CN108570183A

CN108570183A - A kind of PP composite material and preparation method thereof that dimensional stability is strong

Info

Publication number: CN108570183A
Application number: CN201710290670.5A
Authority: CN
Inventors: 田岗; 李继
Original assignee: Ningxia Yanchi West Chagnxiang Agricultural Biological Technology Co ltd
Current assignee: Ningxia Yanchi West Chagnxiang Agricultural Biological Technology Co ltd
Priority date: 2017-03-09
Filing date: 2017-04-28
Publication date: 2018-09-25

Abstract

The invention discloses a kind of PP composite materials that dimensional stability is strong, belong to polypropylene material technical field, taken polypropylene as the base material, optimize composite material raw material type and formula, production technology is improved, science compounding is remarkably improved PP composite material shock resistance and easily biological-degradable, the calcium fruit fiber for reducing production cost；It is remarkably improved the modified Nano carbon of PP composite material high temperature resistant and anti-contracility energy, opposite tensile load, intensity, toughness and elasticity modulus；Polyethylene/winter rye peptide complexes of PP composite material resistance to low temperature are greatly improved, PP composite material lubricity and antioxidative almond oil and composite antioxidant can be effectively improved；It acts synergistically with other processing aids, a kind of PP composite material that the good dimensional stability of physical property is strong is finally made.

Description

A kind of PP composite material and preparation method thereof that dimensional stability is strong

Technical field

The present invention relates to polypropylene materials, and in particular to a kind of PP composite material that dimensional stability is strong and its preparation Method.

Background technology

Polypropylene is a kind of good general-purpose plastics of comprehensive performance, and total output alreadys exceed polyvinyl chloride as being 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 has higher counter-bending fatigue strength, can have good electrical property and high-frequency insulation using at 100 degree or so Property is not influenced by humidity, but becomes fragile when low temperature, is not wear-resisting, is easy to aging.Because it is with notch sensitivity, and heat distortion temperature it is low, Molding shrinkage is big, hardness and wears 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, food packagings, PP high temperature resistants, lower temperature resistance Can be poor, this performance deficiency will seriously restrict its development in above-mentioned field.

105462060 A of Chinese patent CN disclose a kind of flammable modified polypropylene material of improvement polypropylene material And preparation method thereof.Polypropylene bulk material cold resistance is poor, and low temperature is easily broken, and shrinking percentage is big, and creep resistance is poor, and product size is stablized Poor, the mutability of property.And polypropylene is combustible material, and the oxygen index (OI) of virgin pp only has 18 or so.As people recognize fire prevention The intensification of knowledge, on the components such as various equipment, instrument, building, be required to use fire proofing, therefore it is polyacrylic it is fire-retardant be must Indispensable modification.

103205064 B of Chinese patent CN disclose a kind of modified polypropylene agglomerate and multiple using the polypropylene of the master batch Condensation material, modified polypropylene agglomerate are made of the raw material of following parts by weight：100 parts of chlorinated polypropylene, 5~30 parts of organic amine, Assist 10~20 parts of agent, 0.5~2 part of antioxidant, 0.4~1.2 part of stabilizer；Material is answered by following using the polypropylene of the master batch The raw material of parts by weight forms：10~20 parts of modified polypropylene agglomerate, 10~20 parts of chloridized polyolefin, 60~80 parts of polypropylene. The modified polypropylene agglomerate of the invention contains organic amine modified chlorinated polypropylene as Polymer-metallic Catalyst, has persistently anti-quiet Electric effect；Using the PP composite material of the master batch, while ensureing polypropylene material impact strength, improve persistently Antistatic property and anti-flammability.

103483690 B of Chinese patent CN disclose a kind of modified polypropylene composite material, weight percent composition packet It includes：Copolymer polypropylene：60~80%, toughener 2~10%, maleic anhydride inoculated polypropylene 1~10%, coupling agent 0.1~ 2%, halogen-free flame retardants 5~30%, light stabilizer 0.2~2%, stearic acid 1~2%.Modified polypropylene composite material of the present invention With good weatherability, service life is long, and aberration is less than 1 within 3000 hours, that is, reaches what outdoor application was not faded for 8~10 years It is required that；Anti-flammability is excellent, and flame retardant rating reaches V0 grades, and the feature of environmental protection meets the requirement of RoHS standards；In addition, also having excellent Toughness, rigidity and scratch-proofness.

103205064 B of Chinese patent CN disclose a kind of modified polypropylene agglomerate and multiple using the polypropylene of the master batch Condensation material, modified polypropylene agglomerate are made of the raw material of following parts by weight：100 parts of chlorinated polypropylene, 5~30 parts of organic amine, 10~20 parts of synergist, 0.5~2 part of antioxidant, 0.4~1.2 part of stabilizer；Using the master batch PP composite material by with The raw material of lower parts by weight forms：10~20 parts of modified polypropylene agglomerate, 10~20 parts of chloridized polyolefin, polypropylene 60~80 Part.The modified polypropylene agglomerate of the invention contains organic amine modified chlorinated polypropylene as Polymer-metallic Catalyst, and it is lasting to have Antistatic effect；It is improved while ensureing polypropylene material impact strength using the PP composite material of the master batch Permanent antistatic and anti-flammability.

103788495 B of Chinese patent CN disclose the fire-retardant low temperature resistant PP composite material of one kind and its preparation process, Its component ratio percentage：Short glass fiber, resin, barium sulfate, reinforcing agent, toughener, cold-resistant agent, fire retardant, Compatilizer, coupling agent, melting means modifying agent, flow ability modifying agent, stabilizer, curing agent, PH conditioning agents, smoke suppressant, antioxidant, at Core agent, processing aid, mineral-filled agent, lubricant, antistatic agent and eliminating smell agent, remaining is acrylic polymers.The group of the invention Largely experiment obtains appropriate component to lease making excessively, and intensity is low during not only solving existing polypropylene material use, holds Other bad features such as yielding, and also there is good impact resistance and fatigue durability under conditions of low temperature, significantly Improve its service life, reduce the generation of contingency, be widely used in the fields such as automotive upholstery, bumper.

102276920 B of Chinese patent CN disclose a kind of PP composite material, count in parts by weight, including 65~ 70 parts of polypropylene, 25~27 parts of glass fibre, 2~4 parts of compatilizer, 2~4 parts of toughener, 0.2~0.4 part of idol Join agent, 0.2~0.4 part of antioxidant, 0.2~0.5 part of lubricant and 0.2~0.4 part of nucleating agent.Above-mentioned polypropylene is multiple The tool intensity of condensation material is higher and creep-resistant property is preferable.

101712779 B of Chinese patent CN disclose a kind of high heat-resisting polypropylene nano composite wood of low-density high rigidity Material and preparation method thereof, wherein low-density high rigidity high heat-resisting polypropylene nanocomposite by following raw material by weight percentage Composition：Polypropylene 70~98%, organic clay 1~15%, compatilizer 0.1~10%, stabilizer 0.2~2%, other additives 0~5%.The advantages of invention is：1, the use of nanoscale organic clay is filler reinforced polypropylene matrix, only adds a small amount of nanometer Filler can be such that the rigidity of material and heat resistance is significantly improved.2, compared with conventional filler reinforced polypropylene, hence it is evident that drop The low density of material, product are beneficial to mitigate product weight and therefore reduce energy consumption for automobile and other relevant industries. 3, using sub-material mode, make nano-sized filler dispersion effect in a polymer matrix and material property on the basis of prior art Further improved.

Although PP composite material disclosed above solves the defect of polypropylene segment material, but not comprehensively, effect It is still not highly desirable, meanwhile, using inorganic salts such as calcium carbonate, nano-calcium carbonate and silicates (clay, actinolite etc.) as filler material, no Easily biological-degradable easily makes alkalization of soils, can cause severe environmental pollution.

