WO2024041326A1 - Polypropylene composition, method for preparing same, and use thereof - Google Patents
Polypropylene composition, method for preparing same, and use thereof Download PDFInfo
- Publication number
- WO2024041326A1 WO2024041326A1 PCT/CN2023/110466 CN2023110466W WO2024041326A1 WO 2024041326 A1 WO2024041326 A1 WO 2024041326A1 CN 2023110466 W CN2023110466 W CN 2023110466W WO 2024041326 A1 WO2024041326 A1 WO 2024041326A1
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- WO
- WIPO (PCT)
- Prior art keywords
- maleic anhydride
- polypropylene composition
- polypropylene
- composition according
- hypophosphite
- Prior art date
Links
- -1 Polypropylene Polymers 0.000 title claims abstract description 50
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 50
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 50
- 239000000203 mixture Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229920005629 polypropylene homopolymer Polymers 0.000 claims abstract description 20
- HGTUJZTUQFXBIH-UHFFFAOYSA-N (2,3-dimethyl-3-phenylbutan-2-yl)benzene Chemical compound C=1C=CC=CC=1C(C)(C)C(C)(C)C1=CC=CC=C1 HGTUJZTUQFXBIH-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 239000000314 lubricant Substances 0.000 claims description 4
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229910001382 calcium hypophosphite Inorganic materials 0.000 claims description 2
- 229940064002 calcium hypophosphite Drugs 0.000 claims description 2
- WVIIMZNLDWSIRH-UHFFFAOYSA-N cyclohexylcyclohexane Chemical compound C1CCCCC1C1CCCCC1 WVIIMZNLDWSIRH-UHFFFAOYSA-N 0.000 claims description 2
- SEQVSYFEKVIYCP-UHFFFAOYSA-L magnesium hypophosphite Chemical compound [Mg+2].[O-]P=O.[O-]P=O SEQVSYFEKVIYCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001381 magnesium hypophosphite Inorganic materials 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 2
- CNALVHVMBXLLIY-IUCAKERBSA-N tert-butyl n-[(3s,5s)-5-methylpiperidin-3-yl]carbamate Chemical compound C[C@@H]1CNC[C@@H](NC(=O)OC(C)(C)C)C1 CNALVHVMBXLLIY-IUCAKERBSA-N 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 abstract description 20
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 15
- 230000002087 whitening effect Effects 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 6
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001376 inorganic hypophosphite Inorganic materials 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 229920005606 polypropylene copolymer Polymers 0.000 abstract 2
- 230000035882 stress Effects 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000047 product Substances 0.000 description 7
- 229920005604 random copolymer Polymers 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- 241000985630 Lota lota Species 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000006355 external stress Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910001853 inorganic hydroxide Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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
- C08L23/14—Copolymers of propene
-
- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47D—FURNITURE SPECIALLY ADAPTED FOR CHILDREN
- A47D1/00—Children's chairs
-
- 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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/327—Aluminium phosphate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Definitions
- the present invention relates to the technical field of polymer materials, and in particular to a polypropylene composition and its preparation method and application.
- Polypropylene is widely used in various fields due to its low price, easy processing and molding, low density, chemical resistance and excellent physical and mechanical properties.
- polypropylene itself is a flammable material with a limiting oxygen index of only 18%, which cannot meet the flame retardant performance requirements of some related industries. Therefore, flame retardant polypropylene came into being.
- the existing polypropylene flame retardant systems have their own shortcomings:
- the flame retardant technology of polypropylene is mainly based on the addition of halogen flame retardants, followed by inorganic hydroxide flame retardants and intumescent flame retardants.
- the amount of flame retardants added to the above flame retardant systems is large.
- the system density is high and cannot meet the lightweight requirements of some industries.
- the flame retardant system using melamine cyanurate compounded with inorganic hypophosphite has the advantages of low addition amount, low density, excellent mechanical properties and low halogen, and is widely used in electronic components and household products.
- people have higher and higher aesthetic requirements for the appearance of electronic components and home products, they require the surface of the product to have low gloss and the product to whiten under low stress when affected by external forces.
- This system cannot solve the problem that polypropylene is susceptible to whitening due to external stress.
- the object of the present invention is to provide a polypropylene composition with the advantages of low density, low gloss, low stress whitening, and V-2 flame retardancy.
- Another object of the present invention is to provide a preparation method and application of the polypropylene composition.
