylene masterbatch；
In order to achieve the above object, the present invention uses following technical scheme：
A kind of degradable, anti-shrink polypropylene masterbatch, is mainly prepared by the raw material of following parts by weight：
Polypropylene 30-50 parts, 17-19 parts of calcium fruit fiber, polyethylene/8-10 parts of winter rye peptide complexes, modified Nano carbon
8-10 parts, ultra-violet absorber 1-3 parts, ethylene-methyl acrylate copolymer 1.5-2.5 parts, antiaging agent 0.8-1.2 parts, lemon
Lemon 0.8-1.2 parts, coupling agent 0.8-1.2 parts, almond oil 0.6-1 parts, composite antioxidant 0.3-0.5 parts of tributyl of acid；
Further, the almond oil is with semen armeniacae amarae as raw material, soaking detoxification, microwave irradiation go out enzyme, freezing crushing,
The low temperature extraction processes such as biological enzymolysis, biological demulsifying agent demulsification, traditional vacuum are obtained；
Preferably, the preparation method of the almond oil, comprises the following steps：Semen armeniacae amarae is immersed into mass percent concentration
For room temperature rinsing in the sodium bicarbonate solution of 0.01-0.03%, drain, put sealing and standing wetting 0.5-1.5h in container, then
Decortication, decortication semen armeniacae amarae is put into microwave dryer in frequency 2450MHz, power 1000-3000W, 80-90 DEG C of temperature, material
Thickness degree 3-5cm condition microwave irradiations go out enzyme 2-4min；It is then placed in the citric acid that mass percent concentration is 0.1-0.3% molten
Soaking at room temperature 2-4h in liquid, clear water is rinsed 1-3 times, is drained, and in -20--25 DEG C, thickness of feed layer 8-10cm freezing 3-5h, is crushed to
Particle diameter 0.4-0.6mm obtains semen armeniacae amarae powder；To adding the pH value of 3-5 times of its quality to be the deionized water of 4.5-6.5 in semen armeniacae amarae powder,
Uniform mixing, controls mixed material temperature for 45-55 DEG C, is added thereto to the compound enzyme of semen armeniacae amarae silty amount 0.03-0.05%,
Stir, be incubated, digest 40-60min；Enzymolysis liquid is put into vacuum -0.01--0.03MPa, temperature 10- in vacuum centrifuge
20 DEG C, rotating speed 10000r/min, traditional vacuum 5-8min, from top to bottom isolated free oil, emulsion, hydrolyzate and bitter apricot
Benevolence slag, the emulsion that will be obtained controls temperature for 30-50 DEG C, and the biological demulsifying agent of addition emulsion quality 0.02-0.04% breaks
Newborn 40-60min, demulsification is after vacuum -0.01--0.03MPa, 10-20 DEG C of temperature, 5000r/min traditional vacuum 10- again
15min obtains free oil, and the free oil obtained by merging obtains final product almond oil；
The quality group of the compound enzyme turns into：Acid protease:Cellulase:Pectase:Amylase=6-9:2-4:2-
4:1-3；
The quality group of the biological demulsifying agent turns into：Glycolipid class:Lipopeptid class:Cell wall combination class=4-6:2-4:1-3；
The quality group of the glycolipid class biological demulsifying agent turns into：Rhamnolipid:APG=2-5:1-3.
Further, the composite antioxidant is antioxidant 1010, irgasfos 168 and biologic antioxidants 1-2 in mass ratio:
1-3:2-4 uniformly mixes；
Preferably, the preparation method of the biologic antioxidants, comprises the following steps：Take the saccharomyces cerevisiae after the activation of 1 ring
Tlj2016 slant strains, are seeded in the 500mL triangular flasks equipped with 100mL seed culture mediums and cultivate, in 28~30 DEG C, shaking table
25~30h is cultivated under the conditions of 150~200r/min of rotating speed, primary seed solution is obtained；Primary seed solution is pressed into 5~10% (v/v)
Inoculum concentration, being seeded to carries out fermented and cultured in the 500mL triangular flasks equipped with 100mL fermentation mediums, fermentation time 25~
30h, 28~30 DEG C of temperature, 150~200r/min of shaking speed obtains secondary seed solution；By secondary seed solution with 5~10%
(v/v) inoculum concentration is linked into the 5L fermentation tank ferment at constant temperature of dress 3L fermentation mediums, 28~30 DEG C of temperature, 4~6L/ of ventilation
Min, 150~200r/min of rotating speed, fermentation full adjustment zymotic fluid pH value are 6.0~6.5, when fermentation is to 25~30h, with every
The addition of 25~30mmol of zymotic fluid is risen to disposable addition Cys in zymotic fluid, is continued fermentation 20-30h and is obtained most
Whole zymotic fluid；Final zymotic fluid centrifugation, supernatant 1000-1200 mesh sieve net filtrations, lyophilized obtain final product biologic antioxidants at concentration；
GSH final concentrations reach 3308mg/L in the final zymotic fluid；
The quality group of the seed culture medium turns into：(NH4)2SO46g/L, glucose 35g/L, K2HPO4·3H2O 3g/
L, KH2PO40.5g/L, dusty yeast 11g/L, MnSO40.1g/L, KCL 0.1g/L, FeSO40.1g/L, MgSO4·7H2O
0.1g/L, balance of water, pH 6.0；
The quality group of the fermentation medium turns into：(NH4)2SO410g/L, molasses 150g/L, K2HPO4·3H2O 8g/
L, KH2PO40.5g/L, dusty yeast 5g/L, corn pulp 10g/L, MnSO40.1g/L, KCL 0.1g/L, FeSO40.1g/L,
MgSO4·7H2O 0.1g/L, balance of water, pH 6.0.
The saccharomyces cerevisiae is specially saccharomyces cerevisiae (Saccharomyces cerevisiae) tlj2016, and the bacterial strain is
China Committee for Culture Collection of Microorganisms's common micro-organisms center is preserved on July 15th, 2016, deposit number is
CGMCC No.12789, preservation address：Yard 1, BeiChen xi Road, Chaoyang District, Beijing City 3, Institute of Microorganism, Academia Sinica,
Postcode 100101；
The saccharomyces cerevisiae tlj2016 has following characteristic：1) tolerance to glucose reaches 300g/L, beneficial to it
GSH is produced under the conditions of high concentration glucose；2) 3308mg/L is reached in 5L fermentation cylinder for fermentation production GSH final concentrations；3) it is resistance to
By the ability extra-heavy of Cys, slow growth is remained under the effect of 5mmol/L Cys, in 40mmol/L L- half
Remain to keep GSH largely to synthesize under cystine effect；4) salt resistance ability reaches 18%, is conducive to extending its application field.