Carbon fiber is in traditional use in addition to as heat-insulating material.Mostly as reinforcing material be added to resin, metal, In the materials such as ceramics, concrete, composite material is constituted.Carbon fiber has become the most important reinforcing material of advanced composite material.By Have that light and strong, light and rigid, high temperature resistant, corrosion-resistant, endurance, structure size stability is good and sets in carbon fibre composite Meter property it is good, can large area global formation the features such as, obtained extensively in the every field of aerospace, defence and military and civilian industry 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.

Carbon nanotube has high intensity, toughness and elasticity modulus in terms of mechanics.Its elasticity is up to 1TPa, about steel 5 times, almost the same with the elasticity modulus of diamond, elastic strain is about 5%, reaches as high as 12%.No matter is carbon nanotube It is that intensity or toughness are all far superior to any fibrous material.Using carbon nanotube as composite material reinforcement body, can express out good Intensity well, elasticity, fatigue resistance.Carbon nanotube not only has excellent mechanical property, also has excellent electricity, optical Energy.Many experiments show that compared with other reinforcements (such as carbon black, carbon fiber or metal charge), carbon nanotube is to polymerization The improvement of object based composites electric conductivity is more notable, and since carbon nanotube has nano-grade size, addition is few, Polymer composites can also enhance its mechanical performance and other performance while obtaining good electric conductivity, simultaneously also Be conducive to the design of high molecular material other performance, therefore receive significant attention.

But the active group of carbon fiber, carbon nano tube surface is considerably less, the interaction with high molecular material group is very It is weak, and the draw ratio and large specific surface area of carbon nanotube, it is difficult to divide in the polymer when being used to prepare polymer composite It dissipates uniformly, agglomeration easily occurs, its excellent properties can not be embodied.Therefore being modified to the surface of carbon nanotube seems extremely It is important.

To sum up, continue, improve polyacrylic material property comprehensively, inorganic carbonate and silicon are replaced with organic degradable filler Hydrochlorate improves production technology, it is necessary to prepare a kind of good environment-friendly polypropylene composite material of physical property.

Invention content

Technical problem solved by the invention is to overcome the defect of existing PP composite material and preparation method thereof, with poly- Propylene is base-material, optimizes composite material raw material type and formula, improves production technology, it is multiple that science compounding is remarkably improved polypropylene Condensation material shock resistance and easily biological-degradable, the calcium fruit fiber for reducing production cost；It is remarkably improved PP composite material The modified Nano carbon of high temperature resistant and anti-contracility energy, opposite tensile load, intensity, toughness and elasticity modulus；It is greatly improved poly- The polyethylene of acrylic composite resistance to low temperature/winter rye peptide complexes, can effectively improve PP composite material lubricity And antioxidative almond oil and composite antioxidant；It acts synergistically with other processing aids, a kind of dimensionally stable is finally made The strong PP composite material of property

In order to achieve the above object, the present invention uses following technical scheme：

A kind of PP composite material that dimensional stability is strong is mainly prepared by the raw material of following parts by weight：

120-200 parts of polypropylene, 12-18 parts of calcium fruit fiber, 8-10 parts of modified Nano carbon, polyethylene/winter rye peptide are compound 8-10 parts of object, 8-10 parts of ultra-violet absorber, 6-8 parts of ethylene-methyl acrylate copolymer, 6-8 parts of antiaging agent, citric acid 2-4 parts of tributyl, 1.5-1.9 parts of coupling agent, 0.6-1.0 parts of nucleating agent, 0.3-0.5 parts of composite antioxidant, almond oil 0.1- 0.4 part；

Further, the calcium fruit fiber is with calcic, the higher natural plants of iron-calcium stem end, leaf of GAIGUO and waste wood Bits are raw material, through the extraction of ultrasonic cleaning, ultrasound and high-pressure pulse electric, biobleaching and appropriateness enzymolysis, microwave drying, extruding Puffing, ultramicro grinding and be made；

Preferably, the preparation method of the calcium fruit fiber, includes the following steps：By fresh calcium stem end, leaf of GAIGUO and waste wood Consider 6-8 in mass ratio to be worth doing:2-6:1-2 is uniformly mixed, and is placed in supersonic wave cleaning machine and is cleaned 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 high-voltage pulse is carried out under the conditions of electric field strength 20-40kV/cm, burst length 400-600 μ s, pulse frequency 200-400Hz Electric field treatment 10-15min；Adjusting pH value is 6-10, and the biological enzyme of mixture quality 0.1-0.3% is added, in 50-60 DEG C of enzymolysis 10-15min；It is 40-60% that enzymolysis liquid, which is concentrated under reduced pressure into solid content, is put into microwave dryer in 2000W, 130-150 DEG C Intermittent drying is carried out, moisture is allowed to and reaches 8-10%, is then crushed to grain size 0.4-0.6mm, crushed material quality 0.2- is added 0.4% sodium bicarbonate, uniformly mix, adjustment mixture moisture be 15-18%, room temperature, sealing and standing 1.5-2.5h, in 140-160 DEG C of screw speed 105-115r/min, temperature condition extrusion, then ultramicro grinding is to 10-15 μm of grain size, finally In 100-115 DEG C of dry 4-6h up to calcium fruit fiber；

The biological 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 is uniformly mixed.

Further, the modified Nano carbon is with ammonium persulfate by single wall or multi-walled carbon nanotube and carbon fiber in water phase System mild reaction purification, modification after ultrasonic disperse and high-pressure pulse electric processing are made；

Preferably, the preparation method of the modified Nano carbon, includes 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 uniformly mixing, first power 200-400W, Frequency 20-24KHz is ultrasonically treated 20-40min, then in electric field strength 2-6kV/cm, burst length 100-300 μ s, pulse frequency High-pressure pulse electric is carried out under the conditions of rate 200-400Hz handles 10-15min；Mixture after processing is in rotating speed 100- The PP micropore filtering films of 120r/min, 50-70 DEG C of temperature reaction 0.5-2.5h, 0.22 μm of aperture of reaction solution are filtered, and It is washed repeatedly with deionized water to neutrality, constant weight is finally dried under vacuum in 70-80 DEG C, crushed to get modified Nano carbon.

Further, the polyethylene/winter rye peptide complexes are poly- with the synthetic resin with good resistance to low temperature Ethylene and the winter rye antifreeze peptide blending with excellent anti-freezing property, co-melting, extruding pelletization form；

Preferably, the preparation method of the polyethylene/winter rye peptide complexes, includes the following steps：

1) preparation of winter rye peptide：By the seed sabot of winter rye, 6- is handled in electric field strength 8-10kV/cm high-pressure electrostatics 8min；Then the soaking at room temperature 1-3h in the salicylic acid solution of a concentration of 12-18mg/L, while in electric field strength 6-10kV/cm, High-pressure pulse electric processing is carried out under the conditions of burst length 100-200 μ s, pulse frequency 200-400Hz；It rinses, drain, in 3-5 DEG C stand 18-24h, then successively at 1-3 DEG C refrigerate 2-4d, -3--5 DEG C freezing 1-3d, -15--18 DEG C freezing 10-15h, immediately It is placed on outdoor natural light photograph, is crushed immediately after so that seed half is thawed, crushed material grain size 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 It contracts, be freeze-dried up to 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 and polyethylene, maleic anhydride, styrene, initiator and antioxidant are sufficiently mixed in proportion, 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) double screw extruder frit reaction, extruding pelletization is added in the mixture for obtaining step 2), and control twin-screw squeezes Go out machine and die temperature at 145-180 DEG C, screw speed 30-200r/min, stop of the reactant in double screw extruder Time control is at 10-100 seconds to get polyethylene/winter rye peptide complexes.

