CN110655713A - Trans-butyl-amyl copolymer rubber toughened and modified polypropylene composition and preparation method thereof - Google Patents
Trans-butyl-amyl copolymer rubber toughened and modified polypropylene composition and preparation method thereof Download PDFInfo
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- CN110655713A CN110655713A CN201910940049.8A CN201910940049A CN110655713A CN 110655713 A CN110655713 A CN 110655713A CN 201910940049 A CN201910940049 A CN 201910940049A CN 110655713 A CN110655713 A CN 110655713A
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 74
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 70
- 229920001971 elastomer Polymers 0.000 title claims abstract description 66
- 239000005060 rubber Substances 0.000 title claims abstract description 65
- 229920001577 copolymer Polymers 0.000 title claims abstract description 54
- -1 polypropylene Polymers 0.000 title claims abstract description 54
- 239000000203 mixture Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 44
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 20
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 238000004073 vulcanization Methods 0.000 claims abstract description 15
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 7
- 239000000945 filler Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 239000003963 antioxidant agent Substances 0.000 claims description 7
- 230000003078 antioxidant effect Effects 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- 239000004033 plastic Substances 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000005452 bending Methods 0.000 claims description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 3
- 238000004132 cross linking Methods 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical group CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 239000011324 bead Substances 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000000378 calcium silicate Substances 0.000 claims description 2
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 239000002667 nucleating agent Substances 0.000 claims description 2
- 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 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 150000003009 phosphonic acids Chemical class 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- 235000013399 edible fruits Nutrition 0.000 claims 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000012745 toughening agent Substances 0.000 description 3
- 230000032683 aging Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 235000012438 extruded product Nutrition 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920006342 thermoplastic vulcanizate Polymers 0.000 description 1
- 239000004636 vulcanized rubber Substances 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/002—Methods
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/05—Polymer mixtures characterised by other features containing polymer components which can react with one another
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a trans-butyl-pentyl copolymer rubber TBIR toughening modified polypropylene PP composition and a preparation method thereof. The composition of the trans-butadiene-isoprene copolymer rubber toughened and modified polypropylene comprises the following components in parts by weight: 1-90 parts of trans-butadiene-isoprene copolymer rubber master batch, 10-99 parts of polypropylene PP, 0.1-3 parts of an anti-aging agent, 0.5-10 parts of a cross-linking agent and 0-50 parts of a filler, wherein the trans-butadiene-isoprene copolymer rubber master batch is prepared by blending the trans-butadiene-isoprene copolymer rubber and the anti-aging agent. The TBIR/PP composition is prepared by adopting a dynamic vulcanization method, and the in-situ generated graft improves the compatibility of rubber and PP, thereby improving the impact strength of polypropylene.
Description
Technical Field
The invention relates to rubber toughening modified plastic, in particular to a TBIR/PP composition prepared by dynamically vulcanizing and blending trans-butadiene-isoprene copolymer rubber TBIR and polypropylene PP and a preparation method thereof, which are used for improving the impact strength and the impact performance of polypropylene.
Background
In recent years, industries such as automobiles, electric appliances and the like in China are rapidly developed, particularly, the production and sales volume of cars and household appliances keeps a higher growth speed all the time, and China becomes a global and important consumption market of automobiles and household appliances. On the premise of ensuring safety, light weight and plastic integration are the development trend. At present, the plastic for automobiles accounts for more than 15 percent of the total amount of the plastic, the polypropylene material accounts for more than 40 percent of the total amount of the plastic for automobiles, and the total consumption amount reaches 50 ten thousand tons. Wherein more than 80 percent of the polypropylene material is suitable for producing the automobile bumper, and can achieve the effects of reducing cost, being easy to lighten, being recyclable and the like. The polypropylene has the characteristics of low density, low price, good strength, good processing performance and the like compared with metal, but also has the defects of poor low-temperature impact resistance, large molding shrinkage, easy aging, poor heat resistance, poor aging resistance and the like.
Due to the defects of polypropylene, modification is often adopted to improve the service performance of polypropylene materials in the fields of automobiles, household appliances and the like. CN 102649854 discloses a polypropylene composition and a preparation method thereof, wherein high-flow high-impact copolymerized polypropylene is added into polypropylene resin, so that the polypropylene composition with good rigidity-toughness balance and coating performance is obtained. CN 102558736 discloses a polypropylene blending material which can be used in an automobile instrument panel, POE is adopted as a toughening agent, the impact resistance of a polypropylene matrix is improved, and in order to solve the compatibility between POE elastomer and polypropylene, 2-10 parts of polybutene is added as a compatilizer to improve the appearance of an extruded product. The polypropylene blending materials for the automobile bumpers disclosed in CN 102924807 and CN 101759923, wherein different types of toughening agents and polar polymers and inorganic fillers with larger filling amount are added as toughening modifiers and filling reinforcing agents. The common toughening agents are mostly amorphous materials, and can cause adverse effects on the tensile property and the bending property while improving the impact property of PP.
