CN114106455B - Polypropylene composition resistant to thermal oxidative aging and preparation method thereof - Google Patents

Polypropylene composition resistant to thermal oxidative aging and preparation method thereof Download PDF

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CN114106455B
CN114106455B CN202010900138.2A CN202010900138A CN114106455B CN 114106455 B CN114106455 B CN 114106455B CN 202010900138 A CN202010900138 A CN 202010900138A CN 114106455 B CN114106455 B CN 114106455B
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parts
coupling agent
antioxidant
polypropylene composition
stirring
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CN114106455A (en
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许平
郭锐
李延亮
王日辉
高凌雁
孙丽鹏
王秀丽
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China Petroleum and Chemical Corp
Qilu Petrochemical Co of Sinopec
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China Petroleum and Chemical Corp
Qilu Petrochemical Co of Sinopec
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C08K2003/382—Boron-containing compounds and nitrogen
    • C08K2003/385—Binary compounds of nitrogen with boron
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/016—Additives defined by their aspect ratio
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention relates to a polypropylene composition resistant to thermal oxidative aging and a preparation method thereof, and belongs to the technical field of polypropylene modification. The invention relates to a heat and oxygen aging resistant polypropylene composition, which comprises the following raw materials in parts by weight: 100 parts of polypropylene, 8-25 parts of mLLDPE, 0.8-3 parts of nano Boron Nitride (BN), 0.3-1 part of polyethylene glycol (PEG), 0.05-0.2 part of coupling agent, 0.05-0.4 part of phenolic antioxidant, 0.05-0.5 part of thioester antioxidant, 0.05-0.4 part of phosphate antioxidant, 0.02-0.1 part of acid absorber and 0.02-0.08 part of antistatic agent. The anti-thermo-oxidative aging polypropylene composition has good thermo-oxidative aging resistance, impact resistance, dimensional stability and better mechanical property; the invention also provides a simple and easy preparation method.

Description

Polypropylene composition resistant to thermal oxidative aging and preparation method thereof
Technical Field
The invention relates to a polypropylene composition resistant to thermal oxidative aging and a preparation method thereof, and belongs to the technical field of polypropylene modification.
Background
Polypropylene (PP) is a typical crystalline polymer, and has the advantages of heat resistance, corrosion resistance, low density, light weight and the like, so that the polypropylene is widely applied to injection molding parts, biaxially oriented films, fibers, pipes, automobiles, electric appliances and the like. Because the main chain skeleton carbon atom connected with the side methyl is tertiary carbon atom, the PP becomes more active under the induction of methyl, and polypropylene is more easily affected by external environmental factors such as processing temperature, oxygen, light, pollutants in air and the like than polyethylene, and is broken to be aged and degraded. Such as yellowing, reduction of the relative molecular weight, cracking of the surface of the product, loss of gloss, and more serious, a great reduction of mechanical properties such as impact strength, tensile strength, etc., resulting in great waste of materials. Waste products are difficult to degrade under natural conditions, and further, the environment is polluted, so that the service life of PP products is prolonged by improving the thermo-oxidative aging resistance of PP through various modifications, and the method has become a research hot spot at home and abroad.
At present, the main methods for improving and enhancing the thermal oxidative aging performance of PP are as follows:
(1) Physical protection (such as thickening, coating, outer layer compounding and the like), but the methods have some defects of increasing working procedures or affecting the appearance of products, and the like, and are limited to only few applications of products;
(2) The processing technology is improved, and the method can only be implemented from the preparation source of the material and can not solve the aging problem in the reprocessing and using processes;
(3) The structural design or modification of the high polymer material is realized, the ageing-resistant groups are replaced by the ageing-resistant groups through the molecular structural design of the material, so that a good effect can be achieved, or functional groups or structures with ageing resistance are introduced to a high polymer chain through a grafting or copolymerization method, so that the material has excellent ageing resistance, but the cost is high, the difficulty is high, and the large-scale production and application cannot be realized;
(4) The organic ultraviolet absorber is added, and the organic matter is also affected by ultraviolet rays, so that the durability of the use is affected, and a plurality of ultraviolet absorbers can absorb visible light with a certain wavelength, so that the product has yellow or other colors, and the appearance performance of the product is affected;
(5) Adding inorganic filler: the inorganic filler systems are mainly of two types: conventional scaly talc and spherical calcium carbonate, which have a low aspect ratio, are fillers having a high aspect ratio, such as: bamboo fiber, carbon fiber, glass fiber and other materials. The talcum powder and the calcium carbonate have low dimensional stability under certain content, and the talcum powder can strongly adsorb the stabilizer in the resin, thereby obviously reducing the stability of the stabilizer in the resin and the like. The bamboo fiber is used as a filler, the technology is still immature, the carbon fiber cost is extremely high, the glass fiber can be used as a reinforcing agent, the rigidity of the material is remarkably improved, the bamboo fiber also has excellent heat resistance and dimensional stability, but the smoothness and the aesthetic property of the surface are poor, and large-size interior trim parts are easy to warp and deform and are limited by industries in certain application fields.