Further, the calcium fruit fiber is with calcic, iron natural plants higher-calcium stem end, leaf of GAIGUO and waste wood
It is raw material to consider to be worth doing, through ultrasonic cleaning, ultrasound and high-pressure pulse electric extraction, biobleaching and appropriateness enzymolysis, microwave drying, extruding
Expanded, ultramicro grinding and be obtained；
Preferably, the preparation method of the calcium fruit fiber, comprises the following steps：By fresh calcium stem end, leaf of GAIGUO and waste wood
Bits 6-8 in mass ratio:2-6:1-2 uniformly mixes, and is placed in supersonic wave cleaning machine and cleans 3-5min in 200W, 30KHz, drains,
It is broken, the water of 0.8-1.2 times of addition fragment quality, room temperature 200-400W, 35-40KHz condition ultrasonic extraction 10-15min, so
Afterwards in electric-field intensity 20-40kV/cm, burst length 400-600 μ s carry out high-voltage pulse under the conditions of pulse frequency 200-400Hz
Electric field treatment 10-15min；Regulation pH value is 6-10, adds the biology enzyme of mixture quality 0.1-0.3%, in 50-60 DEG C of enzymolysis
10-15min；Enzymolysis liquid is concentrated under reduced pressure into solid content for 40-60%, is put into microwave dryer in 2000W, 130-150 DEG C
Intermittent drying is carried out, moisture is allowed to and is reached 8-10%, be then crushed to particle diameter 0.4-0.6mm, add crushed material quality 0.2-
0.4% sodium acid carbonate, uniform mixing adjusts mixture moisture for 15-18%, room temperature, sealing and standing 1.5-2.5h, in
Screw speed 105-115r/min, 140-160 DEG C of condition extrusion of temperature, then ultramicro grinding is to 10-15 μm of particle diameter, finally
4-6h is dried in 100-115 DEG C and obtains final product calcium fruit fiber；
The biology enzyme is alkalescent xylanase, laccase, dextranase, seminase, pectase, pentosanase by quality
Compare 2-4:1-3:1-2:0.5-1.5:0.4-1:0.2-0.8 uniformly mixes.
Further, the modified Nano carbon is in water phase by single wall or multi-walled carbon nano-tubes and carbon fiber with ammonium persulfate
System gentle reaction purification after being processed through ultrasonic disperse and high-pressure pulse electric, modified it is obtained；
Preferably, the preparation method of the modified Nano carbon, comprises the following steps：By middle modules carbon fibre, single
Pipe, ammonium persulfate and deionized water in mass ratio 1:0.8-1:80-100:1000 uniform mixing, first power 200-400W,
The ultrasonically treated 20-40min of frequency 20-24KHz, then in electric-field intensity 2-6kV/cm, burst length 100-300 μ s, pulse frequency
High-pressure pulse electric treatment 10-15min is carried out under the conditions of rate 200-400Hz；Through the mixture after treatment in rotating speed 100-120r/
Min, 50-70 DEG C of temperature reaction 0.5-2.5h, reaction solution are filtered with the PP micropore filtering films in 0.22 μm of aperture, and spend from
Sub- water cyclic washing is most dried under vacuum to constant weight to neutrality after 70-80 DEG C, crushes, and obtains final product modified Nano carbon.
Further, the polyethylene/winter rye peptide complexes are poly- with the synthetic resin with good resistance to low temperature
Ethene and the blending of the winter rye antifreeze peptide with excellent anti-freezing property, co-melting, extruding pelletization are formed；
Preferably, the preparation method of the polyethylene/winter rye peptide complexes, comprises the following steps：
1) preparation of winter rye peptide：By the seed sabot of winter rye, 6- is processed in electric-field intensity 8-10kV/cm high-pressure electrostatics
8min；Then the soaking at room temperature 1-3h in concentration is for the salicylic acid solution of 12-18mg/L, while in electric-field intensity 6-10kV/cm,
Burst length 100-200 μ s, carry out high-pressure pulse electric treatment under the conditions of pulse frequency 200-400Hz；Rinse, drain, in 3-5
DEG C stand 18-24h, then successively 1-3 DEG C refrigerate 2-4d, -3--5 DEG C freezing 1-3d, -15--18 DEG C freezing 10-15h, immediately
Outdoor natural light photograph is placed on, seed half is crushed immediately after thawing, crushed material particle diameter 0.5-1.5mm is subsequently added into crushing
The water of 2-4 times of amount of substance, is 3.5-5.5 with newborn acid for adjusting pH value；It is eventually adding the mixing of mixed liquor quality 1.3-1.7%
Enzyme, digests 10-30min in 35-50 DEG C first, then digests 20-40min in 50-60 DEG C；Enzymolysis liquid filtering, filtrate decompression are dense
Contracting, freeze-drying obtain final product winter rye peptide；
The mixed enzyme is protease, cellulase, amylase, pectase 5-7 in mass ratio:4-6:1-3:1-2 is uniform
Mixing；
2) winter rye peptide is sufficiently mixed in proportion with polyethylene, maleic anhydride, styrene, initiator and antioxidant, weight
Measuring ratio is：Polyethylene: winter rye peptide: maleic anhydride: styrene: initiator: antioxidant=100: 2-10: 3-20: 1-15: 0.1-
5∶0.1-1；
3) by step 2) compound that obtains adds double screw extruder frit reaction, and extruding pelletization, control twin-screw is squeezed
Go out machine and die temperature at 145-180 DEG C, screw speed is 30-200r/min, stop of the reactant in double screw extruder
Time control obtained final product polyethylene/winter rye peptide complexes at 10-100 seconds.
Preferably, the ultra-violet absorber is UV-531；
Preferably, the ethylene-methyl acrylate copolymer preferably uses Dupont EMA1125AC.
Another object of the present invention is to provide above-mentioned degradable, anti-shrink polypropylene masterbatch preparation method, including following step
Suddenly：It is first according to formula and accurately weighs each raw material, is 0.25- by per kilogram compound power according to equal increments method principle
0.35kW batch mixings while stirring, after being well mixed, controls mixing thickness of feed layer for 5-10cm, then dry 20- in 100-120 DEG C
40min, reinstall and extrude in double screw extruder, granulate, drying and obtain final product degradable, anti-shrink polypropylene masterbatch.