The high trans structure (more than 90 percent) and the multi-block structure of the high trans-1, 4-butadiene-isoprene copolymer rubber (TBIR) endow the rubber with certain crystallization capacity at room temperature. The closely and regularly arranged TBIR crystal regions can possibly endow the rubber material with excellent mechanical properties, particularly under the action of external force. Dynamic vulcanization techniques can produce thermoplastic vulcanizates in which the rubber phase exists in a crosslinked form as a three-dimensional network. The TBIR contains a certain double bond, and when polypropylene is blended with the TBIR, the double bond of the TBIR can carry out self-crosslinking and co-crosslinking with PP or generate a certain graft copolymer, so that a dynamic vulcanized rubber product with excellent impact resistance can be prepared.
Disclosure of Invention
The first purpose of the invention is to provide a composition of trans-butadiene-isoprene copolymer rubber toughened and modified polypropylene.
The second purpose of the invention is to provide a preparation method and a preparation process of the composition by dynamic vulcanization.
The third purpose of the invention is that the performance of the composition, especially the composition prepared by adopting the dynamic vulcanization process, improves the impact strength of the polypropylene on the premise that the tensile strength and the bending strength are basically unchanged.
The composition of the trans-butadiene-isoprene copolymer rubber toughened and modified polypropylene is characterized by being prepared from a trans-butadiene-isoprene copolymer rubber master batch and polypropylene according to the following formula (in parts by weight):
1-90 parts by weight of trans-butadiene-isoprene copolymer rubber master batch
10-99 parts by weight of polypropylene
0.1 to 3 parts by weight of an antioxidant
0.5 to 10 parts by weight of a crosslinking agent
0 to 50 parts by weight of a filler.
In the components of the composition, the trans-butadiene-isoprene copolymer rubber master batch is obtained by blending the trans-butadiene-isoprene copolymer rubber and an anti-aging agent in a mechanical blending or chemical blending mode.
In the TBIR/PP composition, the trans-butadiene-isoprene copolymer rubber has a butadiene unit molar content of 10-60%, an isoprene unit molar content of 90-40%, a trans-1, 4-structure molar content of more than 85%, and a Mooney viscosity of 20-120 in 3+4 minutes at 100 ℃. In the trans-butadiene-isoprene copolymer rubber/polypropylene composition, the polypropylene can be homo-polypropylene, co-polypropylene and impact-resistant polypropylene with different melt indexes, and the melt index of the polypropylene is 0.01-50 g/10min when the polypropylene is tested at 230 ℃ under 2.16 Kg.
In the trans-butadiene-isoprene copolymer rubber/polypropylene composition, trans-butadiene-isoprene copolymer rubber master batch is prepared by blending trans-butadiene-isoprene copolymer rubber and part of an anti-aging agent. The anti-aging agent is used for preventing one or more of RD, D, 4010NA, H, DPD, 264 and MB, and is used in a compounding way, and the dosage of the anti-aging agent is 0.1-5% of the weight percentage of the trans-butadiene-isoprene copolymer rubber in the masterbatch. The blending mode of the trans-butadiene-isoprene copolymer rubber master batch is as follows: and (3) putting the trans-butadiene-isoprene copolymer rubber into an internal mixer or an open mill, setting the temperature to be 20-80 ℃, adding the anti-aging agent after 0.1-5 min, mixing for 1-10 min, and discharging.
In the preparation of the trans-butadiene-isoprene copolymer rubber/polypropylene composition, the filler is one or more of carbon black, white carbon black, calcium carbonate, mica, talcum powder, diatomite, kaolin, calcium silicate, titanium oxide, aluminum hydroxide, glass beads, wood powder and shell powder; the anti-aging agent is one or more of anti-RD, anti-D, 4010NA, anti-H, anti-DPD, 264, anti-MB, antioxidant 1010, antioxidant 1035, antioxidant 1076, antioxidant 168 and antioxidant 626; the cross-linking agent is insoluble sulfur, soluble sulfur, polymer sulfur and peroxide.
In the preparation of the trans-butadiene-isoprene copolymer rubber/polypropylene composition, the nucleating agent is organic phosphonic acids, aryl carboxylates, sorbitol, branched amides or a mixture of two or more of the two.
The trans-butadiene-isoprene copolymer rubber/polypropylene composition is prepared by adopting a dynamic vulcanization mode according to the following steps:
1) after the blending equipment reaches the mixing temperature, sequentially feeding the polypropylene and the anti-aging agent into the blending equipment, and mixing for 1-10 minutes;
2) at any time point of 1-10 minutes of mixing in the step 1), putting the trans-butadiene-isoprene copolymer rubber masterbatch, the cross-linking agent and the filler into a blending device in sequence, mixing for 1-15 minutes, and blending and vulcanizing;
3) discharging at any time point of mixing for 1-15 minutes in the step 2) to obtain the dynamically vulcanized and crosslinked trans-butadiene-isoprene copolymer rubber toughened polypropylene composition.
