CN115322479A - Low-after-shrinkage polypropylene material and preparation method thereof - Google Patents
Low-after-shrinkage polypropylene material and preparation method thereof Download PDFInfo
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- CN115322479A CN115322479A CN202210961287.9A CN202210961287A CN115322479A CN 115322479 A CN115322479 A CN 115322479A CN 202210961287 A CN202210961287 A CN 202210961287A CN 115322479 A CN115322479 A CN 115322479A
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 119
- -1 polypropylene Polymers 0.000 title claims abstract description 112
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 112
- 239000000463 material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000004952 Polyamide Substances 0.000 claims abstract description 37
- 229920002647 polyamide Polymers 0.000 claims abstract description 37
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 12
- 239000003999 initiator Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 239000000155 melt Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 238000001125 extrusion Methods 0.000 claims description 13
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 11
- 239000003963 antioxidant agent Substances 0.000 claims description 11
- 229920005604 random copolymer Polymers 0.000 claims description 11
- 125000003368 amide group Chemical group 0.000 claims description 10
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 10
- 230000003078 antioxidant effect Effects 0.000 claims description 9
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 6
- 229920005653 propylene-ethylene copolymer Polymers 0.000 claims description 6
- 239000000314 lubricant Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000012934 organic peroxide initiator Substances 0.000 claims description 4
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 12
- 239000002131 composite material Substances 0.000 abstract description 11
- 238000010438 heat treatment Methods 0.000 abstract description 7
- 239000000835 fiber Substances 0.000 abstract description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 5
- 239000011707 mineral Substances 0.000 abstract description 5
- 239000000945 filler Substances 0.000 abstract description 4
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 65
- 230000000052 comparative effect Effects 0.000 description 19
- 238000012360 testing method Methods 0.000 description 10
- 239000011159 matrix material Substances 0.000 description 9
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 229920005630 polypropylene random copolymer Polymers 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 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 3
- 230000033001 locomotion Effects 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 description 2
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000012661 block copolymerization Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical group CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
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- 230000008018 melting Effects 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 2
- 241000218691 Cupressaceae Species 0.000 description 1
- 241000985630 Lota lota Species 0.000 description 1
- 229920003188 Nylon 3 Polymers 0.000 description 1
- 229920001007 Nylon 4 Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 210000001320 hippocampus Anatomy 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K5/00—Casings, cabinets or drawers for electric apparatus
- H05K5/02—Details
- H05K5/0217—Mechanical details of casings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a low post-shrinkage polypropylene material and a preparation method thereof, belonging to the field of high polymer materials. The low post-shrinkage polypropylene material of the invention introduces a specific low-shrinkage regulator into polypropylene, and the contained random copolymerization polypropylene and polyamide can be entangled with a composite molecular chain among polypropylene, thereby effectively inhibiting the post-shrinkage effect of the product after the size is stable and even after the heat treatment, and having strong size stability and durability; the appearance performance of the product can be ensured because no filler such as mineral or fiber is added into the components to maintain the stable size of the product. The invention also discloses a preparation method of the low after-shrinkage polypropylene material and application of the low after-shrinkage polypropylene material in preparation of household appliance parts.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a low-after-shrinkage polypropylene material and a preparation method thereof.
Background
The polypropylene material is the most widely used general plastic at present, and in recent years, along with the increasing popularization rate of domestic modified polypropylene materials, the engineering proportion of the polypropylene material is higher and higher. However, polypropylene has obvious disadvantages in some properties, such as large shrinkage, unstable size and the like, in the industry, in order to reduce the shrinkage of polypropylene and improve the dimensional stability, fillers such as mineral powder and fibers are usually added, but the addition of mineral powder fiber fillers usually affects the surface properties of products, for example, polypropylene composite materials prepared by the most common talcum powder generally have poor surface gloss, and polypropylene materials prepared by glass fiber composite often have serious surface fiber floating. In addition, these conventional shrinkage control components actually only reduce the original shrinkage of the material, but after the material is dimensionally stable, there is some post-shrinkage, which is actually the result of the crystallization of the polymer molecular chain under slow motion, and if the product needs to undergo a heating process during use, the shrinkage is greater.