Beneficial effect：
The present invention optimizes masterbatch raw material type and formula with polypropylene as base-material, improves production technology, and science compounding is containing life
The composite antioxidant of thing antioxidant；It is remarkably improved polypropylene masterbatch high temperature resistant and anti-contracility energy, relative tensile load, strong
The modified Nano carbon of degree, toughness and elastic modelling quantity；It is remarkably improved polypropylene masterbatch shock resistance and easily biological-degradable, reduction
The calcium fruit fiber of production cost；Polyethylene/winter rye the peptide complexes of polypropylene masterbatch resistance to low temperature are greatly improved, can be had
Effect improves the almond oil of polypropylene masterbatch lubricity and inoxidizability；With other processing aids synergy, one is finally obtained
Plant physical property good environment protection type easy degraded, anti-shrink polypropylene masterbatch.Experiment shows：1) degradable, anti-shrink of the invention
Polypropylene masterbatch molding shrinkage is relatively low, than the molding shrinkage reduction by 50% of commercially available low-shrinkage modified polypropylene material,
With excellent anti-contracility energy, the product size good stability prepared using above-mentioned raw materials is not shunk.Also illustrate this hair simultaneously
The polypropylene masterbatch of bright preparation is especially suitable for environmental demand during storage, use, and dimensionally stable will not produce contraction to go
For.2) degradable, anti-shrink polypropylene masterbatch the oxidation induction time of the present invention is long, than commercially available anti-oxidant modified polypropene material
The oxidation induction time reduction by 102% of material, with significant antioxygenic property and anti ageing property, is prepared using above-mentioned raw materials
Product weatherability is strong, and environmental suitability is extensive, long service life.3) degradable, anti-shrink polypropylene masterbatch prepared by the present invention
Compared with commercially available degradable, anti-shrink polypropylene masterbatch, its fiber number is high, improves 5.6%；Pull-off force is strong, improves 14.6%；Fracture
Elongation is high, improves 55.6%；It is strong with respect to pull-off force, improve 7.8%；Through 160 DEG C, 14 days high-temperature circulation tests, remain to keep
Preferable physical property and performance, conservation rate are respectively increased 4.4%, 36.6%, 40.1% and 35.1%, and nothing is broken, and
Less, resistance to elevated temperatures is superior for color change, compared with prior art, with preferable advanced and practicality.4) present invention
The degradable of preparation, anti-shrink polypropylene masterbatch are compared with commercially available degradable, anti-shrink polypropylene masterbatch, and its fiber number is high, improve
5.6%；Pull-off force is strong, improves 14.6%；Elongation at break is high, improves 55.6%；It is strong with respect to pull-off force, improve 7.8%；Through-
30 DEG C, the experiment of 14 days low temperature agings, remain to keep preferable physical property and performance, conservation rate is respectively increased 4.4%,
44.2%th, 52.1% and 43.8%, nothing is broken, resistance to low temperature is superior, compared with prior art, with preferable advance
And practicality.Particular technique effect is shown in embodiment 7-10, and particular technique principle is as follows：
1. the calcium fruit fiber that prepared by the present invention is with calcic, iron natural plants higher-calcium stem end, leaf of GAIGUO and gives up
Wood chip is raw material, through ultrasonic cleaning, ultrasound and high-pressure pulse electric extraction, biobleaching and faint enzymolysis, microwave drying, is squeezed
Press expanded, ultramicro grinding and be obtained, various treatment technologies are combined, synergy, particularly after crushed, add a certain amount of
Sodium acid carbonate, sealing and standing after adjusted moisture, then extrusion, can significantly increase the specific surface area of calcium fruit fiber, net
Lattice structure is more enriched, and puffed degree, dilatancy, thickening property are stronger, the increase of cellulose grain specific surface area, absorption affinity and stretch-proof
Power strengthens, and merge with the metal ion such as calcium therein, iron, you can toughness, the elasticity of raising polypropylene masterbatch, and poly- third can be improved again
The shock resistance of alkene masterbatch.Kinds of processes combination simultaneously can effectively improve the draw ratio and surface adhesion of fiber grain, carry
The compatibility of high and polypropylene base-material and other resins, can be dispersed and compatible in polypropylene base-material, by its science compounding
In filling master batch, (clay, sun rise can completely to substitute carbonate of the prior art, calcium carbonate, nano-calcium carbonate and silicate
Stone etc.), polypropylene masterbatch shock resistance, and easily biological-degradable, reduction production cost are not only remarkably improved, improve soil
Composition, increases the content of organic matter, environmentally friendly.The value of calcium stem end leaf and waste wood is improve simultaneously, is turned waste into wealth,
Promote to solve " rural economy, rural development and rural demography ".
2. the modified Nano carbon that prepared by the present invention is by single wall or multi-walled carbon nano-tubes, carbon fiber, ammonium persulfate and water section
Compounding is learned, through ultrasonic disperse and high-pressure pulse electric treatment, alternate electric field and magnetic field, strong concussion, water mutually electricity can be produced
From, oxidation, the nanotube dispersion of homogeneous stabilization is formed, then reacted at a lower temperature, CNT is carried out
Comprehensive surface treatment, hydroxyl, carbonyl and a small amount of carboxyl are produced with the surface of CNT, carbon fiber, and these groups are deposited
In CNT, carbon fiber is soluble in water or in the organic solvent of DMF isopolarities, dissolubility is finally given stronger
CNT soluble long, short carbon nanometer tube and carbon fiber.It is added into comprehensively, uniformly disperseing in filling master batch, fills out
It is charged in polypropylene base-material, gives full play to the material property of CNT and carbon fiber, is remarkably improved the anti-receipts of polypropylene masterbatch
Contracting performance (dimensional stability), relative tensile load, intensity, toughness and elastic modelling quantity；The advantage of the method is：1) CNT
Length is controllable：The distribution of lengths of CNT can have the change of reaction condition and control, when CNT is in temperature higher
When the lower ammonium persulfate solution by high concentration is processed, the CNT that can be truncated；When the concentration of ammonium persulfate is relatively low or
When person's reaction temperature is relatively low, CNT will not be truncated；2) use of traditional strong acid, highly basic, high safety are avoided；3)
Processes and apparatus is simple, and reaction is gentle, efficiency high；4) use of the surfactant of costliness, low cost are avoided；5) with water and
Neutral sulfatase be reaction dissolvent and raw material, it is environmentally friendly；6) scale and can commercially produce.
3. polyethylene/winter rye peptide complexes that prepared by the present invention are poly- with the synthetic resin with good resistance to low temperature
Ethene and the blending of the winter rye antifreeze peptide with excellent anti-freezing property, co-melting, extruding pelletization are formed；The winter rye peptide is to contain
It is raw material preparation to have the winter rye seed of abundant freeze proof matrix, by high-pressure electrostatic treatment, high-pressure pulse electric auxiliary salicylic acid
Induction, low temperature segmentation Stress treatment and natural lighting are organically combined so that active seed containing freeze proof matrix itself is in Wai Jie
Under the stress and induction of environment, freeze proof matrix components have obtained most comprehensive, most abundant synthesis and accumulation, after blended enzyme enzymolysis
Maximizing dissolution, while freeze proof peptide content increase can be made, has significantly delayed the formation of ice crystal, reduces ice crystal to high score
The effect of stabbing of subtree fat, enhances the cryoprotective effects of polypropylene base-material, improves the resistance to low temperature of polypropylene masterbatch, and poly-
Ethene science compound, blending, it is co-melting, generate unexpected cryoprotective effects, its resistance to low temperature is significantly increased；Particularly its
In the seed fat that contains also can further improve mobility, lubricity and the inoxidizability of compound and polypropylene base-material.
4. the almond oil that prepared by the present invention goes out enzyme, freezing crushing, enzymolysis, true with semen armeniacae amarae as raw material through microwave irradiation
Free oil, emulsion, hydrolyzate and almond slag are obtained after sky centrifugation, emulsion therein is carried out into after biological demulsifying vacuum again
Centrifugation obtains free oil, free oil is merged and is obtained final product, relative to the turpentine oil in existing filling master batch, coix seed oil and mandarin oil
Say that the anti-oxidation active substances such as unrighted acid therein and VE are higher, its lubricity, mobility and inoxidizability are stronger.
