CN115340727B - Polypropylene alloy with high surface hardness and preparation method and application thereof - Google Patents
Polypropylene alloy with high surface hardness and preparation method and application thereof Download PDFInfo
- Publication number
- CN115340727B CN115340727B CN202210985722.1A CN202210985722A CN115340727B CN 115340727 B CN115340727 B CN 115340727B CN 202210985722 A CN202210985722 A CN 202210985722A CN 115340727 B CN115340727 B CN 115340727B
- Authority
- CN
- China
- Prior art keywords
- polypropylene
- polypropylene alloy
- resin
- modified polyurethane
- alloy according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 143
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 125
- -1 Polypropylene Polymers 0.000 title claims abstract description 124
- 239000000956 alloy Substances 0.000 title claims abstract description 77
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000011347 resin Substances 0.000 claims abstract description 64
- 229920005989 resin Polymers 0.000 claims abstract description 64
- 229920002635 polyurethane Polymers 0.000 claims abstract description 55
- 239000004814 polyurethane Substances 0.000 claims abstract description 55
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 38
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 70
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 46
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 46
- 239000003963 antioxidant agent Substances 0.000 claims description 25
- 230000003078 antioxidant effect Effects 0.000 claims description 25
- 239000000314 lubricant Substances 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 23
- 238000005303 weighing Methods 0.000 claims description 23
- 238000001125 extrusion Methods 0.000 claims description 21
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 21
- 239000004597 plastic additive Substances 0.000 claims description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 10
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims description 10
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 9
- 239000000155 melt Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- 229920001296 polysiloxane Polymers 0.000 claims description 6
- 239000004970 Chain extender Substances 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 4
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000003086 colorant Substances 0.000 claims description 3
- 125000001188 haloalkyl group Chemical group 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 229920003023 plastic Polymers 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims description 3
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 5
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 21
- 238000007599 discharging Methods 0.000 description 19
- 238000002844 melting Methods 0.000 description 19
- 230000008018 melting Effects 0.000 description 19
- 238000012360 testing method Methods 0.000 description 16
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 4
- 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 3
- 238000011056 performance test Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000012745 toughening agent Substances 0.000 description 2
- UTPYTEWRMXITIN-YDWXAUTNSA-N 1-methyl-3-[(e)-[(3e)-3-(methylcarbamothioylhydrazinylidene)butan-2-ylidene]amino]thiourea Chemical compound CNC(=S)N\N=C(/C)\C(\C)=N\NC(=S)NC UTPYTEWRMXITIN-YDWXAUTNSA-N 0.000 description 1
- IYAZLDLPUNDVAG-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical group CC(C)(C)CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 IYAZLDLPUNDVAG-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- AIBRSVLEQRWAEG-UHFFFAOYSA-N 3,9-bis(2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OCC2(COP(OC=3C(=CC(=CC=3)C(C)(C)C)C(C)(C)C)OC2)CO1 AIBRSVLEQRWAEG-UHFFFAOYSA-N 0.000 description 1
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical group CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 239000006229 carbon black Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 125000004965 chloroalkyl group Chemical group 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000003678 scratch resistant effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
-
- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- 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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Landscapes
- 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
The invention belongs to the technical field of polypropylene alloy, and particularly relates to a polypropylene alloy with high surface hardness, a preparation method and application thereof, wherein the polypropylene alloy comprises the following components based on the total weight of the polypropylene alloy: 30-90wt% of polypropylene resin, 5-68wt% of polymethacrylic acid resin, 1-20wt% of organosilicon modified polyurethane and 1-20wt% of compatilizer master batch; the organosilicon modified polyurethane contains organosilicon structural units, and the organosilicon structural units exist in the organosilicon modified polyurethane in a long-chain branched structure. The polypropylene alloy product obtained by the invention has good appearance effect, and can obviously improve the normal-low temperature impact property and scratch resistance of the polypropylene alloy.
Description
Technical Field
The invention belongs to the technical field of polypropylene alloy, and particularly relates to a polypropylene alloy with high surface hardness, and a preparation method and application thereof.
Background
The polypropylene resin (PP) is a crystalline polymer, has good heat resistance, corrosion resistance, electrical property and processability, and has low density and wide application. However, the polypropylene has a regular molecular chain structure, poor toughness, and low surface hardness, and is easy to scratch.
Polypropylene resins are widely used in the outer shells of various articles, but are rapidly subject to severe surface defects due to their lack of scratch resistance. The prior art is mainly improved by painting the surface of the polypropylene product, but the painting cost is high and the environment is polluted, so that the polypropylene product with high surface hardness is highly desired to be developed.
Polymethyl methacrylate (PMMA) is a transparent material with excellent comprehensive performance, and has higher mechanical strength and higher hardness (pencil hardness 4H); in addition, the insulating material also has excellent cold resistance, weather resistance and corrosion resistance, and good insulating performance. However, its poor thermal stability and poor impact resistance at normal temperature limit its application in many fields.
Many studies have been made in the art to increase the surface hardness of polypropylene. For example, patent document CN 111763395A discloses a high-gloss piano black PP/PMMA alloy resin composition and a preparation method thereof, comprising the following components in parts by weight: 17.40 parts of polypropylene resin master batch, 60.75 parts of polymethyl methacrylate resin, 0 8 parts of toughening agent, 0.3.2.0 parts of black toner, 0.1.5 parts of antioxidant and 0.2.1.5 parts of weather-resistant agent. The PP/PMMA alloy resin obtained by the patent has the appearance of high-gloss piano black, but the application range of the material is relatively narrow because the PMMA addition proportion is high and the low-temperature impact requirement is not considered.
Patent document CN 103694564A discloses a PP/PMMA alloy material and a preparation method thereof, the PP/PMMA alloy material comprises the following components in percentage by weight: 70 to 90 percent of PP, 2 to 15 percent of PMMA, 2 to 15 percent of compatilizer, 0.1 to 0.3 percent of antioxidant and 0.1 to 5 percent of lubricant. The PP is taken as a matrix, the hardness and scratch resistance of the alloy material are enhanced by doping the component PMMA in the PP, and the material has good gloss, but the compatibility of PMMA and PP can not be effectively improved due to the adoption of the compatilizer, so that the hardness is improved, but the impact strength is still lower.
