CN103589069A - High-shock resistance polypropylene/polybutylene composite material as well as preparation method and purposes thereof - Google Patents
High-shock resistance polypropylene/polybutylene composite material as well as preparation method and purposes thereof Download PDFInfo
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- CN103589069A CN103589069A CN201310608858.1A CN201310608858A CN103589069A CN 103589069 A CN103589069 A CN 103589069A CN 201310608858 A CN201310608858 A CN 201310608858A CN 103589069 A CN103589069 A CN 103589069A
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- polypropylene
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- -1 polypropylene Polymers 0.000 title claims abstract description 77
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 72
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 72
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 229920001748 polybutylene Polymers 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 239000011347 resin Substances 0.000 claims abstract description 19
- 229920005989 resin Polymers 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 230000035939 shock Effects 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000012545 processing Methods 0.000 claims abstract description 6
- 229920001083 polybutene Polymers 0.000 claims description 42
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- 239000012764 mineral filler Substances 0.000 claims description 10
- 229920000178 Acrylic resin Polymers 0.000 claims description 9
- 239000004925 Acrylic resin Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 6
- 229940040145 liniment Drugs 0.000 claims description 6
- 239000000865 liniment Substances 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 238000005453 pelletization Methods 0.000 claims description 6
- 235000019260 propionic acid Nutrition 0.000 claims description 6
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- 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 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 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 4
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 claims description 4
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 claims description 4
- 150000003009 phosphonic acids Chemical class 0.000 claims description 4
- 239000000600 sorbitol Substances 0.000 claims description 4
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 4
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 3
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 claims description 2
- OGSPWJRAVKPPFI-UHFFFAOYSA-N Alendronic Acid Chemical compound NCCCC(O)(P(O)(O)=O)P(O)(O)=O OGSPWJRAVKPPFI-UHFFFAOYSA-N 0.000 claims description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 2
- GQJDFTIOKVGUOF-UHFFFAOYSA-N OP(O)OP(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)C(CO)(CO)CO Chemical class OP(O)OP(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)C(CO)(CO)CO GQJDFTIOKVGUOF-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229940062527 alendronate Drugs 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- CZWLNMOIEMTDJY-UHFFFAOYSA-N hexyl(trimethoxy)silane Chemical compound CCCCCC[Si](OC)(OC)OC CZWLNMOIEMTDJY-UHFFFAOYSA-N 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 239000010687 lubricating oil Substances 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- KWUZCAVKPCRJPO-UHFFFAOYSA-N n-ethyl-4-(6-methyl-1,3-benzothiazol-2-yl)aniline Chemical compound C1=CC(NCC)=CC=C1C1=NC2=CC=C(C)C=C2S1 KWUZCAVKPCRJPO-UHFFFAOYSA-N 0.000 claims description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N n-octadecyl alcohol Natural products CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 2
- 229950002083 octabenzone Drugs 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 229960001866 silicon dioxide Drugs 0.000 claims description 2
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 claims description 2
- 239000004711 α-olefin Substances 0.000 claims description 2
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 claims 3
- 238000002844 melting Methods 0.000 claims 1
- 230000008018 melting Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 25
- 239000004033 plastic Substances 0.000 abstract description 20
- 229920003023 plastic Polymers 0.000 abstract description 20
- 239000003963 antioxidant agent Substances 0.000 abstract description 2
- 230000003078 antioxidant effect Effects 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract description 2
- 239000004595 color masterbatch Substances 0.000 abstract 1
- 238000001125 extrusion Methods 0.000 abstract 1
- 239000011256 inorganic filler Substances 0.000 abstract 1
- 229910003475 inorganic filler Inorganic materials 0.000 abstract 1
- 239000004611 light stabiliser Substances 0.000 abstract 1
- 239000002667 nucleating agent Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000005311 nuclear magnetism Effects 0.000 description 5
- 230000032683 aging Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 229920002725 thermoplastic elastomer Polymers 0.000 description 3
- 238000011068 loading method Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 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 description 2
- 238000005457 optimization Methods 0.000 description 2
- 229920006112 polar polymer Polymers 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-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
- 150000001408 amides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect 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
- 230000006353 environmental stress Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009966 trimming 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
- C08L23/12—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
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92514—Pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a high-shock resistance polypropylene/polybutylene composite material as well as a preparation method and purposes thereof, and belongs to the field of high molecular materials. Matrix resins of the composite material consist of 99-50 wt% of polypropylene resins and 1-50 wt% of polybutylene resins, and are added with inorganic fillers, antioxidant, light stabilizer, scrape resistant assistant, color masterbatch and nucleating agent. The composite material is prepared by adopting a two-screw extruder through an extrusion mixing method. The prepared high-shock resistance polypropylene/polybutylene composite material has prominent shock resistance and excellent rigidity and processing performance, and is suitable for automobile plastics, trays, electric wires, cables and electric appliance shells.