5. the nano grade biological antioxidant that prepared by the present invention is fermentation substrate with sugar fermentation medium high, adds feature to make
Brewer yeast is fermented, and can obtain a large amount of reductive glutathiones, and its science is compounded in polypropylene masterbatch, cooperates with antioxidant 1010
And irgasfos 168, its inoxidizability is stronger and biodegradable, environmentally friendly.
It should be noted that the present invention it is degradable, anti-shrink polypropylene masterbatch have the technical effect that each component mutually cooperate with,
The result of interaction, the superposition of not simple raw material function, the science compounding of each raw material components and extraction, the effect of generation
Considerably beyond the superposition of each single component function and effect, with preferable advanced and practicality.
Specific embodiment
The present invention is described below by specific embodiment.Unless stated otherwise, technological means used in the present invention
It is method known in those skilled in the art.In addition, embodiment is interpreted as illustrative, it is not intended to limit the present invention
Scope, the spirit and scope of the invention are limited only by the claims that follow.To those skilled in the art, without departing substantially from this
On the premise of invention spirit and scope, the various changes that are carried out to the material component and consumption in these embodiments or change
Belong to protection scope of the present invention.
It is prepared by the raw material of embodiment 1
1. the preparation of calcium fruit fiber：
The preparation method of the calcium fruit fiber, comprises the following steps：Fresh calcium stem end, leaf of GAIGUO and waste wood are pressed into quality
Than 7:4:1.5 uniform mixing, are placed in supersonic wave cleaning machine and clean 4min in 200W, 30KHz, drain, and crush, and add fragment
The water that 1 times of quality, room temperature 300W, 40KHz condition ultrasonic extraction 12min, then in electric-field intensity 30kV/cm, the burst length 500
μ s, carry out high-pressure pulse electric treatment 12min under the conditions of pulse frequency 300Hz；Regulation pH value is 8, adds mixture quality
0.2% biology enzyme, 12min is digested in 55 DEG C；It is 50% that enzymolysis liquid is concentrated under reduced pressure into solid content, is put into microwave dryer
Intermittent drying is carried out in 2000W, 140 DEG C, moisture is allowed to and is reached 9%, be then crushed to particle diameter 0.5mm, add comminuted material
The sodium acid carbonate of amount 0.3%, uniform mixing, adjustment mixture moisture is 17%, and room temperature, sealing and standing 2h turn in screw rod
Fast 110r/min, 150 DEG C of condition extrusions of temperature, then ultramicro grinding most dry 5h after 105 DEG C and obtain final product to 12 μm of particle diameter
Calcium fruit fiber；
The biology enzyme is alkalescent xylanase, laccase, dextranase, seminase, pectase, pentosanase by quality
Than 3:2:1.5:1:0.7:0.5 uniform mixing.
2. the preparation of modified Nano carbon：
The preparation method of the modified Nano carbon, comprises the following steps：By middle modules carbon fibre, SWCN, over cure
Sour ammonium and deionized water in mass ratio 1:0.9:90:1000 uniform mixing, it is ultrasonically treated in power 300W, frequency 22KHz first
30min, then in electric-field intensity 4kV/cm, the μ s of burst length 200 carry out high-pressure pulse electric under the conditions of pulse frequency 300Hz
Treatment 12min；Through the mixture after treatment in rotating speed 110r/min, temperature 60 C reaction 2h, 0.22 μm of aperture of reaction solution
PP micropore filtering films are filtered, and with deionized water cyclic washing to neutrality, are most dried under vacuum to constant weight, powder after 75 DEG C
It is broken, obtain final product modified Nano carbon.
3. the preparation of polyethylene/winter rye peptide complexes：
The preparation method of the polyethylene/winter rye peptide complexes, comprises the following steps：
1) preparation of winter rye peptide：By the seed sabot of winter rye, 7min is processed in electric-field intensity 9kV/cm high-pressure electrostatics；
Then concentration for 15mg/L salicylic acid solution in soaking at room temperature 2h, while in electric-field intensity 8kV/cm, the μ of burst length 150
S, carries out high-pressure pulse electric treatment under the conditions of pulse frequency 300Hz；Rinse, drain, 21h is stood in 4 DEG C, then successively 2
DEG C refrigeration 3d, -4 DEG C of freezing 2d, -17 DEG C of freezing 12h, are immediately placed at outdoor natural light photograph, seed half is carried out immediately after thawing
Crush, crushed material particle diameter 1mm is subsequently added into the water of 3 times of crushed material quality, be 4.5 with newborn acid for adjusting pH value；It is eventually adding mixing
The mixed enzyme of feed liquid quality 1.5%, digests 20min in 42 DEG C first, then digests 30min in 55 DEG C；Enzymolysis liquid filtering, filtrate
Concentrated under reduced pressure, freeze-drying obtains final product winter rye peptide；
The mixed enzyme is protease, cellulase, amylase, pectase in mass ratio 6:5:2:1.5 uniform mixing；
2) winter rye peptide is sufficiently mixed in proportion with polyethylene, maleic anhydride, styrene, initiator and antioxidant, weight
Measuring ratio is：Polyethylene: winter rye peptide: maleic anhydride: styrene: initiator: antioxidant=100: 6: 10: 7: 2.6: 0.5；
3) by step 2) compound that obtains adds double screw extruder frit reaction, and extruding pelletization, control twin-screw is squeezed
Go out machine and die temperature at 162 DEG C, screw speed is 115r/min, residence time control of the reactant in double screw extruder
At 55 seconds, polyethylene/winter rye peptide complexes are obtained final product.
4. the preparation of almond oil：
The preparation method of the almond oil, comprises the following steps：It is by semen armeniacae amarae immersion mass percent concentration
Room temperature is rinsed, drained in 0.02% sodium bicarbonate solution, puts sealing and standing wetting 1h in container, is then peeled, and decortication is bitter
Almond is put into microwave dryer in frequency 2450MHz, power 2000W, 85 DEG C of temperature, thickness of feed layer 4cm condition microwave irradiations
Go out enzyme 3min；Soaking at room temperature 3h in the citric acid solution that mass percent concentration is 0.2% is then placed in, clear water is rinsed 2 times, drip
It is dry, in -23 DEG C, thickness of feed layer 9cm freezing 4h, it is crushed to particle diameter 0.5mm and obtains semen armeniacae amarae powder；To adding its quality in semen armeniacae amarae powder
4 times of pH value is 5.5 deionized water, uniform mixing, controls mixed material temperature for 50 DEG C, is added thereto to semen armeniacae amarae silty
The compound enzyme of amount 0.04%, stirs, and is incubated, and digests 50min；By enzymolysis liquid put vacuum in vacuum centrifuge-
0.02MPa, 15 DEG C of temperature, rotating speed 10000r/min, traditional vacuum 6min, from top to bottom isolated free oil, emulsion, water
Solution liquid and semen armeniacae amarae slag, the emulsion that will be obtained control temperature for 40 DEG C, the biological demulsifying agent of addition emulsion quality 0.03%
Demulsification 50min, after vacuum -0.02MPa, 15 DEG C of temperature, 5000r/min, traditional vacuum 12min is dissociated again for demulsification
Oil, the free oil obtained by merging obtains final product almond oil；
The quality group of the compound enzyme turns into：Acid protease:Cellulase:Pectase:Amylase=7:3:3:2；
The quality group of the biological demulsifying agent turns into：Glycolipid class:Lipopeptid class:Cell wall combination class=5:3:2；
The quality group of the glycolipid class biological demulsifying agent turns into：Rhamnolipid:APG=3:2.