- a polypropylene composition including the following components in parts by weight:
- the grafting rate of maleic anhydride groups is 0.6-0.9wt%.
- the grafting rate of maleic anhydride groups is 0.7-0.8 wt%.
- Maleic anhydride-grafted homopolypropylene can be a commercial product or a homemade raw material.
- the homemade method is as follows: according to the ratio, mix homopolypropylene, maleic anhydride and peroxide such as dicumyl peroxide through double Screw extruder A is used for extrusion.
- the screw temperature range is 165-200°C to obtain maleic anhydride grafted homopolypropylene.
- the present invention has no special limitation on the melt index of random copolymerized polypropylene resin.
- the melting index of random copolymerized polypropylene resin generally used in household products is 8-32g/10min under the condition of 230°C/2.16kg.
- the hypophosphite is at least one selected from the group consisting of aluminum hypophosphite, calcium hypophosphite, and magnesium hypophosphite.
- the dicyclohexane is 2,3-dimethyl-2,3-diphenylbutane.
- auxiliary agents are selected from at least one of antioxidants and lubricants.
- Antioxidants can be IRGANOX 1010 and IRGAFOS 168.
- the lubricant may be ethylene bisstearamide.
- the preparation method of the polypropylene composition of the present invention includes the following steps: mix each component evenly according to the proportion, and then extrude and granulate through a twin-screw extruder, in which the screw temperature range is 180-210°C and the rotation speed range It is 250-800 rpm, and the polypropylene composition is obtained.
- the application of the polypropylene composition of the present invention is used to prepare household products, such as child seat shells.
- the flame retardant grade of the polypropylene composition of the present invention is V-2, glossiness (60° angle) ⁇ 50, and stress whitening performance: the composition is prepared into a 100*100*3mm square plate, which can withstand a weight of 500g and a diameter of 50mm. In the drop test of the steel ball from a height of 300mm, the diameter of the white area is as small as 3mm.
- the flame retardant synergistic system of melamine cyanurate/inorganic hypophosphite/column can achieve the flame retardant effect of V-2, but it will deteriorate the stress whitening of the composition.
- the present invention grafts a specific amount of maleic anhydride Homopolymerized polypropylene can effectively improve the deterioration of stress whitening caused by flame retardants on random copolymerized polypropylene, and maleic anhydride is used to graft homopolymerized polypropylene and random copolymerized polypropylene.
- the poor olefin compatibility causes maleic anhydride to form a bumpy interface on the surface of the composition, increasing the specific surface area, thereby effectively reducing the surface gloss.
- the sources of raw materials used in the examples and comparative examples are as follows:
- Random copolymer polypropylene A J-570S, Lotte, South Korea, melt index 28g/10min, test conditions 230°C, 2.16kg.
- Random copolymer polypropylene B UT8012M, Maoming Petrochemical, melt index 12g/10min, test conditions 230°C, 2.16kg.
- Block copolymer polypropylene EP548R, CNOOC and Shell, melt index 28g/10min, test conditions 230°C, 2.16kg.
- Homopolymer polypropylene HP500N, CNOOC and Shell, melt index 12g/10min, test conditions 230°C, 2.16kg.
- Maleic anhydride grafted homopolypropylene A Maleic anhydride grafting rate is 0.61wt%, homemade.
- Maleic anhydride grafted homopolypropylene B maleic anhydride grafting rate is 0.71wt%, self-made.
- maleic anhydride grafted homopolypropylene C maleic anhydride grafting rate is 0.79wt%, self-made.
- Maleic anhydride grafted homopolypropylene D maleic anhydride grafting rate is 0.89wt%, homemade.
- Maleic anhydride grafted homopolypropylene E maleic anhydride grafting rate 0.5wt%, homemade.
- Maleic anhydride grafted homopolypropylene F Maleic anhydride grafting rate is 1.1wt%, homemade.
- Maleic anhydride grafted random copolymer polypropylene maleic anhydride grafting rate 0.71wt%, homemade.
- Aluminum hypophosphite commercially available.
- Lubricant ethylene bisstearamide (abbreviation EBS), commercially available.
- the preparation method of the polypropylene composition of Examples and Comparative Examples Mix each component evenly according to the proportion, and then extrude and granulate through a twin-screw extruder, in which the screw temperature range is 180-210°C and the rotation speed range is 300 -450 rpm to obtain a polypropylene composition.