Chinese patent CN 110218388A discloses a preparation method of an ultraviolet-proof anti-aging polypropylene master batch, which increases the compatibility of polypropylene and mineral filler by grafting maleic anhydride with polypropylene, and has the advantages of complicated preparation, high toxicity of maleic anhydride compatilizer and difficult popularization and use.
Chinese patent CN103382274A discloses a granular mixture of 5-10 parts of processing aid, 20-40 parts of long-acting antioxidant, 10-30 parts of antioxidant, 10-20 parts of nucleating agent, 10-30 parts of stearate, 5-20 parts of superfine talcum powder and the like through melt granulation. The dosage of the antioxidant is large, but the actual ageing resistance is not good.
Disclosure of Invention
The invention aims to solve the technical problems of overcoming the defects in the prior art and providing a heat and oxygen aging resistant polypropylene composition which has good heat and oxygen aging resistance, impact resistance, dimensional stability and better mechanical property; the invention also provides a simple and easy preparation method.
The invention relates to a heat and oxygen aging resistant polypropylene composition, which comprises the following raw materials in parts by weight:
polypropylene 100 parts
8-25 parts of metallocene linear low density polyethylene (mLLDPE)
0.8-3 parts of nano Boron Nitride (BN)
Polyethylene glycol (PEG) 0.3-1 parts
0.05 to 0.2 part of coupling agent
0.05-0.4 part of phenolic antioxidant
0.05-0.5 part of thioester antioxidant
0.05 to 0.4 part of phosphite antioxidant
0.02-0.1 part of acid absorber
0.02-0.08 parts of antistatic agent.
The polypropylene is homo-polypropylene or random copolymer polypropylene (PP) powder, the melt Mass Flow Rate (MFR) is 10-40g/10min, the MFR test condition is 230 ℃,2.16kg, wherein the isotacticity of the homo-polypropylene is 97-99%; the comonomer of the random copolymer polypropylene is ethylene, and the mass percentage of the ethylene is 1.5-4%, preferably 2.6-3.3%. The weight average relative molecular weight of the homo-polypropylene or random co-polypropylene tested by GPC method is 20-35 ten thousand, the number average molecular weight is 4-5 ten thousand, and the weight distribution is 4-8. The melting point of the homo-polypropylene is 150-160 ℃, and the melting point of the random copolymer polypropylene resin is 140-150 ℃. The melting point of the resin was measured using a differential scanning calorimeter.
The metallocene linear low density polyethylene mLLDPE is produced by using ethylene and an alpha-olefin (such as 1-butene, 1-hexene, 1-octene, tetramethyl-1-pentene, etc.) under the action of metallocene catalyst on a gas-phase process deviceBinary of (2) a copolymer. The melt mass flow rate (MFR 2.16) is 0.6-2.5g/10min and the density is 0.913-0.928g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The molecular weight distribution Mw/Mn is between 2.4 and 3.6, and the weight average molecular weight is 10 to 15 ten thousand. The comonomer is preferably hexene-1, and the mass percentage of the comonomer hexene is 0.5-3%. The powder with smaller particle size is adopted, the smaller the particle size is, the more uniform the dispersion is, and the stronger the toughening effect on PP is. The polypropylene resin replaces rubber or POE and other elastomers which are conventionally used, has low price, higher melting point and thermal deformation temperature than POE, certain strength and toughness and low crystallinity, can improve the shrinkage of PP resin, solves the problem of reduced heat resistance of materials caused by common toughening agents, and is used in an amount of 8-25 parts, preferably 10-20 parts.
