CN115322479B - Low-post-shrinkage polypropylene material and preparation method thereof - Google Patents
Low-post-shrinkage polypropylene material and preparation method thereof Download PDFInfo
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- CN115322479B CN115322479B CN202210961287.9A CN202210961287A CN115322479B CN 115322479 B CN115322479 B CN 115322479B CN 202210961287 A CN202210961287 A CN 202210961287A CN 115322479 B CN115322479 B CN 115322479B
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 123
- -1 polypropylene Polymers 0.000 title claims abstract description 117
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 116
- 239000000463 material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000004952 Polyamide Substances 0.000 claims abstract description 34
- 229920002647 polyamide Polymers 0.000 claims abstract description 34
- 229920005604 random copolymer Polymers 0.000 claims abstract description 27
- 239000003607 modifier Substances 0.000 claims abstract description 4
- 239000003999 initiator Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 125000003368 amide group Chemical group 0.000 claims description 14
- 238000001125 extrusion Methods 0.000 claims description 13
- 239000000155 melt Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 239000003963 antioxidant agent Substances 0.000 claims description 11
- 239000004594 Masterbatch (MB) Substances 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
- 238000000034 method Methods 0.000 claims description 7
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 6
- 229920005653 propylene-ethylene copolymer Polymers 0.000 claims description 6
- 230000003078 antioxidant effect Effects 0.000 claims description 5
- 239000000314 lubricant Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 239000012934 organic peroxide initiator Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 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
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 11
- 230000000694 effects Effects 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
- 239000000047 product Substances 0.000 description 63
- 230000000052 comparative effect Effects 0.000 description 20
- 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 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
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000001276 controlling effect 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
- 229920001778 nylon Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000003825 pressing Methods 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
- 239000003153 chemical reaction reagent Substances 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
- 238000001746 injection moulding Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 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
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000010561 standard procedure 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
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000013329 compounding Methods 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
- 230000006872 improvement Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
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- 102200017650 rs28383586 Human genes 0.000 description 1
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Classifications
-
- 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
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 disclosed by the invention is characterized in that a specific low-shrinkage modifier is introduced into polypropylene, and the random copolymer polypropylene and polyamide contained in the low-post-shrinkage polypropylene material can be entangled with a composite molecular chain of polypropylene, so that the post-shrinkage effect after the product is stable in size and even after heat treatment is effectively inhibited, and the dimensional stability and durability are strong; since no filler such as mineral or fiber is required to be added to the components to maintain the dimensional stability of the product, the appearance properties of the product can be ensured. The invention also discloses a preparation method of the low-post-shrinkage polypropylene material and application of the low-post-shrinkage polypropylene material in preparation of household electrical parts.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a low-post-shrinkage polypropylene material and a preparation method thereof.
Background
The polypropylene material is the most widely used general plastic at present, and the engineering proportion of the polypropylene material is higher and higher along with the higher popularization rate of the modified polypropylene material in China in recent years. However, polypropylene has obvious disadvantages in terms of properties, such as large shrinkage, unstable size and the like, in order to reduce the shrinkage of polypropylene and improve the dimensional stability in industry, mineral powder, fiber and other fillers are usually added, but the addition of mineral powder fiber fillers generally affects the surface properties of products, such as the surface gloss of polypropylene composite materials prepared from most commonly used talcum powder is poor, and the surface floating fiber of polypropylene materials prepared from glass fiber composite is serious. In addition, these traditional shrinkage-adjusting 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 slow-motion crystallization of the polymer molecular chains, and the degree of shrinkage is greater if the product needs to undergo a heating process during use.
CN111087689a discloses a polypropylene composite material for home appliance shell and its preparation method, the polypropylene composite obtained by adding whisker, talcum powder, nucleating agent and other components has the characteristics of high gloss, scratch resistance and low post-shrinkage, but as mentioned above, the post-shrinkage rate of the material after high temperature annealing is larger; CN111484671a discloses a polypropylene composite material for a low post-shrinkage ratio vehicle and a preparation method thereof, the invention achieves the effect of low post-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 glossiness, 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 the filling shrinkage rate adjusting component 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 entanglement effect of the specific random polypropylene and long carbon chain polyamide and the composite molecular chain of the polypropylene resin matrix is utilized to further inhibit the post-shrinkage effect of the product caused by slow movement of the molecular chain after the product is dimensionally stable, and meanwhile, the surface glossiness and cleanliness of the product can be maintained within a better range, so that the application range is wide.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the low post 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 copolymer 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 the methylene and the amido of the molecular chain on the polyamide can be directly obtained through the structural molecular 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-post-shrinkage polypropylene material, and then adopting infrared spectrum analysis and mass spectrometry analysis and test.