CN111087689A discloses a polypropylene composite material for a household appliance shell and a preparation method thereof, wherein the polypropylene composite material obtained by adding components such as whiskers, talcum powder and nucleating agent has the characteristics of high gloss, scratch resistance and low after shrinkage, but as mentioned above, the material has a large after shrinkage rate after high-temperature annealing; CN111484671A discloses a low after-shrinkage automotive polypropylene composite material and a preparation method thereof, the invention achieves the effect of low after-shrinkage by compounding components such as ultra-high molecular weight polyethylene, talcum powder, nano glass body and the like, but the ultra-high molecular weight polyethylene used in the product has poor processability and low surface gloss, and is not suitable for some appearance type plastic part products.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a low post-shrinkage polypropylene material, wherein a filling shrinkage rate adjusting component which is common in the prior art is not introduced into the product component, but specific random polypropylene and long carbon chain polyamide are introduced into a polypropylene resin matrix, and the post-shrinkage effect of the product which is generated due to slow movement of a molecular chain after the product is stable in size is further inhibited through the entanglement effect of the random polypropylene and the long carbon chain polyamide with the composite molecular chain of the polypropylene resin matrix, and meanwhile, the surface glossiness and cleanliness of the product can be maintained in a better range, and the application range is wide.
In order to achieve the purpose, the invention adopts the technical scheme that:
a low after-shrinkage polypropylene material comprises the following components in parts by weight:
70-90 parts of polypropylene, 15-25 parts of low shrinkage regulator, 0.5-1.5 parts of compatilizer, 0.03-0.05 part of initiator and 0.2-0.6 part of processing aid;
the low-shrinkage regulator comprises random copolymerization polypropylene and polyamide, wherein the molar ratio of methylene to amido in the molecular chain of the polyamide is 10-12.
The molar ratio of methylene groups to amide groups on the molecular chain of the polyamide can be directly obtained through the structural formula of the repeating unit of the polyamide;
preferably, the structural molecular formula of the polyamide can be obtained by melting, dissolving, separating and purifying the polyamide in the low-after-shrinkage polypropylene material, and then testing by infrared spectroscopy analysis and mass spectrometry.
In the components of the low post-shrinkage polypropylene material, in order to not introduce mineral powder or glass fiber and other components which can cause the decrease of the apparent performance of the product, the random copolymerization polypropylene and the polyamide are matched, the two components can be fully entangled with molecular short chains in a polypropylene resin matrix, and amide groups contained in the two components can form a certain amount of hydrogen bonds in the polypropylene resin matrix, so that the difficulty of mutual movement of the molecular chains in a mixture formed by compounding the components is increased, the two components can realize heterogeneous nucleation under the action of an initiator in the preparation process of the product, the problems of phase separation or incompatibility cannot occur, the post-shrinkage rate after the product is stable in size (particularly after heating and annealing treatment) is effectively reduced, and the surface performance of the product can be ensured.
Further, after the component study of the inventors, it was found that when the amount of the low shrinkage modifier is too low, it is difficult to achieve a good low after shrinkage ratio, but when the amount is too high, compatibility of the product components becomes problematic (even if the amount of the compatibilizer is increased, it is difficult to avoid), and not only the after shrinkage ratio does not achieve an optimum effect, but also the surface gloss of the product may be problematic. On the other hand, the molar ratio of methylene to amide in the molecular chain of the polyamide is a key factor for entanglement with a polypropylene resin matrix, if the ratio is too low, the density of amide groups is reduced, so that hydrogen bonds generated among the amide groups are reduced, which is not beneficial to reduction of after-shrinkage, and if the ratio is too high, the content of amide groups is higher, which also causes compatibility problems.
Preferably, the molar ratio of methylene groups to amide groups in the molecular chain of the polyamide is 10 to 11.
Preferably, the mass ratio of the random copolymerization polypropylene to the polyamide in the low shrinkage regulator is (7-9): (1-2).
The content of polyamide or polypropylene random copolymer in the low shrinkage regulator cannot be too high, because the polypropylene resin matrix and the polyamide in the product components are actually in a mutual entangled state to prevent the arrangement and recombination of molecular chain segments after heating, if the content of polypropylene random copolymer is too high, sufficient hydrogen bonds are difficult to generate in the product, and then the difficulty of reducing the shrinkage rate to an ideal degree is increased, while if the content of polyamide is too high, the dispersity of the polyamide in the product components is obviously reduced, and the surface gloss of the product is possibly reduced. The inventor prefers the two, and the glossiness and the after shrinkage rate of the product are stable when the components are matched according to the proportion, and the glossiness and the after shrinkage rate can be maintained in an ideal range.