In view of this, there is a need to develop a polypropylene alloy material having high surface hardness and excellent normal temperature and low temperature impact properties so as to be able to meet the demands of fields such as home appliances, two-wheeled battery cars, consumer electronics and the like.
Disclosure of Invention
The invention aims to provide a polypropylene alloy with high surface hardness, a preparation method and application thereof, aiming at the defects of the prior art, wherein each component in the alloy has excellent compatibility, so that a better surface effect is given to a material, the problems of layering, flow marks and the like are prevented, and the organosilicon modified polyurethane with a special structure is adopted as a toughening agent, so that the excellent normal-temperature and low-temperature impact performance and scratch resistance can be given to the material.
In order to achieve the above object, the present invention provides the following technical solutions:
in a first aspect, there is provided a polypropylene alloy having a high surface hardness comprising the following components in weight percent, based on the total weight of the polypropylene alloy:
30-90wt% (e.g., 35wt%, 40wt%, 50wt%, 60wt%, 70wt%, 85 wt%) of polypropylene resin, preferably 45-80wt%;
5 to 68wt% (e.g., 6wt%, 10wt%, 20wt%, 30wt%, 40wt%, 55wt%, 65 wt%) of a polymethacrylic resin, preferably 15 to 50wt%;
1-20wt% (e.g., 2wt%, 4wt%, 6wt%, 12wt%, 15wt%, 18 wt%) of a silicone modified polyurethane, preferably 5-10wt%;
1-20wt% (e.g., 2wt%, 4wt%, 6wt%, 12wt%, 15wt%, 18 wt%) of the compatibilizer masterbatch, preferably 5-10wt%;
the organosilicon modified polyurethane comprises an organosilicon structural unit, and the organosilicon structural unit exists in the organosilicon modified polyurethane in a long-chain branched structure.
According to the polypropylene alloy provided by the invention, in some embodiments, the structure of the organosilicon modified polyurethane is shown as a formula I:
in formula I:
is a silicone structural (repeating) unit;
R 1 is an aliphatic diisocyanate residue, or an aromatic diisocyanate residue;
R 2 is an aliphatic small molecule chain extender residue;
R 3 and R is 4 The same or different, each independently selected from a H, C C1-C18 saturated alkyl group, a C1-C18 saturated haloalkyl group, a C2-C18 unsaturated hydrocarbon group, a C2-C18 halogenated unsaturated hydrocarbon group, a C6-C18 aromatic hydrocarbon group, or a C6-C18 halogenated aromatic hydrocarbon group;
m is an integer from 1 to 100, e.g., 2, 3, 4, 6, 8, 10, 20, 40, 50, 60, 80, 90, 95, 99;
n is an integer from 1 to 100, e.g., 2, 3, 4, 6, 8, 10, 20, 40, 50, 60, 80, 90, 95, 99.
In the formula I, R 1 The aliphatic diisocyanate residue or the aromatic diisocyanate residue may be a residue obtained by reacting an aliphatic diisocyanate or an aromatic diisocyanate which is conventional in the art. R is R 2 The aliphatic small molecule chain extender residue can be the residue after reaction of the aliphatic small molecule chain extender which is conventional in the field.
Herein, the saturated alkyl groups of C1-C18 may be, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, pentyl, hexyl. The saturated haloalkyl of C1-C18 may be, but is not limited to, saturated chloroalkyl of C1-C18, saturated bromoalkyl of C1-C18.
Herein, the unsaturated hydrocarbon group of C2-C18 may be, but is not limited to, vinyl, propenyl; the C2-C18 halounsaturated hydrocarbon group may be, but is not limited to, a C2-C18 chlorounsaturated alkenyl group, a C2-C18 bromounsaturated alkenyl group.
Herein, C6-C18 aromatic hydrocarbon groups may be, but are not limited to, phenyl, benzyl, tolyl, phenethyl.
Some embodimentsIn the case, the number average molecular weight of the silicone-modified polyurethane is 4X 10 4 ～16×10 4 For example, 4.5X10 4 、5×10 4 、8×10 4 、10×10 4 、12×10 4 、15×10 4 。
In some embodiments, the silicone-modified polyurethane has a silicone structural unit content of 36 to 77wt%, e.g., 38wt%, 40wt%, 45wt%, 50wt%, 60wt%, 65wt%, 70wt%, 75wt%, based on the total weight of the silicone-modified polyurethane.
The substituents, degree of polymerization, etc. in the above structure of the silicone-modified polyurethane can be reflected or integrated to some extent indirectly by the number average molecular weight of the silicone-modified polyurethane and/or the ratio of the silicone structural units contained.
In some embodiments, the polypropylene resin is selected from the group consisting of a copolymer polypropylene or a mixture of a homo-and copolymer polypropylene, preferably a copolymer polypropylene.
In some embodiments, the polypropylene resin has a melt index of 15 to 100g/10min, e.g., 20g/10min, 40g/10min, 60g/10min, 80g/10min, 90g/10min, at 230℃and 2.16 Kg.
In some embodiments, the polypropylene resin has a notched impact strength at room temperature of 50 to 150J/m, for example, 60J/m, 80J/m, 100J/m.
In some embodiments, the polymethacrylic resin is a polymethyl methacrylate resin having a melt index of 3 to 15g/10min, e.g., 5g/10min, 10g/10min, 12g/10min, at 230 ℃ and 3.8 Kg.
In some embodiments, the raw material components of the compatibilizer masterbatch include: polypropylene resin, polymethyl methacrylate resin, maleic anhydride, optionally initiator AIBN.
In some embodiments, based on the total weight of the compatibilizer masterbatch, wherein:
the polypropylene resin is present in an amount of 50 to 84wt% (e.g., 55wt%, 60wt%, 70wt%, 75wt%, 80 wt%),
the content of the polymethyl methacrylate resin is 15 to 50wt% (e.g., 20wt%, 25wt%, 30wt%, 40wt%, 45 wt%),
the maleic anhydride content is 1-5wt% (e.g., 1.5wt%, 2wt%, 3wt%, 4wt%, 4.5 wt%),
the initiator AIBN is present in an amount of 0 to 0.5wt% (e.g., 0.01wt%, 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.45 wt%).