Many ultraviolet absorbers absorb visible light of a certain wavelength, so that the product has yellow or other colors, which affect the appearance performance of the product, and the ultraviolet absorber is an organic matter which is also affected by ultraviolet rays, thereby affecting the durability of the product in use. The nanometer boron nitride has strong ultraviolet absorption capability and can well overcome the defects of organic ultraviolet agents. Its absorption by ultraviolet light results from its semi-conductive nature, and when the excitation photon energy is higher than the bandgap energy of the semiconductor, it absorbs that photon energy. The strength, rigidity and dimensional stability of the material can be greatly improved, and meanwhile, the product still has good surface smoothness and attractive appearance.
The nanometer boron nitride is a novel inorganic white powder, and has a size effect due to the fact that the size of particles is equal to or smaller than that of light waves, so that the nanometer boron nitride has strong light absorption capacity and good ultraviolet shielding and scattering effects. The action principle is as follows: and the polymer serves as a barrier between light radiation and the polymer to block the radiation of light directly to the inside of the polymer, so that the photo-oxidative degradation of the polymer is effectively relieved. It can also raise the crystallization temperature of polypropylene material, increase the number of spherulites and decrease the spherulites size, and has good heat conductivity and chemical stability. The powder has a purity of 99%, a particle diameter of 1-100nm, preferably 20-60nm, a crystal structure having a graphite-like layered structure, and a BET specific surface area of 50-100m 2 /g, aspect ratioIs 13:1, and is white powder with characteristics of looseness, lubrication, easy moisture absorption, light weight and the like. Theoretical Density of 2.27g/cm 3 The mohs hardness was 2. The amount is 0.8 to 3 parts, preferably 1.0 to 2.0 parts.
The nanometer boron nitride has large specific surface area and high surface energy, is directly added in the form of powder, is easy to float, causes certain difficulty in aligning the accurate amount, is easy to agglomerate, is difficult to directly and uniformly disperse in a PP powder matrix, is difficult to play a role to the greatest extent, and has poor product quality stability. However, the polarity of the nano boron nitride surface modified by polyethylene glycol is reduced, the nano boron nitride surface is more matched with the polarity of a high polymer matrix, the dispersibility of the nano boron nitride in a PP powder matrix is obviously enhanced, and the nano boron nitride is efficiently mixed with the PP resin, so that the nano boron nitride is uniformly dispersed in the PP powder resin.
The polyethylene glycol is white granular powder, the purity of the powder is 98%, the powder is analytically pure, and the melting point is 55-60 ℃. The amount is 0.3 to 1 part, preferably 0.45 to 0.75 part. The molecular weight is between 2000 and 3000, preferably between 2050 and 2650. Dissolved in alcohol, ketone, chloroform, etc., and is compatible with many more polar materials. When the ratio of the nanometer boron nitride to the polyethylene glycol is (1-4): the case 1 is the most preferable.
The coupling agent is one of a silane coupling agent, a titanate coupling agent or an aluminate coupling agent. Preferably a titanate coupling agent. The amount is 0.05 to 0.2 part, preferably 0.06 to 0.11 part.
The antioxidant used is a mixture of three, wherein the phenolic antioxidant can be [3- (3, 5-di-tert-butyl-4-hydroxycyclohexyl) propionate ] (1010), 1,3, 5-tris (3, 5-di-tert-butyl, 4-hydroxybenzyl) s-triazine, 2,4,6- (1H, 3H, 5H) trione ] (3114), or [3,3,3,5,5,5-hexatert-butyl-a, a, a- (1, 3, 5-trimethylbenzene-2, 4, 6-triyl) tri-p-cresol ] (1330), and the preferred antioxidant in the invention is 1010 parts by weight of 0.05-0.4 parts, preferably 0.09-0.15 parts; as the phosphite antioxidant, there may be used [ tris (2, 4-di-t-butylphenyl) phosphite ] (168), [ bis (2, 4-di-t-butylphenol) pentaerythritol diphosphite ] (622), [ bis (2, 6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite ] (PEP 36), and 168 is preferable in view of oxidation resistance and yellowness index. The antioxidant is 0.05-0.4 parts by weight, preferably 0.09-0.15 parts by weight.