Description
Technical field
The present invention relates to a kind of high impact resistance polypropylene/polybutylene composite material and its production and use, belong to polymeric material field.
Background technology
The volume of production and marketing of the industrial boom, particularly car such as the automobile of China, electrical equipment and household electrical appliances keeps higher increase speed always in recent years, and China has become the very important automobile in the whole world and the consumption market of household electrical appliances.Under safety assurance prerequisite, lightweight and plastics are integrated is development trend.Automotive plastic accounts for the more than 15% of plastics total amount at present, and polypropylene material accounts for the more than 40% of auto plastics, and total flow has reached 500,000 tons.Wherein more than 80% polypropylene material is applicable to produce bumper, can play and reduce costs, is easy to lightweight, recycling capable of circulation etc.In household electric appliances, quantity of plastics accounts for more than 40%, and product plastic has become one of household electric appliances important development direction, and plastics have become the fastest material of field of household appliances application quantity rate of growth.Polypropylene has that raw material sources are abundant, synthesis technique simple and modernization scale operation, density is low compared with metal, price is low, have the features such as good intensity, good processability, but also have that low-temperature impact-resistant performance is not good, molding shrinkage greatly, easily aging, thermotolerance and the shortcoming such as ageing resistance is poor.
Above-mentioned defect due to polypropylene existence, at automobile and field of household appliances, by the method that often adopts modification, improve the use properties of polypropylene material, at present Co-polypropylene or the impact polypropylenes of adopting as the base material of modification more: SP179 is the trade mark of middle mobility super high impact strength Co-polypropylene, there is higher impact property and good processing characteristics, it is preferred material (the modern plastics processed and applied of bumper, 2006,18 (4): 11-14).CN 102649854 has announced a kind of polypropene composition and preparation method thereof, adopts the high High Impact Polypropylene that flows to add in acrylic resin, thereby has obtained the polypropene composition with good rigidity-toughness balanced and coating performance.CN 102558736 has announced a kind of polypropene blended material that can use in automobile instrument panel, adopted POE as toughner, improve the shock resistance of polypropylene matrix, and in order to solve the consistency between POE elastomerics and polypropylene, add 2～10 parts of polybutene as compatilizer, to improve the exterior appearance of extrudate.The polypropene blended material of bumper materials that CN 102924807 and CN 101759923 announce, wherein all needs to add the mineral filler of different types of toughner and polar polymer and larger loading level as plasticized modifier and packing strengthening agent.Household electric appliances use at present maximum be HIPS and ABS as plastic casing, for improving rigidity, toughness, the surface quality of material and reducing costs, conventionally adopt mineral filler and elastomerics etc. to carry out modification.And no matter be automotive plastic material or household electric appliances at present, development trend integrated, simplification is desired is the use kind that as far as possible reduces plastics, and reduces the auxiliary agent of various different in kinds and the kind of mineral filler and consumption in plastics.Greatly the mineral filler meeting of loading level has influence on plastics recovery and recycling.
Polybutene is that butene monomers obtains through polycoordination, different according to its degree of isotacticity, can be used as high-intensity plastics, thermoplastic elastomer and elastomer material and uses.Polybutene material has outstanding creep resistant, shock resistance and environmental stress crack resistance, and especially its excellent shock resistance can be used in automobile bumper material.Studies have reported that polypropylene and polybutene thermoplastic elastomer blending system study discovery, increase along with polybutene thermoplastic elastomer consumption, the elongation at break of co-mixing system and shock strength all obviously improve (Chinese Plastics, 2004,18 (7): 28; Plastics, 2006,35 (3): 13).
Summary of the invention
For the problem of the above-mentioned current automobile of mentioning and plastics for home appliances existence, one of object of the present invention is to provide a kind of light weight, easy processing, excellent performance, is easy to the polypropylene/polybutylene composite material of recycling.