Further, the almond oil is using semen armeniacae amarae as raw material, soaking detoxification, microwave irradiation enzyme deactivation, freezing crushing, The low temperature extraction processes such as biological enzymolysis, biological demulsifying agent demulsification, traditional vacuum are made；

Preferably, the preparation method of the almond oil, includes the following steps：Semen armeniacae amarae is immersed into mass percent concentration It rinses, drain for room temperature in the sodium bicarbonate solution of 0.01-0.03%, set sealing and standing in container and soak 0.5-1.5h, then Decortication semen armeniacae amarae is put into microwave dryer in frequency 2450MHz, power 1000-3000W, 80-90 DEG C of temperature, material by decortication Layer thickness 3-5cm condition microwave irradiation enzyme deactivations 2-4min；It is molten to be then placed in the citric acid that mass percent concentration is 0.1-0.3% Soaking at room temperature 2-4h in liquid, clear water are rinsed 1-3 times, are drained, and are freezed 3-5h in -20--25 DEG C, thickness of feed layer 8-10cm, are crushed to Grain size 0.4-0.6mm obtains semen armeniacae amarae powder；The pH value that 3-5 times of its quality is added into semen armeniacae amarae powder is the deionized water of 4.5-6.5, Uniformly mixing, control mixed material temperature are 45-55 DEG C, and the compound enzyme of semen armeniacae amarae silty amount 0.03-0.05% is added thereto, It stirs evenly, keeps the temperature, digest 40-60min；Enzymolysis liquid is set into vacuum degree -0.01--0.03MPa, temperature in vacuum centrifuge 10-20 DEG C, rotating speed 10000r/min, traditional vacuum 5-8min, from top to bottom isolated free oil, emulsion, hydrolyzate and Semen armeniacae amarae slag, by obtained emulsion controlled at 30-50 DEG C, the biological demulsifying of addition emulsion quality 0.02-0.04% Agent is demulsified 40-60min, in vacuum degree -0.01--0.03MPa, 10-20 DEG C of temperature, 5000r/min traditional vacuum again after demulsification 10-15min obtains free oil, merges the free oil of gained up to almond oil；

The quality group of the compound enzyme becomes：Acid protease:Cellulase:Pectase:Amylase=6-9:2-4:2- 4:1-3；

The quality group of the biological demulsifying agent becomes：Glycolipid class:Lipopeptid class:Cell wall combination class=4-6:2-4:1-3；

The quality group of the glycolipid class biological demulsifying agent becomes：Rhamnolipid:Alkyl glycosides=2-5:1-3.

Further, the ultra-violet absorber is UV-531.

Further, it is preferable to use Dupont EMA1125AC for the ethylene-methyl acrylate copolymer.

Further, the nucleating agent is Sorbitol Nucleator；

Preferably, the nucleating agent is two sub- (3,4- dimethyl) benzyl D-sorbites (DMDBS).

Further, the composite antioxidant is antioxidant 1010, irgasfos 168 and biologic antioxidants 1-2 in mass ratio: 1-3:2-4 is uniformly mixed；

Preferably, the preparation method of the biologic antioxidants, includes the following steps：Saccharomyces cerevisiae after taking 1 ring to activate Tlj2016 slant strains are seeded in the 500m L triangular flasks equipped with 100m L seed culture mediums and cultivate, 28~30 DEG C, shake 25~30h is cultivated under the conditions of 150~200r/min of bed rotating speed, obtains primary seed solution；Primary seed solution is pressed into 5~10% (v/ V) inoculum concentration is seeded in the 500m L triangular flasks equipped with 100m L fermentation mediums and carries out fermented and cultured, fermentation time 25 ~30h, 28~30 DEG C of temperature, 150~200r/min of shaking speed obtain 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 quantity 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 The additive amount of every liter of 25~30mmol of zymotic fluid disposably adds L-cysteine into zymotic fluid, continues fermentation 20-30h and obtains To final zymotic fluid；Final zymotic fluid centrifugation, the filtering of supernatant 1000-1200 mesh screens are concentrated, are lyophilized up to biological antioxygen Agent；

GSH final concentrations reach 3308mg/L in the final zymotic fluid；

The quality group of the seed culture medium becomes：(NH₄)₂SO₄6g/L, glucose 35g/L, K₂HPO₄·3H₂O 3g/ L, KH₂PO₄0.5g/L, yeast powder 11g/L, MnSO₄0.1g/L, KCL 0.1g/L, FeSO₄0.1g/L, MgSO₄·7H₂O 0.1 g/L, surplus are water, pH 6.0；

The quality group of the fermentation medium becomes：(NH₄)₂SO₄10g/L, molasses 150g/L, K₂HPO₄·3H₂O 8g/ L, KH₂PO₄0.5g/L, yeast powder 5g/L, corn steep liquor 10g/L, MnSO₄0.1g/L, KCL 0.1g/L, FeSO₄0.1g/L, MgSO₄·7H₂O 0.1g/L, surplus are water, pH 6.0.

The saccharomyces cerevisiae is specially saccharomyces cerevisiae (Saccharomyces cerevisiae) tlj2016, and the bacterial strain is It is preserved in China Committee for Culture Collection of Microorganisms's common micro-organisms center 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) 300g/L is reached to the tolerance of glucose, is conducive to it GSH is produced under the conditions of high concentration glucose；2) reach 3308mg/L in 5L fermentation cylinder for fermentation production GSH final concentrations；3) resistance to By the ability extra-heavy of L- cysteines, remain to slowly grow under the effect of 5mmol/L L-cysteines, in 40mmol/L L- It remains to that GSH is kept largely to synthesize under cysteine effect；4) salt resistance ability reaches 18%, is conducive to extend its application field.

Another object of the present invention is to provide the preparation method of the strong PP composite material of above-mentioned dimensional stability, including such as Lower step：Each raw material is accurately weighed first, in accordance with formula, according to equal increments method principle, is by per kilogram mixture power Batch mixing controls mixing thickness of feed layer for 5-10cm, then in 100-120 DEG C to 0.25-0.35kW after mixing while stirring Dry 20-40min, it is reloaded into double screw extruder and squeezes out, is granulated, drying up to the strong polypropylene composite materials of dimensional stability Material.

Advantageous effect：

The present invention taken polypropylene as the base material, optimizes composite material raw material type and formula, improves production technology, science compounding It is remarkably improved PP composite material shock resistance and easily biological-degradable, the calcium fruit fiber for reducing production cost；It can be notable The modification for improving PP composite material high temperature resistant and anti-contracility energy, opposite tensile load, intensity, toughness and elasticity modulus is received Rice carbon；Polyethylene/winter rye peptide complexes of PP composite material resistance to low temperature are greatly improved, poly- third can be effectively improved Alkene composite material lubricity and antioxidative almond oil and composite antioxidant；It acts synergistically with other processing aids, finally A kind of good environment-friendly polypropylene composite material of physical property is made.Test result shows：Compared with commercially available, size of the present invention The strong PP composite material impact resistance of stability is strong, improves 106.3%；Heat distortion temperature is high, and high temperature resistance is strong, improves 37.9%；Stretch-proof, intensity improve 109.5%；Toughness is strong, and elongation at break improves 87.5%；Bending property is excellent, modulus and 92.9% and 225.2% is respectively increased in intensity；Electric conductivity is strong, and antistatic property is good, and sheet resistance reduces by 99.8%；Size is steady Qualitative good, indeformable, shrinking percentage reduces by 76.7%；Oxidation resistance is strong, and anti-aging, service life is long, and oxidation induction time prolongs Long 171.7%.Also illustrate simultaneously, the material property of the strong PP composite material of dimensional stability of the present invention is carried comprehensively Height, effect is ideal, has achieved the purpose that material expands application, has preferable advanced and practicability.Specific test result is shown in Embodiment 19, particular technique principle are as follows：

