CN115058081B - Foamed polypropylene, preparation method of foamed polypropylene and molded product of foamed polypropylene - Google Patents
Foamed polypropylene, preparation method of foamed polypropylene and molded product of foamed polypropylene Download PDFInfo
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- CN115058081B CN115058081B CN202210781433.XA CN202210781433A CN115058081B CN 115058081 B CN115058081 B CN 115058081B CN 202210781433 A CN202210781433 A CN 202210781433A CN 115058081 B CN115058081 B CN 115058081B
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- polypropylene
- titanium dioxide
- nucleating agent
- foaming
- granulating
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 201
- -1 polypropylene Polymers 0.000 title claims abstract description 201
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 201
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 262
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 102
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims abstract description 75
- 238000005187 foaming Methods 0.000 claims abstract description 72
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 70
- 239000002667 nucleating agent Substances 0.000 claims abstract description 66
- 239000000463 material Substances 0.000 claims abstract description 51
- 238000002156 mixing Methods 0.000 claims abstract description 31
- 238000005507 spraying Methods 0.000 claims abstract description 24
- 239000001038 titanium pigment Substances 0.000 claims abstract description 24
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000314 lubricant Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims description 51
- 238000000465 moulding Methods 0.000 claims description 33
- 238000001035 drying Methods 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- 239000013078 crystal Substances 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 17
- 238000000227 grinding Methods 0.000 claims description 14
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000000454 talc Substances 0.000 claims 1
- 229910052623 talc Inorganic materials 0.000 claims 1
- 150000003608 titanium Chemical class 0.000 claims 1
- 230000032683 aging Effects 0.000 abstract description 28
- 230000002035 prolonged effect Effects 0.000 abstract description 10
- 235000010215 titanium dioxide Nutrition 0.000 description 121
- 239000000843 powder Substances 0.000 description 67
- 230000003712 anti-aging effect Effects 0.000 description 58
- 230000000052 comparative effect Effects 0.000 description 34
- 238000001125 extrusion Methods 0.000 description 28
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 26
- 238000012545 processing Methods 0.000 description 23
- 238000003825 pressing Methods 0.000 description 21
- 238000005469 granulation Methods 0.000 description 15
- 230000003179 granulation Effects 0.000 description 15
- 239000003921 oil Substances 0.000 description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 description 13
- 239000001569 carbon dioxide Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000005995 Aluminium silicate Substances 0.000 description 12
- 235000012211 aluminium silicate Nutrition 0.000 description 12
- 239000012752 auxiliary agent Substances 0.000 description 12
- 235000014121 butter Nutrition 0.000 description 12
- 230000006837 decompression Effects 0.000 description 12
- 239000002270 dispersing agent Substances 0.000 description 12
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 12
- 239000011259 mixed solution Substances 0.000 description 12
- 239000012535 impurity Substances 0.000 description 11
- 239000004570 mortar (masonry) Substances 0.000 description 11
- 239000012299 nitrogen atmosphere Substances 0.000 description 11
- 239000002356 single layer Substances 0.000 description 11
- 238000001354 calcination Methods 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- 150000003254 radicals Chemical class 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 239000011324 bead Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- 230000002401 inhibitory effect Effects 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 206010051246 Photodermatosis Diseases 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000012792 core layer Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 230000008845 photoaging Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 238000005562 fading Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 230000036561 sun exposure Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/06—CO2, N2 or noble gases
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/08—Supercritical fluid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
- C08J2491/06—Waxes
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- 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
- C08K2003/387—Borates
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- 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
- C08K9/00—Use of pretreated ingredients
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
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Abstract
The invention provides foaming polypropylene, a preparation method of the foaming polypropylene and a molded part thereof, and relates to the technical field of materials, wherein the preparation method comprises the following steps: purifying the titanium dioxide to obtain purified titanium dioxide; spraying melted ethylene bis stearamide on the surface of the purified titanium dioxide to obtain activated titanium dioxide; mixing activated titanium dioxide, polypropylene and white oil, and extruding and granulating by a double screw to obtain titanium dioxide master batch; mixing polypropylene, a nucleating agent and a lubricant, and then extruding and granulating through double screws to obtain a nucleating agent master batch; extruding and granulating polypropylene, nucleating agent master batches and titanium pigment master batches by using double screws to obtain a special foaming polypropylene material; foaming the special material for foaming polypropylene to obtain the foaming polypropylene. According to the preparation method of the foamed polypropylene, the titanium dioxide modified by EBS mixing is introduced, so that the ageing resistance of the product is improved, and the duration of the ageing resistance is prolonged.
Description
Technical Field
The invention relates to the technical field of materials, in particular to foaming polypropylene, a preparation method of the foaming polypropylene and a molded part thereof.
Background
The foamed polypropylene (EPP for short) is widely applied to automobiles, packaging, high-speed rail aviation and a plurality of industries closely related to daily life of people due to the characteristics of light weight, high strength, environmental protection and the like. More, with the continuous development of industries such as take-out incubator, children amusement park facilities, water float operation tools and the like, the requirements on the weather resistance of EPP are higher and higher, and particularly the ultraviolet ageing resistance is extremely important.
As is known, the polypropylene material has strong acid and alkali resistance, but is unstable due to self tertiary carbon, and is very easy to trigger a system to generate free radicals under the influence of external conditions (stability, oxygen, ultraviolet light and the like) so as to break or crosslink a polypropylene molecular chain, thereby causing pulverization or brittleness of a product and greatly influencing the service life of the product.
Because EPP parts are exposed outdoors for a long time and directly contacted with ultraviolet rays and oxygen, the EPP parts are easy to age, and the surfaces of the EPP parts are chalked and cracked, so that the EPP parts lose service performance and even carry unexpected risks.
In general, polypropylene can be added with a certain amount of antioxidant and ultraviolet resistance auxiliary agent in a mode of inhibiting the generation and the transmission of free radicals in a special environment, so that the ageing resistance and the durability of the product are improved; however, in the method for improving the ageing resistance by adding the auxiliary agent, most of the auxiliary agents on the market have limited free radical capturing capacity, so that the problem of the effective period of the auxiliary agent often exists, and once the effective period is exceeded or the auxiliary agent is exceeded to the maximum extent, the ageing resistance effect is basically absent, so that the service life of the EPP molded part is shorter.
Disclosure of Invention
The invention aims to solve the technical problems that: in order to solve the problem of shorter service life of EPP molded parts in the prior art, the invention provides a preparation method of expanded polypropylene, which introduces titanium pigment modified by mixing ethylene bis stearamide, and on the basis of improving the ageing resistance of expanded polypropylene, the ageing resistance is not limited by the valid period of an auxiliary agent, thereby being beneficial to prolonging the duration of the ageing resistance, prolonging the service life and solving the problem of shorter service life of EPP molded parts in the prior art.