5. the preparation of biologic antioxidants:
The preparation method of the biologic antioxidants, comprises the following steps：The saccharomyces cerevisiae tlj2016 taken after the activation of 1 ring is oblique
Face strain, is seeded in the 500mL triangular flasks equipped with 100mL seed culture mediums and cultivates, in 29 DEG C, shaking speed 180r/min bars
27h is cultivated under part, primary seed solution is obtained；By primary seed solution by the inoculum concentration of 8% (v/v), it is seeded to equipped with 100mL fermentations
Fermented and cultured is carried out in the 500mL triangular flasks of culture medium, fermentation time 28h, 29 DEG C of temperature, shaking speed 180r/min is obtained
Secondary seed solution；Secondary seed solution is sent out with the 5L fermentation tanks constant temperature that 8% (v/v) inoculum concentration is linked into dress 3L fermentation mediums
Ferment, 29 DEG C of temperature, ventilation 5L/min, rotating speed 180r/min, fermentation full adjustment zymotic fluid pH value are 6.2, when fermentation to 28h
When, with every liter of addition of zymotic fluid 27mmol to disposable addition Cys in zymotic fluid, continue fermentation 25h and obtain most
Whole zymotic fluid；Final zymotic fluid centrifugation, the mesh sieve net filtration of supernatant 1100, lyophilized obtains final product biologic antioxidants at concentration.
GSH final concentrations reach 3308mg/L in the final zymotic fluid；
The quality group of the seed culture medium turns into：(NH4)2SO46g/L, glucose 35g/L, K2HPO4·3H2O 3g/
L, KH2PO40.5g/L, dusty yeast 11g/L, MnSO40.1g/L, KCL 0.1g/L, FeSO40.1g/L, MgSO4·7H2O
0.1g/L, balance of water, pH 6.0；
The quality group of the fermentation medium turns into：(NH4)2SO410g/L, molasses 150g/L, K2HPO4·3H2O 8g/
L, KH2PO40.5g/L, dusty yeast 5g/L, corn pulp 10g/L, MnSO40.1g/L, KCL 0.1g/L, FeSO40.1g/L,
MgSO4·7H2O 0.1g/L, balance of water, pH 6.0.
Calcium fruit fiber, modified Nano carbon, polyethylene/winter rye peptide complexes, bitter apricot used in example 2 below -6
Benevolence oil, biologic antioxidants are prepared for embodiment 1, and other are purchased in market.
Embodiment 2
A kind of degradable, anti-shrink polypropylene masterbatch, is mainly prepared by the raw material of following parts by weight：
40 parts of polypropylene, 18 parts of calcium fruit fiber, polyethylene/9 parts of winter rye peptide complexes, 9 parts of modified Nano carbon, ultraviolet
2 parts of absorbent, 2 parts of ethylene-methyl acrylate copolymer, 1 part of antiaging agent, 1 part of ATBC, 1 part of coupling agent, bitter apricot
0.8 part of benevolence oil, 0.4 part of composite antioxidant；
The composite antioxidant is antioxidant 1010, irgasfos 168 and biologic antioxidants in mass ratio 1.5:2:3 is uniform mixed
Close；
The ultra-violet absorber is UV-531；
The ethylene-methyl acrylate copolymer uses Dupont EMA1125AC.
Preparation method, comprises the following steps：It is first according to formula and accurately weighs each raw material, according to equal increments method principle,
It is 0.3kW batch mixings while stirring by per kilogram compound power, after being well mixed, it is 8cm, Ran Houyu to control mixing thickness of feed layer
110 DEG C dry 30min, reinstall and extrude in double screw extruder, granulate, drying that to obtain final product degradable, anti-shrink polypropylene female
Material.
Embodiment 3
A kind of degradable, anti-shrink polypropylene masterbatch, is mainly prepared by the raw material of following parts by weight：
30 parts of polypropylene, 17 parts of calcium fruit fiber, polyethylene/8 parts of winter rye peptide complexes, 8 parts of modified Nano carbon, ultraviolet
1 part of absorbent, 1.5 parts of ethylene-methyl acrylate copolymer, 0.8 part of antiaging agent, 0.8 part of ATBC, coupling agent
0.8 part, 0.6 part of almond oil, 0.3 part of composite antioxidant；
The composite antioxidant is antioxidant 1010, irgasfos 168 and biologic antioxidants in mass ratio 1:1:2 is uniform mixed
Close；
The ultra-violet absorber is UV-531；
The ethylene-methyl acrylate copolymer preferably uses Dupont EMA1125AC.
Preparation method, comprises the following steps：It is first according to formula and accurately weighs each raw material, according to equal increments method principle,
It is 0.25kW batch mixings while stirring by per kilogram compound power, after being well mixed, it is 5cm to control mixing thickness of feed layer, then
20min is dried in 100 DEG C, reinstall and extrude in double screw extruder, granulate, drying that to obtain final product degradable, anti-shrink polypropylene female
Material.
Embodiment 4
A kind of degradable, anti-shrink polypropylene masterbatch, is mainly prepared by the raw material of following parts by weight：
50 parts of polypropylene, 19 parts of calcium fruit fiber, polyethylene/10 parts of winter rye peptide complexes, 10 parts of modified Nano carbon is ultraviolet
3 parts of light absorbers, 2.5 parts of ethylene-methyl acrylate copolymer, 1.2 parts of antiaging agent, 1.2 parts of ATBC, coupling agent
1.2 parts, 1 part of almond oil, 0.5 part of composite antioxidant；
The composite antioxidant is antioxidant 1010, irgasfos 168 and biologic antioxidants in mass ratio 2:3:4 is uniform mixed
Close；
The ultra-violet absorber is UV-531；
The ethylene-methyl acrylate copolymer preferably uses Dupont EMA1125AC.
Preparation method, comprises the following steps：It is first according to formula and accurately weighs each raw material, according to equal increments method principle,
It is 0.35kW batch mixings while stirring by per kilogram compound power, after being well mixed, it is 10cm to control mixing thickness of feed layer, then
40min is dried in 120 DEG C, reinstall and extrude in double screw extruder, granulate, drying that to obtain final product degradable, anti-shrink polypropylene female
Material.