1. calcium fruit fiber prepared by the present invention is with calcic, the higher natural plants of iron-calcium stem end, leaf of GAIGUO and to give up Sawdust is raw material, through the extraction of ultrasonic cleaning, ultrasound and high-pressure pulse electric, biobleaching and faint enzymolysis, microwave drying, is squeezed It presses puffing, ultramicro grinding and is made, a variety for the treatment of technologies are combined, act synergistically, especially after crushed, be added a certain amount of Sodium bicarbonate, sealing and standing after adjusted moisture, then extrusion, can significantly increase the specific surface area of calcium fruit fiber, net Lattice structure is more abundant, and puffed degree, dilatancy, thickening property are stronger, and cellulose specific surface area increases, and adsorption capacity increases with tensile resistence By force, it is merged with metal ions such as calcium therein, iron, you can improve toughness, the elasticity of PP composite material, and can be improved poly- third The high temperature resistant and shock resistance of alkene composite material.Kinds of processes combination simultaneously can effectively improve the draw ratio and table of fiber grain Face binding force improves the compatibility with polypropylene base-material and other resins, can be evenly dispersed and compatible in polypropylene base-material, will Its science compounds in composite material, can substitute completely calcium carbonate in the prior art, nano-calcium carbonate and silicate (clay, Actinolite etc.), not only it is remarkably improved PP composite material shock resistance and high temperature resistance, but also easily biological-degradable, Production cost is reduced, soil constituent is improved, increases the content of organic matter, it is environmentally friendly, while also improving calcium stem end leaf and giving up The value of sawdust, turns waste into wealth, and is conducive to promote agriculture, rural areas and farmers development.

2. modified Nano carbon prepared by the present invention is by single wall or multi-walled carbon nanotube, carbon fiber, ammonium persulfate and water section Compounding is learned, is handled through ultrasonic disperse and high-pressure pulse electric, alternate electric field and magnetic field can generate strong concussion, water phase electricity From, oxidation, nanotube dispersion that is uniform, stablizing is formed, then reacts at a lower temperature, carbon nanotube is carried out Comprehensive surface treatment is deposited with generating hydroxyl, carbonyl and a small amount of carboxyl, these groups on the surface of carbon nanotube, carbon fiber So that carbon nanotube, carbon fiber is soluble in water or in the organic solvent of DMF isopolarities, it is stronger to finally obtain dissolubility The long carbon nanotube of solubility, short carbon nanometer tube and carbon fiber.Being added into PP composite material comprehensively, uniformly to divide It dissipates, be filled into polypropylene base-material, give full play to the material property of carbon nanotube and carbon fiber, be remarkably improved polypropylene composite materials The anti-contracility of material can (dimensional stability), relatively tensile load, intensity, toughness and elasticity modulus；The advantages of the method is： 1) length of carbon nanotube is controllable：The distribution of lengths of carbon nanotube can have the change of reaction condition and control, when carbon nanotube exists When being handled by the ammonium persulfate solution of high concentration at higher temperature, the carbon nanotube that can be truncated；When ammonium persulfate When concentration is relatively low or reaction temperature is relatively low, carbon nanotube will not be truncated；2) use of traditional strong acid, highly basic is avoided, High safety；3) Processes and apparatus is simple, and reaction is mild, efficient；4) use of expensive surfactant, cost are avoided It is low；5) environmentally friendly using water and neutral sulfatase as reaction dissolvent and raw material；6) it scale and can commercially produce.

3. polyethylene prepared by the present invention/winter rye peptide complexes are poly- with the synthetic resin with good resistance to low temperature Ethylene and the winter rye antifreeze peptide blending with excellent anti-freezing property, co-melting, extruding pelletization form；The winter rye peptide is to contain It is prepared by raw material to have the winter rye seed of abundant freeze proof matrix, and high-pressure electrostatic processing, high-pressure pulse electric are assisted salicylic acid Induction, low temperature segmentation Stress treatment and natural lighting organically combine 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 mixed enzyme digests Maximizing dissolves out, while freeze proof peptide content can be made to increase, and has significantly delayed the formation of ice crystal, has reduced 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 PP composite material, It is compounded with polyethylene science, is blended, is co-melting, producing unexpected cryoprotective effects, resistance to low temperature significantly increases；Especially It is the mobility, lubricity and antioxygen that the seed fat wherein contained also can further improve compound and PP composite material The property changed.

4. almond oil prepared by the present invention is using semen armeniacae amarae as raw material, through microwave irradiation enzyme deactivation, freezing crushing, enzymolysis, true Free oil, emulsion, hydrolyzate and almond slag are obtained after sky centrifugation, emulsion therein is subjected to vacuum again after biological demulsifying Centrifugation obtains free oil, free oil is merged to obtain the final product, relative to turpentine oil, coix seed oil and the mandarin oil in existing composite material Say that the anti-oxidation active substances such as unsaturated fatty acid and VE therein are higher, lubricity, mobility and inoxidizability are stronger.

5. functional make is added using high sugared fermentation medium as fermentation substrate in nano grade biological antioxidant prepared by the present invention Brewer yeast ferments, and can obtain a large amount of reductive glutathiones, by its science compounding in PP composite material, cooperates with antioxidant 1010 and irgasfos 168, inoxidizability is stronger, and biodegradable, environmentally friendly.

It should be noted that the strong PP composite material of dimensional stability of the present invention has the technical effect that each component is mutual Collaboration, interaction as a result, the superposition of not simple raw material function, the science compounding of each raw material component and extraction generate Effect considerably beyond the superposition of each single component function and effect, there is preferable advanced and practicability.

Specific implementation mode

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 Range, 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 Under the premise of invention spirit and scope, various changes or change to material component and dosage progress in these embodiments It belongs to the scope of protection of the present invention.

It is prepared by 1 raw material of embodiment

1. the preparation of calcium fruit fiber：

The preparation method of the calcium fruit fiber, includes the following steps：Fresh calcium stem end, leaf of GAIGUO and waste wood are pressed into quality Than 7:4:1.5 uniformly mixing, are placed in supersonic wave cleaning machine and clean 4min in 200W, 30KHz, drain, be crushed, and are added broken The water that 1 times of amount of substance, room temperature 300W, 40KHz condition ultrasonic extraction 12min, then in electric field strength 30kV/cm, burst length High-pressure pulse electric is carried out under the conditions of 500 μ s, pulse frequency 300Hz handles 12min；It is 8 to adjust pH value, and mixture quality is added 0.2% biological enzyme digests 12min in 55 DEG C；It is 50% that enzymolysis liquid, which is concentrated under reduced pressure into solid content, is put into microwave dryer In 2000W, 140 DEG C of progress intermittent dryings, it is allowed to moisture and reaches 9%, be then crushed to grain size 0.5mm, comminuted material is added The sodium bicarbonate of amount 0.3% uniformly mixes, and adjustment mixture moisture is 17%, and room temperature, sealing and standing 2h turn in screw rod 150 DEG C of fast 110r/min, temperature condition extrusions, then ultramicro grinding be in 105 DEG C of dry 5h finally to 12 μm of grain size Obtain calcium fruit fiber；

The biological enzyme is alkalescent xylanase, laccase, dextranase, seminase, pectase, pentosanase by quality Than 3:2:1.5:1:0.7:0.5 uniformly mixing.