The hindered phenol main antioxidant belongs to a chain termination type antioxidant, and the oxidation resistance is achieved by supplying hydrogen atoms and reacting with free radicals to generate inert products in the process of stabilizing the polymer, and terminating chain growth. But the result of the hydrogen transfer results in the formation of polymer hydroperoxides.
The thioester antioxidant can effectively decompose the polymer hydroperoxide to convert the polymer hydroperoxide into a stable product, so that the polymer is more resistant to thermal oxidative aging and does not change color, namely the polymer has a stronger protective effect on color stability. Is not used alone, and is used as an auxiliary antioxidant to be matched with a hindered phenol main antioxidant.
When the ratio of the thioester antioxidant to the phenolic antioxidant is 1-3, a good synergistic effect is generated, the effect of preventing oxidation for a long time is greatly improved, the processability of the product is improved, the service life is prolonged, and the product has a good cost performance.
The thioester antioxidant is preferably DLTP (dilauryl thiodipropionate), has a molecular weight of 514.86, a melting point of 39.5-41.5 ℃, and is white crystal or powder; the fragrance is special sweet and ester-like; saponification value is 210.5mg/kg; acidity of 0.098% (calculated as thiodipropionic acid); the content was 98.0%. The amount is 0.05 to 0.5 part, preferably 0.25 to 0.45 part.
The acid absorber is calcium stearate or zinc stearate, is used for neutralizing residual components of the catalyst in the PP, and reduces corrosion of the catalyst to equipment. Preferably calcium stearate, the calcium stearate of the present invention has a relative calcium content of >19.6% (as measured by fluorescence elemental analysis). The amount of the acid absorber is 0.02 to 0.1 part, preferably 0.04 to 0.06 part.
The antistatic agent is Glycerol Monostearate (GMS), the component has antistatic effect, and has good demolding effect in injection molding products, and the addition amount is 0.02-0.08 part, preferably 0.03-0.05 part. The sulfur ester antioxidant DLTP has good ester solubility because of the fatty chain with twelve carbon atoms, so that the addition of the sulfur ester antioxidant DLTP can further strengthen the dispersion and exert the antioxidation effect.
The preparation method of the thermo-oxidative aging resistant polypropylene composition comprises the following steps:
(1) Adding a coupling agent into a round-bottom flask, pouring isopropanol or petroleum ether and acetone, and stirring for 12 minutes by using a magnetic stirrer to dissolve the coupling agent; adding polyethylene glycol into a coupling agent solution, heating and refluxing in a water bath or an oil bath, magnetically stirring for about 15 minutes, then adding nano boron nitride into the coupling agent solution, continuously heating and refluxing, magnetically stirring for about 20 minutes, then removing a solvent by using a rotary evaporator, drying the rest solid particles in a vacuum drying oven at 110 ℃, taking out and stirring once every 10 minutes to prevent the solid particles from layering with the coupling agent solution, thereby influencing the coupling effect, obtaining powder with a small amount of caking, grinding and crushing by using a vibration mill, and standing by for 30-60 minutes after vibration time;
(2) Mixing and stirring phenolic antioxidants and thioester antioxidants for 2 minutes, and then adding polypropylene powder, metallocene linear low density polyethylene, phosphite antioxidants, acid absorbers, antistatic agents and nano boron nitride treated in the step (1); mixing and stirring in a high-speed stirrer; adding the mixed materials into a double-screw extruder, melting, plasticizing, extruding, granulating and drying to obtain the product.
In the step (2), the materials are mixed and stirred at a high speed in a high-speed stirrer for 4 to 8 minutes, preferably 6 minutes, the stirring speed is 500 to 1000 revolutions per minute, preferably 800 revolutions per minute, and the stirring temperature is 35 to 40 ℃; the length-diameter ratio of the screw is 35-40, and the melting is carried out at 180-210 ℃; the main machine of the extruder has a rotating speed of 150-220 r/min, a feeding rotating speed of 35-50 r/min and drying at 60-80 ℃ for 20-35 minutes.