Embodiment 5
A kind of degradable, anti-shrink polypropylene masterbatch, is mainly prepared by the raw material of following parts by weight：
30 parts of polypropylene, 19 parts of calcium fruit fiber, polyethylene/8 parts of winter rye peptide complexes, 10 parts of modified Nano carbon is ultraviolet
1 part of light absorbers, 2.5 parts of ethylene-methyl acrylate copolymer, 0.8 part of antiaging agent, 1.2 parts of ATBC, coupling agent
0.8 part, 0.6 part of almond oil, 0.5 part of composite antioxidant；
The composite antioxidant is antioxidant 1010, irgasfos 168 and biologic antioxidants in mass ratio 1:3:2 is uniform mixed
Close；
Preparation method, comprises the following steps：It is first according to formula and accurately weighs each raw material, according to equal increments method principle,
It is 0.25kW batch mixings while stirring by per kilogram compound power, after being well mixed, it is 10cm to control mixing thickness of feed layer, then
40min is dried in 100 DEG C, reinstall and extrude in double screw extruder, granulate, drying that to obtain final product degradable, anti-shrink polypropylene female
Material.
Embodiment 6
A kind of degradable, anti-shrink polypropylene masterbatch, is mainly prepared by the raw material of following parts by weight：
50 parts of polypropylene, 17 parts of calcium fruit fiber, polyethylene/10 parts of winter rye peptide complexes, 8 parts of modified Nano carbon is ultraviolet
3 parts of light absorbers, 1.5 parts of ethylene-methyl acrylate copolymer, 1.2 parts of antiaging agent, 0.8 part of ATBC, coupling agent
1.2 parts, 1 part of almond oil, 0.3 part of composite antioxidant；
The composite antioxidant is antioxidant 1010, irgasfos 168 and biologic antioxidants in mass ratio 2:1:4 is uniform mixed
Close；
Preparation method, comprises the following steps：It is first according to formula and accurately weighs each raw material, according to equal increments method principle,
It is 0.35kW batch mixings while stirring by per kilogram compound power, after being well mixed, it is 5cm to control mixing thickness of feed layer, then
20min is dried in 120 DEG C, reinstall and extrude in double screw extruder, granulate, drying that to obtain final product degradable, anti-shrink polypropylene female
Material.
Degradable, anti-shrink polypropylene masterbatch the Material shrinkage characteristic of the present invention of embodiment 7
The polypropylene masterbatch and commercially available low-shrinkage modified polypropene masterbatch prepared with embodiment of the present invention 2-6 are detection sample
Product, GB/T 17037.4-2003 are pressed after batch mixing, extrusion, granulation, drying《The system of plastics thermoplastic material injection-molded test specimens
Standby 4th part：The measure of molding shrinkage》Regulation sampling, sample treatment and detection molding shrinkage, testing result such as table 1：
Table 1：Degradable, anti-shrink polypropylene masterbatch molding shrinkage
| Project | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Average | It is commercially available | Difference |
| Lateral shrinkage (%) | 0.32 | 0.34 | 0.34 | 0.40 | 0.40 | 0.36 | 0.72 | - 50% |
| Longitudinal contraction rate (%) | 0.33 | 0.35 | 0.34 | 0.33 | 0.35 | 0.34 | 0.68 | - 50% |
Result above shows：Degradable, anti-shrink polypropylene masterbatch the molding shrinkage of the present invention is relatively low, lower than commercially available
The molding shrinkage reduction by 50% of shrinkage factor modified polypropylene material, with excellent anti-contracility energy, using above-mentioned raw materials system
Standby product size good stability, does not shrink.Also illustrate the polypropylene masterbatch of present invention preparation during storage, use simultaneously
Environmental demand is especially suitable for, dimensionally stable will not produce Shrinkage behavior.
Degradable, anti-shrink polypropylene masterbatch the material against oxidative of the present invention of embodiment 8
The polypropylene masterbatch and commercially available low-shrinkage modified polypropene masterbatch prepared with embodiment of the present invention 2-6 are detection sample
Product test the oxidation induction period of detection sample, reference after batch mixing, melting, extrusion, granulation, drying using differential scanning calorimeter
GB/T 19466.6-2009 is carried out, and 200 DEG C of test temperature, rate of heat addition 20K/min, nitrogen atmosphere protection air-flow moves speed
60mL/min, purge gass flow rate 20mL/min, the dynamic speed 20mL/min of oxygen atmosphere oxygen stream.Oxidation induction period is in oxygen
In gas or air atmosphere, heated up with constant speed or constant temperature at the specified temperature, determine the anti-oxidant stabilising system in sample
Time needed for suppressing its oxidation.With the thermo oxidative aging performance and antioxidant effect of this relative evaluation material, testing result is such as
Table 2：
Table 2：Degradable, anti-shrink polypropylene masterbatch oxidation induction period
| Project | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Average | It is commercially available | Difference |
| Oxidation induction period (min) | 8.2 | 8.8 | 8.6 | 8.4 | 8.5 | 8.5 | 4.2 | - 102% |
Result above shows：Degradable, anti-shrink polypropylene masterbatch the oxidation induction time of the present invention is long, resists than commercially available
The oxidation induction time reduction by 102% of oxidation modification polypropylene material, with significant antioxygenic property and anti ageing property, adopts
The product weatherability prepared with above-mentioned raw materials is strong, and environmental suitability is extensive, long service life.
Degradable, anti-shrink polypropylene masterbatch the high-temperature circulation test of the present invention of embodiment 9
Same process condition is pressed with commercially available degradable, anti-shrink polypropylene masterbatch with the polypropylene masterbatch of the embodiment of the present invention 2
Flat filament is prepared into, high-temperature circulation test is done respectively at 160 DEG C, 14 days conditions, and determine polypropylene masterbatch flat filament physical property
Primary quality measure, takes its Testing index averagely, statistics such as table 3
Table 3：Degradable, anti-shrink polypropylene masterbatch flat filament quality measurements
Result above shows that degradable, anti-shrink polypropylene masterbatch prepared by the present invention is gathered with commercially available degradable, anti-shrink
Propylene masterbatch is compared, and its fiber number is high, improves 5.6%；Pull-off force is strong, improves 14.6%；Elongation at break is high, improves 55.6%；
It is strong with respect to pull-off force, improve 7.8%；Through 160 DEG C, 14 days high-temperature circulation tests, remain to keep preferable physical property and use
Performance, conservation rate is respectively increased 4.4%, 36.6%, 40.1% and 35.1%, and nothing is broken, and color change is less, heat-resisting quantity
Can be superior, compared with prior art, with preferable advanced and practicality.
It should be noted that：Polypropylene masterbatch prepared by embodiment of the present invention 3-6 equally has above-mentioned experiment effect, each reality
Apply between example and little with above-mentioned experiment effect otherness.