2. the preparation of modified Nano carbon：

The preparation method of the modified Nano carbon, includes the following steps：By middle modules carbon fibre, single-walled carbon nanotube, over cure Sour ammonium and deionized water in mass ratio 1:0.9:90:1000 uniformly mixing are ultrasonically treated in power 300W, frequency 22KHz first Then 30min carries out high-pressure pulse electric under the conditions of electric field strength 4kV/cm, 200 μ s of burst length, pulse frequency 300Hz Handle 12min；Mixture after processing reacts 2h in rotating speed 110r/min, temperature 60 C, 0.22 μm of aperture of reaction solution PP micropore filtering films are filtered, and are used in combination deionized water to be washed repeatedly to neutrality, are finally dried under vacuum to constant weight, powder in 75 DEG C It is broken to get modified Nano carbon.

3. the preparation of polyethylene/winter rye peptide complexes：

The preparation method of the polyethylene/winter rye peptide complexes, includes the following steps：

1) preparation of winter rye peptide：By the seed sabot of winter rye, 7min is handled in electric field strength 9kV/cm high-pressure electrostatics； Then the soaking at room temperature 2h in the salicylic acid solution of a concentration of 15mg/L, while in electric field strength 8kV/cm, 150 μ of burst length High-pressure pulse electric processing is carried out under the conditions of s, pulse frequency 300Hz；It rinses, 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, are carried out immediately after so that seed half is thawed It crushes, crushed material grain size 1mm is subsequently added into the water of 3 times of crushed material quality, is 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 It is concentrated under reduced pressure, is freeze-dried up to winter rye peptide；

The mixed enzyme is protease, cellulase, amylase, pectase in mass ratio 6:5:2:1.5 uniformly mixing；

2) winter rye peptide and polyethylene, maleic anhydride, styrene, initiator and antioxidant are sufficiently mixed in proportion, weight Measuring ratio is：Polyethylene: winter rye peptide: maleic anhydride: styrene: initiator: antioxidant=100: 6: 10: 7: 2.6: 0.5；

3) double screw extruder frit reaction, extruding pelletization is added in the mixture for obtaining step 2), and control twin-screw squeezes Go out machine and die temperature at 162 DEG C, screw speed 115r/min, residence time of the reactant in double screw extruder controls At 55 seconds to get polyethylene/winter rye peptide complexes.

4. the preparation of almond oil：

The preparation method of the almond oil, includes the following steps：It is by semen armeniacae amarae immersion mass percent concentration Room temperature is rinsed, is drained in 0.02% sodium bicarbonate solution, is set sealing and standing in container and is soaked 1h, then peels, 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 Enzyme deactivation 3min；It is then placed in soaking at room temperature 3h in the citric acid solution that mass percent concentration is 0.2%, clear water rinses 2 times, drip It is dry, 4h is freezed in -23 DEG C, thickness of feed layer 9cm, grain size 0.5mm is crushed to and obtains semen armeniacae amarae powder；Its quality is added into semen armeniacae amarae powder The deionized water that 4 times of pH value is 5.5 uniformly mixes, and control mixed material temperature is 50 DEG C, and semen armeniacae amarae silty is added thereto The compound enzyme of amount 0.04%, stirs evenly, and keeps the temperature, and digests 50min；Enzymolysis liquid is set into vacuum degree-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, Hydrolyzate and semen armeniacae amarae slag, by obtained emulsion controlled at 40 DEG C, the biological demulsifying of addition emulsion quality 0.03% Agent demulsification 50min, in vacuum degree -0.02MPa, 15 DEG C of temperature, 5000r/min, traditional vacuum 12min is swum again after demulsification From oil, merge the free oil of gained up to almond oil；

The quality group of the compound enzyme becomes：Acid protease:Cellulase:Pectase:Amylase=7:3:3:2；

The quality group of the biological demulsifying agent becomes：Glycolipid class:Lipopeptid class:Cell wall combination class=5:3:2；

The quality group of the glycolipid class biological demulsifying agent becomes：Rhamnolipid:Alkyl glycosides=3:2.

5. the preparation of biologic antioxidants:

The preparation method of the biologic antioxidants, includes the following steps：Saccharomyces cerevisiae tlj2016 after taking 1 ring to activate is oblique Face strain is seeded in the 500m L triangular flasks equipped with 100m L seed culture mediums and cultivates, in 29 DEG C, shaking speed 180r/min Under the conditions of cultivate 27h, obtain primary seed solution；The inoculum concentration that primary seed solution is pressed to 8% (v/v), is seeded to equipped with 100m L Carry out fermented and cultured in the 500m L triangular flasks of fermentation medium, fermentation time 28h, 29 DEG C, shaking speed 180r/min of temperature, Obtain secondary seed solution；Secondary seed solution is linked into the 5L fermentation tank constant temperature of dress 3L fermentation mediums with 8% (v/v) inoculum concentration Fermentation, 29 DEG C, ventilation quantity 5L/min, rotating speed 180r/min of temperature, fermentation full adjustment zymotic fluid pH value be 6.2, when fermentation extremely When 28h, L-cysteine is disposably added into zymotic fluid with the additive amount of every liter of zymotic fluid 27mmol, continues fermentation 25h and obtains To final zymotic fluid；Final zymotic fluid centrifugation, the filtering of 1100 mesh screen of supernatant are concentrated, are lyophilized up to biologic antioxidants.

GSH final concentrations reach 3308mg/L in the final zymotic fluid；

Calcium fruit fiber, modified Nano carbon, polyethylene/winter rye peptide complexes, bitter apricot used in following example 2-6 Benevolence oil, biologic antioxidants are prepared for embodiment 1, and other is purchased in market.

Embodiment 2

160 parts of polypropylene, 15 parts of calcium fruit fiber, 9 parts of modified Nano carbon, polyethylene/9 parts of winter rye peptide complexes are ultraviolet 9 parts of light absorbers, 7 parts of ethylene-methyl acrylate copolymer, 7 parts of antiaging agent, 3 parts of tributyl citrate, coupling agent 1.7 Part, 0.8 part of nucleating agent, 0.4 part of composite antioxidant, 0.2 part of almond oil；

The ultra-violet absorber is UV-531.

The ethylene-methyl acrylate copolymer is Dupont EMA1125AC.

The nucleating agent is two sub- (3,4- dimethyl) benzyl D-sorbites.

The composite antioxidant is antioxidant 1010, irgasfos 168 and biologic antioxidants in mass ratio 1.5:2:3 is uniformly mixed It closes.

Preparation method includes the following steps：Each raw material is accurately weighed first, in accordance with being formulated, foundation equal increments method principle, Be 0.3kW batch mixings while stirring by per kilogram mixture power, after mixing, control mixing thickness of feed layer is 8cm, then in 110 DEG C of dry 30min, it is reloaded into double screw extruder and squeezes out, is granulated, drying and answered up to the strong polypropylene of dimensional stability Condensation material.

Embodiment 3

120 parts of polypropylene, 12 parts of calcium fruit fiber, 8 parts of modified Nano carbon, polyethylene/8 parts of winter rye peptide complexes are ultraviolet 8 parts of light absorbers, 6 parts of ethylene-methyl acrylate copolymer, 6 parts of antiaging agent, 2 parts of tributyl citrate, coupling agent 1.5 Part, 0.6 part of nucleating agent, 0.3 part of composite antioxidant, 0.1 part of almond oil；

The ultra-violet absorber is UV-531.

The ethylene-methyl acrylate copolymer is Dupont EMA1125AC.

The nucleating agent is two sub- (3,4- dimethyl) benzyl D-sorbites.

The composite antioxidant is antioxidant 1010, irgasfos 168 and biologic antioxidants in mass ratio 1:1:2 is uniformly mixed It closes.

Preparation method includes the following steps：Each raw material is accurately weighed first, in accordance with being formulated, foundation equal increments method principle, It is 0.25kW batch mixings while stirring by per kilogram mixture power, after mixing, control mixing thickness of feed layer is 5cm, then In 100 DEG C of dry 20min, it is reloaded into double screw extruder and squeezes out, is granulated, drying up to the strong polypropylene of dimensional stability Composite material.

