WO2023179486A1 - Polypropylene composition, preparation method therefor and application thereof - Google Patents
Polypropylene composition, preparation method therefor and application thereof Download PDFInfo
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- WO2023179486A1 WO2023179486A1 PCT/CN2023/082194 CN2023082194W WO2023179486A1 WO 2023179486 A1 WO2023179486 A1 WO 2023179486A1 CN 2023082194 W CN2023082194 W CN 2023082194W WO 2023179486 A1 WO2023179486 A1 WO 2023179486A1
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- -1 Polypropylene Polymers 0.000 title claims abstract description 42
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 40
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 40
- 239000000203 mixture Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 229920001864 tannin Polymers 0.000 claims abstract description 9
- 235000018553 tannin Nutrition 0.000 claims abstract description 9
- 239000001648 tannin Substances 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 6
- FVMDYYGIDFPZAX-UHFFFAOYSA-N 3-hydroxyphenylacetic acid Chemical compound OC(=O)CC1=CC=CC(O)=C1 FVMDYYGIDFPZAX-UHFFFAOYSA-N 0.000 claims description 5
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 5
- 239000000314 lubricant Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 239000000344 soap Substances 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 23
- 230000032683 aging Effects 0.000 abstract description 20
- 239000003963 antioxidant agent Substances 0.000 abstract description 9
- 230000003078 antioxidant effect Effects 0.000 abstract description 8
- 238000003878 thermal aging Methods 0.000 abstract description 8
- 239000011347 resin Substances 0.000 abstract description 6
- 229920005989 resin Polymers 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 239000012745 toughening agent Substances 0.000 abstract description 4
- 239000003446 ligand Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 13
- 238000002474 experimental method Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000011056 performance test Methods 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 239000004700 high-density polyethylene Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- HGTUJZTUQFXBIH-UHFFFAOYSA-N (2,3-dimethyl-3-phenylbutan-2-yl)benzene Chemical group C=1C=CC=CC=1C(C)(C)C(C)(C)C1=CC=CC=C1 HGTUJZTUQFXBIH-UHFFFAOYSA-N 0.000 description 2
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 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 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920001083 polybutene Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- LNKJESSHRFPVPE-UHFFFAOYSA-N 5-(diethylamino)pentyl 3,4,5-trimethoxybenzoate;hydrochloride Chemical compound Cl.CCN(CC)CCCCCOC(=O)C1=CC(OC)=C(OC)C(OC)=C1 LNKJESSHRFPVPE-UHFFFAOYSA-N 0.000 description 1
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Chinese gallotannin Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical class OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000000155 melt Substances 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
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 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
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Definitions
- the invention relates to the technical field of general plastics, and in particular to a polypropylene composition and its preparation method and application.
- Multi-axial impact test is a method that can be used to characterize the toughness of materials. It is used to test the performance of interior and exterior materials when subjected to strong impact or destructive force. It is also a common performance of modified polypropylene materials for automobiles and is often used to evaluate materials.
- the toughness especially in the standard of General Motors instrument panel materials, clearly states that the sample molded from the material needs to be tested at -30°C in accordance with the ASTM3763 standard at 105°C and 1000h aging to meet the standard requirements of 100% full toughness. .
- the present invention proposes a polypropylene composition and a preparation method thereof.
- the performance impact of thermal aging on the material can be greatly alleviated, the performance changes caused by thermal aging can be reduced, and the full toughness requirements of low-temperature multiaxial impact after aging can be achieved.
- a polypropylene composition including the following components in parts by weight:
- the compound X has a group capable of forming a hydrogen bond with the tannin.
- the group contained in the compound X is one or more of carboxyl, hydroxyl or amino.
- Compound It can influence and reduce the performance changes caused by thermal aging, and achieve the full toughness requirements of low-temperature multi-axial impact after aging.
- the compound X includes but is not limited to 3-hydroxyphenylacetic acid, polyacrylic acid, caprolactam or polyvinyl alcohol.
- the toughening agent may be selected from one or more of ethylene-butene copolymers or ethylene-octene copolymers.
