CN112662112B - Polypropylene composite material with long-acting heat-oxygen aging resistance and low odor and stickiness resistance and preparation method thereof - Google Patents
Polypropylene composite material with long-acting heat-oxygen aging resistance and low odor and stickiness resistance and preparation method thereof Download PDFInfo
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- -1 Polypropylene Polymers 0.000 title claims abstract description 77
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 76
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 76
- 239000002131 composite material Substances 0.000 title claims abstract description 60
- 230000032683 aging Effects 0.000 title claims abstract description 30
- 229910052760 oxygen Inorganic materials 0.000 title abstract description 8
- 239000001301 oxygen Substances 0.000 title abstract description 8
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 49
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 48
- 229920000734 polysilsesquioxane polymer Polymers 0.000 claims abstract description 28
- 239000003822 epoxy resin Substances 0.000 claims abstract description 25
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 18
- 229920001971 elastomer Polymers 0.000 claims abstract description 17
- 239000000806 elastomer Substances 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000011256 inorganic filler Substances 0.000 claims abstract description 6
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 6
- 239000004593 Epoxy Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 18
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 17
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 claims description 15
- 239000000654 additive Substances 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- 238000012661 block copolymerization Methods 0.000 claims description 4
- 229920005684 linear copolymer Polymers 0.000 claims description 4
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- 150000004665 fatty acids Chemical class 0.000 claims description 3
- 239000004611 light stabiliser Substances 0.000 claims description 3
- 239000000314 lubricant Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- WXCZUWHSJWOTRV-UHFFFAOYSA-N but-1-ene;ethene Chemical compound C=C.CCC=C WXCZUWHSJWOTRV-UHFFFAOYSA-N 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 239000002086 nanomaterial Substances 0.000 claims description 2
- 150000008301 phosphite esters Chemical group 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 150000007970 thio esters Chemical class 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000010456 wollastonite Substances 0.000 claims description 2
- 229910052882 wollastonite Inorganic materials 0.000 claims description 2
- 230000005923 long-lasting effect Effects 0.000 claims 8
- 239000012752 auxiliary agent Substances 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 12
- 239000013078 crystal Substances 0.000 abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 125000003700 epoxy group Chemical group 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 14
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 13
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 12
- 239000000126 substance Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 5
- 238000011056 performance test Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 230000007774 longterm Effects 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 230000003064 anti-oxidating effect Effects 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- VKJLYEDTHCTCOH-UHFFFAOYSA-N 3-(3-octadecoxy-3-oxopropyl)sulfanylpropanoic acid Chemical group CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(O)=O VKJLYEDTHCTCOH-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical group OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Abstract
The invention discloses a polypropylene composite material with long-acting heat-resistant, oxygen-aging-resistant performance and low odor and stickiness resistance and a preparation method thereof, wherein the polypropylene composite material comprises the following raw materials in percentage by weight: 37-97 parts of polypropylene, 0-30 parts of nano inorganic filler, 0.5-5 parts of epoxy resin, 1-10 parts of octaepoxy cage-shaped polysilsesquioxane, 1-15 parts of elastomer, 0.1-0.5 part of antioxidant and 0-2 parts of other auxiliary agents. According to the invention, epoxy resin and octaepoxy cage-shaped polysilsesquioxane are introduced into a nano inorganic filler reinforced polypropylene composite system, and a cross-linked network structure is formed through the internal bonding action of epoxy groups, so that a synergistic antioxidant effect can be formed with a conventional antioxidant; meanwhile, the small-size effect of the octa-epoxy cage-shaped polysilsesquioxane can enable the polypropylene to be smaller in crystal size, more perfect in crystal lattice and more uniform in structure, and can inhibit oxygen from entering the inside of the material and diffusing in the inside of the material, so that the thermal-oxidative aging resistance of the polypropylene composite material is remarkably improved.