Embodiment 4

200 parts of polypropylene, 18 parts of calcium fruit fiber, 10 parts of modified Nano carbon, polyethylene/10 parts of winter rye peptide complexes are purple 10 parts of ultraviolet absorbers, 8 parts of ethylene-methyl acrylate copolymer, 8 parts of antiaging agent, 4 parts of tributyl citrate, coupling agent 1.9 Part, 1.0 parts of nucleating agent, 0.5 part of composite antioxidant, 0.4 part of almond oil；

The ultra-violet absorber is UV-531.

The ethylene-methyl acrylate copolymer is Dupont EMA1125AC.

The nucleating agent is two sub- (3,4- dimethyl) benzyl D-sorbites.

The composite antioxidant is antioxidant 1010, irgasfos 168 and biologic antioxidants in mass ratio 2:3:4 is uniformly mixed It closes.

Preparation method includes the following steps：Each raw material is accurately weighed first, in accordance with being formulated, foundation equal increments method principle, It is 0.35kW batch mixings while stirring by per kilogram mixture power, after mixing, control mixing thickness of feed layer is 10cm, then In 120 DEG C of dry 40min, it is reloaded into double screw extruder and squeezes out, is granulated, drying up to the strong polypropylene of dimensional stability Composite material.

Embodiment 5

120 parts of polypropylene, 18 parts of calcium fruit fiber, 8 parts of modified Nano carbon, polyethylene/10 parts of winter rye peptide complexes are ultraviolet 8 parts of light absorbers, 8 parts of ethylene-methyl acrylate copolymer, 6 parts of antiaging agent, 4 parts of tributyl citrate, coupling agent 1.5 Part, 1.0 parts of nucleating agent, 0.3 part of composite antioxidant, 0.4 part of almond oil；

The composite antioxidant is antioxidant 1010, irgasfos 168 and biologic antioxidants in mass ratio 1:3:2 is uniformly mixed It closes.

The nucleating agent is two sub- (3,4- dimethyl) benzyl D-sorbites.

Preparation method includes the following steps：Each raw material is accurately weighed first, in accordance with being formulated, foundation equal increments method principle, It is 0.25kW batch mixings while stirring by per kilogram mixture power, after mixing, control mixing thickness of feed layer is 10cm, then In 100 DEG C of dry 40min, it is reloaded into double screw extruder and squeezes out, is granulated, drying up to the strong polypropylene of dimensional stability Composite material.

Embodiment 6

200 parts of polypropylene, 12 parts of calcium fruit fiber, 10 parts of modified Nano carbon, polyethylene/8 parts of winter rye peptide complexes are ultraviolet 10 parts of light absorbers, 6 parts of ethylene-methyl acrylate copolymer, 8 parts of antiaging agent, 2 parts of tributyl citrate, coupling agent 1.9 Part, 0.6 part of nucleating agent, 0.5 part of composite antioxidant, 0.1 part of almond oil；

The composite antioxidant is antioxidant 1010, irgasfos 168 and biologic antioxidants in mass ratio 2:1:4 is uniformly mixed It closes.

The nucleating agent is two sub- (3,4- dimethyl) benzyl D-sorbites.

Preparation method includes the following steps：Each raw material is accurately weighed first, in accordance with being formulated, foundation equal increments method principle, It is 0.35kW batch mixings while stirring by per kilogram mixture power, after mixing, control mixing thickness of feed layer is 5cm, then In 120 DEG C of dry 20min, it is reloaded into double screw extruder and squeezes out, is granulated, drying up to the strong polypropylene of dimensional stability Composite material.

Embodiment 7

160 parts of polypropylene, 9 parts of calcium fruit fiber, 5 parts of modified carbon nano-tube, polyethylene/5 parts of winter rye peptide complexes are ultraviolet 5 parts of light absorbers, 4 parts of ethylene-methyl acrylate copolymer, 4 parts of antiaging agent, 1 part of tributyl citrate, 1 part of coupling agent, 0.8 part of nucleating agent, 0.4 part of composite antioxidant, 0.2 part of almond oil；

The ultra-violet absorber is UV-531.

The ethylene-methyl acrylate copolymer is Dupont EMA1125AC.

The nucleating agent is two sub- (3,4- dimethyl) benzyl D-sorbites.

Embodiment 8

120 parts of polypropylene, 8 parts of calcium fruit fiber, 4 parts of modified carbon nano-tube, polyethylene/4 parts of winter rye peptide complexes are ultraviolet 4 parts of light absorbers, 3 parts of ethylene-methyl acrylate copolymer, 3 parts of antiaging agent, 0.8 part of tributyl citrate, coupling agent 0.8 Part, 0.6 part of nucleating agent, 0.3 part of composite antioxidant, 0.1 part of almond oil；

The ultra-violet absorber is UV-531.

The ethylene-methyl acrylate copolymer is Dupont EMA1125AC.

The nucleating agent is two sub- (3,4- dimethyl) benzyl D-sorbites.

Embodiment 9

200 parts of polypropylene, 10 parts of calcium fruit fiber, 6 parts of modified carbon nano-tube, polyethylene/6 parts of winter rye peptide complexes are purple 6 parts of ultraviolet absorbers, 5 parts of ethylene-methyl acrylate copolymer, 5 parts of antiaging agent, 1.2 parts of tributyl citrate, coupling agent 1.2 parts, 1.0 parts of nucleating agent, 0.5 part of composite antioxidant, 0.4 part of almond oil；

The ultra-violet absorber is UV-531.

The ethylene-methyl acrylate copolymer is Dupont EMA1125AC.

The nucleating agent is two sub- (3,4- dimethyl) benzyl D-sorbites.

Embodiment 10

160 parts of polypropylene, 15 parts of calcium fruit fiber, 9 parts of modified Nano carbon, polyethylene/9 parts of winter rye peptide complexes are ultraviolet 9 parts of light absorbers, 7 parts of ethylene-methyl acrylate copolymer, 7 parts of antiaging agent, 3 parts of tributyl citrate, 1 part of coupling agent, 0.8 part of nucleating agent, 0.4 part of composite antioxidant, 0.2 part of almond oil；

The ultra-violet absorber is UV-531.

The ethylene-methyl acrylate copolymer is Dupont EMA1125AC.

The nucleating agent is two sub- (3,4- dimethyl) benzyl D-sorbites.

Embodiment 11

120 parts of polypropylene, 12 parts of calcium fruit fiber, 8 parts of modified Nano carbon, polyethylene/8 parts of winter rye peptide complexes are ultraviolet 8 parts of light absorbers, 6 parts of ethylene-methyl acrylate copolymer, 6 parts of antiaging agent, 2 parts of tributyl citrate, coupling agent 0.8 Part, 0.6 part of nucleating agent, 0.3 part of composite antioxidant, 0.1 part of almond oil；

The ultra-violet absorber is UV-531.

The ethylene-methyl acrylate copolymer is Dupont EMA1125AC.

The nucleating agent is two sub- (3,4- dimethyl) benzyl D-sorbites.

Embodiment 12

200 parts of polypropylene, 18 parts of calcium fruit fiber, 10 parts of modified Nano carbon, polyethylene/10 parts of winter rye peptide complexes are purple 10 parts of ultraviolet absorbers, 8 parts of ethylene-methyl acrylate copolymer, 8 parts of antiaging agent, 4 parts of tributyl citrate, coupling agent 1.2 Part, 1.0 parts of nucleating agent, 0.5 part of composite antioxidant, 0.4 part of almond oil；

The ultra-violet absorber is UV-531.

The ethylene-methyl acrylate copolymer is Dupont EMA1125AC.

The nucleating agent is two sub- (3,4- dimethyl) benzyl D-sorbites.