Degradable, anti-shrink polypropylene masterbatch the low temperature aging experiment of the present invention of embodiment 10
Same process condition is pressed with commercially available degradable, anti-shrink polypropylene masterbatch with the polypropylene masterbatch of the embodiment of the present invention 2
Flat filament is prepared into, low temperature aging experiment is done, and is determined the physical of polypropylene masterbatch flat filament respectively at -30 DEG C, 14 days conditions
Energy primary quality measure, takes its Testing index averagely, statistics such as table 4
Table 4：Degradable, anti-shrink polypropylene masterbatch flat filament quality measurements
Result above shows that degradable, anti-shrink polypropylene masterbatch prepared by the present invention is gathered with commercially available degradable, anti-shrink
Propylene masterbatch is compared, and its fiber number is high, improves 5.6%；Pull-off force is strong, improves 14.6%；Elongation at break is high, improves 55.6%；
It is strong with respect to pull-off force, improve 7.8%；Tested through -30 DEG C, 14 days low temperature agings, remain to keep preferable physical property and use
Performance, conservation rate is respectively increased 4.4%, 44.2%, 52.1% and 43.8%, without broken, resistance to low temperature is superior, and existing
Technology is compared, with preferable advanced and practicality.
It should be noted that：Polypropylene masterbatch prepared by embodiment of the present invention 3-6 equally has above-mentioned experiment effect, each reality
Apply between example and little with above-mentioned experiment effect otherness.
Claims (10)
1. a kind of degradable, anti-shrink polypropylene masterbatch, is mainly prepared by the raw material of following parts by weight：Polypropylene 30-50 parts,
17-19 parts of calcium fruit fiber, polyethylene/8-10 parts of winter rye peptide complexes, 8-10 parts of modified Nano carbon, ultra-violet absorber 1-3
Part, it is ethylene-methyl acrylate copolymer 1.5-2.5 parts, antiaging agent 0.8-1.2 parts, ATBC 0.8-1.2 parts, even
0.8-1.2 parts, almond oil 0.6-1.0 parts, composite antioxidant 0.3-0.5 parts of agent of connection；
The composite antioxidant is antioxidant 1010, irgasfos 168 and biologic antioxidants 1-2 in mass ratio:1-3:2-4 is uniformly mixed
Close；
The preparation method of the biologic antioxidants, comprises the following steps：Take the saccharomyces cerevisiae tlj2016 inclined-planes bacterium after the activation of 1 ring
Kind, be seeded in the 500m L triangular flasks equipped with 100m L seed culture mediums cultivate, 28~30 DEG C, shaking speed 150~
25~30h is cultivated under the conditions of 200r/min, primary seed solution is obtained；Primary seed solution is pressed the inoculum concentration of 5~10% (v/v),
Being seeded in the 500m L triangular flasks equipped with 100m L fermentation mediums carries out fermented and cultured, 25~30h of fermentation time, temperature 28
~30 DEG C, 150~200r/min of shaking speed obtains secondary seed solution；By secondary seed solution with 5~10% (v/v) inoculum concentrations
Be linked into dress 3L fermentation mediums 5L fermentation tank ferment at constant temperature, 28~30 DEG C of temperature, 4~6L/min of ventilation, rotating speed 150~
200r/min, fermentation full adjustment zymotic fluid pH value is 6.0~6.5, when fermentation is to 25~30h, with every liter of zymotic fluid 25~
The addition of 30mmol continues fermentation 20-30h and obtains final zymotic fluid to disposable addition Cys in zymotic fluid；Most
Whole zymotic fluid centrifugation, supernatant 1000-1200 mesh sieve net filtrations, lyophilized obtain final product biologic antioxidants at concentration；
The saccharomyces cerevisiae tlj2016 deposit numbers are CGMCC No.12789.
2. degradable, anti-shrink polypropylene masterbatch as claimed in claim 1, it is characterised in that the preparation of the calcium fruit fiber
Method, comprises the following steps：By fresh calcium stem end, leaf of GAIGUO and waste wood 6-8 in mass ratio:2-6:1-2 uniformly mixes, and is placed in
3-5min is cleaned in 200W, 30KHz in supersonic wave cleaning machine, is drained, crushed, add the water of 0.8-1.2 times of fragment quality, room
Warm 200-400W, 35-40KHz condition ultrasonic extraction 10-15min, then in electric-field intensity 20-40kV/cm, burst length 400-
600 μ s, carry out high-pressure pulse electric treatment 10-15min under the conditions of pulse frequency 200-400Hz；Regulation pH value is 6-10, is added
The biology enzyme of mixture quality 0.1-0.3%, 10-15min is digested in 50-60 DEG C；Enzymolysis liquid is concentrated under reduced pressure into solid content
It is 40-60%, be put into microwave dryer carries out intermittent drying in 2000W, 130-150 DEG C, is allowed to moisture and reaches 8-10%, so
After be crushed to particle diameter 0.4-0.6mm, add the sodium acid carbonate of crushed material quality 0.2-0.4%, uniform mixing adjusts mixture water
Content is divided to be 15-18%, room temperature, sealing and standing 1.5-2.5h, in screw speed 105-115r/min, 140-160 DEG C of bar of temperature
Part extrusion, then ultramicro grinding 4-6h is most dried after 100-115 DEG C and obtains final product calcium fruit fiber to 10-15 μm of particle diameter；
The biology enzyme is alkalescent xylanase, laccase, dextranase, seminase, pectase, pentosanase 2- in mass ratio
4:1-3:1-2:0.5-1.5:0.4-1:0.2-0.8 uniformly mixes.
3. degradable, anti-shrink polypropylene masterbatch as claimed in claim 1, it is characterised in that the system of the modified Nano carbon
Preparation Method, comprises the following steps：By middle modules carbon fibre, SWCN, ammonium persulfate and deionized water in mass ratio 1:
0.8-1:80-100:1000 uniform mixing, first in power 200-400W, the ultrasonically treated 20-40min of frequency 20-24KHz, so
Afterwards in electric-field intensity 2-6kV/cm, burst length 100-300 μ s carry out high-voltage pulse electric under the conditions of pulse frequency 200-400Hz
Field treatment 10-15min；0.5-2.5h is reacted in rotating speed 100-120r/min, 50-70 DEG C of temperature through the mixture after treatment, instead
Liquid is answered to be filtered with the PP micropore filtering films in 0.22 μm of aperture, and with deionized water cyclic washing to neutrality, most after 70-80
DEG C constant weight is dried under vacuum to, crushed, obtain final product modified Nano carbon.