Description
Technical Field
The invention relates to a polypropylene composite material with long-acting heat-resistant, oxygen-aging-resistant performance, low odor and stickiness resistance and a preparation method thereof, which is a polypropylene composite material with simple process, low cost and good comprehensive performance, is mainly applied to household appliances, automobile interior and exterior trim and the like, and belongs to the technical field of polymer modification and processing.
Background
The polypropylene has better processability, excellent mechanical, physical and chemical properties, light weight and low cost, and is widely applied to industries such as automobile interior and exterior trim, household appliances, electronics and the like, thus being a general thermoplastic with the fastest growing speed at present. In recent years, with the rapid development of household appliances and automobile industry, thermoplastic plastic products, particularly polypropylene materials, have been increasingly used in a wide range, and the requirements for properties thereof have been increased. If the polypropylene product is used for a long time, the product is easy to become brittle and even pulverized, and the service life of the plastic product is seriously influenced. Meanwhile, when the polypropylene composite material is used as an automotive interior part, the high temperature of the closed environment and the interior of the automobile provides higher challenges for the thermal oxidative aging resistance and smell of the polypropylene material, and in recent years, consumers complain about the smell in the automobile. Therefore, how to improve the thermo-oxidative aging resistance of the polypropylene composite material and have better odor effect at the same time becomes an urgent problem to be solved in developing the material.
At present, the most common means for improving the thermo-oxidative aging resistance of the polypropylene composite material is to improve the content of the antioxidant, but excessive antioxidant can cause the problem that the antioxidant is separated out and sticky in the use process of the material. The prior art patents increase the thermo-oxidative aging resistance of polypropylene composites by adding other types of additives or increasing the antioxidant levels, but fail to address the problem of tacky bleeding to the surface of the article. For example, in the patent CN101065432a, a primary antioxidant and a secondary antioxidant are added into a composite material, so that the stability of a composite system is improved, and the long-term thermal-oxidative aging resistance is achieved, but the problem of tackiness caused by precipitation of the antioxidants due to the high content of the antioxidants is solved. Patent CN102827422a increases the thermo-oxidative aging resistance of composite materials by adding beta nucleating agents and grafting aids, but does not relate to the anti-tack properties of the material and the odor profile. Patent CN103044776a improves the odor and thermo-oxidative aging properties of polypropylene composites by adding specific deodorants and antioxidants, but does not address the problems of bleeding out and sticking that may occur.
Disclosure of Invention
The invention aims to provide a polypropylene composite material with long-acting heat-oxygen aging resistance and low odor and stickiness resistance and a preparation method thereof, so as to solve the problems in the prior art.
In order to improve the thermo-oxidative aging resistance of the polypropylene composite material, improve the odor problem of the composite system in the molding processing and using process, and solve the problem of sticky precipitation which is easy to occur in the long-term use process, the technical scheme of the invention is that epoxy resin and octaepoxy cage-shaped polysilsesquioxane are added into a basic formula of the nano inorganic filler filled polypropylene composite material, and a cross-linked network structure is formed through the bonding action in epoxy groups in the extrusion blending process, so that a synergistic anti-oxidation effect can be formed with a conventional antioxidant; meanwhile, the small-size effect of the octa-epoxy cage-shaped polysilsesquioxane can enable the polypropylene to be smaller in crystal size, more perfect in crystal lattice and more uniform in structure, and can inhibit oxygen from entering the inside of the material and diffusing in the inside of the material, so that the thermo-oxidative aging resistance of the polypropylene composite material is remarkably improved; meanwhile, the cage structure of the octaepoxy cage polysilsesquioxane and the coating effect of the epoxy resin on the nano particles are utilized, so that small molecular substances generated in the molding and processing process of the composite material can be captured, and a good odor effect is given to the composite material; the obtained composite material has long-acting and lasting antioxidation effect under the condition of adding a small amount of antioxidant, and can avoid the phenomenon of sticky precipitation in the long-time use process.