In some embodiments, the method of preparing the compatibilizer masterbatch comprises the steps of:
(1) Weighing polypropylene resin, polymethyl methacrylate resin, maleic anhydride, an optional initiator AIBN and an optional plastic additive according to a proportion, and putting the polypropylene resin, the polymethyl methacrylate resin, the maleic anhydride, the optional initiator AIBN and the optional plastic additive into a mixer for uniform mixing;
(2) And adding the mixture obtained in the above into an extruder, and obtaining the compatilizer master batch after melt extrusion of the materials.
The proportion of the plastic additive to the compatibilizer masterbatch may be 0-10wt%, for example, 0.01wt%, 0.1wt%, 1wt%, 2wt%, 5wt%, based on the total weight of the compatibilizer masterbatch.
In some embodiments, a plastic additive is also included in the polypropylene alloy.
In some embodiments, the plastic additive is selected from one or more of an antioxidant, a lubricant, an ultraviolet absorber, and a colorant.
In some embodiments, the plastics additive is present in an amount of 0 to 10wt% (e.g., 0.01wt%, 0.2wt%, 0.8wt%, 2wt%, 6 wt%) and preferably 0.1 to 5wt% based on the total weight of the polypropylene alloy.
The plastic additive may be an additive conventional in the art. For example, the antioxidant is selected from the group consisting of n-stearyl beta- [3, 5-di-tert-butyl-4-hydroxyphenyl ] propionate, pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], tris [2, 4-di-tert-butylphenyl ] phosphite, bis [2, 4-di-tert-butylphenyl ] pentaerythritol diphosphite, and the like.
For example, the lubricant is selected from pentaerythritol stearate and/or zinc stearate.
For example, the ultraviolet absorber is selected from 2- (2 ' -hydroxy-5 ' -tert-octylphenyl) benzotriazole and/or 2- (2 ' -hydroxy-3 ',5' -bis (a, a-dimethylbenzyl) phenyl) benzotriazole, and the like.
For example, the colorant is selected from carbon black, titanium dioxide, dyes, and the like.
In a second aspect, there is provided a method for preparing a polypropylene alloy as described above, comprising the steps of:
weighing polypropylene resin, polymethacrylic acid resin, organosilicon modified polyurethane, compatilizer master batch and optional plastic additive according to a proportion, and uniformly mixing the polypropylene resin, the polymethacrylic acid resin, the organosilicon modified polyurethane, the compatilizer master batch and the optional plastic additive in a mixer; and adding the obtained mixture into a double-screw extruder, and granulating after the materials are melted and extruded to obtain the polypropylene alloy.
In some embodiments, the barrel temperature of the twin screw extruder is 180-220 ℃ (e.g., 185 ℃, 195 ℃, 200 ℃, 215 ℃) and the screw speed is 100-800RPM (e.g., 110RPM, 150RPM, 200RPM, 400RPM, 600RPM, 750 RPM). The temperature of the feed inlet of the twin-screw extruder is generally 60-90℃and may be, for example, 80 ℃.
In a third aspect there is provided the use of a polypropylene alloy as described above or a polypropylene alloy with high surface hardness obtainable by a preparation process as described above in the field of household electrical appliances housings, electric vehicles, consumer electronics.
Compared with the common organic silicon modified polyurethane, the organic silicon modified polyurethane with the long-branched organic silicon structural unit is introduced into the polypropylene alloy, and on one hand, the thermoplastic polyurethane elastomer containing the organic silicon modified polyurethane has a unique soft and hard segment structure, so that the material has a good scratch-resistant effect; on the other hand, the existence of the organosilicon component serving as a long-chain branch chain also reduces the surface friction coefficient, so that scratch marks are not easy to leave on the surface of the material, and the surface hardness of the material can be further improved; finally, the organosilicon modified polyurethane can also promote the improvement of the normal-low-temperature impact property by utilizing the good compatibility of the PP and the TPU, so that the normal-low-temperature impact property of the polypropylene alloy can be obviously improved.
PP is a semi-crystalline material that has poor impact at very low temperatures and cannot meet high performance usage requirements. However, by means of the characteristics of the PP material, the organic silicon modified polyurethane is introduced into the polypropylene alloy, so that the normal-low-temperature impact strength and scratch resistance of the polypropylene can be remarkably improved on the basis of good compatibility of the PP and the TPU. In addition, the PP-g-PMMA grafted polymer is formed through the customized compatilizer master batch, plays a role similar to a surfactant, becomes a bridge between PP and PMMA, and remarkably improves the compatibility of the PP and the PMMA.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
the organosilicon modified polyurethane selected by the invention has the special design of the long-chain branched organosilicon structural unit, so that the organosilicon structure in the organosilicon modified polyurethane is easier to externally detect on the surface, thereby being capable of remarkably improving the scratch resistance of the material, and simultaneously, the normal-low temperature impact performance of the organosilicon modified polyurethane can be further improved by utilizing the good compatibility of PP and TPU and the structural design of the long-chain branched organosilicon. And the compatibility of PP and PMMA is obviously improved through the customized compatilizer master batch, and the polypropylene alloy product has good appearance effect under the combined action of the compatibility of the PP and PMMA.
Detailed Description
So that the technical features and content of the present invention can be understood in detail, preferred embodiments of the present invention will be described in more detail below. While the preferred embodiments of the present invention have been described in the examples, it should be understood that the present invention may be embodied in various forms and should not be limited to the embodiments set forth herein.