In the invention, the nanometer boron nitride, the polyethylene glycol and the coupling agent are pretreated, so that the nanometer boron nitride and the polyethylene glycol produce a synergistic effect, and the thermal oxidative aging performance of the product can be effectively enhanced; the invention makes the product easy to store and process, and has low cost without changing the existing production process.
Compared with the prior art, the invention has the following beneficial effects:
(1) The composition has good thermo-oxidative aging resistance, impact resistance, small parallel shrinkage and vertical shrinkage, good dimensional stability and high thermal deformation temperature (0.45 MPa);
(2) The formula can endow the PP filled composite material with high-efficiency light stability and weather resistance, and can obviously prolong the service life of the composite material;
(3) The anti-aging component in the formula has excellent dispersibility in PP, high stability and lasting action time, and ensures the full play of the anti-aging efficacy;
(4) The raw materials used in the invention are completely environment-friendly, and the preparation method has simple process and low cost.
Detailed Description
The invention is further illustrated below in connection with examples, which are not intended to limit the practice of the invention.
Example 1
The heat and oxygen aging resistant polypropylene composition is prepared from the following raw materials in parts by weight:
100 parts of homopolymerized PP powder resin (MFR 40g/10 min)
mLLDPE powder (MFR 2.2 g/10min density 0.920 g/cm) 3 ) 15 parts of
1.4 parts of nano Boron Nitride (BN) with grain diameter of 35nm
Polyethylene glycol (PEG) molecular weight 2100 0.45 parts
0.06 part of coupling agent
Antioxidant 1 1010.10 parts
Antioxidant 2 DLTP 0.3 part
Antioxidant 3 168.10 parts
0.05 part of acid absorber
0.04 parts of antistatic agent.
Example 2
The heat and oxygen aging resistant polypropylene composition is prepared from the following raw materials in parts by weight:
100 parts of a copolyPP powder (MFR 36 g/10min, ethylene content 3.1%)
mLLDPE powder (MFR 2.3 g/10min density 0.921 g/cm) 3 ) 18 parts of
1.2 parts of nano Boron Nitride (BN) with the grain diameter of 32nm
Polyethylene glycol (PEG) molecular weight 2050.52 parts
0.07 part of coupling agent
Antioxidant 1 1330.12 parts
Antioxidant 2 DLTP 0.35 parts
Antioxidant 3 168.12 parts
0.05 part of acid absorber
0.04 parts of antistatic agent.
Example 3
The heat and oxygen aging resistant polypropylene composition is prepared from the following raw materials in parts by weight:
69 parts of a copolymer PP powder (MFR 35g/10min, ethylene content 2.8%)
31 parts of homopolymerized PP powder resin (MFR 36 g/10 min)
mLLDPE powder (MFR 2.5g/10min density 0.918 g/cm) 3 ) 17 parts of
1.0 parts of nano Boron Nitride (BN) with the grain diameter of 40nm
Polyethylene glycol (PEG) molecular weight 2080.55 parts
0.07 part of coupling agent
Antioxidant 1 3114.13 parts
Antioxidant 2 DLTP 0.25 parts
Antioxidant 3.622.13 parts
0.05 part of acid absorber
0.04 parts of antistatic agent.
Example 4
The heat and oxygen aging resistant polypropylene composition is prepared from the following raw materials in parts by weight:
67 parts of a copolymer PP powder (MFR 40g/10min, ethylene content 3.3%)
33 parts of homopolymerized PP powder resin (MFR 37 g/10 min)
mLLDPE powder (MFR 2.4 g/10min density 0.922 g/cm) 3 ) 16 parts of
1.6 portions of nanometer Boron Nitride (BN) with the grain diameter of 50nm
Polyethylene glycol (PEG) molecular weight 2150.60 parts
0.08 part of coupling agent
Antioxidant 1 1010.14 parts
Antioxidant 2 DLTP 0.4 parts
Antioxidant 3 168.12 parts
0.05 part of acid absorber
0.04 parts of antistatic agent.