The technical scheme adopted for solving the technical problems is as follows:
a method for preparing expanded polypropylene, comprising the following steps:
s1: purifying titanium dioxide, converting the crystal state of titanium dioxide in the titanium dioxide into rutile type, and grinding to obtain purified titanium dioxide;
s2: spraying melted ethylene bis stearamide on the surface of the purified titanium dioxide, and stirring to obtain activated titanium dioxide;
s3: mixing the activated titanium dioxide, polypropylene and white oil, and then extruding and granulating by a double screw to obtain titanium dioxide master batch;
s4: mixing polypropylene, a nucleating agent and a lubricant, and then extruding and granulating through double screws to obtain a nucleating agent master batch;
s5: extruding and granulating polypropylene, the nucleating agent master batch and the titanium pigment master batch through double screws, and drying to obtain a special foaming polypropylene material;
s6: foaming the special material for foaming polypropylene to obtain foaming polypropylene.
Optionally, the particle size of the titanium dioxide is in the range of 0.2-0.4 mu m.
Optionally, step S2 includes: heating ethylene bis-stearamide to 140-150 ℃ to obtain the melted ethylene bis-stearamide; spraying the melted ethylene bis stearamide on the surface of the purified titanium dioxide at the temperature of 140-150 ℃ through a spraying device, and sequentially vibrating and cooling to obtain the activated titanium dioxide.
Optionally, the melted ethylene bis stearamide accounts for 3-5% of the mass of the purified titanium dioxide.
Optionally, in step S3, the mass ratio of the activated titanium white powder to the polypropylene to the white oil is (15-25): (70-90): (0.5-2).
Optionally, the mass ratio of the polypropylene, the nucleating agent and the lubricant in step S4 is (80-90): (5-15): (1-10).
Optionally, the nucleating agent is at least one selected from zinc borate, silicon dioxide and talcum powder, and the particle size of the nucleating agent is in the range of 0.8-5 mu m; the lubricant is at least one selected from ethylene bis stearamide, erucamide and stearic acid.
Optionally, in step S5, the mass ratio of the polypropylene, the nucleating agent masterbatch and the titanium pigment masterbatch is (85-99.7): (0.3-5): (3-10).
It is another object of the present invention to provide a foamed polypropylene, prepared by the method for preparing a foamed polypropylene as described above.
It is still another object of the present invention to provide a molded article of expanded polypropylene prepared from the expanded polypropylene as described above by steam molding.
The beneficial effects of the invention are as follows:
according to the preparation method of the foamed polypropylene, titanium dioxide modified by EBS mixing is introduced, so that the titanium dioxide can be better dispersed in the polypropylene, and after mixing by a screw, granulating and foaming, milky anti-aging polypropylene foaming beads can be obtained, and then a molded part of milky anti-aging foamed polypropylene can be obtained by molding; the molded part of the foaming polypropylene has higher brightness, can totally reflect light, thereby realizing the shielding effect on ultraviolet light, inhibiting the generation of photoinitiated polypropylene free radicals, improving the ageing resistance of the part on one hand, and on the other hand, as the ageing resistance is realized by adding the titanium dioxide modified by mixing, compared with the ageing resistance improved by adding the auxiliary agent, the problem of effective period does not exist, thereby being beneficial to prolonging the duration time of the ageing resistance and prolonging the service life of the EPP molded part; specifically, the EPP molded part prepared by the method provided by the invention has the advantages that under the condition of the same outdoor direct sunlight, the service life can be prolonged by 2-3 times compared with that of the traditional EPP molded product, the continuous service life in sea water can reach more than 3 years, the comprehensive performance of the product is improved to a certain extent compared with that of the conventional EPP, the apparent beautification degree of the part is improved, the technical support is greatly provided for the whole foamed polypropylene, particularly the scene needing to be subjected to wind and sun exposure, and the service life of the original EPP packaging raw material is prolonged.
Drawings
The invention will be further described with reference to the drawings and examples.
FIG. 1 is a schematic structural diagram of a special material for foamed polypropylene prepared by a double-layer coextrusion process.
Detailed Description
The present invention will now be described in further detail. The embodiments described below are exemplary and intended to illustrate the invention and should not be construed as limiting the invention, as all other embodiments, based on which a person of ordinary skill in the art would obtain without inventive faculty, are within the scope of the invention.
In order to solve the problem of shorter service life of EPP molded parts in the prior art, the invention provides a preparation method of foaming polypropylene, which comprises the following steps:
s1: purifying titanium dioxide, converting the crystal state of titanium dioxide in the titanium dioxide into rutile type, and grinding to obtain purified titanium dioxide;
s2: spraying melted Ethylene Bis Stearamide (EBS) on the surface of the purified titanium dioxide, and stirring to obtain activated titanium dioxide;
s3: mixing activated titanium dioxide, polypropylene and white oil, and extruding and granulating by a double screw to obtain titanium dioxide master batch;
S4: mixing polypropylene, a nucleating agent and a lubricant, and then extruding and granulating through double screws to obtain a nucleating agent master batch;
s5: extruding and granulating polypropylene, nucleating agent master batch and titanium pigment master batch by using double screws, and drying to obtain a special foaming polypropylene material;
s6: foaming the special material for foaming polypropylene to obtain the foaming polypropylene.
The preferred purification process of the titanium dioxide in the step S1 is that the purchased titanium dioxide powder is put into a muffle furnace at 1000 ℃, calcined for 6 hours in a nitrogen atmosphere, impurities in the powder are removed, meanwhile, the crystal state of titanium dioxide in the powder can be completely converted into rutile type (tetragonal crystal), and the rutile type (tetragonal crystal) is put into a mortar for grinding and drying, so that the purified titanium dioxide is obtained.
The titanium dioxide is converted into rutile type through the purification process, and the rutile type titanium dioxide has stable crystal lattice, so that the whiteness, weather resistance and chemical stability of the titanium dioxide are improved after the purification process, and particularly, the whiteness of the titanium dioxide is preferably more than or equal to 99 percent after the purification, so that the brightness (L value) of the surface of a product is improved, the light can be subjected to total reflection by the higher brightness, the ultraviolet light is shielded, the generation of photo-induced polypropylene free radicals is reduced, the ageing resistance of the product is improved, and the service life of the product is prolonged.
Further mixing and modifying the purified titanium dioxide through EBS to obtain activated titanium dioxide, so that the activated titanium dioxide can be better dispersed in the polypropylene matrix; and preparing titanium white master batches by taking activated titanium white, polypropylene and white oil as raw materials, preparing nucleating agent master batches by taking polypropylene, nucleating agent and softener as raw materials, granulating by taking the polypropylene, the nucleating agent master batches and the titanium white master batches as raw materials in a screw mixing mode to obtain a special material for the milky anti-aging foamed polypropylene, performing kettle pressure foaming by using supercritical carbon dioxide to obtain milky anti-aging polypropylene foaming beads, and performing molding to obtain a milky anti-aging foamed polypropylene product, namely a molded product of the foamed polypropylene.