4. degradable, anti-shrink polypropylene masterbatch as claimed in claim 1, it is characterised in that the polyethylene/winter rye peptide
The preparation method of compound, comprises the following steps：
1) preparation of winter rye peptide：By the seed sabot of winter rye, 6- is processed in electric-field intensity 8-10kV/cm high-pressure electrostatics
8min；Then the soaking at room temperature 1-3h in concentration is for the salicylic acid solution of 12-18mg/L, while in electric-field intensity 6-10kV/cm,
Burst length 100-200 μ s, carry out high-pressure pulse electric treatment under the conditions of pulse frequency 200-400Hz；Rinse, drain, in 3-5
DEG C stand 18-24h, then successively 1-3 DEG C refrigerate 2-4d, -3--5 DEG C freezing 1-3d, -15--18 DEG C freezing 10-15h, immediately
Outdoor natural light photograph is placed on, seed half is crushed immediately after thawing, crushed material particle diameter 0.5-1.5mm is subsequently added into crushing
The water of 2-4 times of amount of substance, is 3.5-5.5 with newborn acid for adjusting pH value；It is eventually adding the mixing of mixed liquor quality 1.3-1.7%
Enzyme, digests 10-30min in 35-50 DEG C first, then digests 20-40min in 50-60 DEG C；Enzymolysis liquid filtering, filtrate decompression are dense
Contracting, freeze-drying obtain final product winter rye peptide；
The mixed enzyme is protease, cellulase, amylase, pectase 5-7 in mass ratio:4-6:1-3:1-2 uniformly mixes；
2) winter rye peptide is sufficiently mixed in proportion with polyethylene, maleic anhydride, styrene, initiator and antioxidant, weight ratio
For：Polyethylene: winter rye peptide: maleic anhydride: styrene: initiator: antioxidant=100: 2-10: 3-20: 1-15: 0.1-5:
0.1-1；
3) by step 2) compound that obtains adds double screw extruder frit reaction, and extruding pelletization controls double screw extruder
And die temperature, at 145-180 DEG C, screw speed is 30-200r/min, residence time of the reactant in double screw extruder
Control obtained final product polyethylene/winter rye peptide complexes at 10-100 seconds.
5. degradable, anti-shrink polypropylene masterbatch as claimed in claim 1, it is characterised in that the preparation of the almond oil
Method, comprises the following steps：It is room temperature in the sodium bicarbonate solution of 0.01-0.03% by semen armeniacae amarae immersion mass percent concentration
Rinse, drain, put sealing and standing wetting 0.5-1.5h in container, then peel, decortication semen armeniacae amarae is put into microwave dryer
Gone out enzyme 2-4min in frequency 2450MHz, power 1000-3000W, 80-90 DEG C of temperature, thickness of feed layer 3-5cm condition microwave irradiations；
Soaking at room temperature 2-4h in the citric acid solution that mass percent concentration is 0.1-0.3% is then placed in, clear water is rinsed 1-3 times, drip
It is dry, in -20--25 DEG C, thickness of feed layer 8-10cm freezing 3-5h, it is crushed to particle diameter 0.4-0.6mm and obtains semen armeniacae amarae powder；To semen armeniacae amarae
The pH value of 3-5 times of its quality is added in powder for the deionized water of 4.5-6.5, uniform mixing, it is 45-55 to control mixed material temperature
DEG C, the compound enzyme of semen armeniacae amarae silty amount 0.03-0.05% is added thereto to, stir, it is incubated, digest 40-60min；By enzyme
Solution liquid puts vacuum -0.01--0.03MPa, 10-20 DEG C of temperature, rotating speed 10000r/min, traditional vacuum 5- in vacuum centrifuge
8min, isolated free oil, emulsion, hydrolyzate and semen armeniacae amarae slag from top to bottom, the emulsion that will be obtained controls the temperature to be
30-50 DEG C, the biological demulsifying agent demulsification 40-60min of addition emulsion quality 0.02-0.04%, demulsification after vacuum-
Traditional vacuum 10-15min obtains free oil again for 0.01--0.03MPa, 10-20 DEG C of temperature, 5000r/min, obtained by merging
Free oil obtains final product almond oil；
The quality group of the compound enzyme turns into：Acid protease:Cellulase:Pectase:Amylase=6-9:2-4:2-4:1-
3。
6. degradable, anti-shrink polypropylene masterbatch as claimed in claim 5, it is characterised in that the matter of the biological demulsifying agent
Measuring composition is：Glycolipid class:Lipopeptid class:Cell wall combination class=4-6:2-4:1-3.
7. degradable, anti-shrink polypropylene masterbatch as claimed in claim 6, it is characterised in that the glycolipid class biological demulsifying
The quality group of agent turns into：Rhamnolipid:APG=2-5:1-3.
8. degradable, anti-shrink polypropylene masterbatch as claimed in claim 1, it is characterised in that the matter of the seed culture medium
Measuring composition is：(NH4)2SO46g/L, glucose 35g/L, K2HPO4·3H2O 3g/L, KH2PO40.5g/L, dusty yeast 11g/L,
MnSO40.1g/L, KCL 0.1g/L, FeSO40.1g/L, MgSO4·7H2O 0.1g/L, balance of water, pH 6.0.
9. degradable, anti-shrink polypropylene masterbatch as claimed in claim 1, it is characterised in that the matter of the fermentation medium
Measuring composition is：(NH4)2SO410g/L, molasses 150g/L, K2HPO4·3H2O 8g/L, KH2PO40.5g/L, dusty yeast 5g/L,
Corn pulp 10g/L, MnSO40.1g/L, KCL 0.1g/L, FeSO40.1g/L, MgSO4·7H2O 0.1g/L, balance of water,
pH 6.0。
10. degradable as described in claim 1-9 is any, anti-shrink polypropylene masterbatch preparation method, it is characterised in that including
Following steps：It is first according to formula and accurately weighs each raw material, according to equal increments method principle, is by per kilogram compound power
0.25-0.35kW batch mixings while stirring, after being well mixed, it is 5-10cm control mixing thickness of feed layer, is then done in 100-120 DEG C
Dry 20-40min, reinstalls and extrude in double screw extruder, granulates, drying and obtain final product degradable, anti-shrink polypropylene masterbatch.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107973415A (en) * | 2017-11-30 | 2018-05-01 | 天津大学 | The purposes of Pseudomonas anguilliseptica degraded ultraviolet absorber PBSA |
| CN108587033A (en) * | 2018-05-16 | 2018-09-28 | 黄欣 | A kind of expanded material that ageing-resistant performance is good |
| CN109503739A (en) * | 2018-11-19 | 2019-03-22 | 李开民 | A kind of solid degradation agent and preparation method thereof |
| CN111087657A (en) * | 2019-12-13 | 2020-05-01 | 江阴市鸿萌橡塑制品有限公司 | Polyisoprene rubber remaining needle gasket and preparation method thereof |
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2016
- 2016-12-09 CN CN201611131537.7A patent/CN106674728A/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107973415A (en) * | 2017-11-30 | 2018-05-01 | 天津大学 | The purposes of Pseudomonas anguilliseptica degraded ultraviolet absorber PBSA |
| CN107973415B (en) * | 2017-11-30 | 2020-07-31 | 天津大学 | Application of diseased eel pseudomonas degradation ultraviolet absorbent PBSA |
| CN108587033A (en) * | 2018-05-16 | 2018-09-28 | 黄欣 | A kind of expanded material that ageing-resistant performance is good |
| CN109503739A (en) * | 2018-11-19 | 2019-03-22 | 李开民 | A kind of solid degradation agent and preparation method thereof |
| CN111087657A (en) * | 2019-12-13 | 2020-05-01 | 江阴市鸿萌橡塑制品有限公司 | Polyisoprene rubber remaining needle gasket and preparation method thereof |
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