- Glossiness According to GB/T8807-1988 standard, 60° angle, unit is dimensionless.
- the polypropylene composition within the scope of the present invention has a flame retardancy of V-2.
- maleic anhydride-grafted homopolypropylene can significantly reduce the gloss.
- the content of maleic anhydride-grafted homopolypropylene is too low, the gloss will not decrease significantly, while if the content is too high, the stress resistance will be reduced. Whiteness is severely reduced.
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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)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Disclosed is a polypropylene composition having low gloss, a low stress whitening effect, and a low density. According to the present invention, a small amount of a melamine cyanurate/inorganic hypophosphite/2,3-dimethyl-2,3-diphenylbutane synergistic flame-retardant system is added to achieve a V-2 flame-retardant effect. A specific amount of a maleic anhydride grafted homo-polypropylene is added to effectively ameliorate the stress whitening effect of the flame retardant on the random polypropylene copolymer. Moreover, maleic anhydride forms an uneven interface on the surface of the composition due to the poor compatibility between the maleic anhydride grafted homo-polypropylene and the random polypropylene copolymer, thus increasing the specific surface area and effectively reducing the surface glossiness. The polypropylene composition of the present invention is suitable for preparing household products such as the housing of a child seat.
Description
本发明涉及高分子材料技术领域，特别是涉及一种聚丙烯组合物及其制备方法和应用。The present invention relates to the technical field of polymer materials, and in particular to a polypropylene composition and its preparation method and application.
聚丙烯由于价格低廉，易于加工成型及其具有密度低，耐化学腐蚀和自身优异的物理力学性能等优点，广泛应用于各领域。但聚丙烯本身属于易燃材料，其极限氧指数仅为18％，无法满足一些相关行业对材料的阻燃性能要求，因此阻燃聚丙烯应运而生。但是现有技术的聚丙烯阻燃体系具有各自的缺点：Polypropylene is widely used in various fields due to its low price, easy processing and molding, low density, chemical resistance and excellent physical and mechanical properties. However, polypropylene itself is a flammable material with a limiting oxygen index of only 18%, which cannot meet the flame retardant performance requirements of some related industries. Therefore, flame retardant polypropylene came into being. However, the existing polypropylene flame retardant systems have their own shortcomings:
第一，聚丙烯的阻燃技术主要以添加卤素阻燃剂为主，其次还有无机氢氧化物类阻燃剂、膨胀型阻燃剂，但以上阻燃体系中阻燃剂添加量大，导致体系密度大，不以满足部分行业轻量化要求。First, the flame retardant technology of polypropylene is mainly based on the addition of halogen flame retardants, followed by inorganic hydroxide flame retardants and intumescent flame retardants. However, the amount of flame retardants added to the above flame retardant systems is large. As a result, the system density is high and cannot meet the lightweight requirements of some industries.
第二，以三聚氰胺氰尿酸盐复配无机次磷酸盐类阻燃体系具有添加量低、密度低、力学性能优异以及低卤的优点，被广泛应用于电子元器件、家居产品中。但随着人们对电子元器件、家居产品的外观的审美要求越来越高，如要求制件表面具有低光泽及制件在受到外力影响而低应力发白。而该体系无法解决聚丙烯易受外力应力发白的缺陷。Second, the flame retardant system using melamine cyanurate compounded with inorganic hypophosphite has the advantages of low addition amount, low density, excellent mechanical properties and low halogen, and is widely used in electronic components and household products. However, as people have higher and higher aesthetic requirements for the appearance of electronic components and home products, they require the surface of the product to have low gloss and the product to whiten under low stress when affected by external forces. This system cannot solve the problem that polypropylene is susceptible to whitening due to external stress.
现阶段家居产品中普遍要求低光泽度，如中国专利CN101173075A通过添加二氧化硅来达到低光泽效果，但同样由于添加无机填料、弹性体也恶化了体系的应力发白。At present, low gloss is generally required in household products. For example, Chinese patent CN101173075A achieves a low gloss effect by adding silica. However, the addition of inorganic fillers and elastomers also worsens the stress whitening of the system.
因此，如何同时得到V-2阻燃等级、低应力发白、低光泽度的聚丙烯组合物是一个业界难题。Therefore, how to obtain a polypropylene composition with V-2 flame retardant grade, low stress whitening, and low gloss at the same time is a difficult problem in the industry.