< source of raw materials >
Polypropylene resin: all purchased from the chemical company of Wanhua,
the melt index of the copolymer polypropylene EP548R at 230 ℃ and 2.16kg is 28g/10min;
the melt index of the polypropylene copolymer EP648V at 230 ℃ and 2.16kg is 100g/10min;
the melt index of the homo-polypropylene HP500P is 18g/10min at 230 ℃ and 2.16 kg;
polymethyl methacrylate resin: the melt index of the Wanhua chemical HD03 at 230 ℃ and 3.8kg is 3.5g/10min;
thermoplastic polyurethane: wanhua chemistry, thermoplastic polyurethane elastomer WHT-1185;
organosilicon modified polyurethane: all purchased from Wanhua chemical Co., ltd;
the organosilicon modified polyurethane C185FA (the organosilicon structure is linear), the number average molecular weight is 40000, and the proportion (in weight percent) of the organosilicon is 37%;
the organosilicon modified polyurethane S885FA (the organosilicon structure is branched), the number average molecular weight is 80000, and the proportion of the organosilicon is 40 percent (by weight percent);
the organosilicon modified polyurethane S175FA (the organosilicon structure is branched), the number average molecular weight is 100000, and the proportion (in weight percent) of the organosilicon is 51%;
the organosilicon modified polyurethane S165FA (the organosilicon structure is branched), the number average molecular weight is 40000, and the proportion of the organosilicon is 36 percent (in percentage by weight);
the organosilicon modified polyurethane S895FA (the organosilicon structure is branched), the number average molecular weight is 160000, and the proportion (in weight percent) of the organosilicon is 77%;
an antioxidant: basf B900 wherein the mass ratio of beta- [3, 5-di-tert-butyl-4-hydroxyphenyl ] propionic acid n-stearyl alcohol ester (1076) to tris [2, 4-di-tert-butylphenyl ] phosphite (168) is 1:4;
and (3) a lubricant: italian hair base, zinc stearate;
ultraviolet absorber: li Anlong UV329;
maleic anhydride: MAH national drug agent;
and (3) an initiator: AIBN Ala Ding Shiji.
The preparation process of the compatilizer master batch comprises the following steps:
(1) Weighing 6.5kg of copolymerized polypropylene EP548R, 3.19kg of polymethyl methacrylate resin HD03, 0.3kg of maleic anhydride, 0.01kg of AIBN, 0.02kg of antioxidant B900 and 0.03kg of lubricant ZnSt, mixing in a high-speed mixer for 5min, and discharging;
(2) The mixed materials were fed into a twin screw extruder, and the temperatures of the extruder sections were set as follows (from the feed port to the head):
80 ℃, 180 ℃, 220 ℃ and 220 DEG 220 ℃, 210 ℃; the die temperature was 210℃and the extrusion speed was 300RPM;
and melting the materials, extruding the materials from a die, and granulating to obtain the compatilizer master batch.
Example 1
(1) Weighing 4.5kg of copolymerized polypropylene EP548R, 4.5kg of polymethyl methacrylate resin HD03, 0.5kg of organosilicon modified polyurethane S885FA, 0.5kg of compatilizer master batch, 0.03kg of ultraviolet absorbent UV329, 0.02kg of antioxidant B900 and 0.03kg of lubricant ZnSt, mixing in a high-speed mixer for 5min, and discharging;
(2) The mixed materials were fed into a twin screw extruder, and the temperatures of the extruder sections were set as follows (from the feed port to the head):
80℃、180℃、210℃、210℃、210℃、210℃、210℃、210℃、200℃、200℃；
the die temperature was 200℃and the extrusion speed was 600RPM;
and melting the materials, extruding the materials from a die, and granulating to obtain the polypropylene alloy.
Example 2
(1) Weighing 6kg of copolymerized polypropylene EP548R, 2kg of polymethyl methacrylate resin HD03, 1kg of organosilicon modified polyurethane S885FA, 1kg of compatilizer master batch, 0.03kg of ultraviolet absorber UV329, 0.02kg of antioxidant B900 and 0.03kg of lubricant ZnSt, mixing in a high-speed mixer for 5min, and discharging;
(2) The mixed materials were fed into a twin screw extruder, and the temperatures of the extruder sections were set as follows (from the feed port to the head):
80℃、180℃、210℃、210℃、210℃、210℃、210℃、210℃、200℃、200℃；
the die temperature was 200℃and the extrusion speed was 300RPM;
and melting the materials, extruding the materials from a die, and granulating to obtain the polypropylene alloy.
Example 3
(1) Weighing 8kg of copolymerized polypropylene EP548R, 1kg of polymethyl methacrylate resin HD03, 0.5kg of organosilicon modified polyurethane S885FA, 0.5kg of compatilizer master batch, 0.03kg of ultraviolet absorber UV329, 0.02kg of antioxidant B900 and 0.03kg of lubricant ZnSt, mixing in a high-speed mixer for 5min, and discharging;
(2) The mixed materials were fed into a twin screw extruder, and the temperatures of the extruder sections were set as follows (from the feed port to the head):
80℃、180℃、210℃、210℃、210℃、210℃、210℃、210℃、200℃、200℃；
the die temperature was 200℃and the extrusion speed was 300RPM;
and melting the materials, extruding the materials from a die, and granulating to obtain the polypropylene alloy.
Example 4
(1) Weighing 4kg of copolymerized polypropylene EP548R, 5kg of polymethyl methacrylate resin HD03, 0.5kg of organosilicon modified polyurethane S885FA, 0.5kg of compatilizer master batch, 0.03kg of ultraviolet absorber UV329, 0.02kg of antioxidant B900 and 0.03kg of lubricant ZnSt, mixing in a high-speed mixer for 5min, and discharging;
(2) The mixed materials were fed into a twin screw extruder, and the temperatures of the extruder sections were set as follows (from the feed port to the head):
80℃、180℃、210℃、210℃、210℃、210℃、210℃、210℃、200℃、200℃；
the die temperature is 200 ℃, and the extrusion rotating speed is 200RPM;
and melting the materials, extruding the materials from a die, and granulating to obtain the polypropylene alloy.
Example 5
(1) Weighing 6kg of copolymerized polypropylene EP548R, 2.6kg of polymethyl methacrylate resin HD03, 0.7kg of organosilicon modified polyurethane S885FA, 0.7kg of compatilizer master batch, 0.03kg of ultraviolet absorber UV329, 0.02kg of antioxidant B900 and 0.03kg of lubricant ZnSt, mixing in a high-speed mixer for 5min, and discharging;
(2) The mixed materials were fed into a twin screw extruder, and the temperatures of the extruder sections were set as follows (from the feed port to the head):
80℃、180℃、210℃、210℃、210℃、210℃、210℃、210℃、200℃、200℃；
the die temperature was 200℃and the extrusion speed was 300RPM;
and melting the materials, extruding the materials from a die, and granulating to obtain the polypropylene alloy.