Embodiment 13

160 parts of polypropylene, 15 parts of calcium fruit fiber, 5 parts of modified Nano carbon, polyethylene/5 parts of winter rye peptide complexes are ultraviolet 5 parts of light absorbers, 4 parts of ethylene-methyl acrylate copolymer, 4 parts of antiaging agent, 1 part of tributyl citrate, 1 part of coupling agent, 0.8 part of nucleating agent, 0.4 part of composite antioxidant, 0.2 part of almond oil；

The ultra-violet absorber is UV-531.

The ethylene-methyl acrylate copolymer is Dupont EMA1125AC.

The nucleating agent is two sub- (3,4- dimethyl) benzyl D-sorbites.

Embodiment 14

120 parts of polypropylene, 12 parts of calcium fruit fiber, 4 parts of modified Nano carbon, polyethylene/4 parts of winter rye peptide complexes are ultraviolet 4 parts of light absorbers, 3 parts of ethylene-methyl acrylate copolymer, 3 parts of antiaging agent, 0.8 part of tributyl citrate, coupling agent 0.8 Part, 0.6 part of nucleating agent, 0.3 part of composite antioxidant, 0.1 part of almond oil；

The ultra-violet absorber is UV-531.

The ethylene-methyl acrylate copolymer is Dupont EMA1125AC.

The nucleating agent is two sub- (3,4- dimethyl) benzyl D-sorbites.

Embodiment 15

200 parts of polypropylene, 18 parts of calcium fruit fiber, 6 parts of modified Nano carbon, polyethylene/6 parts of winter rye peptide complexes are ultraviolet 6 parts of light absorbers, 5 parts of ethylene-methyl acrylate copolymer, 5 parts of antiaging agent, 1.2 parts of tributyl citrate, coupling agent 1.2 Part, 1.0 parts of nucleating agent, 0.5 part of composite antioxidant, 0.4 part of almond oil；

The ultra-violet absorber is UV-531.

The ethylene-methyl acrylate copolymer is Dupont EMA1125AC.

The nucleating agent is two sub- (3,4- dimethyl) benzyl D-sorbites.

Embodiment 16

160 parts of polypropylene, 15 parts of calcium fruit fiber, 9 parts of modified Nano carbon, polyethylene/9 parts of winter rye peptide complexes are ultraviolet 9 parts of light absorbers, 4 parts of ethylene-methyl acrylate copolymer, 7 parts of antiaging agent, 1 part of tributyl citrate, 1 part of coupling agent, 0.8 part of nucleating agent, 0.4 part of composite antioxidant, 0.2 part of almond oil；

The ultra-violet absorber is UV-531.

The ethylene-methyl acrylate copolymer is Dupont EMA1125AC.

The nucleating agent is two sub- (3,4- dimethyl) benzyl D-sorbites.

Embodiment 17

120 parts of polypropylene, 12 parts of calcium fruit fiber, 8 parts of modified Nano carbon, polyethylene/8 parts of winter rye peptide complexes are ultraviolet 8 parts of light absorbers, 3 parts of ethylene-methyl acrylate copolymer, 6 parts of antiaging agent, 0.8 part of tributyl citrate, coupling agent 0.8 Part, 0.6 part of nucleating agent, 0.3 part of composite antioxidant, 0.1 part of almond oil；

The ultra-violet absorber is UV-531.

The ethylene-methyl acrylate copolymer is Dupont EMA1125AC.

The nucleating agent is two sub- (3,4- dimethyl) benzyl D-sorbites.

Embodiment 18

200 parts of polypropylene, 18 parts of calcium fruit fiber, 10 parts of modified Nano carbon, polyethylene/10 parts of winter rye peptide complexes are purple 10 parts of ultraviolet absorbers, 5 parts of ethylene-methyl acrylate copolymer, 8 parts of antiaging agent, 1.2 parts of tributyl citrate, coupling agent 1.2 parts, 1.0 parts of nucleating agent, 0.5 part of composite antioxidant, 0.4 part of almond oil；

The ultra-violet absorber is UV-531.

The ethylene-methyl acrylate copolymer is Dupont EMA1125AC.

The nucleating agent is two sub- (3,4- dimethyl) benzyl D-sorbites.

The performance test of 19 PP composite material of the present invention of embodiment

Take the PP composite material and commercially available same type, same specification that dimensional stability prepared by the embodiment of the present invention 2 is strong PP composite material, using national standard GB/T1843-2008《Plastics izodtest method》Test cantilever beam notch Impact strength performance, using national standard GB/T1634-2004《Plastics bending load heat distortion temperature test method》Test thermal deformation Temperature performance, using national standard GB/T1040-2006《Plastic tensile test method》It is forthright to test tensile strength, extension at break Can, using GB9341-2008《Plastics-Oetermination of flexural properties method》Bending strength and bending modulus are tested, by GB/T 17037.4-2003《The 4th part of preparation of plastics thermoplastic material injection-molded test specimens：The measurement of molding shrinkage》It measures into Type shrinking percentage tests oxidation induction period, according to GB/T1410-2006 with reference to GB/T19466.6-2009《Solid insulating material body Product resistivity and surface resistivity test method》Surface resistivity is measured, performance test results are shown in Table 1.

Table 1：The performance test results of PP composite material

The above test results show that：Compared with commercially available, the strong PP composite material shock resistance of dimensional stability of the present invention Property it is strong, improve 106.3%；Heat distortion temperature is high, and high temperature resistance is strong, improves 37.9%；Stretch-proof, intensity improve 109.5%； Toughness is strong, and elongation at break improves 87.5%；Bending property is excellent, and 92.9% and 225.2% is respectively increased in modulus and intensity；It leads Electrical property is strong, and antistatic property is good, and sheet resistance reduces by 99.8%；Good stability of the dimension, indeformable, shrinking percentage reduces 76.7%；Oxidation resistance is strong, and anti-aging, service life is long, and oxidation induction time extends 171.7%.Also illustrate simultaneously, this hair The material property of the strong PP composite material of bright dimensional stability is improved comprehensively, and effect is ideal, has reached material and has opened up The purpose of application is opened up, there is preferable advanced and practicability.

It should be noted that：The PP composite material that the dimensional stability of 3-18 preparations of the embodiment of the present invention is strong equally has There is an above-mentioned experiment effect, it is little between each embodiment and with above-mentioned experiment effect otherness.

Claims

1. a kind of PP composite material that dimensional stability is strong is mainly prepared by the raw material of following parts by weight：Polypropylene 120-200 parts, 12-18 parts of calcium fruit fiber, 8-10 parts of modified Nano carbon, polyethylene/8-10 parts of winter rye peptide complexes, ultraviolet light 8-10 parts of absorbent, 6-8 parts of ethylene-methyl acrylate copolymer, 6-8 parts of antiaging agent, 2-4 parts of tributyl citrate, coupling 1.5-1.9 parts of agent, 0.6-1.0 parts of nucleating agent, 0.3-0.5 parts of composite antioxidant, 0.1-0.4 parts of almond oil；

The composite antioxidant is antioxidant 1010, irgasfos 168 and biologic antioxidants 1-2 in mass ratio:1-3:2-4 is uniformly mixed It closes；

The preparation method of the biologic antioxidants, includes the following steps：The inclined-planes saccharomyces cerevisiae tlj2016 bacterium after taking 1 ring to activate Kind, be seeded in the 500m L triangular flasks equipped with 100m L seed culture mediums and cultivate, 28~30 DEG C, shaking speed 150~ 25~30h is cultivated under the conditions of 200r/min, obtains primary seed solution；Primary seed solution is pressed to the inoculum concentration of 5~10% (v/v), It is seeded in the 500m L triangular flasks equipped with 100m L fermentation mediums and 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, 4~6L/min of ventilation quantity of temperature, rotating speed 150~ 200r/min, fermentation full adjustment zymotic fluid pH value be 6.0~6.5, when fermentation to 25~30h when, with every liter of zymotic fluid 25~ The additive amount of 30mmol disposably adds L-cysteine into zymotic fluid, continues fermentation 20-30h and obtains final zymotic fluid；Most Whole zymotic fluid centrifugation, the filtering of supernatant 1000-1200 mesh screens are concentrated, are lyophilized up to biologic antioxidants；

The saccharomyces cerevisiae tlj2016 deposit numbers are CGMCC No.12789.