In the dynamic vulcanization process, an internal mixer or an open mill or a single screw extruder or a twin screw extruder can be used for processing. In the processing process, the adopted mixing temperature is 150-230 ℃, and the mixing rotating speed is 20-70 r/min.
The trans-butadiene-isoprene copolymer rubber/polypropylene composition prepared by the dynamic vulcanization method is characterized in that the vulcanization process is carried out when the trans-butadiene-isoprene copolymer rubber master batch enables rubber to be crosslinked, and the co-vulcanization is carried out between the polypropylene and the trans-butadiene-isoprene copolymer rubber to generate polypropylene grafted trans-butadiene-isoprene copolymer rubber, so that the size of a rubber phase is greatly reduced, and the compatibility between the rubber and the polypropylene is improved.
The trans-butadiene-isoprene copolymer rubber prepared by the preparation method is blended with polypropylene in a dynamic vulcanization mode, and the impact strength of the polypropylene is improved on the premise that the tensile strength and the bending strength of the composition are basically unchanged.
Detailed Description
The following examples are intended to better illustrate the invention but are not intended to limit the claims of the invention.
Polypropylene (PP) as powder, homopolymerizationPolypropylene having a weight-average relative molecular weight (Mw) of 7.2X 105Melt Flow Rate (MFR) of 1.70g/10min (230 ℃, 2.16kg), isotacticity of 96.9%, Ma-Mi-Hua Ltd, Guangdong province. Trans-1, 4-butadiene-isoprene copolymer rubber (TBIR), butadiene molar content 20.1%, Mooney viscosity ML3+4 100℃73.4, weight average molecular weight Mw 6.40 × 105Molecular weight dispersion index Mw/Mn of 3.1, santong hua polymer materials ltd.
Examples 1 to 5
The materials were weighed according to the components and formulations provided in table 1 (in weight percent, the following examples are the same).
Preparing a trans-butadiene-isoprene copolymer rubber master batch: the trans-butadiene-isoprene copolymer rubber TBIR and the antioxidant are added into a Hapu mixer to prepare the TBIR master batch, so that the TBIR is prevented from being degraded when being blended with PP at high temperature. Setting the banburying temperature of the banbury mixer to be 70 ℃ and the rotating speed to be 70 r/min, banburying TBIR rubber for 2 min, adding an anti-aging agent, and continuing banburying for 5 min.
Preparing a trans-butadiene-isoprene copolymer rubber/polypropylene composition by dynamic vulcanization:
1) setting an internal mixer at 170 ℃, and after the mixing temperature is reached, sequentially feeding polypropylene and an anti-aging agent into blending equipment for mixing for 3 minutes;
2) sequentially putting the trans-butadiene-isoprene copolymer rubber master batch, the cross-linking agent and the filler into blending equipment, mixing for 8 minutes, and blending and vulcanizing;
3) discharging to obtain the composition of the dynamically vulcanized and crosslinked trans-butadiene-isoprene copolymer rubber toughened polypropylene.
The results of the performance tests are shown in Table 1.
Comparative example 1
The formulation is shown in Table 1, and the performance test results are shown in Table 1.
As can be seen from Table 1, after the TBIR/PP blending system is dynamically vulcanized, the fracture elongation of the blend is improved under the condition that the tensile strength is not reduced much, and after the TBIR part reaches 20, the impact strength is improved by nearly 20 times compared with pure PP, so that a quite good toughening effect is obtained.
TABLE 1 Components and formulations of examples 1-4 and comparative example 1
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | |
| Polypropylene | 95 | 90 | 85 | 80 | 75 | 100 |
| TBIR | 5 | 10 | 15 | 20 | 25 | 0 |
| Antiager RD | 0.01 | 0.02 | 0.03 | 0.04 | 0.05 | 0 |
| Anti-aging agent 4010 | 0.01 | 0.02 | 0.03 | 0.04 | 0.05 | 0 |
| Antioxidant 1010 | 0.1 | 0.1 | 0.09 | 0.08 | 0.08 | 0.1 |
| Antioxidant 626 | 0.2 | 0.2 | 0.18 | 0.17 | 0.17 | 0.2 |
| Sulfur | 1 | 1 | 1 | 1 | 1 | 0 |
| Carbon black | 0 | 0 | 5 | 5 | 0 | 0 |
| Tensile strength/MPa | 30 | 35 | 30 | 25 | 25 | 31 |
| Flexural Strength/MPa | 30 | 25 | 21 | 21 | 19 | 35 |
| Impact Strength/kJ/m2 | 7 | 9 | 18 | 51 | 53 | 2.5 |
| Compatibility (poor Tg) | - | 42 | 59 | 66 | - | 90 |
Claims (10)
1. The composition of the trans-butadiene-isoprene copolymer rubber toughened polypropylene is characterized by being prepared from a trans-butadiene-isoprene copolymer rubber master batch and polypropylene by adopting a dynamic vulcanization blending mode according to the following formula:
the trans-butadiene-isoprene copolymer rubber master batch is prepared by blending trans-butadiene-isoprene copolymer rubber and an anti-aging agent.
2. The trans-butadiene-isoprene copolymer rubber masterbatch according to claim 1, wherein the trans-butadiene copolymer rubber has a butadiene unit molar content of 10% to 60%, an isoprene unit molar content of 90% to 40%, a trans-1, 4-structure molar content of more than 85%, and a Mooney viscosity of 20 to 120 at 100 ℃ for 3+4 minutes.
3. The trans-butadiene-isoprene copolymer rubber masterbatch of claim 1, wherein the anti-aging agent is one or more of anti-RD, anti-D, 4010NA, anti-H, anti-DPD, 264 and anti-MB, and the amount of the anti-aging agent is 0.1-5% by weight of the trans-butadiene-isoprene copolymer rubber in the masterbatch.
4. The trans-butadiene-isoprene copolymer rubber master batch according to claim 1, wherein said blending manner is: and (3) putting the trans-butadiene-isoprene copolymer rubber into an internal mixer or an open mill, setting the temperature to be 20-80 ℃, adding the anti-aging agent after 0.1-5 min, mixing for 1-10 min, and discharging.
5. The composition according to claim 1, wherein the polypropylene is homo-polypropylene or co-polypropylene, and the melt index of the polypropylene is 0.01-50 g/10min when measured at 230 ℃ and 2.16 Kg.
6. The composition according to claim 1, wherein the filler is one or more of carbon black, white carbon black, calcium carbonate, mica, talcum powder, diatomite, kaolin, calcium silicate, titanium oxide, aluminum hydroxide, glass beads, wood powder and fruit shell powder; the anti-aging agent is one or more of anti-RD, anti-D, 4010NA, anti-H, anti-DPD, 264, anti-MB, antioxidant 1010, antioxidant 1035, antioxidant 1076, antioxidant 168 and antioxidant 626; the cross-linking agent is insoluble sulfur, soluble sulfur, polymer sulfur and peroxide; the nucleating agent is organic phosphonic acids, aryl carboxylate, sorbitol, branched amide or a mixture of two or more than two.
7. A preparation method of a trans-butadiene-isoprene copolymer rubber toughened polypropylene composition is characterized by comprising the following dynamic vulcanization steps:
1) after the blending equipment reaches the mixing temperature, sequentially feeding the polypropylene and the anti-aging agent into the blending equipment, and mixing for 1-10 minutes;
2) at any time point of 1-10 minutes of mixing in the step 1), putting the trans-butadiene-isoprene copolymer rubber masterbatch, the cross-linking agent and the filler into a blending device in sequence, mixing for 1-15 minutes, and blending and vulcanizing;
3) discharging at any time point of mixing for 1-15 minutes in the step 2) to obtain the dynamically vulcanized and crosslinked trans-butadiene-isoprene copolymer rubber toughened polypropylene composition.
8. The method according to claim 7, wherein the blending device is an internal mixer or an open mill or a screw extruder; the mixing temperature is 150-230 ℃, and the mixing speed is 20-70 r/min.
9. The method of claim 7, wherein the trans-butadiene-isoprene copolymer rubber undergoes a crosslinking reaction and a grafting reaction with polypropylene during the dynamic vulcanization, the size of the rubber phase is greatly reduced, and the compatibility between the rubber phase and the plastic phase is improved.
10. The composition of claim 1, wherein the trans-butadiene-isoprene copolymer rubber is blended with the polypropylene by means of dynamic vulcanization, and the impact strength of the composition is significantly improved compared with that of the polypropylene on the premise of keeping the tensile strength and the bending strength basically unchanged.
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Non-Patent Citations (3)
| Title |
|---|
| ZHAOBO SUN 等: "In situ reactive compatibilization of polypropylene/trans-1,4-poly(isoprene-co-butadiene) rubber (TBIR) blends with balanced toughness and stiffness via dynamic vulcanization", 《REACTIVE AND FUNCTIONAL POLYMERS》 * |
| 孙照博 等: "动态硫化制备结晶性反式丁戊共聚橡胶增韧聚丙烯", 《第十四届中国橡胶基础研究研讨会会议摘要集》 * |
| 孙照博: "PP/TBIR共混物的结构与性能", 《青岛科技大学硕士学位论文》 * |
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