Example 5
The heat and oxygen aging resistant polypropylene composition is prepared from the following raw materials in parts by weight:
68 parts of a copolymer PP powder (MFR 39 g/10min, ethylene content 3.3%)
32 parts of homopolymerized PP powder resin (MFR 38 g/10 min)
mLLDPE powder (MFR 2.5g/10min density 0.925 g/cm) 3 ) 20 parts of
1.8 portions of nanometer Boron Nitride (BN) with the grain diameter of 45nm
Polyethylene glycol (PEG) molecular weight 2205.70 parts
0.09 part of coupling agent
Antioxidant 1 1010.15 parts
Antioxidant 2 DLTP 0.45 parts
Antioxidant 3 168.12 parts
0.05 part of acid absorber
0.04 parts of antistatic agent.
The preparation steps for examples 1-5 are as follows:
(1) The coupling agent was added to the round bottom flask and then poured into isopropanol or petroleum ether, acetone and stirred with a magnetic stirrer for 12 minutes to dissolve. Adding polyethylene glycol into a coupling agent solution, heating and refluxing in a water bath or an oil bath, magnetically stirring for about 15 minutes, then adding boron nitride into the coupling agent solution, continuously heating and refluxing, magnetically stirring for about 20 minutes, then removing a solvent by using a rotary evaporator, drying the rest solid particles in a vacuum drying oven at 110 ℃, taking out and stirring once every 10 minutes to prevent the solid particles from layering with the coupling agent solution, thereby influencing the coupling effect, obtaining powder with a small amount of caking, grinding and crushing by using a vibration mill, and standing by for 30 minutes after the vibration time.
(2) The antioxidant 1 and the antioxidant 2 are firstly mixed and stirred for 2 minutes, and then PP powder, mLLDPE, the antioxidant 3, an acid absorber, an antistatic agent and the nano boron nitride treated in the step (1) are added. Mixing and stirring at high speed in a high-speed stirrer for 4-8 minutes, wherein the stirring speed is 800 revolutions per minute, and the stirring temperature is 38+/-2 ℃; adding the uniformly mixed materials into a double-screw extruder, melting, plasticizing, extruding and granulating at 190+/-20 ℃ with the length-diameter ratio of the screw being 38, wherein the rotating speed of the main machine of the extruder is 180r/min, the feeding rotating speed is 45r/min, and drying is carried out at 70+/-10 ℃ for 30 minutes to obtain the product.
Comparative example 1
The polypropylene composition is prepared from the following raw materials in parts by weight:
100 parts of homo-PP powder (MFR 40g/10 min)
Antioxidant 1 1010.10 parts
Antioxidant 3 168.10 parts
0.05 part of acid absorber
0.04 parts of antistatic agent.
Comparative example 2
The polypropylene composition is prepared from the following raw materials in parts by weight:
100 parts of a copolyPP powder (MFR 32 g/10min, ethylene content 3.1%)
mLLDPE powder (MFR 2.2 g/10min density 0.920 g/cm) 3 ) 15 parts of
1.4 parts of nano Boron Nitride (BN) with grain diameter of 35nm
0.07 part of coupling agent
Antioxidant 1 1010.10 parts
Antioxidant 3 168.10 parts
0.05 part of acid absorber
0.04 parts of antistatic agent.
Comparative example 3
The polypropylene composition is prepared from the following raw materials in parts by weight:
100 parts of copolymerized PP powder (MFR 35g/10min, Z-olefin content 2.8%)
mLLDPE powder (MFR 2.2 g/10min density 0.920 g/cm) 3 ) 15 parts of
Talcum powder with 10um particle size 1.4 portions
0.1 part of coupling agent
Antioxidant 1 3114.08 parts
Antioxidant 3.622.10 parts
0.05 part of acid absorber
0.04 parts of antistatic agent.
Comparative example 4
The polypropylene composition is prepared from the following raw materials in parts by weight:
100 parts of homopolymerized PP powder resin (MFR 37 g/10 min)
mLLDPE powder (MFR 2.4 g/10min density 0.922 g/cm) 3 ) 16 parts of
Antioxidant 1 1010.10 parts
Antioxidant 2 DLTP 0.4 parts
Antioxidant 3 168.10 parts
0.05 part of acid absorber
Antistatic agent 0.04 parts
0.08 part of ultraviolet absorber (UV 531).