The low-odor anti-tacky polypropylene composite material with long-acting heat-oxygen aging resistance is prepared from the following raw materials in percentage by weight:
in the polypropylene composite material system suitable for the invention,
the melt flow rate of the polypropylene is 5-60 g/10min under the conditions of 230 ℃ and 2.16kg load.
The polypropylene is homo-polypropylene or block copolymerization propylene; the crystallinity of the homopolypropylene is more than 70%, and the isotacticity is more than 99%; the comonomer of the block copolymerization polypropylene is ethylene, and the molar content of the ethylene monomer repeating units is 4-10%.
The nanometer inorganic filler is one or a combination of more of nanometer talcum powder, nanometer calcium carbonate, nanometer silicon dioxide, nanometer wollastonite and the like, and the average grain diameter is 50-150 nm.
The epoxy resin is bisphenol A type epoxy resin, and the epoxy equivalent is 550-650 g/eq.
The octaepoxy cage-shaped polysilsesquioxane is a novel organic-inorganic nano-structure hybrid system, and the particle size range of the octaepoxy cage-shaped polysilsesquioxane is 10-50 nm.
The elastomer is ethylene-octene linear copolymer or ethylene-butene linear copolymer or the combination of the two, and the density is 0.88-0.90 g/cm 3 The melt flow rate is 0.5-10 g/10min.
The antioxidant comprises a main antioxidant and an auxiliary antioxidant, wherein the main antioxidant is a hindered phenol antioxidant; the auxiliary antioxidant is phosphite ester or thioester antioxidant. The main antioxidant is one or two of 3114 and 1010; the auxiliary antioxidant is one or more of 618, 168 and DSTP.
The other additives are various color additives, light stabilizers, various esters or fatty acid lubricants, and the like.
The preparation method of the polypropylene composite material with long-acting heat-oxygen aging resistance and low odor and stickiness resistance comprises the following specific steps:
(1) Weighing the raw materials according to the weight ratio;
(2) Placing the raw materials into a high-speed mixer for mixing for 3-5 minutes;
(3) Putting the mixed raw materials into a double-screw machine, and carrying out melt extrusion and granulation, wherein the process comprises the following steps: 190-200 ℃ in the first area, 200-210 ℃ in the second area, 210-220 ℃ in the third area and 205-215 ℃ in the fourth area; the residence time of the whole extrusion process is 1-2 minutes, the pressure is 12-18 MPa, and the vacuum degree of exhaust reaches 5-20 kPa.
The invention has the advantages that:
1. according to the invention, epoxy resin and octaepoxy cage-shaped polysilsesquioxane are introduced into a nano inorganic filler filled reinforced polypropylene composite system, and a cross-linked network structure is formed through the internal bonding action of epoxy groups, so that a synergistic antioxidant effect can be formed with a conventional antioxidant;
2. the invention utilizes the small-size effect of the octa-epoxy cage-shaped polysilsesquioxane, can lead the crystal size of the polypropylene to be smaller, the crystal lattice to be more perfect, the structure to be more uniform, and can inhibit oxygen from entering the inside of the material and diffusing in the inside of the material, thereby improving the thermo-oxidative aging resistance of the polypropylene composite material;
3. the invention utilizes the cage-shaped hollow structure of the octaepoxy cage-shaped polysilsesquioxane and the better coating effect of the epoxy resin on the nano particles, can capture small molecular substances generated in the molding and processing process of the composite material, and endows the composite material with good odor effect;
4. the invention can achieve the long-acting and durable thermal-oxidative aging resistance effect under the condition of adding a very small amount of antioxidant, and can avoid the phenomenon of sticky precipitation in the long-time use process;
5. the preparation process of the polypropylene composite material with long-acting heat-resistant, oxygen-aging-resistant and low-odor anti-sticking performance is simple, and industrial production can be realized.