In the components of the low post-shrinkage polypropylene material, in order to avoid introducing mineral powder, glass fiber and other components which can cause the reduction of the apparent performance of the product, random copolymerized polypropylene and polyamide are adopted to match, the two components can be fully entangled with the molecular short chains in the polypropylene resin matrix, and the amide groups contained in the components can form a certain amount of hydrogen bonds in the polypropylene resin matrix, so that the difficulty of the mutual movement between the molecular chains in the mixture after the components are compounded is increased, the two components can realize heterogeneous nucleation under the action of an initiator in the preparation process of the product, the problem of phase separation or incompatibility can not occur, the post-shrinkage rate of the product after the size is stable (especially after the product is subjected to heating annealing treatment) is effectively reduced, and the surface performance of the product can be ensured.
In addition, as the inventor has studied the components, it is found that it is difficult to achieve good low post-shrinkage when the amount of the low-shrinkage regulator added is too low, but if the amount of the low-shrinkage regulator added is too high, the compatibility of the product components becomes problematic (even if the compatibilizing agent is increased, it is difficult to avoid), and not only the post-shrinkage is not optimal, but also the surface gloss of the product may be problematic. On the other hand, the molar ratio of the methylene group to the amide group in the molecular chain in the polyamide is a key factor for entanglement with the polypropylene resin matrix, and if the ratio is too small, the density of the amide group is reduced, so that the hydrogen bond generated between the amide groups is reduced, the post shrinkage is not reduced, and if the ratio is too high, the content of the amide group is high, and the compatibility problem is also caused.
Preferably, the molar ratio of methylene to amide groups in the molecular chain of the polyamide is 10 to 11.
Preferably, the mass ratio of the random copolymer polypropylene and the polyamide in the low shrinkage regulator is (7-9): (1-2).
The content of polyamide or random copolymer polypropylene in the low shrinkage regulator cannot be too high because the polypropylene resin matrix and polyamide in the product component are actually in a mutually entangled state to prevent the arrangement and recombination of molecular chain segments after heating, if the random copolymer polypropylene is too much, it is difficult to generate enough hydrogen bonds in the product, and then the difficulty of reducing the shrinkage to an ideal degree increases, whereas if the polyamide is too much, the dispersibility in the product component will be significantly reduced, and the surface gloss of the product may be reduced. The inventor prefers the two, and the glossiness and the post shrinkage of the product are stable when the two are matched according to the proportion, so that the ideal range can be maintained.
Preferably, the random copolymer polypropylene is a random propylene-ethylene copolymer.
More preferably, the random copolymer polypropylene is tested according to GB/T3682.1-2018 melt Mass Flow Rate (MFR) and melt volume flow Rate (MVR) of plastics thermoplastics, at 230℃and a melt Mass flow Rate of from 10 to 30g/10min at 2.16 kg.
The inventor has found through experimental screening that any random copolymer polypropylene that can achieve entanglement with polyamide can be used in the product component of the invention. On the basis, if the melt mass flow rate of the random copolymer polypropylene is 10-30 g/min, the post shrinkage of the product can be lower.
Preferably, the polypropylene is at least one of block copolymerized polypropylene and homo-polymerized 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 method for testing melt Mass Flow Rate (MFR) and melt volume flow Rate (MVR) of plastics thermoplastics.
Preferably, the compatibilizing agent 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, polyethylene grafted maleic anhydride.
Through the invention experiment, the maleic anhydride graft has good effect on the respective compatibility of the random copolymer polypropylene and polyamide (especially polyamide) in polypropylene and the improvement of the compatibility between the two, so that two key components in the low-shrinkage regulator are well compatible and uniformly entangled with the molecular chain of the polypropylene resin matrix.
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 hindered phenol antioxidants, phosphite antioxidants and lubricants, and the mass ratio of the hindered phenol antioxidants, the phosphite antioxidants and the lubricants is 1:2:2.