Comparative example 5
The polypropylene composition is prepared from the following raw materials in parts by weight:
100 parts of a copolyPP powder (MFR 36 g/10min, ethylene content 3.1%)
mLLDPE powder (MFR 2.3 g/10min density 0.921 g/cm) 3 ) 18 parts of
1.2 parts of nano Boron Nitride (BN) with the grain diameter of 32nm
Polyethylene glycol (PEG) molecular weight 2050.52 parts
0.07 part of coupling agent
Antioxidant 1 1010.12 parts
Antioxidant 2 DLTP 0.35 parts
Antioxidant 3 168.12 parts
0.05 part of acid absorber
0.04 parts of antistatic agent.
The preparation procedure of the comparative example is as follows:
placing the components into a high-speed stirrer, stirring for 3+/-1 min at the rotating speed of 1500+/-30 r/min, and uniformly mixing; and then adding the obtained premix into a co-rotating double-screw extruder for melt mixing, wherein the temperature of the highest section of the extruder is 220+/-10 ℃, the rotating speed of a main machine of the extruder is 180+/-10 r/min, the feeding rotating speed is 40+/-5 r/min, and extruding and granulating to obtain the polypropylene composition.
The yellow index refers to the extent to which a colorless transparent or translucent or nearly white plastic deviates from white. By measuring the yellowness index of the plastic, its aging properties can be examined. The larger the number, the more yellow the sample, i.e. the deeper the degree of aging. Most plastic articles are desirably as white as possible, however, the quality of the product or article can be controlled by measurement of the yellowness index due to yellowing of the product or article during the molding process, or yellowing due to aging by heat, radiation, ultraviolet light irradiation, etc., the yellowness index can be measured to see the degree of uv aging.
The very obvious appearance of PP after aging is chalking or embrittlement, and the performance index reflecting this phenomenon is to detect changes in notched impact strength.
The polypropylene composition pellets prepared in examples and comparative examples were dried and injection-molded on a K-TEC85 type injection molding machine manufactured by MILACRON corporation of Germany to prepare performance test specimens.
The test is carried out according to the following national standard and industry standard:
the notch impact strength of the simply supported beam is tested according to GB/T1043-2008;
tensile properties were tested according to GB/T1040.2-2006;
flexural properties were tested according to GB/T9341-2008;
load deflection temperature was measured according to GB/T1634.2-2004;
the yellowness index (pellet) was measured according to HG_T 3862-2006;
oxidation induction time: the test was carried out according to GB/T8807-1988.
The molding shrinkage was measured according to GB/T17037.4-2003, and refers to the dimensional difference between the dried test specimen and the mold cavity in which it was molded, measured at laboratory temperature, within 16-24 hours after the test specimen was molded, the test specimen being 60x 2mm small square pieces, the length l 1 and width b 1 of the test specimen and the length l 0 and width b 0 of the mold cavity, the molding shrinkage SMp parallel to the melt flow direction being measured in the middle of the specimen width; the molding shrinkage SMn perpendicular to the melt flow direction, measured in the middle of the sample length, was calculated as: SMp =100 (l 0-l 1)/l 0 and smn=100 (b 0-b 1)/b 0.
The basic properties of examples 1-5 are as follows:
table 1 test results for examples 1-5
The basic properties of comparative examples 1-4 are as follows:
table 2 test results for comparative examples 1-4
As is evident from the comparison of the test results of examples and comparative examples, the composites of the comparative examples have respective defects in properties, or are poor in thermal oxidative aging resistance, or low in heat distortion temperature, or insufficient in toughness, or low in shrinkage but also low in strength and flexural modulus. The preparation process of comparative example 5 and example 2 was different, thus producing different results.
The polypropylene composition provided by the invention has high thermal oxidative aging resistance, excellent mechanical property and impact toughness, high thermal deformation temperature and further improved dimensional stability, and is a composite material with excellent comprehensive performance. If one or more components in the deleted formulation do not have good comprehensive properties, the object of the invention can be achieved only by adopting the components at the same time.