- the antioxidant may be selected from organic phosphites, alkylated monohydric phenols or polyhydric phenols, alkylation reaction products of polyhydric phenols and dienes, p-cresol or butyl dicyclopentadiene. reaction product, one or more of alkylated hydroquinones, hydroxylated thiodiphenyl ethers, alkylene-bisphenols, benzyl compounds or polyol ester antioxidants, preferably Preferably, the antioxidant is one or more of antioxidant 412S, antioxidant 1010, antioxidant 1076, and antioxidant 168.
- the weather-resistant agent may be selected from one or more benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers or hindered amine light stabilizers.
- the polypropylene composition further includes 0.1-30 parts of talc powder, and adding talc powder can improve the rigidity of the material.
- the auxiliary agent is a lubricant, and the lubricant is one or more of metal soaps, stearic acid complex esters or amines.
- the amines include but are not limited to erucamide or oleic acid amide, and amines can play a role in lubrication and demoulding.
- the present invention also provides a preparation method of the above-mentioned polypropylene composition, which includes the following steps:
- step S2 Put the premix in step S1 into an extruder, perform melt blending and extrusion granulation to obtain the polypropylene composition.
- each section of the twin-screw extruder is: 170°C in the first zone, 190°C in the second zone, Zone three is 230°C, zone four is 232°C, zone five is 234°C, zone six is 236°C, zone seven is 240°C, zone eight is 240°C, and zone nine is 230°C; the screw speed of the twin-screw extruder is 500r/min.
- the present invention also provides the application of the above-mentioned polypropylene composition in preparing vehicle parts, such as preparing automobile dashboards, etc.
- the invention discloses a polypropylene composition to which tannin and compound X capable of forming hydrogen bonds with the tannin are added. Introducing hydrogen bonding ligands into polypropylene resin. Hydrogen bonds have a certain strength and are distributed in polypropylene, which has a similar reinforcing effect. Therefore, the heat resistance of polypropylene resin is also improved, which can greatly alleviate the effects of thermal aging.
- the performance impact brought by the material reduces the performance changes caused by thermal aging and achieves the full toughness requirements of low-temperature multi-axial impact after aging.
- Polypropylene resin copolymerized polypropylene, model EP548R, purchased from China Shipping and Shell, melt flow rate at 230°C/2.16kg is 25g/10min;;
- Tannin CAS number 1401-55-4, purchased from Nanjing Chemical Reagent Company;
- Compound X2 polyacrylic acid, CAS number 9003-01-4, purchased from Aladdin Reagent Company;
- Toughening agent ethylene-butylene copolymer, brand POE 7467, purchased from Dow Chemical;
- Antioxidant A Antioxidant 1010, commercially available, the same antioxidant A was used in parallel experiments;
- Antioxidant B Antioxidant 168, commercially available, the same antioxidant B was used in parallel experiments;
- Weathering agent 3808PP5, a hindered amine substance, commercially available, the same kind of weathering agent was used in parallel experiments;
- Talc powder commercially available, mesh size 3000, the same kind of talc powder was used in parallel experiments;
- XPOE Its preparation method is obtained by cross-linking POE 7447 with dicumyl oxide (DCP). In XPOE, the mass percentage of POE is 98% and the mass percentage of DCP is 2%;
- High-density polyethylene HDPE DMDA8008, Lanzhou Petrochemical, melt mass flow rate at 190°C, 2.16KG load is 8g/10min;
- Homopolymer polybutene PB-1, PB 8510, purchased from LyondellBasell Industries, with a melt mass flow rate of 20g/10min at 190°C and a load of 2.16KG;
- Benzamide (nucleating agent), brand name TMB-5 was purchased from Shanxi Research Institute of Chemical Industry.
- step S2 Put the premix in step S1 into a twin-screw extruder, perform melt blending, extrusion and granulation, and dry at 80°C to obtain a polypropylene composition.
- the processing temperatures of each section of the twin-screw extruder are: zone one 170°C, zone two 190°C, zone three 230°C, zone four 232°C, zone five 234°C, zone six 236°C, zone seven 240°C, zone eight 240°C °C, zone 9 is 230°C; the screw speed of the twin-screw extruder is 500r/min.