2. the strong PP composite material of dimensional stability as described in claim 1, which is characterized in that the calcium fruit fiber Preparation method includes the following steps：By fresh calcium stem end, leaf of GAIGUO and waste wood 6-8 in mass ratio:2-6:1-2 is uniformly mixed, It is placed in supersonic wave cleaning machine and cleans 3-5min in 200W, 30KHz, drain, be crushed, 0.8-1.2 times of fragment quality is added Water, room temperature 200-400W, 35-40KHz condition ultrasonic extraction 10-15min, then in electric field strength 20-40kV/cm, pulse Between carry out high-pressure pulse electric under the conditions of 400-600 μ s, pulse frequency 200-400Hz and handle 10-15min；Adjusting pH value is 6- 10, the biological enzyme of mixture quality 0.1-0.3% is added, 10-15min is digested in 50-60 DEG C；Enzymolysis liquid is concentrated under reduced pressure into solid Object content is 40-60%, is put into microwave dryer and carries out intermittent drying in 2000W, 130-150 DEG C, is allowed to moisture and reaches 8- 10%, it is then crushed to grain size 0.4-0.6mm, the sodium bicarbonate of crushed material quality 0.2-0.4% is added, uniformly mixes, adjustment Mixture moisture is 15-18%, room temperature, sealing and standing 1.5-2.5h, in screw speed 105-115r/min, temperature 140- 160 DEG C of condition extrusions, then ultramicro grinding is finally fine up to calcium fruit in 100-115 DEG C of dry 4-6h to 10-15 μm of grain size Dimension；

The biological 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 is uniformly mixed.

3. the strong PP composite material of dimensional stability as described in claim 1, which is characterized in that the modified Nano carbon Preparation method, include the following steps：In mass ratio by middle modules carbon fibre, single-walled carbon nanotube, ammonium persulfate and deionized water 1:0.8-1:80-100:1000 uniformly mixing are ultrasonically treated 20-40min in power 200-400W, frequency 20-24KHz first, Then high-voltage pulse is carried out under the conditions of electric field strength 2-6kV/cm, burst length 100-300 μ s, pulse frequency 200-400Hz Electric field treatment 10-15min；Mixture after processing reacts 0.5-2.5h in rotating speed 100-120r/min, 50-70 DEG C of temperature, The PP micropore filtering films in 0.22 μm of aperture of reaction solution are filtered, and deionized water is used in combination to be washed repeatedly to neutrality, finally in 70- 80 DEG C are dried under vacuum to constant weight, crush to get modified Nano carbon.

4. the strong PP composite material of dimensional stability as described in claim 1, which is characterized in that the polyethylene/winter The preparation method of rye peptide complexes, includes the following steps：

The mixed enzyme is protease, cellulase, amylase, pectase 5-7 in mass ratio:4-6:1-3:1-2 is uniformly mixed；

2) winter rye peptide and polyethylene, maleic anhydride, styrene, initiator and antioxidant are sufficiently mixed in proportion, 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) double screw extruder frit reaction is added in the mixture for obtaining step 2), and extruding pelletization controls double screw extruder And die temperature is at 145-180 DEG C, screw speed 30-200r/min, residence time of the reactant in double screw extruder Control is at 10-100 seconds to get polyethylene/winter rye peptide complexes.

5. the strong PP composite material of dimensional stability as described in claim 1, which is characterized in that the almond oil Preparation method includes the following steps：Semen armeniacae amarae is immersed in the sodium bicarbonate solution that mass percent concentration is 0.01-0.03% Room temperature rinsing drains, and sets sealing and standing in container and soaks 0.5-1.5h, then peels, and decortication semen armeniacae amarae is put into microwave drying In frequency 2450MHz, power 1000-3000W, 80-90 DEG C of temperature, thickness of feed layer 3-5cm condition microwave irradiation enzyme deactivations 2- in machine 4min；It is then placed in soaking at room temperature 2-4h in the citric acid solution that mass percent concentration is 0.1-0.3%, clear water rinses 1-3 It is secondary, it drains, freezes 3-5h in -20--25 DEG C, thickness of feed layer 8-10cm, be crushed to grain size 0.4-0.6mm and obtain semen armeniacae amarae powder；To hardship The pH value that 3-5 times of its quality is added in almond powder is the deionized water of 4.5-6.5, is uniformly mixed, and control mixed material temperature is 45-55 DEG C, the compound enzyme of semen armeniacae amarae silty amount 0.03-0.05% is added thereto, stirs evenly, keep the temperature, digests 40-60min； By enzymolysis liquid set vacuum degree -0.01--0.03MPa in vacuum centrifuge, 10-20 DEG C of temperature, rotating speed 10000r/min, vacuum from Heart 5-8min, isolated free oil, emulsion, hydrolyzate and semen armeniacae amarae slag, temperature is controlled by obtained emulsion from top to bottom Degree is 30-50 DEG C, the biological demulsifying agent demulsification 40-60min of addition emulsion quality 0.02-0.04%, in vacuum degree-after demulsification Traditional vacuum 10-15min obtains free oil again by 0.01--0.03MPa, 10-20 DEG C of temperature, 5000r/min, merges gained Free oil is up to almond oil；

The quality group of the compound enzyme becomes：Acid protease:Cellulase:Pectase:Amylase=6-9:2-4:2-4:1- 3。

6. the strong PP composite material of dimensional stability as claimed in claim 5, which is characterized in that the biological demulsifying agent Quality group become：Glycolipid class:Lipopeptid class:Cell wall combination class=4-6:2-4:1-3.

7. the strong PP composite material of dimensional stability as claimed in claim 6, which is characterized in that the sugar lipidic biomass The quality group of demulsifier becomes：Rhamnolipid:Alkyl glycosides=2-5:1-3.

8. the strong PP composite material of dimensional stability as described in claim 1, which is characterized in that the seed culture medium Quality group become：(NH₄)₂SO₄6g/L, glucose 35g/L, K₂HPO₄·3H₂O 3g/L, KH₂PO₄0.5g/L, yeast powder 11g/L, MnSO₄0.1g/L, KCL 0.1g/L, FeSO₄0.1g/L, MgSO₄·7H₂O 0.1g/L, surplus are water, pH 6.0.

9. the strong PP composite material of dimensional stability as described in claim 1, which is characterized in that the fermentation medium Quality group become：(NH₄)₂SO₄10g/L, molasses 150g/L, K₂HPO₄·3H₂O 8g/L, KH₂PO₄0.5g/L, yeast powder 5g/L, corn steep liquor 10g/L, MnSO₄0.1g/L, KCL 0.1g/L, FeSO₄0.1g/L, MgSO₄·7H₂O 0.1g/L, surplus For water, pH 6.0.

10. the preparation method of the strong PP composite material of dimensional stability, feature exist as described in claim 1-9 is any In including the following steps：Each raw material is accurately weighed first, in accordance with formula, according to equal increments method principle, by per kilogram mixture Power is 0.25-0.35kW batch mixings while stirring, and after mixing, control mixing thickness of feed layer is 5-10cm, then in 100- 120 DEG C of dry 20-40min are reloaded into double screw extruder and squeeze out, are granulated, drying up to the strong polypropylene of dimensional stability Composite material.