According to the preparation method of the foamed polypropylene, titanium dioxide modified by EBS mixing is introduced, so that the titanium dioxide can be better dispersed in the polypropylene, and after mixing by a screw, granulating and foaming, milky anti-aging polypropylene foaming beads can be obtained, and then a molded part of milky anti-aging foamed polypropylene can be obtained by molding; the molded part of the foaming polypropylene has higher brightness, can totally reflect light, thereby realizing the shielding effect on ultraviolet light, inhibiting the generation of photoinitiated polypropylene free radicals, improving the ageing resistance of the part on one hand, and on the other hand, as the ageing resistance is realized by adding the titanium dioxide modified by mixing, compared with the ageing resistance improved by adding the auxiliary agent, the problem of effective period does not exist, thereby being beneficial to prolonging the duration time of the ageing resistance and prolonging the service life of the EPP molded part; specifically, the EPP molded part prepared by the method provided by the invention has the advantages that under the condition of the same outdoor direct sunlight, the service life can be prolonged by 2-3 times compared with that of the traditional EPP molded product, the continuous service life in sea water can reach more than 3 years, the comprehensive performance of the product is improved to a certain extent compared with that of the conventional EPP, the apparent beautification degree of the part is improved, the technical support is greatly provided for the whole foamed polypropylene, particularly the scene needing to be subjected to wind and sun exposure, and the service life of the original EPP packaging raw material is prolonged.
In addition, in the foaming industry, the addition of the auxiliary agent often affects the melt strength of the product, so that the cell distribution and the closed pore rate of the product are affected, and the comprehensive mechanical properties of the product are finally irreversibly affected; according to the preparation method of the foaming polypropylene, provided by the invention, on the basis of no addition of traditional anti-aging auxiliary agents, the anti-aging performance is improved, and the duration of the anti-aging effect is prolonged, so that the comprehensive mechanical performance of the EPP molded part is improved on the basis of improving the anti-aging effect and prolonging the duration of the anti-aging effect.
In addition, the common hindered amine or hindered phenol anti-aging agent has limited dispersing ability with the polypropylene matrix due to the self characteristic, and in addition, the product can be subjected to yellowing and fading phenomena after long-time exposure, so that the applicability is general in the foaming industry, particularly in light-colored products; the invention does not need to add traditional anti-aging agent, so the EPP molded part is not easy to generate yellowing and fading phenomena, and the invention is beneficial to improving the beautiful appearance of the product.
In order to give consideration to the ageing resistance and the comprehensive mechanical properties of the EPP molded parts, the preferred particle size range of the titanium dioxide is 0.2-0.4 mu m.
The preferred step S2 of the present invention comprises: heating ethylene bis-stearamide to 140-150 ℃ to obtain melted ethylene bis-stearamide; spraying the melted ethylene bis stearamide on the surface of the purified titanium white powder at the temperature of 140-150 ℃ by a spraying device, and sequentially vibrating and cooling to obtain the activated titanium white powder.
Specifically, the activated titanium dioxide can be obtained after the EBS wrapped on the surface is solidified after the EBS evenly wraps the surface of the purified titanium dioxide and is cooled through continuous vibration of a vibration device.
The ethylene bis stearamide after melting is preferably 3-5% of the mass of the purified titanium dioxide, so that the aging resistance effect is poor due to the fact that the EBS consumption is too small, and the subsequent processing is difficult due to the fact that the EBS consumption is too large.
In order to give consideration to the ageing resistance and the comprehensive mechanical properties of the EPP molded part, the mass ratio of the titanium white powder, the polypropylene and the white oil after being activated in the step S3 is preferably (15-25): (70-90): (0.5-2); and preferably the twin screw processing temperature in this step is 150-170 ℃; the granulation size is 1.5-2.5mm, and the weight is 10-15mg.
The mass ratio of the polypropylene, the nucleating agent and the lubricant in the preferred step S4 is (80-90): (5-15): (1-10); wherein the nucleating agent is at least one selected from zinc borate, silicon dioxide and talcum powder, and the grain diameter of the nucleating agent ranges from 0.8 to 5 mu m, so as to ensure the uniformity of the cell size of the foaming particles and the uniform distribution of the nucleating agent in the system during processing; the lubricant is at least one selected from ethylene bis stearamide, erucamide and stearic acid; preferably, the twin-screw processing temperature in this step is controlled to 150-170 ℃, the granulation size is controlled to be 1.5-2.5mm long, and the weight is 10-15mg.
The preferred mass ratio of the polypropylene to the nucleating agent master batch to the titanium dioxide master batch in the step S5 is (85-99.7): (0.3-5): (3-10), and preferably granulating by twin-screw at 150-170deg.C, with the granulation size controlled to be 1.0-2.0mm long and weight 0.5-1.2mg.
Further, the extrusion granulation process in the step S5 may be a single-layer extrusion process or a double-layer co-extrusion process; specifically, when a monolayer extrusion process is selected, the mass ratio of polypropylene, nucleating agent master batch and titanium pigment master batch is (85-92): (3-5): (5-10); when a double-layer coextrusion process is selected, the mass ratio of polypropylene and nucleating agent master batch is preferably (99.5-99.7): (0.3-0.5), the consumption of the titanium pigment master batch is 3-5% of the mass of the polypropylene and the nucleating agent master batch; the invention is preferably a double-layer coextrusion process, as shown in fig. 1, polypropylene and nucleating agent master batch are preferably used as a core layer, and titanium pigment master batch is used as a coating layer to cover the outer side of the core layer, so that the consumption of titanium pigment is reduced to the greatest extent, and meanwhile, the EPP molded part is ensured to have better appearance.
The preferred step S6 of the invention comprises the steps of putting special materials of the foaming polypropylene into a reaction kettle, controlling the water-material ratio to be 2.6-60, simultaneously adding a certain amount of dispersing agent (mixed solution of butter and kaolin, the dosage is 0.3-0.4% of the water amount), heating in a steam auxiliary way, controlling the pressure in the reaction kettle in a supercritical carbon dioxide input way, after the temperature and the pressure are stable (the temperature is 140-150 ℃ and the pressure is 1.8-2.8 MPa), and obtaining the milky anti-aging foaming polypropylene beads with the density of 40-60g/L in a rapid decompression way.
It is another object of the present invention to provide a foamed polypropylene, prepared by the method for preparing a foamed polypropylene as described above.
According to the foamed polypropylene provided by the invention, the titanium dioxide modified by EBS mixing is introduced, so that the titanium dioxide can be better dispersed in the polypropylene, and on the basis that the traditional anti-aging agent is not required to be added, milky-white anti-aging polypropylene foaming beads can be obtained, so that a molded part prepared from the foamed polypropylene has higher brightness, light can be totally reflected, the ultraviolet light shielding effect is realized, the generation of photoinitiated polypropylene free radicals is inhibited, on one hand, the anti-aging performance of the part is improved, and on the other hand, the anti-aging effect is realized by adding the mixing modified titanium dioxide, so that compared with the anti-aging performance improved by adding an auxiliary agent, the problem of the effective period does not exist, the duration of the anti-aging performance is further prolonged, and the service life of the EPP molded part is prolonged.
It is still another object of the present invention to provide a molded article of expanded polypropylene prepared from the expanded polypropylene as described above by steam molding.
The molded part of the foamed polypropylene provided by the invention has higher brightness, can fully reflect light, thereby realizing the shielding effect on ultraviolet light and inhibiting the generation of photoinitiated polypropylene free radicals, on one hand, the anti-aging performance of the part is improved, and on the other hand, the anti-aging effect is realized by adding the titanium white modified by mixing, so that compared with the improvement of the anti-aging performance by adding the auxiliary agent, the molded part has no problem of effective period, further contributes to prolonging the duration of the anti-aging performance and prolonging the service life of the EPP molded part.