Detailed Description
The present invention will be described in further detail by way of examples and comparative examples, which are not intended to limit the scope of the invention.
Example 1
The main components of the polypropylene composite material comprise 69.6% of polypropylene, 20% of nano talcum powder, 1% of epoxy resin, 2% of octaepoxy cage-shaped polysilsesquioxane, 5% of elastomer, 0.1% of antioxidant 1010, 0.1% of auxiliary antioxidant DSTP, 0.2% of auxiliary antioxidant 168 and 2% of other auxiliary agents.
Example 2
The polypropylene composite material comprises 68.6% of polypropylene, 20% of nano talcum powder, 2% of epoxy resin, 2% of octaepoxy cage-shaped polysilsesquioxane, 5% of elastomer, 0.1% of antioxidant 1010, 0.1% of auxiliary antioxidant DSTP, 0.2% of auxiliary antioxidant 168 and 2% of other auxiliary agents.
Example 3
The main components of the polypropylene composite material comprise 67.6% of polypropylene, 20% of nano talcum powder, 2% of epoxy resin, 3% of octaepoxy cage-shaped polysilsesquioxane, 5% of elastomer, 0.1% of antioxidant 1010, 0.1% of auxiliary antioxidant DSTP, 0.2% of auxiliary antioxidant 168 and 2% of other auxiliary agents.
Example 4
The polypropylene composite material comprises the main components of 64.6% of polypropylene, 20% of nano talcum powder, 3% of epoxy resin, 5% of octaepoxy cage-shaped polysilsesquioxane, 5% of elastomer, 0.1% of antioxidant 1010, 0.1% of auxiliary antioxidant DSTP, 0.2% of auxiliary antioxidant 168 and 2% of other auxiliary agents.
Example 5
The main components of the polypropylene composite material comprise 51.6% of polypropylene, 30% of nano talcum powder, 3% of epoxy resin, 5% of octaepoxy cage-shaped polysilsesquioxane, 8% of elastomer, 0.1% of antioxidant 1010, 0.1% of auxiliary antioxidant DSTP, 0.2% of auxiliary antioxidant 168 and 2% of other auxiliary agents.
Example 6
The polypropylene composite material comprises 50.6% of polypropylene, 30% of nano talcum powder, 4% of epoxy resin, 5% of octaepoxy cage-shaped polysilsesquioxane, 8% of elastomer, 0.1% of antioxidant 1010, 0.1% of auxiliary antioxidant DSTP, 0.2% of auxiliary antioxidant 168 and 2% of other auxiliary agents.
Example 7
The main components of the polypropylene composite material comprise 47.6% of polypropylene, 30% of nano talcum powder, 4% of epoxy resin, 8% of octaepoxy cage-shaped polysilsesquioxane, 8% of elastomer, 0.1% of antioxidant 1010, 0.1% of auxiliary antioxidant DSTP, 0.2% of auxiliary antioxidant 168 and 2% of other auxiliary agents.
Comparative example 1
The main components of the polypropylene composite material comprise 72.6% of polypropylene, 20% of nano talcum powder, 5% of elastomer, 0.1% of antioxidant 1010, 0.1% of auxiliary antioxidant DSTP, 0.2% of auxiliary antioxidant 168 and 2% of other auxiliary agents.
Comparative example 2
The main components of the polypropylene composite material comprise 71.6% of polypropylene, 20% of nano talcum powder, 1% of epoxy resin, 5% of elastomer, 0.1% of antioxidant 1010, 0.1% of auxiliary antioxidant DSTP, 0.2% of auxiliary antioxidant 168 and 2% of other auxiliary agents.
Comparative example 3
The polypropylene composite material comprises the main components of 70.6 percent of polypropylene, 20 percent of nano talcum powder, 2 percent of octaepoxy cage-shaped polysilsesquioxane, 5 percent of elastomer, 0.1 percent of antioxidant 1010, 0.1 percent of auxiliary antioxidant DSTP, 0.2 percent of auxiliary antioxidant 168 and 2 percent of other auxiliary agents.