Claims (6)

1. A heat and oxygen aging resistant polypropylene composition characterized by: the material comprises the following raw materials in parts by weight:
polypropylene 100 parts
8-25 parts of metallocene linear low density polyethylene
0.8-3 parts of nano boron nitride
Polyethylene glycol 0.3-1 parts
0.05 to 0.2 part of coupling agent
0.05-0.4 part of phenolic antioxidant
0.05-0.5 part of thioester antioxidant
0.05 to 0.4 part of phosphite antioxidant
0.02-0.1 part of acid absorber
0.02-0.08 parts of antistatic agent;
the antistatic agent is glycerol monostearate;
the purity of the nanometer boron nitride is 99%, the grain diameter is 1-100nm, and the specific surface area of BET method is 50-100m 2 G, aspect ratio 13:1;
the molecular weight of polyethylene glycol is 2000-3000;
the preparation method of the thermo-oxidative aging resistant polypropylene composition comprises the following steps:
(1) Adding a coupling agent into a round-bottom flask, pouring isopropanol or petroleum ether or acetone, and stirring by a magnetic stirrer to dissolve the coupling agent; adding polyethylene glycol into a coupling agent solution, heating and refluxing in a water bath or an oil bath, magnetically stirring, then weighing nano boron nitride, adding the coupling agent solution, continuously heating and refluxing, magnetically stirring, removing a solvent by using a rotary evaporator, drying the rest solid particles in a vacuum drying oven, taking out and stirring once every 10 minutes, grinding and crushing the obtained powder by using a vibration mill, and vibrating for 30-60 minutes for later use;
(2) Mixing and stirring phenolic antioxidants and thioester antioxidants, and then adding polypropylene powder, metallocene linear low-density polyethylene, phosphite antioxidants, acid absorbers, antistatic agents and nano boron nitride treated in the step (1); mixing and stirring in a high-speed stirrer; adding the mixed materials into a double-screw extruder, melting, plasticizing, extruding, granulating and drying to obtain the product.
2. The thermo-oxidative aging resistant polypropylene composition according to claim 1, wherein: the polypropylene is homo-polypropylene or random co-polypropylene powder, the melt mass flow rate is 10-40g/10min, and the test condition is 230 ℃ and 2.16kg.
3. The thermo-oxidative aging resistant polypropylene composition according to claim 1, wherein: metallocene linear low density polyethylene is binary copolymer produced by ethylene and alpha-olefin under the action of metallocene catalyst on gas phase process deviceThe melt mass flow rate is 0.6-2.5g/10min under the condition of 2.16kg, and the density is 0.913-0.928g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The molecular weight distribution Mw/Mn is between 2.4 and 3.6, and the weight average molecular weight is 10 to 15 ten thousand.
4. The thermo-oxidative aging resistant polypropylene composition according to claim 1, wherein: the coupling agent is one of silane coupling agent, titanate coupling agent or aluminate coupling agent.
5. The thermo-oxidative aging resistant polypropylene composition according to claim 1, wherein: the acid absorbing agent is calcium stearate or zinc stearate.
6. The thermo-oxidative aging resistant polypropylene composition according to claim 1, wherein: in the step (2), high-speed mixing and stirring are carried out in a high-speed stirrer for 4-8 minutes, the stirring speed is 500-1000 revolutions per minute, and the stirring temperature is 35-40 ℃; the length-diameter ratio of the screw is 35-40, and the melting is carried out at 180-210 ℃; the main machine of the extruder has a rotating speed of 150-220 r/min, a feeding rotating speed of 35-50 r/min and drying at 60-80 ℃ for 20-35 minutes.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105153538A (en) * 2015-07-28 2015-12-16 苏州荣昌复合材料有限公司 Degradable PP (Polypropylene) plastics and preparation method therefor
CN110878158A (en) * 2018-09-06 2020-03-13 中国石油化工股份有限公司 Thermal-oxidative-aging-resistant impact-resistant polypropylene composition and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105153538A (en) * 2015-07-28 2015-12-16 苏州荣昌复合材料有限公司 Degradable PP (Polypropylene) plastics and preparation method therefor
CN110878158A (en) * 2018-09-06 2020-03-13 中国石油化工股份有限公司 Thermal-oxidative-aging-resistant impact-resistant polypropylene composition and preparation method thereof

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