In order that the above objects, features and advantages of the invention will be readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
Example 1
S1: placing purchased titanium dioxide powder (with the particle size of 0.3 μm) into a muffle furnace at 1000 ℃, calcining for 6 hours in nitrogen atmosphere, removing impurities in the powder, completely converting the crystal state of titanium dioxide in the powder into rutile type, and placing into a mortar for grinding and drying to obtain purified titanium dioxide;
s2: heating and melting the EBS to 145 ℃ to liquefy the EBS, uniformly spraying the purified titanium white powder prepared in the step 1 by a spraying device, simultaneously keeping 145 ℃ for the titanium white powder purified in the process, continuously vibrating by a vibrating device, cooling after the EBS is uniformly wrapped on the surface of the titanium white powder, and obtaining activated titanium white powder after the surface is coated with the EBS to be solidified; wherein the EBS melt is 4% of the mass of the titanium dioxide;
s3: according to parts by weight, mixing and fully stirring 20 parts of activated titanium dioxide, 79 parts of polypropylene and 1 part of white oil, and then extruding and granulating by a double screw to obtain titanium dioxide master batch; wherein the twin-screw processing temperature is 160 ℃; the granulating size is 2mm, and the weight is 12mg;
S4: according to parts by weight, fully stirring 85 parts of polypropylene, 10 parts of nucleating agent zinc borate and 5 parts of lubricant ethylene bis stearamide, and then extruding and granulating by a double screw to obtain nucleating agent master batch; wherein the processing temperature of the twin-screw is controlled to 160 ℃, the granulating size is 2mm, and the weight is 12mg;
s5: according to the weight portions, the special foaming polypropylene material is obtained by extruding and granulating 87 portions of polypropylene, 3 portions of nucleating agent master batch and 10 portions of titanium pigment master batch through double screws and drying; the extrusion granulation process is a single-layer extrusion process;
s6: adding a special material of foaming polypropylene into a reaction kettle, controlling the water-to-material ratio to be 30, simultaneously adding a certain amount of dispersing agent (the mixed solution of butter and kaolin, the dosage is 0.4 percent of the water amount), heating with the assistance of steam, controlling the pressure in the reaction kettle in a supercritical carbon dioxide input mode, and obtaining milky anti-aging foaming polypropylene (marked as A1) in a rapid decompression mode after the temperature and the pressure are stable (the temperature is 145 ℃ and the pressure is 2.2 MPa);
s7: and (3) pre-pressing the milky anti-aging foamed polypropylene, and performing steam molding (the pre-pressing pressure is 3.0MPa, the time is 12 hours, and the molding pressure is 2.4 bar) to obtain the required milky anti-aging foamed polypropylene molded part.
Example 2
S1: placing purchased titanium dioxide powder (with the particle size of 0.3 μm) into a muffle furnace at 1000 ℃, calcining for 6 hours in nitrogen atmosphere, removing impurities in the powder, completely converting the crystal state of titanium dioxide in the powder into rutile type, and placing into a mortar for grinding and drying to obtain purified titanium dioxide;
s2: heating and melting the EBS to 145 ℃ to liquefy the EBS, uniformly spraying the purified titanium white powder prepared in the step 1 by a spraying device, simultaneously keeping 145 ℃ for the titanium white powder purified in the process, continuously vibrating by a vibrating device, cooling after the EBS is uniformly wrapped on the surface of the titanium white powder, and obtaining activated titanium white powder after the surface is coated with the EBS to be solidified; wherein the EBS melt is 4% of the mass of the titanium dioxide;
s3: according to parts by weight, mixing and fully stirring 20 parts of activated titanium dioxide, 79 parts of polypropylene and 1 part of white oil, and then extruding and granulating by a double screw to obtain titanium dioxide master batch; wherein the twin-screw processing temperature is 160 ℃; the granulating size is 2mm, and the weight is 12mg;
s4: according to parts by weight, fully stirring 85 parts of polypropylene, 10 parts of nucleating agent zinc borate and 5 parts of lubricant ethylene bis stearamide, and then extruding and granulating by a double screw to obtain nucleating agent master batch; wherein the processing temperature of the twin-screw is controlled to 160 ℃, the granulating size is 2mm, and the weight is 12mg;
S5: according to the weight portions, extruding and granulating 90 portions of polypropylene, 5 portions of nucleating agent master batch and 5 portions of titanium pigment master batch by a double screw, and drying to obtain the special foaming polypropylene material; the extrusion granulation process is a single-layer extrusion process;
s6: adding a special material of foaming polypropylene into a reaction kettle, controlling the water-to-material ratio to be 30, simultaneously adding a certain amount of dispersing agent (the mixed solution of butter and kaolin, the dosage is 0.4 percent of the water amount), heating with the assistance of steam, controlling the pressure in the reaction kettle in a supercritical carbon dioxide input mode, and obtaining milky anti-aging foaming polypropylene (marked as A2) in a rapid decompression mode after the temperature and the pressure are stable (the temperature is 145.5 ℃ and the pressure is 2.0 MPa);
s7: and (3) pre-pressing the milky anti-aging foamed polypropylene, and performing steam molding (the pre-pressing pressure is 3.0MPa, the time is 12 hours, and the molding pressure is 2.4 bar) to obtain the required milky anti-aging foamed polypropylene molded part.
Example 3
S1: placing purchased titanium dioxide powder (with the particle size of 0.3 μm) into a muffle furnace at 1000 ℃, calcining for 6 hours in nitrogen atmosphere, removing impurities in the powder, completely converting the crystal state of titanium dioxide in the powder into rutile type, and placing into a mortar for grinding and drying to obtain purified titanium dioxide;
S2: heating and melting the EBS to 145 ℃ to liquefy the EBS, uniformly spraying the purified titanium white powder prepared in the step 1 by a spraying device, simultaneously keeping 145 ℃ for the titanium white powder purified in the process, continuously vibrating by a vibrating device, cooling after the EBS is uniformly wrapped on the surface of the titanium white powder, and obtaining activated titanium white powder after the surface is coated with the EBS to be solidified; wherein the EBS melt is 4% of the mass of the titanium dioxide;
s3: according to parts by weight, mixing and fully stirring 20 parts of activated titanium dioxide, 79 parts of polypropylene and 1 part of white oil, and then extruding and granulating by a double screw to obtain titanium dioxide master batch; wherein the twin-screw processing temperature is 160 ℃; the granulating size is 2mm, and the weight is 12mg;
s4: according to parts by weight, fully stirring 85 parts of polypropylene, 10 parts of nucleating agent zinc borate and 5 parts of lubricant ethylene bis stearamide, and then extruding and granulating by a double screw to obtain nucleating agent master batch; wherein the processing temperature of the twin-screw is controlled to 160 ℃, the granulating size is 2mm, and the weight is 12mg;
s5: according to the weight portions, extruding and granulating 85 portions of polypropylene, 5 portions of nucleating agent master batch and 10 portions of titanium pigment master batch by a double screw, and drying to obtain the special foaming polypropylene material; the extrusion granulation process is a single-layer extrusion process;
S6: adding a special material of foaming polypropylene into a reaction kettle, controlling the water-to-material ratio to be 30, simultaneously adding a certain amount of dispersing agent (the mixed solution of butter and kaolin, the dosage is 0.4 percent of the water amount), heating with the assistance of steam, controlling the pressure in the reaction kettle in a supercritical carbon dioxide input mode, and obtaining milky anti-aging foaming polypropylene (marked as A3) in a rapid decompression mode after the temperature and the pressure are stable (the temperature is 145.8 ℃ and the pressure is 1.9 MPa);
s7: and (3) pre-pressing the milky anti-aging foamed polypropylene, and performing steam molding (the pre-pressing pressure is 3.0MPa, the time is 12 hours, and the molding pressure is 2.4 bar) to obtain the required milky anti-aging foamed polypropylene molded part.