Another object of the present invention is to provide a method for preparing the low post-shrinkage polypropylene material, comprising the steps of:
and uniformly mixing the components, then placing the mixture into a double-screw extruder for extrusion, and cooling and granulating the mixture to obtain the low-post-shrinkage polypropylene material.
The preparation method of the low-post 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 210-230 ℃.
Preferably, the low shrinkage regulator, the compatibilizer, and the initiator are added in masterbatch form when the components are mixed.
The inventor finds that when the random copolymer polypropylene and the polyamide in the low shrinkage regulator are pre-mixed and are prepared into master batches under the action of a compatilizer and an initiator to be introduced into a preparation final product, the optimal melting crystallization temperature of the random copolymer polypropylene and the polyamide can be selected to realize the heterogeneous nucleation of advanced crystallization, and the master batches are mixed with a polypropylene resin matrix at the moment, the generated hydrogen bond action strength is better, the problem of possible phase separation is further restrained, the post shrinkage of the product can be further restrained, and the surface glossiness 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 random copolymer polypropylene, a compatilizer and an initiator, and then placing the mixture into a double-screw extruder for one-stage extrusion to obtain a first product;
(2) And uniformly mixing the first product and polyamide, then placing 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 extrusion stage is 190-200 ℃.
More preferably, the speed of mixing in the step (2) is 400-600 rpm, the time is 1-3 min, and the temperature of the two-stage extrusion is 200-220 ℃.
It is another object of the present invention to provide the use of said low post-shrink polypropylene material for the preparation of household electrical appliances.
The product disclosed by the invention not only meets the high requirements on the appearance of parts in the field of household appliances on the surface performance (glossiness and apparent degree), but also can ensure low post-shrinkage after long-time use or heat treatment, and is especially suitable for preparing parts with changeable use environments such as household appliance shells and the like, but also has high requirements on dimensional stability.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a low post-shrinkage polypropylene material, which introduces a specific low-shrinkage regulator into polypropylene, wherein random copolymer polypropylene and polyamide contained in the low-shrinkage polypropylene material can be entangled with a composite molecular chain between polypropylene, so that the post-shrinkage effect after the product is dimensionally stable and even after heat treatment is effectively inhibited, and the dimensional stability and the durability are strong; since no filler such as mineral or fiber is required to be added to the components to maintain the dimensional stability of the product, the appearance properties of the product can be ensured. The invention also provides a preparation method of the low-post-shrinkage polypropylene material and application of the low-post-shrinkage polypropylene material in preparation of household electrical parts.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples. It is intended that the invention be interpreted in detail and not as a limitation. All other embodiments, which can be made by those skilled in the art without the inventive effort, are intended to be within the scope of the present invention. The experimental reagents and instruments involved in the practice of the present invention are common reagents and instruments unless otherwise specified.
The polypropylene composite material of the present invention (except example 17) was prepared by the following method:
mixing the components in a high-speed mixer at the speed of 800rpm and the temperature of 50 ℃ for 5-8 min until the components are uniform, then placing the mixture into a double-screw extruder, controlling the temperature to be 190-220 ℃ for extrusion, and obtaining the low-post-shrinkage polypropylene material after cooling and granulating.