The low-temperature impact-resistant performance that exists for acrylic resin is not good, molding shrinkage greatly, easily aging, thermotolerance and the shortcoming such as ageing resistance is poor, two of object of the present invention is to provide formula and the preparation method with the good polypropylene/polybutylene composite material of outstanding shock resistance, consistency and dimensional stability.
The formula of high impact resistance polypropylene/polybutylene composite material of the present invention (mass fraction, the total mass umber of acrylic resin and polybutene resin is 100 parts):
99～50 parts of acrylic resins
1～50 part of polybutene resin
0～30 part of mineral filler
0.1～3 part, oxidation inhibitor
0.1～2 part of photostabilizer
0～5 part of scrape resistant auxiliary agent
0.1～3 part of colour batch
0.1～5 part of nucleator
Described acrylic resin be a kind of in homo-polypropylene, Co-polypropylene or anti-impact type polypropylene or and several mixing, resin is 230 ℃ in temperature, load for the melt flow rate (MFR) of testing under 2.16kg condition be 0.1～50g/10min.
To be chevron or butylene mix with one or both in the alpha-olefin copolymer of 2～8 carbon atoms except butylene described polybutene resin, resin is 190 ℃ in temperature, load for the melt flow rate (MFR) of testing under 2.16kg condition be 0.01～50g/10min; Nuclear-magnetism test degree of isotacticity mmmm=50～95%, preferably 75～95%.Described polybutene resin add toughness and the dimensional stability that can improve acrylic resin, improve processing characteristics.
Described oxidation inhibitor is Hinered phenols, phosphite ester kind antioxidant, hindered amines or both and mixing above.Include but not limited to four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, β-(3, 5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid, thio-2 acid 2 stearyl ester, three [2.4-di-tert-butyl-phenyl] phosphorous acid ester, two (2, 4-di-tert-butyl-phenyl) pentaerythritol diphosphites, Octabenzone, 2-(the 2'-hydroxyl-3'-tertiary butyl-5'-aminomethyl phenyl)-5-chlorinated benzotriazole, two (2, 2, 6, 6-tetramethyl--4-piperidyl) sebate, preferred four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (1010) and three [2.4-di-tert-butyl-phenyl] phosphorous acid ester (168).
Described nucleator is aryl carboxylic acid salt, glucitols, branching amides or two kinds and two or more mixing.Include but not limited to dibenzal sorbitol, two (p-methyl benzal) sorbyl alcohol, 2,2 '-methylene-bis (4,6-t-butyl phenol) phosphonic acids aluminium, 2,2 '-methylene-bis (4,6-t-butyl phenol) Alendronate, 2,2 '-methylene-bis (4,6-t-butyl phenol) phosphonic acids potassium, diamide compound and derivative thereof, preferred dibenzal sorbitol (DBS), the consumption of nucleator is the 0.1-5wt.% of polypropylene and the total consumption of polybutene resin, preferably 0.2-2wt.%.
Described high impact resistance polypropylene/polybutylene composite material, it is characterized in that, described mineral filler is one or more mixing in calcium carbonate, talcum powder, mica, magnesium hydroxide, silicon-dioxide, polynite, consumption is the 0-30wt.% of polypropylene and the total consumption of polybutene resin, wherein preferred 5-15wt.%.
Described photostabilizer is one or more mixing in benzophenone and hindered amines, preferably hindered amine 783 photostabilizers; Scratch resistance liniment is one or more mixing in ethyl trimethoxy silane oligopolymer, hexyl trimethoxysilane oligomer, ethyl triethoxysilane oligopolymer, vinyltriethoxysilane oligopolymer, hydro carbons lubricating oil and talcum powder, preferably ethyl trimethoxy silane oligopolymer (TMA).Consumption is respectively 0.1-2wt.% and the 0-5wt.% of polypropylene and the total consumption of polybutene resin.
Described look mother is that polypropylene special color is female.
The preparation method of polybutene for bumper/polypropene blended material of the present invention comprises the following steps:
(1) polybutene, polypropylene, mineral filler, oxidation inhibitor, photostabilizer, scrape resistant auxiliary agent, colour batch and nucleator are prepared burden according to described ratio, and mix at homogenizer;
(2) material mixing step (1) being obtained, by twin screw extruder extrude, granulation.