Example 6
(1) Weighing 8kg of copolymerized polypropylene EP648V, 1kg of polymethyl methacrylate resin HD03, 0.5kg of organosilicon modified polyurethane S885FA, 0.5kg of compatilizer master batch, 0.03kg of ultraviolet absorber UV329, 0.02kg of antioxidant B900 and 0.03kg of lubricant ZnSt, mixing in a high-speed mixer for 5min, and discharging;
(2) The mixed materials were fed into a twin screw extruder, and the temperatures of the extruder sections were set as follows (from the feed port to the head):
80℃、180℃、210℃、210℃、210℃、210℃、210℃、210℃、200℃、200℃；
the die temperature was 200℃and the extrusion speed was 300RPM;
and melting the materials, extruding the materials from a die, and granulating to obtain the polypropylene alloy.
Example 7
(1) Weighing 8kg of copolymerized polypropylene EP648V, 1kg of polymethyl methacrylate resin HD03, 0.5kg of organosilicon modified polyurethane S175FA, 0.5kg of compatilizer master batch, 0.03kg of ultraviolet absorber UV329, 0.02kg of antioxidant B900 and 0.03kg of lubricant ZnSt, mixing in a high-speed mixer for 5min, and discharging;
(2) The mixed materials were fed into a twin screw extruder, and the temperatures of the extruder sections were set as follows (from the feed port to the head):
80℃、180℃、210℃、210℃、210℃、210℃、210℃、210℃、200℃、200℃；
the die temperature was 200℃and the extrusion speed was 300RPM;
and melting the materials, extruding the materials from a die, and granulating to obtain the polypropylene alloy.
Example 8
(1) Weighing 3kg of copolymerized polypropylene EP548R, 6kg of polymethyl methacrylate resin HD03, 1kg of organosilicon modified polyurethane S175FA, 1kg of compatilizer master batch, 0.03kg of ultraviolet absorber UV329, 0.02kg of antioxidant B900 and 0.03kg of lubricant ZnSt, mixing in a high-speed mixer for 5min, and discharging;
(2) The mixed materials were fed into a twin screw extruder, and the temperatures of the extruder sections were set as follows (from the feed port to the head):
80℃、180℃、210℃、210℃、210℃、210℃、210℃、210℃、200℃、200℃；
the die temperature was 200℃and the extrusion speed was 600RPM;
and melting the materials, extruding the materials from a die, and granulating to obtain the polypropylene alloy.
Example 9
(1) Weighing 9kg of copolymerized polypropylene EP548R, 0.5kg of polymethyl methacrylate resin HD03, 0.1kg of organosilicon modified polyurethane S175FA, 0.4kg of compatilizer master batch, 0.03kg of ultraviolet absorber UV329, 0.02kg of antioxidant B900 and 0.03kg of lubricant ZnSt, mixing in a high-speed mixer for 5min, and discharging;
(2) The mixed materials were fed into a twin screw extruder, and the temperatures of the extruder sections were set as follows (from the feed port to the head):
80℃、180℃、210℃、210℃、210℃、210℃、210℃、210℃、200℃、200℃；
the die temperature was 200℃and the extrusion speed was 600RPM;
and melting the materials, extruding the materials from a die, and granulating to obtain the polypropylene alloy.
Example 10
(1) Weighing 3kg of copolymerized polypropylene EP548R, 3kg of polymethyl methacrylate resin HD03, 2kg of organosilicon modified polyurethane S175FA, 2kg of compatilizer master batch, 0.03kg of ultraviolet absorber UV329, 0.02kg of antioxidant B900 and 0.03kg of lubricant ZnSt, mixing in a high-speed mixer for 5min, and discharging;
(2) The mixed materials were fed into a twin screw extruder, and the temperatures of the extruder sections were set as follows (from the feed port to the head):
80℃、180℃、210℃、210℃、210℃、210℃、210℃、210℃、200℃、200℃；
the die temperature was 200℃and the extrusion speed was 600RPM;
and melting the materials, extruding the materials from a die, and granulating to obtain the polypropylene alloy.
Example 11
(1) Weighing 3kg of copolymerized polypropylene EP548R, 6.8kg of polymethyl methacrylate resin HD03, 0.1kg of organosilicon modified polyurethane S175FA, 0.1kg of compatilizer master batch, 0.03kg of ultraviolet absorber UV329, 0.02kg of antioxidant B900 and 0.03kg of lubricant ZnSt, mixing in a high-speed mixer for 5min, and discharging;
(2) The mixed materials were fed into a twin screw extruder, and the temperatures of the extruder sections were set as follows (from the feed port to the head):
80℃、180℃、210℃、210℃、210℃、210℃、210℃、210℃、200℃、200℃；
the die temperature was 200℃and the extrusion speed was 600RPM;
and melting the materials, extruding the materials from a die, and granulating to obtain the polypropylene alloy.
Example 12
(1) Weighing 3kg of copolymerized polypropylene EP548R, 6kg of polymethyl methacrylate resin HD03, 0.5kg of organosilicon modified polyurethane S175FA, 0.5kg of compatilizer master batch, 0.03kg of ultraviolet absorber UV329, 0.02kg of antioxidant B900 and 0.03kg of lubricant ZnSt, mixing in a high-speed mixer for 5min, and discharging;
(2) The mixed materials were fed into a twin screw extruder, and the temperatures of the extruder sections were set as follows (from the feed port to the head):
80℃、180℃、210℃、210℃、210℃、210℃、210℃、210℃、200℃、200℃；
the die temperature was 200℃and the extrusion speed was 600RPM;
and melting the materials, extruding the materials from a die, and granulating to obtain the polypropylene alloy.