Example 4
S1: placing purchased titanium dioxide powder (with the particle size of 0.3 μm) into a muffle furnace at 1000 ℃, calcining for 6 hours in nitrogen atmosphere, removing impurities in the powder, completely converting the crystal state of titanium dioxide in the powder into rutile type, and placing into a mortar for grinding and drying to obtain purified titanium dioxide;
s2: heating and melting the EBS to 145 ℃ to liquefy the EBS, uniformly spraying the purified titanium white powder prepared in the step 1 by a spraying device, simultaneously keeping 145 ℃ for the titanium white powder purified in the process, continuously vibrating by a vibrating device, cooling after the EBS is uniformly wrapped on the surface of the titanium white powder, and obtaining activated titanium white powder after the surface is coated with the EBS to be solidified; wherein the EBS melt is 4% of the mass of the titanium dioxide;
S3: according to parts by weight, mixing and fully stirring 20 parts of activated titanium dioxide, 79 parts of polypropylene and 1 part of white oil, and then extruding and granulating by a double screw to obtain titanium dioxide master batch; wherein the twin-screw processing temperature is 160 ℃; the granulating size is 2mm, and the weight is 12mg;
s4: according to parts by weight, fully stirring 85 parts of polypropylene, 10 parts of nucleating agent zinc borate and 5 parts of lubricant ethylene bis stearamide, and then extruding and granulating by a double screw to obtain nucleating agent master batch; wherein the processing temperature of the twin-screw is controlled to 160 ℃, the granulating size is 2mm, and the weight is 12mg;
s5: according to the weight portions, extruding and granulating 99.7 portions of polypropylene, 0.3 portion of nucleating agent master batch and 3 portions of titanium pigment master batch by a double screw, and drying to obtain the special foaming polypropylene material; the extrusion granulation process is a double-layer co-extrusion process;
s6: adding a special material of foaming polypropylene into a reaction kettle, controlling the water-to-material ratio to be 30, simultaneously adding a certain amount of dispersing agent (the mixed solution of butter and kaolin, the dosage is 0.4 percent of the water amount), heating with the assistance of steam, controlling the pressure in the reaction kettle in a supercritical carbon dioxide input mode, and obtaining milky anti-aging foaming polypropylene (marked as B1) in a rapid decompression mode after the temperature and the pressure are stable (the temperature is 143.5 ℃ and the pressure is 2.8 MPa);
S7: and (3) pre-pressing the milky anti-aging foamed polypropylene, and performing steam molding (the pre-pressing pressure is 3.0MPa, the time is 12 hours, and the molding pressure is 2.0 bar) to obtain the required milky anti-aging foamed polypropylene molded part.
Example 5
S1: placing purchased titanium dioxide powder (with the particle size of 0.3 μm) into a muffle furnace at 1000 ℃, calcining for 6 hours in nitrogen atmosphere, removing impurities in the powder, completely converting the crystal state of titanium dioxide in the powder into rutile type, and placing into a mortar for grinding and drying to obtain purified titanium dioxide;
s2: heating and melting the EBS to 145 ℃ to liquefy the EBS, uniformly spraying the purified titanium white powder prepared in the step 1 by a spraying device, simultaneously keeping 145 ℃ for the titanium white powder purified in the process, continuously vibrating by a vibrating device, cooling after the EBS is uniformly wrapped on the surface of the titanium white powder, and obtaining activated titanium white powder after the surface is coated with the EBS to be solidified; wherein the EBS melt is 4% of the mass of the titanium dioxide;
s3: according to parts by weight, mixing and fully stirring 20 parts of activated titanium dioxide, 79 parts of polypropylene and 1 part of white oil, and then extruding and granulating by a double screw to obtain titanium dioxide master batch; wherein the twin-screw processing temperature is 160 ℃; the granulating size is 2mm, and the weight is 12mg;
S4: according to parts by weight, fully stirring 85 parts of polypropylene, 10 parts of nucleating agent zinc borate and 5 parts of lubricant ethylene bis stearamide, and then extruding and granulating by a double screw to obtain nucleating agent master batch; wherein the processing temperature of the twin-screw is controlled to 160 ℃, the granulating size is 2mm, and the weight is 12mg;
s5: according to the weight portions, extruding and granulating 99.5 portions of polypropylene, 0.5 portion of nucleating agent master batch and 5 portions of titanium pigment master batch by a double screw, and drying to obtain the special foaming polypropylene material; the extrusion granulation process is a double-layer co-extrusion process;
s6: adding a special material of foaming polypropylene into a reaction kettle, controlling the water-to-material ratio to be 30, simultaneously adding a certain amount of dispersing agent (the mixed solution of butter and kaolin, the dosage is 0.4 percent of the water amount), heating with the assistance of steam, controlling the pressure in the reaction kettle in a supercritical carbon dioxide input mode, and obtaining milky anti-aging foaming polypropylene (marked as B2) in a rapid decompression mode after the temperature and the pressure are stable (the temperature is 143.8 ℃ and the pressure is 2.5 MPa);
s7: and (3) pre-pressing the milky anti-aging foamed polypropylene, and performing steam molding (the pre-pressing pressure is 3.0MPa, the time is 12 hours, and the molding pressure is 2.0 bar) to obtain the required milky anti-aging foamed polypropylene molded part.