Comparative example 4
The polypropylene composite material comprises the main components of 70% of polypropylene, 20% of nano talcum powder, 1% of epoxy resin, 2% of octaepoxy cage-shaped polysilsesquioxane, 5% of elastomer and 2% of other auxiliary agents.
Comparative example 5
The main components of the polypropylene composite material comprise 72.3 percent of polypropylene, 20 percent of nano talcum powder, 5 percent of elastomer, 0.2 percent of antioxidant 1010, 0.2 percent of auxiliary antioxidant DSTP, 0.3 percent of auxiliary antioxidant 168 and 2 percent of other auxiliary agents.
Comparative example 6
The polypropylene composite material comprises 58.9% of polypropylene, 30% of nano talcum powder, 8% of elastomer, 0.3% of antioxidant 1010, 0.3% of auxiliary antioxidant DSTP, 0.5% of auxiliary antioxidant 168 and 2% of other auxiliary agents.
The mass percentages of the main components of the examples and the comparative examples are shown in Table 1.
TABLE 1 Material formulation tables (wt.%) for examples 1-7 and comparative examples 1-6
In the above-described composite formulations of examples and comparative examples, the polypropylene was copolymerized from Shanghai petrochemical production under the trade designation M2600R and had a melt flow rate of 30g/10min (test conditions: 230 ℃ C. Times.2.16 kg). The talcum powder is 10000 meshes, the average grain diameter is 100nm, and the talcum powder is commercially available. The epoxy resin is KD-213 produced in national chemical industry. The octaepoxy cage-shaped polysilsesquioxane has an average particle diameter of 20nm and a molecular weight of 40000-80000, and is self-made. The elastomer used was an ethylene-octene copolymer of DOW under the trade name Engage8150 having a density of 0.868g/cm3 and a melt index of 0.5g/10min (test conditions: 190 ℃ C. Times.2.16 kg). The main antioxidant is 1010 from BASF company, the chemical name is pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], the auxiliary antioxidant is DSTP from British ICE company, the chemical name is stearyl thio-dipropionate, and the chemical name is 168 from BASF company, and the chemical name is tri (2, 4-di-tert-butylphenyl) phosphite. The other auxiliary agents comprise various color additives, light stabilizers, various esters or fatty acid lubricants and the like.
The resins and various additives in the above examples and comparative examples were dry mixed in a high speed mixer for 3 to 5 minutes, and then melt extruded in a twin screw extruder, and pelletized, the process of which was: 190-200 ℃ in the first area, 200-210 ℃ in the second area, 210-220 ℃ in the third area and 205-215 ℃ in the fourth area; the residence time of the whole extrusion process is 1-2 minutes, the pressure is 12-18 MPa, and the vacuum degree of exhaust reaches 5-20 kPa.
The particle material prepared by the method is dried in a blast oven at 90-100 ℃ for 2-3 hours, and then the dried particle material is subjected to injection molding sample preparation on an injection molding machine, and performance test is carried out.