发明内容Contents of the invention
本发明的目的在于，提供一种聚丙烯组合物，具有低密度、低光泽度、低应力发白、V-2阻燃的优点。The object of the present invention is to provide a polypropylene composition with the advantages of low density, low gloss, low stress whitening, and V-2 flame retardancy.
本发明的另一目的在于，提供聚丙烯组合物的制备方法和应用。Another object of the present invention is to provide a preparation method and application of the polypropylene composition.
本发明是通过以下技术方案实现的：The present invention is achieved through the following technical solutions:
一种聚丙烯组合物，按重量份计，包括以下组分：
A polypropylene composition, including the following components in parts by weight:
A polypropylene composition, including the following components in parts by weight:
所述的马来酸酐接枝均聚聚丙烯中，马来酸酐基团的接枝率为0.6-0.9wt％。In the maleic anhydride grafted homopolypropylene, the grafting rate of maleic anhydride groups is 0.6-0.9wt%.
优选的，按重量份计，包括以下组分：
Preferably, the following components are included in parts by weight:
Preferably, the following components are included in parts by weight:
所述的马来酸酐接枝均聚聚丙烯中，马来酸酐基团的接枝率为0.7-0.8wt％。In the maleic anhydride grafted homopolypropylene, the grafting rate of maleic anhydride groups is 0.7-0.8 wt%.
马来酸酐接枝均聚聚丙烯可以是市售产品也可以是自制原料，自制方法如下：按照配比，将均聚聚丙烯、马来酸酐及过氧化物如过氧化二异丙苯通过双螺杆挤出机A挤出，螺杆温度范围是165-200℃，得到马来酸酐接枝均聚聚丙烯。Maleic anhydride-grafted homopolypropylene can be a commercial product or a homemade raw material. The homemade method is as follows: according to the ratio, mix homopolypropylene, maleic anhydride and peroxide such as dicumyl peroxide through double Screw extruder A is used for extrusion. The screw temperature range is 165-200°C to obtain maleic anhydride grafted homopolypropylene.
本发明对于无规共聚聚丙烯树脂的熔指没有特别的限定，一般用于家居制品的无规共聚聚丙烯树脂在230℃/2.16kg条件下的熔融指数为8-32g/10min。The present invention has no special limitation on the melt index of random copolymerized polypropylene resin. The melting index of random copolymerized polypropylene resin generally used in household products is 8-32g/10min under the condition of 230°C/2.16kg.
所述的次磷酸盐选自次磷酸铝、次磷酸钙、次磷酸镁中的至少一种。The hypophosphite is at least one selected from the group consisting of aluminum hypophosphite, calcium hypophosphite, and magnesium hypophosphite.
所述的联枯为2,3-二甲基-2,3-二苯基丁烷。The dicyclohexane is 2,3-dimethyl-2,3-diphenylbutane.
按重量份计，还包括0-2份助剂，所述的助剂选自抗氧剂、润滑剂中的至少一种。It also includes 0-2 parts by weight of auxiliary agents, and the auxiliary agents are selected from at least one of antioxidants and lubricants.
抗氧剂可以是IRGANOX 1010与IRGAFOS 168。Antioxidants can be IRGANOX 1010 and IRGAFOS 168.
润滑剂可以是乙撑双硬脂酰胺。The lubricant may be ethylene bisstearamide.
本发明的聚丙烯组合物的制备方法，包括以下步骤：按照配比，将各组分混合均匀，再通过双螺杆挤出机挤出造粒，其中螺杆温度范围是180-210℃，转速范围是250-800转/分，得到聚丙烯组合物。The preparation method of the polypropylene composition of the present invention includes the following steps: mix each component evenly according to the proportion, and then extrude and granulate through a twin-screw extruder, in which the screw temperature range is 180-210°C and the rotation speed range It is 250-800 rpm, and the polypropylene composition is obtained.
本发明的聚丙烯组合物的应用，用于制备家居产品，如儿童座椅外壳。The application of the polypropylene composition of the present invention is used to prepare household products, such as child seat shells.
本发明的聚丙烯组合物阻燃等级V-2、光泽度(60角度)＜50、应力发白性能：将组合物制备成100*100*3mm的方板，承受重500g、直径为50mm的钢球从300mm高度的跌落测试，其发白区域直径小至3mm。The flame retardant grade of the polypropylene composition of the present invention is V-2, glossiness (60° angle) <50, and stress whitening performance: the composition is prepared into a 100*100*3mm square plate, which can withstand a weight of 500g and a diameter of 50mm. In the drop test of the steel ball from a height of 300mm, the diameter of the white area is as small as 3mm.