The length-to-diameter ratio 30-50:1 of described twin screw extruder.
Described extruding and pelletizing process is: 220～230 ℃, 180～200 200～215 210～225 ℃， 4th district, ℃， 3rd district, ℃， 2nd district, a district, 230 ℃ of heads, melt pressure 10-18MPa.
Polybutene/polypropylene composite material prepared by the present invention, there is outstanding shock resistance, good consistency, dimensional stability and processibility, do not add and appoint polar polymer, be applicable to automobile exterior trimming parts and inside gadget, as dashboard, supervisory control desk, door-plate, collision bumper, side shield panel, threshold etc. and pallet, electric wire, electric appliance casing etc.
Embodiment
Following examples are in order to explain better the present invention, but, be not the restriction to the claims in the present invention book.
Tensile yield strength is tested according to GB/T1040-2006, adopts I type dumbbell shape sample, 23 ℃ of probe temperatures; Melt flow rate (MFR) (MFR) is according to the standard testing of GB/T3682-2000; Modulus in flexure is tested according to GB/T9341-2008, and probe temperature is 23 ℃; Room temperature Izod notched Izod impact strength is according to GB/T1843-2008 standard testing, A type breach, pendulum 2.75J; Vicat softening temperature is according to GB/T1633-2000 standard testing, load 50N, 50 ℃/min of heat-up rate; Shrinking percentage is according to GB15585-1995 standard testing.
Embodiment 1～3
The component providing by table 1 and formula are (according to weight percent meter, following examples all with) material of weighing, in homogenizer, mix after 5 minutes, in the twin screw extruder of length-to-diameter ratio 45, diameter 50, extruding pelletization obtains polybutene/polypropylene composite material.Polybutene used is homopolymerization polybutene, the degree of isotacticity mmmm=90% of nuclear-magnetism test, and its melt flow rate (MFR) (190 ℃, load 2.16kg) is 5.5g/10min; Polypropylene is impact polypropylene 8003, degree of isotacticity 92%, and its melt flow rate (MFR) (230 ℃, load 2.16kg) is 13g/10min, modulus in flexure 1250MPa, shock strength 60J/M.Each interval temperature of forcing machine is: 230 ℃, 180 200 200 ℃， 4th district, ℃， 3rd district, ℃， 2nd district, a district, 230 ℃ of heads, melt pressure 17MPa.
The performance test results is in Table 2.
The component of table 1 embodiment 1～3 and comparative example 1 and formula
| Component (parts by weight) | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 |
| Polypropylene | 80 | 70 | 99 | 100 |
| Polybutene | 20 | 30 | 1 | 0 |
| Nucleator DBS | 1.5 | 1.5 | 1.5 | 1.5 |
| Antioxidant 1010 | 0.1 | 0.1 | 0.1 | 0.1 |
| Irgasfos 168 | 0.2 | 0.2 | 0.2 | 0.2 |
| Calcium carbonate | 25 | 25 | 25 | 25 |
| Photostabilizer 783 | 0.8 | 0.8 | 0.8 | 0.8 |
| Scratch resistance liniment TMA | 2 | 2 | 2 | 2 |
| The female zzcy of polypropylene special color | 2 | 2 | ? | 2 |
The performance of table 2 embodiment 1～3 and comparative example 1
Comparative example 1
The component providing by table 1 and formula (according to weight percent meter, following examples all with) material of weighing mixed after 5 minutes in homogenizer, and in twin screw extruder length-to-diameter ratio 45, diameter 50, extruding pelletization obtains polypropylene material.Except not using polybutene, all the other parameters and processing conditions are with embodiment 1.
From the test result of comparative example and embodiment, can find out, by suitable proportioning and the fabrication process condition of optimization, can prepare the polypropylene/polybutylene composite material with bumper performance requriements.In modulus in flexure, substantially change under little prerequisite, room temperature socle girder notched Izod impact strength has increased more than 5 times than virgin pp, and impact property improves greatly.