Comparative example 1
S1: placing purchased titanium dioxide powder (with the particle size of 0.3 μm) into a muffle furnace at 1000 ℃, calcining for 6 hours in nitrogen atmosphere, removing impurities in the powder, completely converting the crystal state of titanium dioxide in the powder into rutile type, and placing into a mortar for grinding and drying to obtain purified titanium dioxide;
s2: heating and melting the EBS to 145 ℃ to liquefy the EBS, uniformly spraying the purified titanium white powder prepared in the step 1 by a spraying device, simultaneously keeping 145 ℃ for the titanium white powder purified in the process, continuously vibrating by a vibrating device, cooling after the EBS is uniformly wrapped on the surface of the titanium white powder, and obtaining activated titanium white powder after the surface is coated with the EBS to be solidified; wherein the EBS melt is 4% of the mass of the titanium dioxide;
s3: according to parts by weight, mixing and fully stirring 20 parts of activated titanium dioxide, 79 parts of polypropylene and 1 part of white oil, and then extruding and granulating by a double screw to obtain titanium dioxide master batch; wherein the twin-screw processing temperature is 160 ℃; the granulating size is 2mm, and the weight is 12mg;
s4: according to parts by weight, fully stirring 85 parts of polypropylene, 10 parts of nucleating agent zinc borate and 5 parts of lubricant ethylene bis stearamide, and then extruding and granulating by a double screw to obtain nucleating agent master batch; wherein the processing temperature of the twin-screw is controlled to 160 ℃, the granulating size is 2mm, and the weight is 12mg;
S5: according to the weight portions, extruding and granulating 80 portions of polypropylene, 5 portions of nucleating agent master batch and 15 titanium white master batch by double screws, and drying to obtain the special foaming polypropylene material; the extrusion granulation process is a single-layer extrusion process;
s6: adding a special material of foaming polypropylene into a reaction kettle, controlling the water-to-material ratio to be 30, simultaneously adding a certain amount of dispersing agent (the mixed solution of butter and kaolin, the dosage is 0.4 percent of the water amount), heating with the assistance of steam, controlling the pressure in the reaction kettle in a supercritical carbon dioxide input mode, and obtaining milky anti-aging foaming polypropylene (marked as A4) in a rapid decompression mode after the temperature and the pressure are stable (the temperature is 146.2 ℃ and the pressure is 1.7 MPa);
s7: the milky anti-aging foamed polypropylene is pre-pressed and then formed by steam molding (pre-pressing pressure: 3.0MPa, time: 12 hours, molding pressure: 2.8 bar), and the required milky anti-aging foamed polypropylene molded part is obtained.
Comparative example 2
S1: placing purchased titanium dioxide powder (with the particle size of 0.3 μm) into a muffle furnace at 1000 ℃, calcining for 6 hours in nitrogen atmosphere, removing impurities in the powder, completely converting the crystal state of titanium dioxide in the powder into rutile type, and placing into a mortar for grinding and drying to obtain purified titanium dioxide;
S2: heating and melting the EBS to 145 ℃ to liquefy the EBS, uniformly spraying the purified titanium white powder prepared in the step 1 by a spraying device, simultaneously keeping 145 ℃ for the titanium white powder purified in the process, continuously vibrating by a vibrating device, cooling after the EBS is uniformly wrapped on the surface of the titanium white powder, and obtaining activated titanium white powder after the surface is coated with the EBS to be solidified; wherein the EBS melt is 4% of the mass of the titanium dioxide;
s3: according to parts by weight, mixing and fully stirring 20 parts of activated titanium dioxide, 79 parts of polypropylene and 1 part of white oil, and then extruding and granulating by a double screw to obtain titanium dioxide master batch; wherein the twin-screw processing temperature is 160 ℃; the granulating size is 2mm, and the weight is 12mg;
s4: according to parts by weight, fully stirring 85 parts of polypropylene, 10 parts of nucleating agent zinc borate and 5 parts of lubricant ethylene bis stearamide, and then extruding and granulating by a double screw to obtain nucleating agent master batch; wherein the processing temperature of the twin-screw is controlled to 160 ℃, the granulating size is 2mm, and the weight is 12mg;
s5: according to the weight portions, extruding and granulating 99.5 portions of polypropylene, 0.5 portion of nucleating agent master batch and 1 portion of titanium pigment master batch by a double screw, and drying to obtain the special foaming polypropylene material; the extrusion granulation process is a double-layer co-extrusion process;
S6: adding a special material of foaming polypropylene into a reaction kettle, controlling the water-to-material ratio to be 30, simultaneously adding a certain amount of dispersing agent (the mixed solution of butter and kaolin, the dosage is 0.4 percent of the water amount), heating with the assistance of steam, controlling the pressure in the reaction kettle in a supercritical carbon dioxide input mode, and obtaining milky anti-aging foaming polypropylene (marked as B3) in a rapid decompression mode after the temperature and the pressure are stable (the temperature is 143.8 ℃ and the pressure is 2.5 MPa);
s7: and (3) pre-pressing the milky anti-aging foamed polypropylene, and performing steam molding (the pre-pressing pressure is 3.0MPa, the time is 12 hours, and the molding pressure is 2.0 bar) to obtain the required milky anti-aging foamed polypropylene molded part.
Comparative example 3
S1: according to parts by weight, fully stirring 85 parts of polypropylene, 10 parts of nucleating agent zinc borate and 5 parts of lubricant ethylene bis stearamide, and then extruding and granulating by a double screw to obtain nucleating agent master batch; wherein the processing temperature of the twin-screw is controlled to 160 ℃, the granulating size is 2mm, and the weight is 12mg;
s2: according to the parts by weight, extruding and granulating 95 parts of polypropylene and 5 parts of nucleating agent master batches through double screws, and drying to obtain the special foaming polypropylene material; the extrusion granulation process is a single-layer extrusion process;
S3: adding a special material of foaming polypropylene into a reaction kettle, controlling the water-to-material ratio to be 30, simultaneously adding a certain amount of dispersing agent (the mixed solution of butter and kaolin, the dosage is 0.4 percent of the water amount), heating with the assistance of steam, controlling the pressure in the reaction kettle in a supercritical carbon dioxide input mode, and obtaining milky anti-aging foaming polypropylene (marked as A0) in a rapid decompression mode after the temperature and the pressure are stable (the temperature is 145.2 ℃ and the pressure is 2.1 MPa);
s4: and (3) pre-pressing the milky anti-aging foamed polypropylene, and performing steam molding (the pre-pressing pressure is 3.0MPa, the time is 12 hours, and the molding pressure is 2.4 bar) to obtain the required milky anti-aging foamed polypropylene molded part.
Comparative example 4
S1: placing purchased titanium dioxide powder (with the particle size of 0.3 μm) into a muffle furnace at 1000 ℃, calcining for 6 hours in nitrogen atmosphere, removing impurities in the powder, completely converting the crystal state of titanium dioxide in the powder into rutile type, and placing into a mortar for grinding and drying to obtain purified titanium dioxide;
s2: according to parts by weight, mixing and fully stirring 20 parts of purified titanium dioxide, 79 parts of polypropylene and 1 part of white oil, and then extruding and granulating by a double screw to obtain titanium dioxide master batch; wherein the twin-screw processing temperature is 160 ℃; the granulating size is 2mm, and the weight is 12mg;
S3: according to parts by weight, fully stirring 85 parts of polypropylene, 10 parts of nucleating agent zinc borate and 5 parts of lubricant ethylene bis stearamide, and then extruding and granulating by a double screw to obtain nucleating agent master batch; wherein the processing temperature of the twin-screw is controlled to 160 ℃, the granulating size is 2mm, and the weight is 12mg;
s4: according to the weight portions, the special foaming polypropylene material is obtained by extruding and granulating 87 portions of polypropylene, 3 portions of nucleating agent master batch and 10 portions of titanium pigment master batch through double screws and drying; the extrusion granulation process is a single-layer extrusion process;
s5: adding a special material of foaming polypropylene into a reaction kettle, controlling the water-to-material ratio to be 30, simultaneously adding a certain amount of dispersing agent (the mixed solution of butter and kaolin, the dosage is 0.4 percent of the water amount), heating with the assistance of steam, controlling the pressure in the reaction kettle in a supercritical carbon dioxide input mode, and obtaining milky anti-aging foaming polypropylene (marked as A5) in a rapid decompression mode after the temperature and the pressure are stable (the temperature is 145 ℃ and the pressure is 2.2 MPa);
s6: and (3) pre-pressing the milky anti-aging foamed polypropylene, and performing steam molding (the pre-pressing pressure is 3.0MPa, the time is 12 hours, and the molding pressure is 2.4 bar) to obtain the required milky anti-aging foamed polypropylene molded part.