The raw material information used in the examples and comparative examples of the present invention is as follows:
polypropylene 1: homopolymerizing polypropylene, and preparing PPH-T03 product by sea-pressing, wherein the mass flow rate of melt at 230 ℃ under the load of 2.16kg is 2.0g/10min;
polypropylene 2: block copolymerized polypropylene, producing PP K8003 product by Yangzi petrochemical industry, and having a melt mass flow rate of 2.2g/10min under the load of 2.16kg at 230 ℃;
polypropylene 3: homopolymerizing polypropylene, and preparing PP M60T product by sea-pressing, wherein the melt mass flow rate is 60.0g/10min under the conditions of 230 ℃ and 2.16kg load;
polypropylene 4: block-copolymerized polypropylene, producing PP M60RHC product by sea-pressing, and the melt mass flow rate under the load of 2.16kg at 230 ℃ is 59.8g/10min;
random copolymer polypropylene 1: random propylene-ethylene copolymer polypropylene PP RP346R, lyondellBasell Industries produced with a melt mass flow rate of 24g/10min;
random copolymer polypropylene 2: random propylene-ethylene copolymer polypropylene PP SM198, lotte Chemical Titan (M) sdn.bhd. Product, melt mass flow rate 2.3g/10min;
random copolymer polypropylene 3: random propylene-ethylene copolymer PP K4912, a product produced by Shanghai Seaceae, has a melt mass flow rate of 12g/10min;
random copolymer polypropylene 4: random propylene-ethylene copolymer polypropylene PP R340S, produced by Braskem, has a melt mass flow rate of 45g/10min;
polyamide 1: nylon 1012, wherein the molar ratio of the molecular chain methylene to the amido is 11, and the product is produced by eastern east cinrison;
polyamide 2: nylon 1010, the molar ratio of the molecular chain methylene to the amido is 10, and the product is produced by eastern east cinrison;
polyamide 3: nylon 1212, the ratio of molecular chain methylene to amido is 12, and products are produced by eastern east cinrison;
polyamide 4; PA66 EPR24, wherein the ratio of molecular chain methylene to amido is 6, and the product is produced by Pingshan God horse;
a compatibilizer; polypropylene is grafted with maleic anhydride, and the AD-105 of the south China sea cypress morning;
organic peroxide initiator: the organic peroxide initiator Enox 101 is available from Qiangsheng Co., ltd.
Processing aid: a mixture of a commercially available hindered phenol antioxidant, a commercially available phosphite antioxidant and a commercially available erucamide, wherein the mass ratio of the three is 1:2:2;
the starting materials used in each of the examples and comparative examples were the same as those used in the parallel experiments except for the above specific description.
Examples 1 to 16
The components and amounts of the low post-shrink polypropylene materials described in the examples are shown in Table 1.
Example 17
Example 17 differs from example 1 only in that the polypropylene composite material of this example was prepared by:
mixing the components in a high-speed mixer at the speed of 800rpm and the temperature of 50 ℃ for 5-8 min until the components are uniform, then placing the mixture into a double-screw extruder, controlling the temperature to be 190-220 ℃ for extrusion, and obtaining the low-post-shrinkage polypropylene material after cooling and granulating; wherein, the low shrinkage regulator, the compatilizer and the initiator are added in the form of master batch;
the preparation method of the master batch comprises the following steps:
(1) Mixing the random copolymer polypropylene, the compatilizer and the initiator at the speed of 700rpm for 4min to be uniform, and then placing the mixture into a double-screw extruder to control the temperature of 190-200 ℃ for one-stage extrusion so as to obtain a first product;
(2) Mixing the first product and polyamide at 500rpm for 2min to uniformity, then placing the mixture into a double-screw extruder, controlling the temperature of 200-220 ℃ for two-stage extrusion, and granulating to obtain the master batch.
Comparative examples 1 to 6
The components and amounts of the polypropylene composites described in each comparative example are shown in Table 2.
TABLE 1
TABLE 2
Effect example 1
To examine the properties of the low post-shrinkage polypropylene material of the present invention, the following tests were carried out on the products obtained in each example and comparative example:
(1) Shrinkage test: according to the GB/T15585-1995 standard method, injection molding the products of each example and comparative example, standing for 24 hours in an environment with the temperature of 21-25 ℃ and the relative humidity of 45-55%, and measuring the injection molding shrinkage rate L1 of each product;
(2) Post shrinkage test: testing according to the method of the step (1) and obtaining a resultant shrinkage rate L1, then placing each sample in an oven at 80 ℃ for 2h, 4h and 6h respectively, then taking out the sample and standing for 24h under the environment of 21-25 ℃ and relative humidity of 45-55%, obtaining a resultant shrinkage rate L2, and then obtaining a post-shrinkage rate L0=L2-L1 (finally counting the post-shrinkage rate);
(3) Gloss test: cutting each sample into square plates of 100 x 2mm, standing for 24 hours at the temperature of 21-25 ℃ and the relative humidity of 45-55%, and carrying out glossiness test (angle of 60 degrees) by adopting a glossiness meter according to a GB/T8807-1988 standard method;
the results of each product test are shown in tables 3 and 4.