本发明具有如下有益效果The present invention has the following beneficial effects
三聚氰胺氰尿酸盐/无机次磷酸盐/联枯的阻燃协效体系能够达到V-2的阻燃效果，但是会劣化组合物应力发白，本发明通过采用特定量的马来酸酐接枝均聚聚丙烯能够有效改善阻燃剂对无规共聚聚丙烯应力发白的恶化，并且利用马来酸酐接枝均聚聚丙烯与无规共聚聚丙
烯相容性较差的特性使得马来酸酐在组合物表面形成凹凸不平的界面，增加比表面积，从而有效降低表面光泽度。The flame retardant synergistic system of melamine cyanurate/inorganic hypophosphite/column can achieve the flame retardant effect of V-2, but it will deteriorate the stress whitening of the composition. The present invention grafts a specific amount of maleic anhydride Homopolymerized polypropylene can effectively improve the deterioration of stress whitening caused by flame retardants on random copolymerized polypropylene, and maleic anhydride is used to graft homopolymerized polypropylene and random copolymerized polypropylene. The poor olefin compatibility causes maleic anhydride to form a bumpy interface on the surface of the composition, increasing the specific surface area, thereby effectively reducing the surface gloss.
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。The present invention will be described in detail below with reference to specific embodiments. The following examples will help those skilled in the art to further understand the present invention, but do not limit the present invention in any form. It should be noted that, for those of ordinary skill in the art, several modifications and improvements can be made without departing from the concept of the present invention. These all belong to the protection scope of the present invention.
实施例和对比例所用原料来源如下：The sources of raw materials used in the examples and comparative examples are as follows:
无规共聚聚丙烯A：J-570S，韩国乐天，熔融指数28g/10min，测试条件230℃、2.16kg。Random copolymer polypropylene A: J-570S, Lotte, South Korea, melt index 28g/10min, test conditions 230℃, 2.16kg.
无规共聚聚丙烯B：UT8012M，茂名石化，熔融指数12g/10min，测试条件230℃、2.16kg。Random copolymer polypropylene B: UT8012M, Maoming Petrochemical, melt index 12g/10min, test conditions 230℃, 2.16kg.
嵌段共聚聚丙烯：EP548R，中海壳牌，熔融指数28g/10min，测试条件230℃、2.16kg。Block copolymer polypropylene: EP548R, CNOOC and Shell, melt index 28g/10min, test conditions 230℃, 2.16kg.
均聚聚丙烯：HP500N，中海壳牌，熔融指数12g/10min，测试条件230℃、2.16kg。Homopolymer polypropylene: HP500N, CNOOC and Shell, melt index 12g/10min, test conditions 230℃, 2.16kg.
马来酸酐接枝均聚聚丙烯A：马来酸酐接枝率0.61wt％，自制。Maleic anhydride grafted homopolypropylene A: Maleic anhydride grafting rate is 0.61wt%, homemade.
马来酸酐接枝均聚聚丙烯B：马来酸酐接枝率0.71wt％，自制。Maleic anhydride grafted homopolypropylene B: maleic anhydride grafting rate is 0.71wt%, self-made.
马来酸酐接枝均聚聚丙烯C：马来酸酐接枝率0.79wt％，自制。Maleic anhydride grafted homopolypropylene C: maleic anhydride grafting rate is 0.79wt%, self-made.
马来酸酐接枝均聚聚丙烯D：马来酸酐接枝率0.89wt％，自制。Maleic anhydride grafted homopolypropylene D: maleic anhydride grafting rate is 0.89wt%, homemade.
马来酸酐接枝均聚聚丙烯E：马来酸酐接枝率0.5wt％，自制。Maleic anhydride grafted homopolypropylene E: maleic anhydride grafting rate 0.5wt%, homemade.
马来酸酐接枝均聚聚丙烯F：马来酸酐接枝率1.1wt％，自制。Maleic anhydride grafted homopolypropylene F: Maleic anhydride grafting rate is 1.1wt%, homemade.
马来酸酐接枝无规共聚聚丙烯：马来酸酐接枝率0.71wt％，自制。Maleic anhydride grafted random copolymer polypropylene: maleic anhydride grafting rate 0.71wt%, homemade.
三聚氰胺氰尿酸盐：牌号为南京意特MHB。Melamine cyanurate: The brand name is Nanjing Yite MHB.
次磷酸铝：市售。Aluminum hypophosphite: commercially available.
联枯：市售。Lianku: commercially available.
润滑剂：乙撑双硬脂酰胺(缩写EBS)，市售。Lubricant: ethylene bisstearamide (abbreviation EBS), commercially available.
实施例和对比例聚丙烯组合物的制备方法：按照配比，将各组分混合均匀，再通过双螺杆挤出机挤出造粒，其中螺杆温度范围是180-210℃，转速范围是300-450转/分，得到聚丙烯组合物。The preparation method of the polypropylene composition of Examples and Comparative Examples: Mix each component evenly according to the proportion, and then extrude and granulate through a twin-screw extruder, in which the screw temperature range is 180-210°C and the rotation speed range is 300 -450 rpm to obtain a polypropylene composition.
各项测试方法：Various test methods:
光泽度：按照GB/T8807-1988标准，60°角，单位为无量纲。Glossiness: According to GB/T8807-1988 standard, 60° angle, unit is dimensionless.
耐应力发白：在环境温度约23℃条件下，将组合物制备成100*100*3mm的方板，承受重500g,直径为50mm的钢球从300mm高度的跌落测试，记录发白区的直径(每个待测材料
取10个样品的平均值)。Resistance to stress whitening: Under the ambient temperature of about 23°C, prepare the composition into a square plate of 100*100*3mm, withstand a weight of 500g and a 50mm diameter steel ball from a height of 300mm for a drop test, and record the whitening area. Diameter (for each material to be tested Take the average of 10 samples).
阻燃性能：根据UL94-2006将各样品经过注塑打样得到125±5mm*13±0.5mm*1.5mm的样条，进行阻燃等级测试。Flame retardant performance: According to UL94-2006, each sample was injection molded to obtain a sample of 125±5mm*13±0.5mm*1.5mm, and the flame retardant grade test was carried out.
表1：实施例1-7聚丙烯组合物各组分含量(重量份)及测试结果
Table 1: Contents (parts by weight) and test results of each component of the polypropylene composition of Examples 1-7
Table 1: Contents (parts by weight) and test results of each component of the polypropylene composition of Examples 1-7
由实施例可知，本发明范围内聚丙烯组合物具有V-2的阻燃性。It can be seen from the examples that the polypropylene composition within the scope of the present invention has a flame retardancy of V-2.
由实施例2-6可知，优选的各组分配比的范围内表面光泽度小于37，耐应力发白最好。It can be seen from Examples 2-6 that the surface glossiness is less than 37 within the preferred range of the proportion of each component, and the stress whitening resistance is the best.
表2：实施例8-9和对比例1-5聚丙烯组合物各组分含量(重量份)及测试结果
Table 2: Contents (weight parts) and test results of each component of the polypropylene compositions of Examples 8-9 and Comparative Examples 1-5
Table 2: Contents (weight parts) and test results of each component of the polypropylene compositions of Examples 8-9 and Comparative Examples 1-5
由实施例2/7/8/9可知，优选的马来酸酐接枝均聚聚丙烯的接枝率范围内光泽度更低、耐应力发白更好。It can be seen from Examples 2/7/8/9 that the preferred maleic anhydride grafted homopolypropylene has lower gloss within the grafting rate range and better stress whitening resistance.
由对比例1-3可知，马来酸酐接枝均聚聚丙烯能够显著降低光泽度，当马来酸酐接枝均聚聚丙烯含量过低光泽度降低不明显，而含量过高则导致耐应力发白性严重降低。It can be seen from Comparative Examples 1-3 that maleic anhydride-grafted homopolypropylene can significantly reduce the gloss. When the content of maleic anhydride-grafted homopolypropylene is too low, the gloss will not decrease significantly, while if the content is too high, the stress resistance will be reduced. Whiteness is severely reduced.
由对比例4/5可知，嵌段共聚聚丙烯、均聚聚丙烯无法实现本发明的技术效果。
It can be seen from Comparative Example 4/5 that block copolymerized polypropylene and homopolymerized polypropylene cannot achieve the technical effects of the present invention.