Tensile property test: the sample size was 170X 10X 4mm and the stretching speed was 50mm/min, performed according to ISO 527-2 standard;
bending performance test: the sample size is 80X 10X 4mm, the bending speed is 2mm/min and the span is 64mm according to ISO 178 standard;
notched impact strength test: the sample size is 80 multiplied by 10 multiplied by 4mm, and the notch depth is one third of the sample thickness according to ISO 179-1 standard;
thermal oxidative aging resistance test: injecting a template of 1mm and 3mm by referring to DIN 53497 standard, and storing in a forced convection oven at 150 ℃ until embrittlement of the template occurs, wherein the template is used as an evaluation standard;
tack performance test: the test was performed according to the mass standard PV1306, and the samples were evaluated according to the scale described in table 2 below:
table 2 surface tack grade and evaluation results
| Grade | Evaluation results | Grade | Evaluation results |
| 1 | OK | 5 | Very sticky |
| 2 | Slightly tacky | H | Resinifying |
| 3 | Tacky | W | Smooth, waxy surface |
| 4 | More viscous | X | The sample is cracked and cannot be evaluated |
Odor test: the process was performed according to the mass PV3900 standard using a 50g template, 1L odor bottle. Placing the sample in an odor bottle, placing the odor bottle in an oven at the temperature of 80+/-2 ℃ for 2 hours+/-10 minutes, and after the odor bottle is cooled to 60+/-5 ℃, judging the odor bottle according to the grade (half-grade and other grades in the middle) described in the table 3;
TABLE 3 odor rating and evaluation results
| Grade | Evaluation results | Grade | Evaluation results |
| Level 1 | Not feel it | Grade 4 | Harassment of human |
| Level 2 | Can feel undisturbed | Grade 5 | Strong dislike |
| 3 grade | Can obviously feel but not disturb people | Grade 6 | Is difficult to tolerate |
The results of performance tests on polypropylene composites of examples 1 to 7 and comparative examples 1 to 6 of the present invention are shown in Table 4, respectively.
TABLE 4 Material Properties Table for examples 1-7 and comparative examples 1-6
From the comparison of examples 1-7 and the comparison of examples 1-4 and comparative examples 1-4, it can be seen that the simultaneous addition of the epoxy resin and the octaepoxy cage-like polysilsesquioxane can significantly improve the thermo-oxidative aging resistance of the polypropylene composite material, and the thermo-oxidative aging resistance of the composite material is further improved along with the increase of the content of the epoxy resin and the octaepoxy cage-like polysilsesquioxane; meanwhile, compared with the system which does not contain or only contains one of epoxy resin and octaepoxy group cage-shaped polysilsesquioxane, the odor of the composite system can be obviously improved under the condition that the epoxy resin and the octaepoxy group cage-shaped polysilsesquioxane exist at the same time, and even the level of the more ideal odor of the level 3 can be reached. From the comparison of the examples 1 and 5 and the examples 5 and 6, it can be found that the higher heat-resistant and oxygen-aging resistance can be achieved by adding higher antioxidant, but the problem of sticky precipitation exists on the surface of the material after the sticky resistance test, so that the long-term use effect of the product is affected; in the presence of epoxy resin and octaepoxy cage-shaped polysilsesquioxane, the long-acting thermo-oxidative aging resistance can be achieved under the condition of adding a low-content antioxidant, and meanwhile, the material has good comprehensive mechanical properties.
Claims (10)
1. A low odor, tacky polypropylene composite having long-acting thermo-oxidative aging resistance, characterized by: the material is prepared from the following raw materials in percentage by weight:
2. a low odor, tacky polypropylene composite having long lasting thermo-oxidative aging resistance according to claim 1, wherein: the melt flow rate of the polypropylene is 5-60 g/10min under the conditions of 230 ℃ and 2.16kg load.
3. A low odor, tacky polypropylene composite having long lasting thermo-oxidative aging resistance according to claim 1, wherein: the polypropylene is homo-polypropylene or block copolymerization propylene; the crystallinity of the homopolypropylene is more than 70%, and the isotacticity is more than 99%; the comonomer of the block copolymerization polypropylene is ethylene, and the molar content of the ethylene monomer repeating units is 4-10%.
4. A low odor, tacky polypropylene composite having long lasting thermo-oxidative aging resistance according to claim 1, wherein: the nanometer inorganic filler is one or the combination of more of nanometer talcum powder, nanometer calcium carbonate, nanometer silicon dioxide and nanometer wollastonite, and the average grain diameter is 50-150 nm.
5. A low odor, tacky polypropylene composite having long lasting thermo-oxidative aging resistance according to claim 1, wherein: the epoxy resin is bisphenol A type epoxy resin, and the epoxy equivalent is 550-650 g/eq.