TABLE 3 Table 3
TABLE 4 Table 4
| Test item | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 |
| Gloss level | 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, and still has a low post-shrinkage after heat treatment (less than 1% after 6 hours), while maintaining good gloss, and as can be seen from comparison of example 1 and example 17, when the low shrinkage modifier and the like are introduced into the prepared product in the form of a masterbatch, the retention effect of gloss is better, more similar to the original polypropylene resin matrix. From comparison of examples 5-7, it is clear that the melt mass flow rate of the random copolymer polypropylene in the product components has a certain influence on the product performance, and when the melt mass flow rate is maintained in the range of 10-30 g/10min, the product performance can achieve both good glossiness and lower post shrinkage; from the product performances of the examples 1, 8, 9 and 4, it can be seen that the ratio of methylene number to amido group in the molecular chain of the polyamide is a key influencing factor of the product performance, and the polyamide can only exert ideal effects when the ratio is maintained between 10 and 12; as can be seen from the comparison of the properties of the products of example 1 and examples 10 to 14, when the total amount of the random copolymer polypropylene and the polyamide in the components is constant, but the ratio is changed, the glossiness and the post shrinkage of the product are also affected, and only the ratio of the two is maintained to be (7 to 9): the gloss and the post-shrinkage of the product at (1-2) can be maintained in a stable and desirable range. In contrast, the product of comparative example 1 did not incorporate a low post-shrinkage modifier, and the post-shrinkage of the product was higher; the comparative examples 2 and 3 respectively only introduce the random copolymer polypropylene and the polyamide as the regulating components, wherein the shrinkage after 6 hours of the product of the comparative example 2 reaches 3.2%, no obvious difference is generated between the product of the comparative example 1 and the product of the comparative example 3, the ideal effect of regulating the shrinkage after the regulation is still difficult to be realized even though the shrinkage after the product of the comparative example 3 is reduced to a certain extent, and meanwhile, the glossiness of the product of the comparative example 3 is obviously reduced; although both low shrinkage adjusting components were incorporated in comparative examples 5 and 6, too much or too little total amount was added, and the effect of both the surface property gloss and the long-term dimensional stability could not be achieved.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (9)
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 is a mixture of random copolymer polypropylene and polyamide, and the molar ratio of methylene to amido in the molecular chain of the polyamide is 10-12; the mass ratio of the random copolymer polypropylene to the polyamide in the low-shrinkage regulator is (7-9): (1-2); the melt mass flow rate of the random copolymer polypropylene at 230 ℃ and under the load of 2.16kg is 10-30 g/10min.
2. The low post-shrink polypropylene material of claim 1, wherein the random copolymer polypropylene is a random propylene-ethylene copolymer.
3. The low post-shrink polypropylene material of claim 1, wherein the polypropylene is at least one of block copolymerized polypropylene and homo-polymerized polypropylene; the mass flow rate of the melt of the polypropylene at 230 ℃ and under the load of 2.16kg is 1-60 g/10min.
4. The low post-shrink polypropylene material of claim 1, wherein the compatibilizing agent is maleic anhydride grafts; the initiator is at least one of organic peroxide initiator, azo initiator and benzoyl peroxide initiator.
5. The low post-shrink polypropylene material of claim 1, wherein the processing aid comprises at least one of an antioxidant and a lubricant.
6. The method for producing a low post-shrinkage polypropylene material according to any one of claims 1 to 5, comprising the steps of:
and uniformly mixing the components, then placing the mixture into a double-screw extruder for extrusion, and cooling and granulating the mixture to obtain the low-post-shrinkage polypropylene material.
7. The method of preparing a low post-shrink polypropylene material as defined in claim 6 wherein the components are mixed together and the low shrinkage modifier, compatibilizer and initiator are added as a masterbatch.
8. The method for preparing a low post-shrinkage polypropylene material according to claim 7, wherein the method for preparing the master batch comprises the steps of:
(1) Uniformly mixing random copolymer polypropylene, a compatilizer and an initiator, and then placing the mixture into a double-screw extruder for one-stage extrusion to obtain a first product;
(2) And uniformly mixing the first product and polyamide, then placing the mixture into a double-screw extruder for two-stage extrusion, and granulating to obtain the master batch.
9. Use of the low post-shrinkage polypropylene material according to any one of claims 1 to 5 for the preparation of household electrical appliances.
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| PCT/CN2023/110666 WO2024032433A1 (en) | 2022-08-11 | 2023-08-02 | Low post-shrinkage polypropylene material and preparation method therefor |
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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 |
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