表3：对比例6-9聚丙烯组合物各组分含量(重量份)及测试结果
Table 3: Contents (weight parts) and test results of each component of the polypropylene composition of Comparative Examples 6-9
Table 3: Contents (weight parts) and test results of each component of the polypropylene composition of Comparative Examples 6-9
由对比例6/7和实施例2/7/8/9可知，马来酸酐接枝均聚聚丙烯的接枝率需要达到0.6wt％时才能够实现显著的降低光泽度的作用，但是接枝率过高会导致应力发白性差。It can be seen from Comparative Examples 6/7 and Examples 2/7/8/9 that the grafting rate of maleic anhydride grafted homopolypropylene needs to reach 0.6wt% to achieve a significant gloss reduction effect. However, the grafting rate of maleic anhydride grafted homopolypropylene needs to reach 0.6wt%. Excessive branch rate will lead to poor stress whitening.
由对比例8可知，马来酸酐接枝无规共聚聚丙烯的耐应力发白性差。It can be seen from Comparative Example 8 that maleic anhydride grafted random copolymerized polypropylene has poor stress whitening resistance.
由对比例9可知，均聚聚丙烯/马来酸酐接枝无规共聚聚丙烯的复配也无法实现本发明的技术效果。
It can be seen from Comparative Example 9 that the compounding of homopolymerized polypropylene/maleic anhydride grafted random copolymerized polypropylene cannot achieve the technical effects of the present invention.
Claims (8)
- 一种聚丙烯组合物，其特征在于，按重量份计，包括以下组分：
A polypropylene composition, characterized by comprising the following components in parts by weight:
所述的马来酸酐接枝均聚聚丙烯中，马来酸酐基团的接枝率为0.6-0.9wt％。In the maleic anhydride grafted homopolypropylene, the grafting rate of maleic anhydride groups is 0.6-0.9wt%. - 根据权利要求1所述的聚丙烯组合物，其特征在于，按重量份计，包括以下组分：
The polypropylene composition according to claim 1, characterized in that, in parts by weight, it includes the following components:
所述的马来酸酐接枝均聚聚丙烯中，马来酸酐基团的接枝率为0.7-0.8wt％。In the maleic anhydride grafted homopolypropylene, the grafting rate of maleic anhydride groups is 0.7-0.8 wt%. - 根据权利要求1或2所述的聚丙烯组合物，其特征在于，所述的无规共聚聚丙烯树脂在230℃/2.16kg条件下的熔融指数为8-32g/10min。The polypropylene composition according to claim 1 or 2, characterized in that the melt index of the random copolymerized polypropylene resin under the condition of 230°C/2.16kg is 8-32g/10min.
- 根据权利要求1或2所述的聚丙烯组合物，其特征在于，所述的次磷酸盐选自次磷酸铝、次磷酸钙、次磷酸镁中的至少一种。The polypropylene composition according to claim 1 or 2, characterized in that the hypophosphite is selected from at least one of aluminum hypophosphite, calcium hypophosphite, and magnesium hypophosphite.
- 根据权利要求1或2所述的聚丙烯组合物，其特征在于，所述的联枯为2,3-二甲基-2,3-二苯基丁烷。The polypropylene composition according to claim 1 or 2, characterized in that the dicyclohexane is 2,3-dimethyl-2,3-diphenylbutane.
- 根据权利要求1或2所述的聚丙烯组合物，其特征在于，按重量份计，还包括0-2份助剂，所述的助剂选自抗氧剂、润滑剂中的至少一种。The polypropylene composition according to claim 1 or 2, characterized in that, by weight, it also includes 0-2 parts of auxiliary agents, and the auxiliary agents are selected from at least one of antioxidants and lubricants. .
- 权利要求1-6任一项所述聚丙烯组合物的制备方法，其特征在于，包括以下步骤：按照配比，将各组分混合均匀，再通过双螺杆挤出机挤出造粒，其中螺杆温度范围是180-210℃，转速范围是250-800转/分，得到聚丙烯组合物。The preparation method of the polypropylene composition according to any one of claims 1 to 6, characterized in that it includes the following steps: mixing each component evenly according to the proportion, and then extruding and granulating through a twin-screw extruder, wherein The screw temperature range is 180-210°C, the rotation speed range is 250-800 rpm, and a polypropylene composition is obtained.
- 权利要求1-6任一项所述聚丙烯组合物的应用，其特征在于，用于制备家居产品，如儿童座椅外壳。 The application of the polypropylene composition according to any one of claims 1 to 6, characterized in that it is used to prepare household products, such as child seat shells.
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