Comparative example 5
S1: placing purchased titanium dioxide powder (with the particle size of 0.3 μm) into a muffle furnace at 1000 ℃, calcining for 6 hours in nitrogen atmosphere, removing impurities in the powder, completely converting the crystal state of titanium dioxide in the powder into rutile type, and placing into a mortar for grinding and drying to obtain purified titanium dioxide;
s2: according to parts by weight, mixing and fully stirring 20 parts of purified titanium dioxide, 79 parts of polypropylene and 1 part of white oil, and then extruding and granulating by a double screw to obtain titanium dioxide master batch; wherein the twin-screw processing temperature is 160 ℃; the granulating size is 2mm, and the weight is 12mg;
s3: according to parts by weight, fully stirring 85 parts of polypropylene, 10 parts of nucleating agent zinc borate and 5 parts of lubricant ethylene bis stearamide, and then extruding and granulating by a double screw to obtain nucleating agent master batch; wherein the processing temperature of the twin-screw is controlled to 160 ℃, the granulating size is 2mm, and the weight is 12mg;
s4: according to the weight portions, extruding and granulating 99.7 portions of polypropylene, 0.3 portion of nucleating agent master batch and 3 portions of titanium pigment master batch by a double screw, and drying to obtain the special foaming polypropylene material; the extrusion granulation process is a double-layer co-extrusion process;
s5: adding a special material of foaming polypropylene into a reaction kettle, controlling the water-to-material ratio to be 30, simultaneously adding a certain amount of dispersing agent (the mixed solution of butter and kaolin, the dosage is 0.4 percent of the water amount), heating with the assistance of steam, controlling the pressure in the reaction kettle in a supercritical carbon dioxide input mode, and obtaining milky anti-aging foaming polypropylene (marked as B4) in a rapid decompression mode after the temperature and the pressure are stable (the temperature is 143.5 ℃ and the pressure is 2.8 MPa);
S6: and (3) pre-pressing the milky anti-aging foamed polypropylene, and performing steam molding (the pre-pressing pressure is 3.0MPa, the time is 12 hours, and the molding pressure is 2.0 bar) to obtain the required milky anti-aging foamed polypropylene molded part.
Comparative example 6
S1: placing purchased titanium dioxide powder (with the particle size of 0.3 μm) into a muffle furnace at 1000 ℃, calcining for 6 hours in nitrogen atmosphere, removing impurities in the powder, completely converting the crystal state of titanium dioxide in the powder into rutile type, and placing into a mortar for grinding and drying to obtain purified titanium dioxide;
s2: according to the weight portions, 87 portions of polypropylene, 3 portions of nucleating agent zinc borate and 10 portions of purified titanium pigment are extruded by double screws to granulate and dried to obtain the special material for the foaming polypropylene; the extrusion granulation process is a single-layer extrusion process;
s3: adding a special material of foaming polypropylene into a reaction kettle, controlling the water-to-material ratio to be 30, simultaneously adding a certain amount of dispersing agent (the mixed solution of butter and kaolin, the dosage is 0.4 percent of the water amount), heating with the assistance of steam, controlling the pressure in the reaction kettle in a supercritical carbon dioxide input mode, and obtaining milky anti-aging foaming polypropylene (marked as A6) in a rapid decompression mode after the temperature and the pressure are stable (the temperature is 145 ℃ and the pressure is 2.2 MPa);
S4: and (3) pre-pressing the milky anti-aging foamed polypropylene, and performing steam molding (the pre-pressing pressure is 3.0MPa, the time is 12 hours, and the molding pressure is 2.4 bar) to obtain the required milky anti-aging foamed polypropylene molded part.
The formulation of the special materials for the expanded polypropylene in each of the above examples and comparative examples is shown in Table 1.
TABLE 1
The foaming conditions of the foamed polypropylene special material in each of the above examples and comparative examples are shown in Table 2.
TABLE 2
| Sample | Foaming temperature (DEG C) | Back pressure MPa | Foam Density g/L | DSC | Cell size μm |
| Example 1 (A1) | 145 | 2.2 | 45-55 | 14-17 | 45-55 |
| Example 2 (A2) | 145.5 | 2.0 | 45-55 | 14-17 | 40-50 |
| Example 3 (A3) | 145.8 | 1.9 | 45-55 | 14-17 | 35-45 |
| Example 4 (B1) | 143.5 | 2.8 | 45-55 | 14-17 | 200-250 |
| Example 5 (B2) | 143.8 | 2.5 | 45-55 | 14-17 | 180-220 |
| Comparative example 1 (A4) | 146.2 | 1.7 | 45-55 | 14-17 | 30-40 |
| Comparative example 2 (B3) | 143.8 | 2.5 | 45-55 | 14-17 | 180-230 |
| Comparative example 3 (A0) | 145.2 | 2.1 | 45-55 | 14-17 | 50-65 |
| Comparative example 4 (A5) | 145 | 2.2 | 45-55 | 14-17 | 30-100 |
| Comparative example 5 (B4) | 143.5 | 2.8 | 45-55 | 14-17 | 50-250 |
| Comparative example 6 (A6) | 145 | 2.2 | 45-55 | 14-17 | 50-250 |
The molding conditions of the foamed polypropylene special materials in the above examples and comparative examples are shown in Table 3.
TABLE 3 Table 3
| Sample | Molding pressure bar | Drying time H | Shrinkage percentage% | Product appearance | LAB value (L) |
| Example 1 (A1) | 2.4 | 6H | 1.7-1.9 | ★★★☆☆ | 94.1 |
| Example 2 (A2) | 2.4 | 6H | 1.7-1.9 | ★★★★☆ | 95.3 |
| Example 3 (A3) | 2.4 | 6H | 1.7-1.9 | ★★★☆☆ | 95.7 |
| Example 4 (B1) | 2.0 | 12H | 1.7-2.1 | ★★★★★ | 98.3 |
| Example 5 (B2) | 2.0 | 12H | 1.7-2.1 | ★★★★★ | 98.5 |
| Comparative example 1 (A4) | 2.8 | 6H | 1.8-2.3 | ★★☆☆☆ | 95.4 |
| Comparative example 2 (B3) | 2.0 | 12H | 1.7-2.1 | ★★★★★ | 78.2 |
| Comparative example 3 (A0) | 2.4 | 12H | 1.8-2.2 | ★★★☆☆ | 72.5 |
| Comparative example 4 (A5) | 2.4 | 8H | 1.8-2.2 | ★★☆☆☆ | 86.2 |
| Comparative example 5 (B4) | 2.0 | 12H | 1.8-2.1 | ★★★☆☆ | 90.5 |
| Comparative example 6 (A6) | 2.4 | 6H | 1.8-2.2 | ★☆☆☆☆ | 90.1 |
Wherein, the ∈4 represents that the product has the highest appearance flatness and the best appearance quality; four times? the appearance quality of the product is the worst.
The properties of the molded articles in the above examples and comparative examples are shown in Table 4.
TABLE 4 Table 4
| Sample | 10% compression strength MPa | Simulating photo aging time/year (chalking has occurred to criticalPoint (C) |
| Example 1 (A1) | 255 | 3↑ |
| Example 2 (A2) | 242 | 3↑ |
| Example 3 (A3) | 235 | 3↑ |
| Example 4 (B1) | 220 | 5↑ |
| Example 5 (B2) | 235 | 6↑ |
| Comparative example 1 (A4) | 200 | 3↑ |
| Comparative example 2 (B3) | 238 | 1↓ |
| Comparative example 3 (A0) | 210 | 1↓ |
| Comparative example 4 (A5) | 230 | 2↑ |
| Comparative example 5 (B4) | 200 | 2↑ |
| Comparative example 6 (A6) | 220 | 1↑ |
Wherein 3 ∈ represents 3 years or more and 5 years or less; 1 ∈ represents less than 1 year, and so on; 10% compressive stress was according to GB/T8813-2008; the simulated photo-aging time is detected by adopting a xenon lamp simulated photo-aging test.
According to the data, the titanium dioxide modified by EBS mixing is introduced in the preparation method of the foamed polypropylene, so that the brightness (L value) of the surface of the product can be effectively improved, and the higher brightness can perform the total reflection function on light, so that the ultraviolet light is shielded, the generation of photoinitiated polypropylene free radicals is reduced, the ageing resistance of the product is improved, and the service life of the product is prolonged; in addition, the titanium dioxide master batch can be directly coated on the particle surface by adopting a double-layer coextrusion process, and the brightness (L value) of the product surface can be greatly improved by using a very small amount of titanium dioxide, so that the irradiation of ultraviolet light is better shielded, and the ageing resistance time of the product is better improved than that of single-layer extrusion; in particular, the coextrusion process can be considered as a preferred scheme for adjusting the addition amount of the core layer nucleating agent, thereby expanding the cell size of a product system, improving the expansibility of the product, reducing the molding pressure and improving the apparent quality of a product part; however, the ratio of the coating must be strictly limited, otherwise, the molding pressure of the product is significantly affected by side effects on the molding of the product.
Comparing the test data of examples 1-3 with those of examples 4-5, it can be seen that better product quality can be obtained by using less titanium dioxide with the double-layer coextrusion process than with the single-layer extrusion process.
The comparative example 1 was compared with example 3, the addition amount of the titanium pigment master batch was increased, resulting in deterioration of the product appearance, and at the same time, the product cost was increased.
Compared with the comparative example 2 and the example 5, the addition amount of the titanium dioxide master batch is reduced, and the L value is obviously reduced and the ageing resistance is poor although the appearance of the product is better.
Compared with the comparative example 3, the product has poor appearance quality, obviously reduced L value and poor ageing resistance without adding titanium dioxide master batch.
Comparative example 4 compared with example 1, titanium white powder was not activated, the cell size distribution of the product was remarkably widened, the appearance quality of the product was poor, and the L value was remarkably lowered, and the aging resistance was deteriorated.
Comparative example 5 compared with example 4, the titanium white powder was not activated, the cell size distribution of the product was remarkably widened, the appearance quality was poor, and the L value was remarkably lowered, and the aging resistance was deteriorated.
The difference between comparative example 6 and example 1 is that the nucleating agent master batch and the titanium white master batch are not prepared separately, the polypropylene, the nucleating agent and the titanium white are directly mixed and foamed, the cell size distribution of the product is obviously widened, the surface of the product is uneven, and the ageing resistance is still poor although the L value is higher.
With the above-described preferred embodiments according to the present invention as an illustration, the above-described descriptions can be used by persons skilled in the relevant art to make various changes and modifications without departing from the scope of the technical idea of the present invention. The technical scope of the present invention is not limited to the description, but must be determined according to the scope of claims.
Claims (9)
1. The preparation method of the foaming polypropylene is characterized by comprising the following steps:
s1: purifying titanium dioxide, converting the crystal state of titanium dioxide in the titanium dioxide into rutile type, and grinding to obtain purified titanium dioxide;
s2: spraying melted ethylene bis stearamide on the surface of the purified titanium dioxide, and stirring to obtain activated titanium dioxide;
s3: mixing the activated titanium dioxide, polypropylene and white oil, and then extruding and granulating by a double screw to obtain titanium dioxide master batch;
s4: mixing polypropylene, a nucleating agent and a lubricant, and then extruding and granulating through double screws to obtain a nucleating agent master batch;
s5: extruding and granulating polypropylene, the nucleating agent master batch and the titanium pigment master batch through double screws, and drying to obtain a special foaming polypropylene material;
S6: foaming the special material for foaming polypropylene to obtain foaming polypropylene;
the step S2 comprises the following steps: heating ethylene bis-stearamide to 140-150 ℃ to obtain the melted ethylene bis-stearamide; spraying the melted ethylene bis stearamide on the surface of the purified titanium dioxide at the temperature of 140-150 ℃ through a spraying device, and sequentially vibrating and cooling to obtain the activated titanium dioxide.
2. The method for preparing expanded polypropylene according to claim 1, wherein the titanium pigment has a particle size ranging from 0.2 to 0.4 μm.
3. The method for preparing expanded polypropylene according to claim 1, wherein the amount of ethylene bis stearamide after melting is 3 to 5% by mass of the purified titanium pigment.
4. The method for preparing the foamed polypropylene according to claim 1, wherein the mass ratio of the activated titanium pigment, the polypropylene and the white oil in the step S3 is (15-25): (70-90): (0.5-2).
5. The method for producing a foamed polypropylene according to claim 1, wherein the mass ratio of said polypropylene, said nucleating agent, said lubricant in step S4 is (80-90): (5-15): (1-10).
6. The method for producing a foamed polypropylene according to claim 5, wherein said nucleating agent is at least one selected from the group consisting of zinc borate, silica and talc, and wherein the particle size of said nucleating agent is in the range of 0.8 to 5 μm; the lubricant is at least one selected from ethylene bis stearamide, erucamide and stearic acid.
7. The method for preparing the foamed polypropylene according to claim 1, wherein in the step S5, the mass ratio of the polypropylene, the nucleating agent masterbatch and the titanium pigment masterbatch is (85-99.7): (0.3-5): (3-10).
8. Foamed polypropylene, characterized in that it is produced by a process for producing a foamed polypropylene according to any one of claims 1 to 7.
9. A molded article of expanded polypropylene prepared from the expanded polypropylene of claim 8 by steam molding.
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