Embodiment 4～6
The component providing by table 3 and formula are (according to weight percent meter, following examples all with) material of weighing, in homogenizer, mix after 5 minutes, in twin screw extruder length-to-diameter ratio 45, diameter 50, extruding pelletization obtains polybutene/polypropylene composite material.Polybutene used is the degree of isotacticity mmmm=78% homopolymerization polybutene of nuclear-magnetism test, and its melt flow rate (MFR) (190 ℃, load 2.16kg) is 0.8g/10min; Polypropylene is homo-polypropylene, and its melt flow rate (MFR) (230 ℃, load 2.16kg) is 20g/10min, modulus in flexure 1.4GPa, shock strength 30J/M.Each interval temperature of forcing machine is: 230 ℃, 180 200 200 ℃， 4th district, ℃， 3rd district, ℃， 2nd district, a district, 230 ℃ of heads, melt pressure 17MPa.
The performance test results is in Table 4.
From table 4 test result, can find out, by suitable proportioning and the fabrication process condition of optimization, can prepare the polypropylene/polybutylene composite material that meets automobile and plastics for home appliances requirement.By changing the consumption of nucleator, room temperature socle girder notched Izod impact strength and the modulus in flexure of its polypropylene/polybutylene composite material all can reach the index of bumper materials.Toughness is better than virgin pp.
The component of table 3 embodiment 4～6 and formula
| Component | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Polybutene | 27 | 5 | 30 |
| Polypropylene | 73 | 95 | 70 |
| Nucleator DBS | 0 | 1 | 2 |
| Antioxidant 1076 | 0.1 | 0.1 | 0.1 |
| Irgasfos 168 | 0.2 | 0.2 | 0.2 |
| Calcium carbonate | 25 | 25 | 25 |
| Photostabilizer 783 | 0.8 | 0.8 | 0.8 |
| Scratch resistance liniment TMA | 2 | 2 | 2 |
| The female zzcy of polypropylene special color | 2 | 2 | 2 |
The performance of table 4 embodiment 4～6
Embodiment 7～8
The component providing by table 5 and formula are (according to weight percent meter, following examples all with) material of weighing, in homogenizer, mix after 5 minutes, in twin screw extruder length-to-diameter ratio 45, diameter 50, extruding pelletization obtains polybutene/polypropylene composite material.Polybutene a used is the homopolymerization polybutene of nuclear-magnetism test degree of isotacticity mmmm=91%, and its melt flow rate (MFR) (190 ℃, load 2.16kg) is 0.8g/10min; Polybutene b is the homopolymerization polybutene of nuclear-magnetism test degree of isotacticity mmmm=63%, and its melt flow rate (MFR) (190 ℃, load 2.16kg) is 0.8g/10min; Polypropylene is Co-polypropylene EPF30R, and its melt flow rate (MFR) (230 ℃, load 2.16kg) is 15g/10min.Each interval temperature of forcing machine is: 230 ℃, 180 200 200 ℃， 4th district, ℃， 3rd district, ℃， 2nd district, a district, 230 ℃ of heads, melt pressure 17MPa.
The performance test results is in Table 6.
From table 6 test result, can find out, adopt polybutene shock strength when keeping the original high modulus in flexure of polypropylene of high isotactic to increase substantially.And adopt the prepared intermingling material shock strength of low grade polybutene excellent, but modulus in flexure reduction is more.The toughness of the polypropylene composite material of two kinds of polybutene modifications is all better than pure Co-polypropylene.Can meet in automobile, pallet, plastics for home appliances occasion and use.
The component of table 5 embodiment 7～8 and formula
| Component | Embodiment 7 | Embodiment 8 |
| Polybutene a | 20 | 0 |
| Polybutene b | 0 | 20 |
| Polypropylene | 80 | 80 |
| Nucleator DBS | 1 | 1 |
| Antioxidant 1076 | 0.1 | 0.1 |
| Irgasfos 168 | 0.2 | 0.2 |
| Calcium carbonate | 25 | 25 |
| Photostabilizer 783 | 0.8 | 0.8 |
| Scratch resistance liniment TMA | 2 | 2 |
| The female zzcy of polypropylene special color | 2 | 2 |
The performance of table 6 embodiment 7～8
Claims (9)
1. high impact resistance polypropylene/polybutylene composite material, is characterized in that, by following raw material, forms (in parts by weight, wherein the total mass umber of acrylic resin and polybutene resin is 100 parts):
99～50 parts of acrylic resins
1～50 part of polybutene resin
0～30 part of mineral filler
0.1～3 part, oxidation inhibitor
0.1～2 part of photostabilizer
0～5 part of scrape resistant auxiliary agent
0.1～3 part of colour batch
0.1～5 part of nucleator.