6. A low odor, tacky polypropylene composite having long lasting thermo-oxidative aging resistance according to claim 1, wherein: the octaepoxy cage-shaped polysilsesquioxane is a novel organic-inorganic nano-structure hybrid system, and the particle size range of the octaepoxy cage-shaped polysilsesquioxane is 10-50 nm.
7. A low odor, tacky polypropylene composite having long lasting thermo-oxidative aging resistance according to claim 1, wherein: the elastomer is ethylene-octene linear copolymer or ethylene-butene linear copolymer or the combination of the two, and the density is 0.88-0.90 g/cm 3 The melt flow rate is 0.5-10 g/10min.
8. A low odor, tacky polypropylene composite having long lasting thermo-oxidative aging resistance according to claim 1, wherein: the antioxidant comprises a main antioxidant and an auxiliary antioxidant, wherein the main antioxidant is a hindered phenol antioxidant; the auxiliary antioxidant is phosphite ester or thioester antioxidant; the main antioxidant is one or two of 3114 and 1010; the auxiliary antioxidant is one or more of 618, 168 and DSTP.
9. A low odor, tacky polypropylene composite having long lasting thermo-oxidative aging resistance according to claim 1, wherein: the other additives are various color additives, light stabilizers, various esters or fatty acid lubricants.
10. The process for preparing a low odor, tacky polypropylene composite having long-acting thermo-oxidative aging resistance according to any one of claims 1 to 9, characterized in that: the method comprises the following specific steps:
(1) Weighing the raw materials according to the weight ratio;
(2) Placing the raw materials into a high-speed mixer for mixing for 3-5 minutes;
(3) Putting the mixed raw materials into a double-screw machine, and carrying out melt extrusion and granulation, wherein the process comprises the following steps: 190-200 ℃ in the first area, 200-210 ℃ in the second area, 210-220 ℃ in the third area and 205-215 ℃ in the fourth area; the residence time of the whole extrusion process is 1-2 minutes, the pressure is 12-18 MPa, and the vacuum degree of exhaust reaches 5-20 kPa.
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| CN101870784A (en) * | 2010-03-29 | 2010-10-27 | 金发科技股份有限公司 | Impact resisting weather-proof polypropylene and preparation method thereof |
| CN103146141A (en) * | 2013-01-25 | 2013-06-12 | 西北工业大学 | Low dielectric constant polyhedral oligomeric silsesquioxane (POSS)/ epoxy resin hybrid material and preparation method |
| CN109679216A (en) * | 2018-12-28 | 2019-04-26 | 重庆普利特新材料有限公司 | A kind of high rigid-tough balance, resistance to stress whiten, halogen-free flame retardant polypropylene composite material and preparation method thereof |
| CN111087694A (en) * | 2019-12-26 | 2020-05-01 | 上海普利特复合材料股份有限公司 | Functional POSS hybridization-based high-performance modified polypropylene composite material for vehicles and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101870784A (en) * | 2010-03-29 | 2010-10-27 | 金发科技股份有限公司 | Impact resisting weather-proof polypropylene and preparation method thereof |
| CN103146141A (en) * | 2013-01-25 | 2013-06-12 | 西北工业大学 | Low dielectric constant polyhedral oligomeric silsesquioxane (POSS)/ epoxy resin hybrid material and preparation method |
| CN109679216A (en) * | 2018-12-28 | 2019-04-26 | 重庆普利特新材料有限公司 | A kind of high rigid-tough balance, resistance to stress whiten, halogen-free flame retardant polypropylene composite material and preparation method thereof |
| CN111087694A (en) * | 2019-12-26 | 2020-05-01 | 上海普利特复合材料股份有限公司 | Functional POSS hybridization-based high-performance modified polypropylene composite material for vehicles and preparation method thereof |
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