Preferably, the random copolymer polypropylene is a random propylene-ethylene copolymer.
More preferably, the random copolymerized polypropylene has a melt mass flow rate of 10-30 g/10min at 230 ℃ and 2.16kg according to GB/T3682.1-2018 test methods for melt Mass Flow Rate (MFR) and melt volume flow rate (MVR) of thermoplastics.
Through experimental screening of the inventor, the random copolymerization polypropylene can be used in the product component of the invention as long as the random copolymerization polypropylene can realize entanglement combination with polyamide. On the basis, if the melt mass flow rate of the random copolymerization polypropylene is 10-30 g/min, the post shrinkage rate of the product can be lower.
Preferably, the polypropylene is at least one of block co-polypropylene and homo-polypropylene.
Preferably, the polypropylene has a melt mass flow rate of 1 to 60g/10min at 230 ℃ under 2.16kg according to GB/T3682.1-2018 test methods for melt Mass Flow Rate (MFR) and melt volume flow rate (MVR) of thermoplastics.
Preferably, the compatibilizer is a maleic anhydride graft.
More preferably, the maleic anhydride graft is at least one of ethylene-propylene copolymer grafted maleic anhydride, ethylene-octene copolymer grafted maleic anhydride, ethylene-butene copolymer grafted maleic anhydride, polypropylene grafted maleic anhydride and polyethylene grafted maleic anhydride.
The maleic anhydride graft has good effects on respective compatibility of the polypropylene and the polyamide (especially the polyamide) in the polypropylene and improvement of the compatibility between the polypropylene and the polyamide through invention experiments, so that two key components in the low-shrinkage regulator are well compatible and uniformly entangled with a polypropylene resin matrix molecular chain.
Preferably, the initiator is at least one of an organic peroxide initiator, an azo initiator and a benzoyl peroxide initiator.
Preferably, the processing aid comprises at least one of an antioxidant and a lubricant.
More preferably, the antioxidant is at least one of hindered phenol antioxidants and phosphite antioxidants.
More preferably, the lubricant is erucamide.
More preferably, the processing aid is a mixture of a hindered phenol antioxidant, a phosphite antioxidant and a lubricant, and the mass ratio of the hindered phenol antioxidant to the phosphite antioxidant to the lubricant is 1.
Another object of the present invention is to provide a preparation method of the low after-shrinkage polypropylene material, comprising the following steps:
and uniformly mixing all the components, then putting the mixture into a double-screw extruder for extrusion, and cooling and granulating the mixture to obtain the low after-shrinkage polypropylene material.
The preparation method of the low after-shrinkage polypropylene material has simple operation steps and can realize industrial mass production.
Preferably, the speed of mixing is 600-1200 rpm, the time is 5-8 min, and the temperature is 40-60 ℃.
Preferably, the temperature of the twin-screw extruder during extrusion is 210 to 230 ℃.
Preferably, the low shrinkage regulator, the compatibilizer and the initiator are added as master batches when the components are mixed.
The inventor finds that when the random copolymerization polypropylene and the polyamide in the low shrinkage regulator are mixed in advance and are prepared into master batch under the action of the compatilizer and the initiator to be introduced into a final product, the random copolymerization polypropylene and the polyamide can select the optimal melting crystallization temperature to realize crystallization in advance and heterogeneous nucleation, and when the master batch is mixed with a polypropylene resin matrix, the generated hydrogen bond action strength is better, the problem of phase separation possibility is further inhibited, the after shrinkage of the product can be further inhibited, and the surface gloss of the product is equivalent to that of a pure polypropylene product.
More preferably, the preparation method of the master batch comprises the following steps:
(1) Uniformly mixing the random copolymerization polypropylene, the compatilizer and the initiator, and then putting the mixture into a double-screw extruder for first-stage extrusion to obtain a first product;
(2) And uniformly mixing the first product and polyamide, then putting the mixture into a double-screw extruder for two-stage extrusion, and granulating to obtain the master batch.
More preferably, the speed of mixing in the step (1) is 600-800 rpm, and the time is 3-5 min; the temperature of the first-stage extrusion is 190-200 ℃.
More preferably, the mixing speed in the step (2) is 400-600 rpm, the mixing time is 1-3 min, and the temperature in the two-stage extrusion is 200-220 ℃.
Another object of the present invention is to provide the use of said low post-shrinkage polypropylene material in the manufacture of household electrical components.
The product of the invention not only has surface properties (glossiness and apparent degree) meeting the high requirements of the appearance of parts in the field of household appliances, but also can ensure lower post-shrinkage rate after long-time use or heat treatment, and is particularly suitable for preparing parts with variable use environments such as household appliance shells and the like but also has higher requirements on dimensional stability.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a low post-shrinkage polypropylene material, which is characterized in that a specific low-shrinkage regulator is introduced into polypropylene, and the contained polypropylene random copolymer and polyamide can be entangled with a composite molecular chain among the polypropylene, so that the post-shrinkage effect of a product after the product is stable in size and even after the product is subjected to heating treatment is effectively inhibited, and the material is stable in size and strong in durability; the appearance performance of the product can be ensured because no filler such as mineral or fiber is added into the components to maintain the stable size of the product. The invention also provides a preparation method of the low after-shrinkage polypropylene material and application of the low after-shrinkage polypropylene material in preparation of household appliance parts.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples. It is intended that the present invention not be limited thereto, but that it be understood in detail. All other embodiments obtained by a person skilled in the art without making any inventive step are within the scope of protection of the present invention. The experimental reagents and instruments involved in the practice of the present invention are, unless otherwise specified, common reagents and instruments.
The preparation method of the polypropylene composite material in the embodiment (except the embodiment 17) and the comparative example comprises the following steps:
mixing the components in a high-speed mixer at the speed of 800rpm and at the temperature of 50 ℃ for 5-8 min until the components are uniform, then putting the components in a double-screw extruder, controlling the temperature to be 190-220 ℃ for extrusion, and cooling and granulating the components to obtain the low post-shrinkage polypropylene material.
The information on the raw materials used in the examples of the present invention and the comparative examples is as follows:
polypropylene 1: homopolymerized polypropylene, producing PPH-T03 products by land-to-sea refining, wherein the melt mass flow rate is 2.0g/10min at 230 ℃ under the load of 2.16 kg;
polypropylene 2: the block copolymerization polypropylene is used for producing PP K8003 products by using a winnowing petrochemical process, and the melt mass flow rate is 2.2g/10min at 230 ℃ under the load of 2.16 kg;
polypropylene 3: homopolymerized polypropylene, producing PP M60T products by land-to-sea refining, wherein the melt mass flow rate is 60.0g/10min at 230 ℃ under the load of 2.16 kg;
polypropylene 4: block copolymerization polypropylene, producing PP M60RHC products by land-to-sea refining, wherein the melt mass flow rate is 59.8g/10min at 230 ℃ under the load of 2.16 kg;
random copolymer polypropylene 1: the random propylene-ethylene copolymer polypropylene PP RP346R, lyondellBasell Industries produces products, and the melt mass flow rate is 24g/10min;
random copolymer polypropylene 2: random propylene-ethylene copolymer polypropylene PP SM198, lotte Chemical Titan (M) Sdn. Bhd. Product with melt mass flow rate of 2.3g/10min;
random copolymer polypropylene 3: the random propylene-ethylene copolymer polypropylene PP K4912 is a product produced by Shanghai seideae, and the melt mass flow rate is 12g/10min;
random copolymer polypropylene 4: the random propylene-ethylene copolymer polypropylene PP R340S and Braskem produce products, and the melt mass flow rate is 45g/10min;
polyamide 1: nylon 1012, the molar ratio of methylene and amide in a molecular chain is 11, and a product is produced by Shandong Chen Ruisen;
polyamide 2: nylon 1010, the molar ratio of methylene and amide in a molecular chain is 10, and a product is produced by Shandongthenruisen;
polyamide 3: nylon 1212, the ratio of methylene and amide of molecular chain is 12, the product produced by Shandongthenruisen;
polyamide 4; PA66 EPR24 with a molecular chain methylene to amido ratio of 6, and producing a product by using Hippocampus;
a compatibilizing agent; polypropylene grafted maleic anhydride, foshan south sea cypress morning AD-105;
organic peroxide initiator: an organic peroxide initiator Enox 101, qiangsheng, china company Limited.
Processing aid: the mixture of the commercially available hindered phenol antioxidant, the commercially available phosphite antioxidant and the commercially available erucamide, wherein the mass ratio of the three is 1;
the raw materials used in the respective examples and comparative examples were the same species as those used in the parallel experiments unless otherwise specified above.
Examples 1 to 16
The components and amounts of the low post-shrinkage polypropylene materials described in the examples are shown in table 1.
Example 17
The difference between example 17 and example 1 is only that the preparation method of the polypropylene composite material in this example is as follows:
mixing the components in a high-speed mixer at the speed of 800rpm at the temperature of 50 ℃ for 5-8 min until the components are uniform, then putting the components in a double-screw extruder, controlling the temperature to be 190-220 ℃ for extrusion, and cooling and dicing the components to obtain the low post-shrinkage polypropylene material; wherein, the low shrinkage regulator, the compatilizer and the initiator are added in a master batch form;
the preparation method of the master batch comprises the following steps:
(1) Mixing the random copolymerization polypropylene, the compatilizer and the initiator at the speed of 700rpm for 4min until the mixture is uniform, and then putting the mixture into a double-screw extruder to perform first-stage extrusion by controlling the temperature to be 190-200 ℃ to obtain a first product;
(2) And (3) mixing the first product and polyamide at the speed of 500rpm for 2min to be uniform, then placing the mixture into a double-screw extruder, controlling the temperature to be 200-220 ℃ for two-stage extrusion, and pelletizing to obtain the master batch.
Comparative examples 1 to 6
The components and the amounts of the polypropylene composite in each proportion are shown in table 2.
TABLE 1
TABLE 2
Effect example 1
In order to investigate the properties of the low post-shrinkage polypropylene material according to the invention, the following tests were carried out on the products obtained in the examples and comparative examples:
(1) And (3) shrinkage testing: according to the method of GB/T15585-1995 standard, after injection molding of products of each example and comparative example, standing is carried out for 24 hours at the temperature of 21-25 ℃ and under the relative humidity of 45-55%, and the injection molding shrinkage rate L1 of each product is measured;
(2) Post shrinkage test: testing according to the method in the step (1) to obtain a result shrinkage rate L1, then placing each sample in an oven at 80 ℃ for 2h, 4h and 6h respectively, taking out the sample, standing for 24h in an environment at 21-25 ℃ and a relative humidity of 45-55%, and then performing a shrinkage rate test to obtain a result shrinkage rate L2, wherein the post shrinkage rate L0= L2-L1 (finally counting the post shrinkage rate);
(3) And (3) testing the glossiness: cutting each sample into 100 × 2mm square plates, standing for 24h at 21-25 ℃ under the environment of relative humidity of 45-55%, and performing a glossiness test (with an angle of 60 ℃) by using a glossiness instrument according to a GB/T8807-1988 standard method;
the results of the tests on each product are shown in tables 3 and 4.
TABLE 3
TABLE 4
| Test items | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 |
| Degree of gloss | 83.8 | 82.1 | 75.1 | 73.1 | 81.2 | 73.8 |
| Shrinkage after 2h L0 (%) | 2.3 | 2.1 | 1.8 | 2.7 | 0.8 | 0.5 |
| Shrinkage after 4h L0 (%) | 3.2 | 2.8 | 2.6 | 3.6 | 1.2 | 0.7 |
| Shrinkage after 6h L0 (%) | 3.5 | 3.2 | 2.8 | 4.0 | 1.8 | 0.8 |
As can be seen from Table 1, the low post-shrinkage polypropylene material of the present invention has good stability, still has a low post-shrinkage rate after heat treatment (the shrinkage rate after 6h is less than 1%), and simultaneously can maintain good glossiness, and as can be seen from comparison between example 1 and example 17, when components such as a low shrinkage regulator are introduced into a prepared product in the form of master batch, the retention effect of glossiness is better and is closer to the original polypropylene resin matrix. As can be seen from the comparison of examples 5 to 7, the melt mass flow rate of the random copolymer polypropylene in the product components has a certain influence on the performance of the product, and when the melt mass flow rate is maintained within the range of 10 to 30g/10min, the product performance can give consideration to both good glossiness and lower after-shrinkage rate; as can be seen from the performances of the products in the examples 1, 8, 9 and 4, the ratio of methylene number to amide group in the molecular chain of the polyamide is a key influence factor of the product performance, and the polyamide can exert ideal effects only when the ratio is maintained between 10 and 12; from the comparison of the product performances of the example 1 and the examples 10 to 14, when the total amount of the polypropylene random copolymer and the polyamide in the components is constant, but the mixture ratio is changed, the gloss and the after shrinkage rate of the product are also influenced, and only the mixture ratio of the polypropylene random copolymer and the polyamide is maintained to be (7-9): (1-2) the gloss and the post shrinkage of the product can be maintained in a stable and desirable range. In contrast, the product of comparative example 1 does not incorporate a low post-shrinkage modifier, and the post-shrinkage rate of the product is higher; compared with the prior art, only random copolymer polypropylene and polyamide are respectively introduced into the comparative examples 2 and 3 to serve as adjusting components, wherein the shrinkage of the product in the comparative example 2 reaches 3.2 percent after 6 hours, no obvious difference exists between the product in the comparative example 1 and the product in the comparative example 3, although the shrinkage is reduced to a certain extent, the ideal shrinkage effect after adjustment is still difficult to achieve, and meanwhile, the glossiness of the product in the comparative example 3 is also obviously reduced; in comparative examples 5 and 6, although both low shrinkage adjusting components were introduced, the effect of achieving both surface property gloss and long-term dimensional stability was not achieved by adding too much or too little in total.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The low post-shrinkage polypropylene material is characterized by comprising the following components in parts by weight:
70-90 parts of polypropylene, 15-25 parts of low shrinkage regulator, 0.5-1.5 parts of compatilizer, 0.03-0.05 part of initiator and 0.2-0.6 part of processing aid;
the low-shrinkage regulator comprises random copolymerization polypropylene and polyamide, wherein the molar ratio of methylene to amido in the molecular chain of the polyamide is 10-12.
2. The low post-shrinkage polypropylene material according to claim 1, wherein the mass ratio of the random copolymer polypropylene to the polyamide in the low shrinkage regulator is (7-9): (1-2).
3. The low post shrinkage polypropylene material of claim 1, wherein the random copolymer polypropylene is a random propylene-ethylene copolymer.
4. The low post-shrinkage polypropylene material of claim 1, wherein the melt mass flow rate of the random copolymer polypropylene at 230 ℃ under a load of 2.16kg is 10 to 30g/10min.
5. The low post shrinkage polypropylene material of claim 1, wherein the polypropylene is at least one of block co-polypropylene and homo-polypropylene; the melt mass flow rate of the polypropylene at 230 ℃ under a load of 2.16kg is 1-60 g/10min.
6. The low post shrinkage polypropylene material of claim 1, wherein the compatibilizer is maleic anhydride graft; the initiator is at least one of organic peroxide initiator, azo initiator and benzoyl peroxide initiator.
7. The low post shrinkage polypropylene material of claim 1, wherein the processing aid comprises at least one of an antioxidant and a lubricant.
8. The process for preparing a low post-shrinkage polypropylene material according to any one of claims 1 to 7, comprising the steps of:
and uniformly mixing all the components, then putting the mixture into a double-screw extruder for extrusion, and cooling and granulating the mixture to obtain the low after-shrinkage polypropylene material.
9. The method for preparing the low post-shrinkage polypropylene material of claim 8, wherein the low shrinkage regulator, the compatibilizer and the initiator are added in the form of master batch when the components are mixed;
preferably, the preparation method of the master batch comprises the following steps:
(1) Uniformly mixing the random copolymer polypropylene, the compatilizer and the initiator, and then placing the mixture into a double-screw extruder for first-stage extrusion to obtain a first product;
(2) And uniformly mixing the first product and polyamide, then putting the mixture into a double-screw extruder for two-stage extrusion, and granulating to obtain the master batch.
10. Use of a low post-shrinkage polypropylene material according to any one of claims 1 to 7 in the manufacture of a household appliance component.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116239838A (en) * | 2022-12-30 | 2023-06-09 | 上海金发科技发展有限公司 | Polypropylene composition and preparation method and application thereof |
| WO2024032433A1 (en) * | 2022-08-11 | 2024-02-15 | 上海金发科技发展有限公司 | Low post-shrinkage polypropylene material and preparation method therefor |
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