- Parts in this specification means “parts by weight” unless otherwise specified.
- Izod notched impact strength test standard ISO180/1eA-2010, sample size is 80 ⁇ 10 ⁇ 4mm, type A notch;
- Multi-axis impact performance test take out the 100mm*100mm*3mm sample under conditions 1105°C, after aging for 1000h; 2150°C, 500h, and then test according to ASTM D3763, the temperature is -30°C, the impact speed is 6.6m/s, and the maximum energy is obtained value. Make 10 parallel samples for each set of experiments.
- the notched Izod impact strength after aging is the result of testing the specimen at 150°C and aging for 700h.
- Comparative Examples 5 and 6 only used tannin and 3-hydroxyphenylacetic acid alone respectively. Compared with Example 1, it was found that the impact properties of Comparative Examples 5 and 6 dropped sharply after aging, and the multi-axial impact of the materials before and after aging was Both are brittle failures, indicating that using either alone cannot improve the thermal stability of the material.
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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 in the present invention are a polypropylene composition, a preparation method therefor and an application thereof. The polypropylene composition comprises the following components in parts by weight: 38-83.7 parts of polypropylene resin, 0.5-2 parts of tannin, 0.1-2 parts of compound X, 15-25 parts of toughening agent, 0.3-1 part of antioxidant, and 0.2-1 part of weather-resistant agent, wherein the compound X has a group capable of generating a hydrogen bond with the tannin. By introducing a hydrogen bond ligand into the polypropylene resin, the performance influence of thermal aging on the material can be greatly relieved, the performance change caused by thermal aging is reduced, and the full-toughness requirement of low-temperature multi-axis impact after aging is realized.
Description
本发明涉及通用塑料技术领域，具体涉及一种聚丙烯组合物及其制备方法和应用。The invention relates to the technical field of general plastics, and in particular to a polypropylene composition and its preparation method and application.
多轴冲击试验是一种能用于表征材料韧性的方法，用来检验内外饰材料在受到强大冲击力或破坏力时的表现，也是车用改性聚丙烯材料常见的性能，常用来评估材料的韧性，特别是在通用汽车仪表板材料的标准中，明确指出，材料注塑成的样板需要在105℃，1000h老化之后，在-30℃按照ASTM3763标准进行测试，满足100％全韧的标准要求。Multi-axial impact test is a method that can be used to characterize the toughness of materials. It is used to test the performance of interior and exterior materials when subjected to strong impact or destructive force. It is also a common performance of modified polypropylene materials for automobiles and is often used to evaluate materials. The toughness, especially in the standard of General Motors instrument panel materials, clearly states that the sample molded from the material needs to be tested at -30°C in accordance with the ASTM3763 standard at 105°C and 1000h aging to meet the standard requirements of 100% full toughness. .
一般而言，老化之前改性聚丙烯材料的-30℃多轴冲击全韧比较常见，采用常规增韧方法就可以实现，这方面的研究报告已经屡见不鲜，例如中国发明专利CN 112625348 A报道了一种新能源汽车外饰用聚丙烯复合材料及其制备方法，此发明采用高密度聚乙烯、均聚聚丁烯和β型成核剂之间具有协同作用，可以显著提高聚丙烯复合材料的低温多轴冲击。专利CN 103665570 A中报道了一种超低温韧性聚丙烯组合物及其制备方法，其核心技术是采用低密度、低熔指并且玻璃化转变温度低的弹性体与氧化二异丙苯(DCP)交联而得到XPOE作为增韧剂，制备的聚丙烯组合物具有良好的低温冲击韧性，可以满足-40℃多轴冲击全韧的目标，但这些报道都没有提及老化之后的多轴冲击性能。Generally speaking, -30°C multi-axial impact full toughening of modified polypropylene materials before aging is relatively common and can be achieved using conventional toughening methods. Research reports in this area have been common. For example, Chinese invention patent CN 112625348 A reported a A polypropylene composite material for new energy automobile exterior decoration and its preparation method. This invention uses high-density polyethylene, homopolymer polybutene and β-type nucleating agent to have a synergistic effect, which can significantly improve the low-temperature resistance of the polypropylene composite material. Multi-axis impact. Patent CN 103665570 A reports an ultra-low temperature tough polypropylene composition and its preparation method. Its core technology is to use an elastomer with low density, low melting index and low glass transition temperature and dicumyl oxide (DCP). XPOE was obtained as a toughening agent. The prepared polypropylene composition has good low-temperature impact toughness and can meet the target of full multi-axial impact toughness at -40°C. However, these reports did not mention the multi-axial impact properties after aging.