Example 13
(1) Weighing 6kg of copolymerized polypropylene EP548R, 2kg of polymethyl methacrylate resin HD03, 1kg of organosilicon modified polyurethane S165FA, 1kg of compatilizer master batch, 0.03kg of ultraviolet absorber UV329, 0.02kg of antioxidant B900 and 0.03kg of lubricant ZnSt, mixing in a high-speed mixer for 5min, and discharging;
(2) The mixed materials were fed into a twin screw extruder, and the temperatures of the extruder sections were set as follows (from the feed port to the head):
80℃、180℃、210℃、210℃、210℃、210℃、210℃、210℃、200℃、200℃；
the die temperature was 200℃and the extrusion speed was 300RPM;
and melting the materials, extruding the materials from a die, and granulating to obtain the polypropylene alloy.
Example 14
(1) Weighing 6kg of copolymerized polypropylene EP548R, 2kg of polymethyl methacrylate resin HD03, 1kg of organosilicon modified polyurethane S895FA, 1kg of compatilizer master batch, 0.03kg of ultraviolet absorber UV329, 0.02kg of antioxidant B900 and 0.03kg of lubricant ZnSt, mixing in a high-speed mixer for 5min, and discharging;
(2) The mixed materials were fed into a twin screw extruder, and the temperatures of the extruder sections were set as follows (from the feed port to the head):
80℃、180℃、210℃、210℃、210℃、210℃、210℃、210℃、200℃、200℃；
the die temperature was 200℃and the extrusion speed was 300RPM;
and melting the materials, extruding the materials from a die, and granulating to obtain the polypropylene alloy.
Comparative example 1
(1) Weighing 6kg of copolymerized polypropylene EP548R, 4kg of polymethyl methacrylate resin HD03, 0.03kg of ultraviolet absorber UV329, 0.02kg of antioxidant B900 and 0.03kg of lubricant ZnSt, mixing in a high-speed mixer for 5min, and discharging;
(2) The mixed materials were fed into a twin screw extruder, and the temperatures of the extruder sections were set as follows (from the feed port to the head):
80℃、180℃、220℃、220℃、220℃、220℃、220℃、220℃、210℃、210℃；
the die temperature was 210℃and the extrusion speed was 300RPM;
and melting the materials, extruding the materials from a die, and granulating to obtain the polypropylene alloy.
Comparative example 2
(1) Weighing 6kg of homo-polypropylene HP500P, 4kg of polymethyl methacrylate resin HD03, 0.03kg of ultraviolet absorber UV329, 0.02kg of antioxidant B and 0.03kg of lubricant ZnSt, mixing in a high-speed mixer for 5min, and discharging;
(2) The mixed materials were fed into a twin screw extruder, and the temperatures of the extruder sections were set as follows (from the feed port to the head):
80℃、150℃、190℃、190℃、190℃、190℃、190℃、190℃、180℃、180℃；
the die temperature was 180℃and the extrusion speed was 600RPM;
and melting the materials, extruding the materials from a die, and granulating to obtain the polypropylene alloy.
Comparative example 3
(1) Weighing 6kg of copolymerized polypropylene EP548R, 3kg of polymethyl methacrylate resin HD03, 1kg of thermoplastic polyurethane WHT 1185, 0.03kg of ultraviolet absorber UV329, 0.02kg of antioxidant B900 and 0.03kg of lubricant ZnSt, mixing in a high-speed mixer for 5min, and discharging;
(2) The mixed materials were fed into a twin screw extruder, and the temperatures of the extruder sections were set as follows (from the feed port to the head):
80℃、180℃、210℃、210℃、210℃、210℃、210℃、210℃、200℃、200℃；
the die temperature was 200℃and the extrusion speed was 600RPM;
and melting the materials, extruding the materials from a die, and granulating to obtain the polypropylene alloy.
Comparative example 4
(1) Weighing 6kg of copolymerized polypropylene EP548R, 2kg of polymethyl methacrylate resin HD03, 1kg of organosilicon modified polyurethane S185FA, 1kg of compatilizer master batch, 0.03kg of ultraviolet absorber UV329, 0.02kg of antioxidant B900 and 0.03kg of lubricant ZnSt, mixing in a high-speed mixer for 5min, and discharging;
(2) The mixed materials were fed into a twin screw extruder, and the temperatures of the extruder sections were set as follows (from the feed port to the head):
80℃、180℃、210℃、210℃、210℃、210℃、210℃、210℃、200℃、200℃；
the die temperature was 200℃and the extrusion speed was 300RPM;
and melting the materials, extruding the materials from a die, and granulating to obtain the polypropylene alloy.
< test method >
(1) Melt index test
Test standard: ASTM D0013,
test conditions: 230 ℃ and 2.16kg of the temperature-sensitive adhesive,
test unit: g/10min.
(2) Cantilever Liang Changwen notch impact strength test
Test standard: ASTM D256 is set to be,
test conditions: notch impact at 23 c (type a notch),
test unit: j/m.
(3) Impact strength of cantilever beam low-temperature notch
Test standard: ASTM D256 is set to be,
test conditions: notch impact at-30 c (type a notch),
test unit: j/m.
(4) Pencil hardness test
Test standard: the number of the ATSM D3363,
test conditions: 1kg weight, mitsubishi pencil.
(5) Appearance test
Test standard: visually, the surface of the color plate was observed for the presence of adverse appearance effects such as flow marks, weld marks, delamination, and the like.
The polypropylene alloys prepared in the above examples and comparative examples were subjected to the performance test results shown in tables 1 and 2.
TABLE 1 results of product Performance test
/>
TABLE 2 results of product Performance test
From the experimental results of tables 1-2, it can be seen that:
compared with a system without the addition of the compatilizer master batch and/or the organosilicon modified polyurethane, the surface hardness and the compatibility of the polypropylene alloy obtained by the system with the addition of the compatilizer master batch and the organosilicon modified polyurethane are obviously enhanced, so that the polypropylene alloy product has good appearance effect and can obviously improve the normal-low temperature impact performance and the scratch resistance of the polypropylene alloy.
Comparative example 4 differs from the silicone-modified polyurethane selected in example 2; in example 2, the silicone-modified polyurethane having a long-chain branched silicone structural unit was used, and thus, the polypropylene alloy obtained was more excellent in various performance indexes, as compared with comparative example 4.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the spirit of the invention.