2. high impact resistance polypropylene/polybutylene composite material claimed in claim 1, it is characterized in that, to be chevron or butylene mix with one or both in the alpha-olefin copolymer of 2～8 carbon atoms except butylene described polybutene resin, (190 ℃ of melt flow rate (MFR)s, load 2.16kg) 0.01～50g/10min, the polybutene resin degree of isotacticity mmmm% being recorded by nucleus magnetic resonance is 50～95%, preferably 75～95%.
3. high impact resistance polypropylene/polybutylene composite material claimed in claim 1, it is characterized in that, described acrylic resin is one or more mixing of homo-polypropylene, Co-polypropylene or impact polypropylene, its melt flow rate (MFR) (230 ℃, load 2.16kg) 0.1～50g/10min.
4. high impact resistance polypropylene/polybutylene composite material claimed in claim 1, it is characterized in that, described oxidation inhibitor is four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, β-(3, 5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid, thio-2 acid 2 stearyl ester, three [2.4-di-tert-butyl-phenyl] phosphorous acid ester, two (2, 4-di-tert-butyl-phenyl) pentaerythritol diphosphites, Octabenzone, 2-(the 2'-hydroxyl-3'-tertiary butyl-5'-aminomethyl phenyl)-5-chlorinated benzotriazole, two (2, 2, 6, 6-tetramethyl--4-piperidyl) one or more mixing in sebate, preferred four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and three [2.4-di-tert-butyl-phenyl] phosphorous acid ester.
5. high impact resistance polypropylene/polybutylene composite material claimed in claim 1, it is characterized in that, described mineral filler is one or more mixing in calcium carbonate, talcum powder, mica, magnesium hydroxide, silicon-dioxide, polynite, consumption is the 0-30wt.% of polypropylene and the total consumption of polybutene resin, wherein preferred 5-15wt.%.
6. high impact resistance polypropylene/polybutylene composite material claimed in claim 1, it is characterized in that, described nucleator is dibenzal sorbitol, two (p-methyl benzal) sorbyl alcohol, 2, 2 '-methylene-bis (4, 6-t-butyl phenol) phosphonic acids aluminium, 2, 2 '-methylene-bis (4, 6-t-butyl phenol) Alendronate, 2, 2 '-methylene-bis (4, 6-t-butyl phenol) phosphonic acids potassium, one or both in diamide compound and derivative thereof and two or more mixing, preferred dibenzal sorbitol (DBS), the consumption of nucleator is the 0.1-5wt.% of polypropylene and the total consumption of polybutene resin, preferred 0.2-2wt.%.
7. high impact resistance polypropylene/polybutylene composite material claimed in claim 1, is characterized in that, described photostabilizer is one or more mixing in benzophenone and hindered amines, preferably hindered amine 783 photostabilizers; Scratch resistance liniment is one or more mixing in ethyl trimethoxy silane oligopolymer, hexyl trimethoxysilane oligomer, ethyl triethoxysilane oligopolymer, vinyltriethoxysilane oligopolymer, hydro carbons lubricating oil and talcum powder; preferred ethyl trimethoxy silane oligopolymer (TMA), consumption is respectively 0.1-2wt.% and the 0-5wt.% of polypropylene and the total consumption of polybutene resin; Described look mother is that polypropylene special color is female.
8. high impact resistance polypropylene/polybutylene composite material claimed in claim 1, it is characterized in that, concrete preparation process is: after polybutene, polypropylene, photostabilizer, oxidation inhibitor, mineral filler, nucleator and scratch resistance liniment etc. are mixed in high-speed mixer, joining melting in the twin screw extruder of length-to-diameter ratio 30-50:1 disperses, extruding pelletization, technique is: 180～200 ℃, a district, two 200～215 ℃, districts, three 210～225 ℃, districts, four 220～230 ℃, districts, 230 ℃ of heads, melt pressure 10-18MPa.
9. high impact resistance polypropylene/polybutylene composite material claimed in claim 1, is characterized in that, has outstanding shock resistance, good rigidity and processing characteristics, is applicable to inner and outer decorative parts of automobile, pallet, electric wire, electric appliance casing and uses.
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Application publication date: 20140219 |