可见，实现材料在经过105℃、1000h老化之后-30℃多轴冲击100％全韧的要求，具有一定的技术难度，需要对材料配方进行结构设计，才能实现这一超高要求，而目前在这一方面的研究报道还属于空白。
It can be seen that it is technically difficult to achieve the requirement of 100% full toughness of the material after aging at 105°C and 1000h under -30°C multi-axial impact. The material formula needs to be structurally designed to achieve this ultra-high requirement. Currently, in Research reports in this area are still blank.
发明内容Contents of the invention
为了克服上述现有技术的缺陷，本发明提出了一种聚丙烯组合物及其制备方法。通过在聚丙烯树脂中引入氢键配体，可以大幅缓解热老化对材料带来的性能影响，减小热老化引起的性能变化，实现老化后低温多轴冲击的全韧要求。In order to overcome the above-mentioned shortcomings of the prior art, the present invention proposes a polypropylene composition and a preparation method thereof. By introducing hydrogen bonding ligands into polypropylene resin, the performance impact of thermal aging on the material can be greatly alleviated, the performance changes caused by thermal aging can be reduced, and the full toughness requirements of low-temperature multiaxial impact after aging can be achieved.
具体通过以下技术方案实现：This is specifically 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:
所述化合物X具有能与所述单宁生成氢键的基团。The compound X has a group capable of forming a hydrogen bond with the tannin.
优选地，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:
进一步地，所述化合物X含有的基团为羧基、羟基或氨基中的一种或多种。化合物X能与单宁上的羟基、羧基或氨基形成氢键，而氢键是具备一定强度的，并且分布在聚丙烯中，可以大幅缓解热老化对材料带来的性
能影响，减小热老化引起的性能变化，实现老化后低温多轴冲击的全韧要求。Further, the group contained in the compound X is one or more of carboxyl, hydroxyl or amino. Compound It can influence and reduce the performance changes caused by thermal aging, and achieve the full toughness requirements of low-temperature multi-axial impact after aging.
进一步地，所述化合物X包括但不限于3-羟基苯乙酸、聚丙烯酸、己内酰胺或聚乙烯醇。Further, the compound X includes but is not limited to 3-hydroxyphenylacetic acid, polyacrylic acid, caprolactam or polyvinyl alcohol.
进一步地，所述增韧剂可以选自乙烯-丁烯共聚物或乙烯-辛烯共聚物的一种或多种。Further, the toughening agent may be selected from one or more of ethylene-butene copolymers or ethylene-octene copolymers.
进一步地，所述抗氧剂可以选自有机亚磷酸酯、烷基化的一元酚或者多元酚、多元酚和二烯的烷基化反应产物、对甲酚或者二环戊二烯的丁基化反应产物、烷基化的氢醌类、羟基化的硫代二苯基醚类、亚烷基-双酚、苄基化合物或多元醇酯类抗氧剂中的一种或多种，优选地，所述抗氧剂为抗氧剂412S、抗氧剂1010、抗氧剂1076、抗氧剂168中的一种或多种。Further, the antioxidant may be selected from organic phosphites, alkylated monohydric phenols or polyhydric phenols, alkylation reaction products of polyhydric phenols and dienes, p-cresol or butyl dicyclopentadiene. reaction product, one or more of alkylated hydroquinones, hydroxylated thiodiphenyl ethers, alkylene-bisphenols, benzyl compounds or polyol ester antioxidants, preferably Preferably, the antioxidant is one or more of antioxidant 412S, antioxidant 1010, antioxidant 1076, and antioxidant 168.
进一步地，所述耐候剂可以选自二苯甲酮类紫外线吸收剂、苯并三唑类紫外线吸收剂或受阻胺类光稳定剂中的一种或多种。Further, the weather-resistant agent may be selected from one or more benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers or hindered amine light stabilizers.
进一步地，所述聚丙烯组合物还包括0.1-30份的滑石粉，添加滑石粉可以提高材料的刚性。Further, the polypropylene composition further includes 0.1-30 parts of talc powder, and adding talc powder can improve the rigidity of the material.
进一步地，还包括0.2-1份的助剂。所述助剂为润滑剂，所述润滑剂为金属皂类、硬脂酸复合酯类或胺类中的一种或多种。Furthermore, 0.2-1 parts of auxiliaries are included. The auxiliary agent is a lubricant, and the lubricant is one or more of metal soaps, stearic acid complex esters or amines.
所述胺类包括但不限于芥酸酰胺或油酸酰胺，胺类物质可起到润滑、脱模的作用。The amines include but are not limited to erucamide or oleic acid amide, and amines can play a role in lubrication and demoulding.
本发明还提供上述聚丙烯组合物的制备方法，包括如下步骤：The present invention also provides a preparation method of the above-mentioned polypropylene composition, which includes the following steps:
S1:按照配比,称取各组分预混合后，得到预混物；S1: According to the proportion, weigh each component and premix it to obtain a premix;
S2：将步骤S1的预混物投入到挤出机中，进行熔融共混并挤出造粒，得到所述聚丙烯组合物。S2: Put the premix in step S1 into an extruder, perform melt blending and extrusion granulation to obtain the polypropylene composition.
进一步地，双螺杆挤出机各段的加工温度为：一区170℃，二区190℃，
三区230℃，四区232℃，五区234℃，六区236℃，七区240℃，八区240℃，九区230℃；双螺杆挤出机的螺杆转速为500r/min。Further, the processing temperature of each section of the twin-screw extruder is: 170°C in the first zone, 190°C in the second zone, Zone three is 230°C, zone four is 232°C, zone five is 234°C, zone six is 236°C, zone seven is 240°C, zone eight is 240°C, and zone nine is 230°C; the screw speed of the twin-screw extruder is 500r/min.
本发明还提供上述聚丙烯组合物在制备车辆制件中的应用，如制备汽车仪表板等。The present invention also provides the application of the above-mentioned polypropylene composition in preparing vehicle parts, such as preparing automobile dashboards, etc.
与现有技术相比，本发明的有益效果是：Compared with the prior art, the beneficial effects of the present invention are:
本发明公开了一种聚丙烯组合物，添加了单宁以及能够与单宁形成氢键的化合物X。在聚丙烯树脂中引入氢键配体，氢键是具备一定强度的，并且分布在聚丙烯中，起到了类似增强的效果，因此聚丙烯树脂的耐热性能也提高，可以大幅缓解热老化对材料带来的性能影响，减小热老化引起的性能变化，实现老化后低温多轴冲击的全韧要求。The invention discloses a polypropylene composition to which tannin and compound X capable of forming hydrogen bonds with the tannin are added. Introducing hydrogen bonding ligands into polypropylene resin. Hydrogen bonds have a certain strength and are distributed in polypropylene, which has a similar reinforcing effect. Therefore, the heat resistance of polypropylene resin is also improved, which can greatly alleviate the effects of thermal aging. The performance impact brought by the material reduces the performance changes caused by thermal aging and achieves the full toughness requirements of low-temperature multi-axial impact after aging.
下面对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅是本发明的一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solutions in the embodiments of the present invention are clearly and completely described below. Obviously, the described embodiments are only some of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of the present invention.
<实施例和对比例的制备><Preparation of Examples and Comparative Examples>
本发明实施例和对比例所用的原材料均来源于市购，但不限于这些材料：The raw materials used in the examples and comparative examples of the present invention are all commercially available, but are not limited to these materials:
聚丙烯树脂：共聚聚丙烯，型号EP548R，购自中海壳牌，230℃/2.16kg条件下的熔体流动速率为25g/10min；；Polypropylene resin: copolymerized polypropylene, model EP548R, purchased from China Shipping and Shell, melt flow rate at 230°C/2.16kg is 25g/10min;;
单宁：CAS号1401-55-4，购自南京化学试剂公司；Tannin: CAS number 1401-55-4, purchased from Nanjing Chemical Reagent Company;
化合物X1：3-羟基苯乙酸，CAS号621-37-4，购自国药化学试剂有限公司；Compound X1: 3-hydroxyphenylacetic acid, CAS number 621-37-4, purchased from Sinopharm Chemical Reagent Co., Ltd.;
化合物X2：聚丙烯酸，CAS号9003-01-4，购自阿拉丁试剂公司；
Compound X2: polyacrylic acid, CAS number 9003-01-4, purchased from Aladdin Reagent Company;
化合物X3：己内酰胺，CAS号105-60-2，购自Sigma-Aldrich公司；Compound X3: caprolactam, CAS number 105-60-2, purchased from Sigma-Aldrich;
增韧剂：乙烯-丁烯共聚物，牌号POE 7467，购自陶氏化学；Toughening agent: ethylene-butylene copolymer, brand POE 7467, purchased from Dow Chemical;
抗氧剂A：抗氧剂1010，市售，平行实验中采用同种抗氧剂A；Antioxidant A: Antioxidant 1010, commercially available, the same antioxidant A was used in parallel experiments;
抗氧剂B：抗氧剂168，市售，平行实验中采用同种抗氧剂B；Antioxidant B: Antioxidant 168, commercially available, the same antioxidant B was used in parallel experiments;
耐候剂：3808PP5，受阻胺类物质，市售，平行实验中采用同种耐候剂；Weathering agent: 3808PP5, a hindered amine substance, commercially available, the same kind of weathering agent was used in parallel experiments;
滑石粉：市售，目数3000目，平行实验中采用同种滑石粉；Talc powder: commercially available, mesh size 3000, the same kind of talc powder was used in parallel experiments;
助剂：芥酸酰胺，市售，平行实验中采用同种助剂；Auxiliary: erucamide, commercially available, the same kind of auxiliary was used in parallel experiments;
XPOE：其制备方法由POE 7447与氧化二异丙苯(DCP)交联得到，在XPOE中，POE质量百分比为98％，DCP质量百分比为2％；XPOE: Its preparation method is obtained by cross-linking POE 7447 with dicumyl oxide (DCP). In XPOE, the mass percentage of POE is 98% and the mass percentage of DCP is 2%;
高密度聚乙烯：HDPE DMDA8008，兰州石化，在190℃，2.16KG负荷下熔体质量流动速率为8g/10min；High-density polyethylene: HDPE DMDA8008, Lanzhou Petrochemical, melt mass flow rate at 190℃, 2.16KG load is 8g/10min;
均聚聚丁烯：PB-1，PB 8510，购自利安德巴赛尔工业公司，在190℃，2.16KG负荷下熔体质量流动速率为20g/10min；Homopolymer polybutene: PB-1, PB 8510, purchased from LyondellBasell Industries, with a melt mass flow rate of 20g/10min at 190°C and a load of 2.16KG;
苯酰胺(成核剂)，牌号TMB-5，购自山西省化工研究院。Benzamide (nucleating agent), brand name TMB-5, was purchased from Shanxi Research Institute of Chemical Industry.
本发明实施例和对比例的制备方法如下：The preparation methods of the embodiments and comparative examples of the present invention are as follows:
S1:按照表1、表3的配比,称取各组分投入高速混合机中以400r/min的速度预混合5min后，得到预混物；S1: According to the proportions in Table 1 and Table 3, weigh each component and put it into a high-speed mixer to premix for 5 minutes at a speed of 400r/min to obtain a premix;
S2：将步骤S1的预混物投入到双螺杆挤出机中，进行熔融共混并挤出造粒，在80℃下烘干，得到聚丙烯组合物。S2: Put the premix in step S1 into a twin-screw extruder, perform melt blending, extrusion and granulation, and dry at 80°C to obtain a polypropylene composition.
双螺杆挤出机各段的加工温度为：一区170℃，二区190℃，三区230℃，四区232℃，五区234℃，六区236℃，七区240℃，八区240℃，九区230℃；双螺杆挤出机的螺杆转速为500r/min。The processing temperatures of each section of the twin-screw extruder are: zone one 170°C, zone two 190°C, zone three 230°C, zone four 232°C, zone five 234°C, zone six 236°C, zone seven 240°C, zone eight 240°C ℃, zone 9 is 230℃; the screw speed of the twin-screw extruder is 500r/min.
关于本说明书中“份”，除非特别说明，表示“重量份”。"Parts" in this specification means "parts by weight" unless otherwise specified.
<测试标准>
<Test Standard>
本发明各实施例和对比例的性能测试标准如下：The performance test standards of each embodiment and comparative example of the present invention are as follows:
悬臂梁缺口冲击强度：测试标准ISO180/1eA-2010，试样尺寸为80×10×4mm，A型缺口；Izod notched impact strength: test standard ISO180/1eA-2010, sample size is 80×10×4mm, type A notch;
多轴冲击性能测试：将100mm*100mm*3mm样板在条件①105℃，老化1000h后；②150℃，500h取出，然后按ASTM D3763测试，温度-30℃，冲击速度为6.6m/s，得到最大能量值。每组试验做10个平行样板。Multi-axis impact performance test: take out the 100mm*100mm*3mm sample under conditions ①105℃, after aging for 1000h; ②150℃, 500h, and then test according to ASTM D3763, the temperature is -30℃, the impact speed is 6.6m/s, and the maximum energy is obtained value. Make 10 parallel samples for each set of experiments.
老化后的悬臂梁缺口冲击强度是将样条在150℃，老化700h进行测试得到的结果。The notched Izod impact strength after aging is the result of testing the specimen at 150°C and aging for 700h.
表1.实施例1-11配方
注：表中“-”表示未添加该组分。Table 1. Formulations of Examples 1-11
Note: “-” in the table means that the component is not added.
注：表中“-”表示未添加该组分。Table 1. Formulations of Examples 1-11
Note: “-” in the table means that the component is not added.
表2.实施例1-11的性能测试结果
Table 2. Performance test results of Examples 1-11
Table 2. Performance test results of Examples 1-11
表3.对比例1-9配方
注：表中“-”表示未添加该组分。 Table 3. Formulas of Comparative Examples 1-9
Note: “-” in the table means that the component is not added.
注：表中“-”表示未添加该组分。 Table 3. Formulas of Comparative Examples 1-9
Note: “-” in the table means that the component is not added.
表4.对比例1-9的性能测试结果
Table 4. Performance test results of Comparative Examples 1-9
Table 4. Performance test results of Comparative Examples 1-9
从表中的测试结果可看出：相比于对比例1的聚丙烯材料，使用实施例1的聚丙烯材料在老化前后均保持了韧性破坏的低温多轴冲击性能，并且实施例1的样品在经历老化条件①和②后，均保持低温多轴冲击韧性破坏，说明本发明的技术可有效减小热老化对聚丙烯材料低温多轴冲击性能的影响，提升材料性能稳定性。It can be seen from the test results in the table that compared to the polypropylene material of Comparative Example 1, the polypropylene material of Example 1 maintains the low-temperature multiaxial impact properties of ductile failure before and after aging, and the sample of Example 1 After experiencing aging conditions ① and ②, the low-temperature multi-axial impact toughness damage was maintained, indicating that the technology of the present invention can effectively reduce the impact of thermal aging on the low-temperature multi-axial impact properties of polypropylene materials and improve the stability of material performance.
对比例2-4及对比例9中，单宁和化合物X的添加量超范围，导致材料的热稳定性也不好。In Comparative Examples 2-4 and 9, the added amounts of tannin and compound X are beyond the range, resulting in poor thermal stability of the material.
对比例5和6分别只单独使用了单宁和3-羟基苯乙酸，与实施例1相比，结果发现对比例5和6老化后的冲击性能急剧下降，并且材料在老化前后的多轴冲击都是脆性破坏，说明单独使用二者之一无法起到提升材料热稳定性的效果。Comparative Examples 5 and 6 only used tannin and 3-hydroxyphenylacetic acid alone respectively. Compared with Example 1, it was found that the impact properties of Comparative Examples 5 and 6 dropped sharply after aging, and the multi-axial impact of the materials before and after aging was Both are brittle failures, indicating that using either alone cannot improve the thermal stability of the material.
采用专利CN 103665570 A的技术(对比例7)后，材料的老化前多轴冲击呈现韧性破坏，但是老化后脆性破坏，说明CN 103665570 A中的技术可实现老化前低温多轴冲击韧性，但是无法保证在老化后仍保持韧性的多轴
冲击性能。After using the technology of patent CN 103665570 A (Comparative Example 7), the material showed ductile damage before aging in multi-axial impact, but brittle failure after aging, indicating that the technology in CN 103665570 A can achieve low-temperature multi-axial impact toughness before aging, but cannot Multi-axis guaranteed to remain tough after aging Impact performance.
采用专利CN 112625348 A的技术(对比例8)后，材料的老化前后低温多轴冲击呈现脆性破坏，均无法满足多轴冲击韧性的技术要求。实施例与对比例相比，具备明显的技术先进性。After adopting the technology of patent CN 112625348 A (Comparative Example 8), the material showed brittle failure under low-temperature multi-axial impact before and after aging, and it was unable to meet the technical requirements of multi-axial impact toughness. Compared with the comparative example, the embodiment has obvious technological advancement.
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention shall be included in the protection of the present invention. within the range.
Claims (9)
- 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:
所述化合物X具有能与所述单宁生成氢键的基团。The compound X has a group capable of forming a hydrogen bond with the tannin. - 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:
- 根据权利要求1或2所述的聚丙烯组合物，其特征在于，所述化合物X含有的基团为羧基、羟基或氨基中的一种或多种。The polypropylene composition according to claim 1 or 2, characterized in that the group contained in the compound X is one or more of carboxyl group, hydroxyl group or amino group.
- 根据权利要求3所述的聚丙烯组合物，其特征在于，所述化合物X为3-羟基苯乙酸、聚丙烯酸、己内酰胺或聚乙烯醇中的至少一种。The polypropylene composition according to claim 3, wherein the compound X is at least one of 3-hydroxyphenylacetic acid, polyacrylic acid, caprolactam or polyvinyl alcohol.
- 根据权利要求1或2所述的聚丙烯组合物，其特征在于，所述聚丙烯组合物还包括0.1-30份的滑石粉。The polypropylene composition according to claim 1 or 2, characterized in that the polypropylene composition further includes 0.1-30 parts of talc powder.
- 根据权利要求1或2所述的聚丙烯组合物，其特征在于，还包括0.2-1份的助剂。 The polypropylene composition according to claim 1 or 2, further comprising 0.2-1 parts of auxiliaries.
- 根据权利要求6所述的聚丙烯组合物，其特征在于，所述助剂为润滑剂，所述润滑剂为金属皂类、硬脂酸复合酯类或胺类中的一种或多种。The polypropylene composition according to claim 6, wherein the auxiliary agent is a lubricant, and the lubricant is one or more of metal soaps, stearic acid complex esters or amines.
- 一种根据权利要求1-7任一项所述的聚丙烯组合物的制备方法，其特征在于，包括以下步骤：A method for preparing the polypropylene composition according to any one of claims 1 to 7, characterized in that it includes the following steps:S1：按照配比，称取各组分预混合后，得到预混物；S1: According to the proportion, weigh each component and premix it to obtain a premix;S2：将步骤S1的预混物投入到挤出机中，进行熔融共混并挤出造粒，得到所述聚丙烯组合物。S2: Put the premix in step S1 into an extruder, perform melt blending and extrusion granulation to obtain the polypropylene composition.
- 根据权利要求1-7任一项所述聚丙烯组合物在制备车辆制件中的应用。 Use of the polypropylene composition according to any one of claims 1 to 7 in the preparation of vehicle parts.
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| CN114621522B (en) | 2024-01-02 |
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