Claims (17)
1. A polypropylene alloy having a high surface hardness, characterized by comprising the following components in weight percent, based on the total weight of the polypropylene alloy:
the organic silicon modified polyurethane comprises an organic silicon structural unit, and the organic silicon structural unit exists in the organic silicon modified polyurethane in a long-chain branched structure;
the number average molecular weight of the organosilicon modified polyurethane is 4 multiplied by 10 4 ～16×10 4 ；
The weight ratio of the organic silicon structural unit is 36-77 wt% based on the total weight of the organic silicon modified polyurethane;
the raw material components of the compatilizer master batch comprise: polypropylene resin, polymethyl methacrylate resin, maleic anhydride, optionally initiator AIBN; wherein the content of maleic anhydride is 1-5wt%.
2. The polypropylene alloy according to claim 1, comprising the following components in weight percent, based on the total weight of the polypropylene alloy:
3. the polypropylene alloy according to claim 1, wherein the silicone modified polyurethane has a structure as shown in formula I:
in formula I:
is an organosilicon structural unit;
R 1 is an aliphatic diisocyanate residue, or an aromatic diisocyanate residue;
R 2 is an aliphatic small molecule chain extender residue;
R 3 and R is 4 The same or different, each independently selected from the group consisting of H, C C18 saturated alkyl, C1C 18 saturated haloalkyl, C2C 18 unsaturated hydrocarbyl, C2C 18 halogenated unsaturated hydrocarbyl;
m is an integer of 1 to 100;
n is an integer of 1 to 100.
4. A polypropylene alloy according to claim 3, wherein the C2-C18 unsaturated hydrocarbon group is a C6-C18 aromatic hydrocarbon group.
5. A polypropylene alloy according to claim 3, wherein the C2-C18 halounsaturated hydrocarbon group is a C6-C18 haloaromatic hydrocarbon group.
6. The polypropylene alloy according to claim 1, wherein the polypropylene resin is selected from the group consisting of co-polypropylene or a mixture of homo-polypropylene and co-polypropylene; and/or
The melt index of the polypropylene resin at 230 ℃ and 2.16Kg is 15-100g/10min.
7. The polypropylene alloy according to claim 6, wherein the polypropylene resin is a copolymerized polypropylene.
8. The polypropylene alloy according to claim 1, wherein the polymethacrylic resin is a polymethyl methacrylate resin having a melt index of 3 to 15g/10min at 230 ℃ and 3.8 Kg.
9. The polypropylene alloy according to claim 1, wherein the compatibilizing agent masterbatch is based on total weight, wherein:
the content of the polypropylene resin is 50-84wt%,
the content of polymethyl methacrylate resin is 15-50wt%,
the content of maleic anhydride is 1-5wt%,
the initiator AIBN content is 0-0.5wt%.
10. The polypropylene alloy according to claim 1, wherein the preparation method of the compatibilizer masterbatch comprises the steps of:
(1) Weighing polypropylene resin, polymethyl methacrylate resin, maleic anhydride, an optional initiator AIBN and an optional plastic additive according to a proportion, and putting the polypropylene resin, the polymethyl methacrylate resin, the maleic anhydride, the optional initiator AIBN and the optional plastic additive into a mixer for uniform mixing;
(2) And adding the mixture obtained in the above into an extruder, and obtaining the compatilizer master batch after melt extrusion of the materials.
11. The polypropylene alloy according to any one of claims 1 to 10, wherein the polypropylene alloy further comprises a plastic additive.
12. The polypropylene alloy according to claim 10, wherein the plastic additive is selected from one or more of an antioxidant, a lubricant, an ultraviolet absorber and a colorant.
13. The polypropylene alloy according to claim 10, wherein the plastics additive is present in an amount of 0 to 10wt% based on the total weight of the polypropylene alloy.
14. The polypropylene alloy according to claim 13, wherein the plastics additive is present in an amount of 0.1 to 5wt% based on the total weight of the polypropylene alloy.
15. The method for producing a polypropylene alloy according to any one of claims 1 to 14, comprising the steps of:
weighing polypropylene resin, polymethacrylic acid resin, organosilicon modified polyurethane, compatilizer master batch and optional plastic additive according to a proportion, and uniformly mixing the polypropylene resin, the polymethacrylic acid resin, the organosilicon modified polyurethane, the compatilizer master batch and the optional plastic additive in a mixer; and adding the obtained mixture into a double-screw extruder, and granulating after the materials are melted and extruded to obtain the polypropylene alloy.
16. The process of claim 15 wherein the twin screw extruder has a barrel temperature of 180 to 220 ℃ and a screw speed of 100 to 800RPM.
17. Use of the polypropylene alloy according to any one of claims 1 to 14 or of the polypropylene alloy with high surface hardness produced by the production process according to claim 15 or 16 in the field of household electrical appliances, electric vehicles, consumer electronics.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210985722.1A CN115340727B (en) | 2022-08-17 | 2022-08-17 | Polypropylene alloy with high surface hardness and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210985722.1A CN115340727B (en) | 2022-08-17 | 2022-08-17 | Polypropylene alloy with high surface hardness and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115340727A CN115340727A (en) | 2022-11-15 |
| CN115340727B true CN115340727B (en) | 2023-10-17 |
Family
ID=83951362
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210985722.1A Active CN115340727B (en) | 2022-08-17 | 2022-08-17 | Polypropylene alloy with high surface hardness and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115340727B (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR19990025669A (en) * | 1997-09-13 | 1999-04-06 | 이영일 | Resin composition excellent in scratch resistance and impact strength |
| CN103910933A (en) * | 2014-04-02 | 2014-07-09 | 合肥杰事杰新材料股份有限公司 | High-hardness scraping-resistant polypropylene material and preparation method thereof |
| CN104086740A (en) * | 2014-07-09 | 2014-10-08 | 温州柯莱恩科技有限公司 | Method for preparing organic silicon graft modified polyurethane resin for synthetic leather |
| JP2016050272A (en) * | 2014-09-01 | 2016-04-11 | 株式会社オートネットワーク技術研究所 | Composition for wire covering material, insulated wire and wire harness |
| CN107163215A (en) * | 2017-06-22 | 2017-09-15 | 广东元星工业新材料有限公司 | High rigidity self-lubricating polyurethane elastomer and preparation method thereof |
| CN107805346A (en) * | 2017-11-15 | 2018-03-16 | 四川科立鑫新材料有限公司 | A kind of polypropylene material with Soft touch |
| CN110903654A (en) * | 2019-11-15 | 2020-03-24 | 中广核三角洲集团（苏州）特威塑胶有限公司 | Environment-friendly thermoplastic silicone rubber elastomer and preparation method thereof |
| JP2020139142A (en) * | 2019-02-27 | 2020-09-03 | Ｍｃｐｐイノベーション合同会社 | Resin composition, crosslinked resin composition, molding, wire coating material and wire |
| CN111909457A (en) * | 2020-08-24 | 2020-11-10 | 苏州润佳高分子材料有限公司 | Degradable soft touch polypropylene composite material |
| CN113544325A (en) * | 2019-04-05 | 2021-10-22 | 株式会社可乐丽 | Grain leather-like sheet |
| CN114211845A (en) * | 2021-12-08 | 2022-03-22 | 日丰企业集团有限公司 | Multifunctional PB oxygen-barrier pipe and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI747455B (en) * | 2020-08-24 | 2021-11-21 | 南亞塑膠工業股份有限公司 | Organic silicon modified polyurethane resin and manufacturing method thereof |
-
2022
- 2022-08-17 CN CN202210985722.1A patent/CN115340727B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR19990025669A (en) * | 1997-09-13 | 1999-04-06 | 이영일 | Resin composition excellent in scratch resistance and impact strength |
| CN103910933A (en) * | 2014-04-02 | 2014-07-09 | 合肥杰事杰新材料股份有限公司 | High-hardness scraping-resistant polypropylene material and preparation method thereof |
| CN104086740A (en) * | 2014-07-09 | 2014-10-08 | 温州柯莱恩科技有限公司 | Method for preparing organic silicon graft modified polyurethane resin for synthetic leather |
| JP2016050272A (en) * | 2014-09-01 | 2016-04-11 | 株式会社オートネットワーク技術研究所 | Composition for wire covering material, insulated wire and wire harness |
| CN107163215A (en) * | 2017-06-22 | 2017-09-15 | 广东元星工业新材料有限公司 | High rigidity self-lubricating polyurethane elastomer and preparation method thereof |
| CN107805346A (en) * | 2017-11-15 | 2018-03-16 | 四川科立鑫新材料有限公司 | A kind of polypropylene material with Soft touch |
| JP2020139142A (en) * | 2019-02-27 | 2020-09-03 | Ｍｃｐｐイノベーション合同会社 | Resin composition, crosslinked resin composition, molding, wire coating material and wire |
| CN113544325A (en) * | 2019-04-05 | 2021-10-22 | 株式会社可乐丽 | Grain leather-like sheet |
| CN110903654A (en) * | 2019-11-15 | 2020-03-24 | 中广核三角洲集团（苏州）特威塑胶有限公司 | Environment-friendly thermoplastic silicone rubber elastomer and preparation method thereof |
| CN111909457A (en) * | 2020-08-24 | 2020-11-10 | 苏州润佳高分子材料有限公司 | Degradable soft touch polypropylene composite material |
| CN114211845A (en) * | 2021-12-08 | 2022-03-22 | 日丰企业集团有限公司 | Multifunctional PB oxygen-barrier pipe and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 有机硅改性聚氨酯的制备方法及应用进展;王丽;《化学与生物工程》;第28卷(第9期);第14-16页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115340727A (en) | 2022-11-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101367992B (en) | Method of manufacturing polycarbonate/polyester alloy | |
| CN101311223B (en) | High impact resistance fiberglass reinforced fire retardant engineering plastics and preparation method | |
| CN101311222B (en) | High impact resistance fiberglass reinforced engineering plastics and preparation method | |
| CN101367991B (en) | Method of manufacturing polycarbonate/vinyl cyanide-butadiene-styrol copolymer alloy | |
| CN101311221A (en) | Fiberglass reinforced fire retardant engineering plastics and preparation method | |
| CN1216101C (en) | Preparation method of toughness enhanced and reinforced polybutanediol terephthalate nanometer composition | |
| CN102558837A (en) | Low temperature impact resistant nylon flexibilizer and preparation method of low temperature impact resistant nylon flexibilizer | |
| JPS6160746A (en) | Thermoplastic resin composition | |
| CN110105738B (en) | Flame-retardant PC/ABS material and preparation method and application thereof | |
| JPH0618929B2 (en) | Glass fiber reinforced polypropylene composition | |
| CN102876002A (en) | Rapid molding high heat-resistant polyamide-polyphenyl ether alloy and preparation method thereof | |
| CN103694564A (en) | PP/PMMA (polypropylene/polymethyl methacrylate) alloy material and preparation method thereof | |
| CN107892734B (en) | Polypropylene composite material suitable for electroplating reaction and preparation method thereof | |
| CN102807746B (en) | High-hardness and high-flowability PC/PMMA/AS (polycarbonate/polymethyl methacrylate/acrylonitrile-styrene copolymer) alloy and preparation method thereof | |
| CN101787190B (en) | Flame-retarding environment-friendly high-intensity PC-AS composite material and preparation method thereof | |
| CN101338054A (en) | Modified polypropylene material for top cover of refrigerator and method for preparing same | |
| CN111171542B (en) | High CTI flame-retardant polycarbonate alloy material and preparation method and application thereof | |
| CN103160052A (en) | High-gloss ABS/PMMA alloy material, and preparation method and application thereof | |
| CN109486156B (en) | Flame-retardant extrusion-grade PC/ABS composite material | |
| CN115340727B (en) | Polypropylene alloy with high surface hardness and preparation method and application thereof | |
| CN109971058B (en) | Flame-retardant polyethylene material and preparation method thereof | |
| CN110684348B (en) | Polyamide material with metal texture and preparation method thereof | |
| CN111205615B (en) | Flame-retardant blister PC/ABS alloy material and preparation method and application thereof | |
| CN110862655B (en) | PBT/SAN composite material and preparation method and application thereof | |
| CN106543670A (en) | Exempt from sprayed biological base PLA/PC composites and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |