CN109836618A - Modification method of aluminum oxide - Google Patents
Modification method of aluminum oxide Download PDFInfo
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- CN109836618A CN109836618A CN201711212814.1A CN201711212814A CN109836618A CN 109836618 A CN109836618 A CN 109836618A CN 201711212814 A CN201711212814 A CN 201711212814A CN 109836618 A CN109836618 A CN 109836618A
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- Prior art keywords
- acid
- aromatic carboxylic
- aluminium oxide
- modified
- carboxylic acid
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 title claims description 11
- 238000002715 modification method Methods 0.000 title 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 156
- 239000002245 particle Substances 0.000 claims abstract description 55
- -1 polypropylene Polymers 0.000 claims abstract description 52
- 239000004743 Polypropylene Substances 0.000 claims abstract description 46
- 229920001155 polypropylene Polymers 0.000 claims abstract description 46
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000002667 nucleating agent Substances 0.000 claims abstract description 29
- 239000002105 nanoparticle Substances 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 48
- 239000000654 additive Substances 0.000 claims description 23
- 230000000996 additive effect Effects 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 9
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 claims description 8
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- 235000010233 benzoic acid Nutrition 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 7
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 5
- UOBYKYZJUGYBDK-UHFFFAOYSA-N 2-naphthoic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CC=C21 UOBYKYZJUGYBDK-UHFFFAOYSA-N 0.000 claims description 4
- ALKYHXVLJMQRLQ-UHFFFAOYSA-N 3-Hydroxy-2-naphthoate Chemical compound C1=CC=C2C=C(O)C(C(=O)O)=CC2=C1 ALKYHXVLJMQRLQ-UHFFFAOYSA-N 0.000 claims description 4
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims description 4
- 239000005711 Benzoic acid Substances 0.000 claims description 4
- 229960004050 aminobenzoic acid Drugs 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- VUVIRKAVBZITDO-UHFFFAOYSA-N 1-bromonaphthalene-2-carboxylic acid Chemical compound C1=CC=CC2=C(Br)C(C(=O)O)=CC=C21 VUVIRKAVBZITDO-UHFFFAOYSA-N 0.000 claims description 3
- KDVYCTOWXSLNNI-UHFFFAOYSA-N 4-t-Butylbenzoic acid Chemical compound CC(C)(C)C1=CC=C(C(O)=O)C=C1 KDVYCTOWXSLNNI-UHFFFAOYSA-N 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 150000001559 benzoic acids Chemical class 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 150000005209 naphthoic acids Chemical class 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 2
- XUDBVJCTLZTSDC-UHFFFAOYSA-N 2-ethenylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C=C XUDBVJCTLZTSDC-UHFFFAOYSA-N 0.000 claims description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- VOIZNVUXCQLQHS-UHFFFAOYSA-N 3-bromobenzoic acid Chemical compound OC(=O)C1=CC=CC(Br)=C1 VOIZNVUXCQLQHS-UHFFFAOYSA-N 0.000 claims description 2
- ZQVKTHRQIXSMGY-UHFFFAOYSA-N 4-Ethylbenzoic acid Chemical compound CCC1=CC=C(C(O)=O)C=C1 ZQVKTHRQIXSMGY-UHFFFAOYSA-N 0.000 claims description 2
- XRHGYUZYPHTUJZ-UHFFFAOYSA-N 4-chlorobenzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C=C1 XRHGYUZYPHTUJZ-UHFFFAOYSA-N 0.000 claims description 2
- ZEYHEAKUIGZSGI-UHFFFAOYSA-N 4-methoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C=C1 ZEYHEAKUIGZSGI-UHFFFAOYSA-N 0.000 claims description 2
- SIVYRLBDAPKADZ-UHFFFAOYSA-N 4-methylnaphthalene-1-carboxylic acid Chemical compound C1=CC=C2C(C)=CC=C(C(O)=O)C2=C1 SIVYRLBDAPKADZ-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 claims 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims 1
- GPSDUZXPYCFOSQ-UHFFFAOYSA-N m-toluic acid Chemical compound CC1=CC=CC(C(O)=O)=C1 GPSDUZXPYCFOSQ-UHFFFAOYSA-N 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 18
- 238000002425 crystallisation Methods 0.000 abstract description 15
- 230000008025 crystallization Effects 0.000 abstract description 15
- 238000005406 washing Methods 0.000 abstract description 3
- 239000011342 resin composition Substances 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 description 54
- 229910001845 yogo sapphire Inorganic materials 0.000 description 54
- 102220040412 rs587778307 Human genes 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 17
- 239000000805 composite resin Substances 0.000 description 17
- 239000004925 Acrylic resin Substances 0.000 description 14
- 229920000178 Acrylic resin Polymers 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 9
- 239000004411 aluminium Substances 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 239000012528 membrane Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 238000010899 nucleation Methods 0.000 description 5
- 230000006911 nucleation Effects 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229910000077 silane Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000005452 bending Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 235000013339 cereals Nutrition 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920005629 polypropylene homopolymer Polymers 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- WRQHSQDGYYDRMX-UHFFFAOYSA-N 4-methoxynaphthalene-1-carboxylic acid Chemical compound C1=CC=C2C(OC)=CC=C(C(O)=O)C2=C1 WRQHSQDGYYDRMX-UHFFFAOYSA-N 0.000 description 1
- 241001436679 Adama Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 125000000131 cyclopropyloxy group Chemical group C1(CC1)O* 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention provides a modified alumina particle and a preparation method and application thereof. Adding aromatic carboxylic acid and alumina particles into an organic solvent, reacting for 2-12h at 90-130 ℃, washing the obtained product, and drying at 20-90 ℃ to obtain the surface aromatic carboxylic acid modified alumina particles. The aromatic carboxylic acid is used in an amount of 50 to 100 parts by mass based on 100 parts by mass of the alumina nanoparticles. The modified alumina particles are used as a polypropylene nucleating agent, and compared with unmodified alumina particles, the crystallization property and the mechanical property of the polypropylene resin composition can be obviously improved.
Description
Technical field
The present invention relates to a kind of modified aluminas, preparation method and as the application of nucleating agent.
Background technique
Polypropylene (PP) is used as a kind of versatile material, has good mechanical property, nontoxic, heat-resisting, chemicals-resistant, is easily worked
The advantages that forming and is cheap, can be widely applied to chemical industry, building materials, automobile and other industries.But PP also has transparent at the same time
Property it is poor, creep resistance is poor, shock resistance is poor, be easy aging the disadvantages of, limit the popularization and use of PP.For this purpose, both at home and abroad
The modification of PP is had made extensive and intensive studies.It is simple easy for mixing with other polymers or adding filler in PP
Capable, low in cost, effective method of modifying.Wherein, the filler with nucleating effect is referred to as nucleating agent.
Nucleating agent plays nucleation during crystalling propylene, on the one hand nucleation efficiencies have with nucleating agent structure
It closes, on the other hand also depends on into the quantity of nuclear particle.Currently, common nucleating agent has glucitols, substituted aryl heterocycle phosphorus
The small organic molecules such as acid esters salt.Inorganic particulate also receives more and more attention in recent years as the research of nucleating agent.But
The Van der Waals'attractive force of inorganic particulate itself is very strong, is easy to happen reunion, cause finally in polypropylene at nuclear particle number
Amount decline, reduces nucleation efficiencies.Therefore it needs to carry out chemical modification to inorganic particulate particle surface, to improve inorganic particulate
Interaction between grain and polymer, to improve nucleation efficiencies.
Alumina particle is added to the research in polypropylene as inorganic particulate nucleating agent and has and reports successively.However it aoxidizes
It is very undesirable that alumina particles are added to the modified effect generated in nonpolar inert polyolefin such as polypropylene.Also there is research to oxygen
It is modified to change alumina particles progress surface, typically it is surface modified using silane coupling agent.Although oxidation can be improved
Interaction between alumina particles and polymer, but there is still a need for very big additive amounts can be only achieved preferable modified effect.Such as
Document " Crystallization, mechanical, and fracture behaviors of spherical alumina
Filled polypropylene nanocomposites " 43 (24): 3652-3664, Journal of Polymer
Science Part B:Polymer Physics (publishing for 2005) is described, adds silane coupler modified alumina particle
Afterwards, additive amount is in 1.5wt%-5wt%, and polyacrylic crystallization temperature is compared with blank acrylic resin only improves 4 DEG C, and
When alumina particle additive amount after silane coupler modified is less than 1.5wt%, polyacrylic crystallization temperature is without being obviously improved.
Therefore still very urgent to the modified research in the surface of alumina particle, it is necessary to use novel surface modifying method, change
The chemical environment of kind Membranes On Alumina Particles Surface promotes dispersion of the alumina particle in polypropylene, plays good nucleating agent effect
Fruit.
Summary of the invention
The present invention provides a kind of new Membranes On Alumina Particles Surface method of modifying, anti-by aromatic carboxylic acid and alumina particle
It answers, the aromatic carboxylic acid modified alumina particles being prepared, when being applied to polypropylene nucleater, additive amount is small and nucleation is imitated
Fruit is good.
Membranes On Alumina Particles Surface method of modifying of the present invention includes:
In the reactor under stirring condition, aromatic carboxylic acid and alumina particle are added in organic solvent, 90 DEG C-
2-12h is reacted at 130 DEG C, products therefrom is washed, 20 DEG C -90 DEG C be dried to obtain surface aromatic carboxylic acid modified aluminas
Grain.
Wherein, 100 mass parts alumina particles are based on, the aromatic carboxylic acid additive amount is 50 to 100 mass parts.50 to
100 all individual values and subrange are included in the application and are disclosed in the application；For example, aromatic carboxylic acid adds
Dosage can be from lower limit 51,55,60,75,80 or 90 mass parts to the upper limit 55,65,75,85,90 or 100 mass parts.For example,
The additive amount of carboxylic acid can be within the scope of 50 to 100 mass parts or the additive amount of carboxylic acid can be in 50 to 90 mass parts
In range or the additive amount of carboxylic acid can be within the scope of 65 to 90 mass parts.
The alumina particle is the alumina particle that can be used as polyolefin nucleating agent, and preferable particle size range is received for 1-100
The aluminum oxide nanoparticle of rice.
The organic solvent includes but is not limited to toluene, ortho-xylene or meta-xylene etc., preferably toluene.
The aromatic carboxylic acid includes but is not limited to benzoic acid, p-methylbenzoic acid, o-toluic acid, methylbenzene first
Acid, p-ethylbenzoic acid, p-tert-butyl benzoic acid, p t butylbenzoic acid, to vinyl benzoic acid, P-methoxybenzoic acid,
P-hydroxybenzoic acid, septichen, parachlorobenzoic-acid, m-bromobenzoic acid, p-aminobenzoic acid, terephthalic acid (TPA), 1- naphthalene
Formic acid, 2- naphthoic acid, 4- methyl-1-naphthoic acid, 4- Methoxy-1-naphthoic Acid, 2- hydroxyl-3- naphthoic acid, the bromo- 2- naphthalene first of 6-
Acid.Embodiment in the present invention more preferably, the aromatic carboxylic acid are selected from one of following substance: benzoic acid, right
Methyl benzoic acid, P-hydroxybenzoic acid, p-aminobenzoic acid, 2- naphthoic acid, 2- hydroxyl -3- naphthoic acid, the bromo- 2- naphthoic acid of 6-.
In Membranes On Alumina Particles Surface method of modifying of the present invention, different types of aromatic carboxylic acid and alumina particle are being had
It is mixed in solvent, aromatic carboxylic acid can be reacted with the hydroxyl of Membranes On Alumina Particles Surface, thus with Membranes On Alumina Particles Surface chemistry
Connection obtains the alumina particle for the surface aromatic carboxylic acid modification that structure is logical formula (I) or logical formula (II).
When aromatic carboxylic acid is benzoic acids, gained modified aluminas has the structure of logical formula (I),
Wherein, general formula (I) R11, R12, R13, R14And R15Each independently represent hydrogen atom, C1-C10Alkyl, C2-C10's
Alkenyl, C2-C10Alkoxy, halogen, hydroxyl or amino.
When aromatic carboxylic acid is naphthoic acid class, gained modified aluminas has the structure of logical formula (II),
Wherein, general formula (II) R21, R22, R23, R24, R25, R26And R27Each independently represent hydrogen atom, C1-C10Alkyl,
C2-C10Alkenyl, C2-C10Alkoxy, halogen, hydroxyl or amino.
In general formula (I) or general formula (II), C1-C10Alkyl include but is not limited to methyl, ethyl, propyl, isopropyl, fourth
Base or cyclopropyl；Preferably, the C1-C10Alkyl be methyl or ethyl.C2-C10Alkenyl include but is not limited to ethylene
Base, acrylic, allyl or 1- n-butene base；Preferably, the C2-C10Alkenyl be vinyl or acrylic.C2-C10
Alkoxy include but is not limited to methoxyl group, ethyoxyl, propoxyl group, isopropoxy or cyclopropyl oxygroup etc.；Preferably, described
C2-C10Alkoxy be methoxy or ethoxy.The halogen includes but is not limited to fluorine, chlorine or bromine；Preferably, the halogen
For chlorine or bromine.
The aromatic carboxylic acid modified alumina particles that method of modifying of the present invention obtains can be used as polypropylene nucleater use,
Its additional amount is 0.01wt% to 1wt%.All individual values and subrange of 0.01wt% to 1wt% are included in the application
In and be disclosed in the application；For example, the total amount of surface carboxylic's modified alumina particles can be from lower limit 0.01,0.015,
0.05,0.1,0.2,0.3,0.6,0.8 or 0.9wt% is to the upper limit 0.02,0.025,0.08,0.15,0.3,0.4,0.65,0.9
Or 1wt%.For example, the total amount of surface carboxylic's modified alumina particles can be within the scope of 0.01wt% to 1wt% or surface
The total amount of carboxyl acid modified alumina particle can be within the scope of 0.03wt% to 0.8wt% or 0.01wt% to 0.8wt%
In range.Either type progress in the prior art can be used in adding manner, such as squeezes out, injection molding, molding.
Compared with unmodified alumina particle nucleating agent, the polypropylene of 0.01wt% to 1wt% nucleating agent of the present invention is added
Resin combination, crystallization temperature and blank polypropylene resin composite compare at least 7 DEG C of raising.For example, the phase of crystallization temperature
It can be at least 7,8,10,12,14 or 15 DEG C of lower limit than improving.And unmodified alumina particle is used, when its additive amount is small
When 1.5wt%, polyacrylic crystallization temperature is without being obviously improved.
Compared with silane coupled modified alumina particles nucleating agent, addition 0.01wt% to 1wt% nucleating agent of the present invention
Polypropylene resin composite, crystallization temperature and blank polypropylene resin composite compare at least 7 DEG C of raising.At least 7 DEG C of institute
Have and is included in the application and is disclosed in the application in individual value and subrange；For example, comparing for crystallization temperature improves
It can be at least 7,8,10,12,14 or 15 DEG C of lower limit.And use it is silane coupler modified after alumina particle, when it adds
When dosage is less than 1.5wt%, polyacrylic crystallization temperature is without being obviously improved；Alumina particle addition after silane coupler modified
Amount in 1.5wt% to 5wt%, compare with blank acrylic resin and just only improve 4 DEG C by polyacrylic crystallization temperature.
The present invention is reacted by aromatic carboxylic acid with the hydroxyl of Membranes On Alumina Particles Surface, thus with Membranes On Alumina Particles Surface
Connection is learned, the modified alumina particle of surface aromatic carboxylic acid is obtained.Using aromatic carboxylic acid modified alumina particles surface, change
It has been apt to the mi-crochemistry environment of Membranes On Alumina Particles Surface, has obtained the excellent inorganic particulate nucleating agent of nucleating effect.Pass through addition
After modified alumina particles, crystalling propylene is effectively facilitated, improves polyacrylic crystallization temperature, improves Mechanical Properties of PP,
And good improvement can be reached in the case where modified alumina particles additive amount is minimum.
Detailed description of the invention
Fig. 1 is aromatic carboxylic acid gained modified aluminas general formula when being benzoic acids.
Fig. 2 is aromatic carboxylic acid gained modified aluminas general formula when being naphthoic acid class.
Specific embodiment
The following examples illustrate the present invention, but are not intended to limit the scope of the invention.
1, technological parameter
Procession parameters such as table 1.
1 nucleated polypropylene extruding pelletization condition of table
Molding proces s parameters such as table 2.
2 nucleated polypropylene injecting condition of table
2, test method
Using following methods evaluation use the method for the present invention prepare aromatic carboxylic acid modification alumina particle as at
The polyolefine resin composition performance of core agent.
It is tested using tensile property and bending property of the tensilon to polypropene composition.Tensile property is pressed
ASTM D638-2003 is tested, rate of extension 20mm/min；Bending property is tested by ASTM D790-2003, bending
Rate is 1.3mm/min.
(DSC liter is characterized to the Crystallization peak temperature of polypropylene resin composite using differential scanning calorimeter (DSC)
Rate of temperature fall is 10 DEG C/min).Measured value is bigger, and crystal property is better.
All test materials as nucleating agent are dried before using and with acrylic resin compounding.
The preparation of modified aluminas
Aluminum oxide nanoparticle first: this company of Adama, partial size 10nm；
Aluminum oxide nanoparticle second: Nanjing Tian Hang new material Co., Ltd, partial size 80nm；
Aromatic carboxylic acid and organic solvent are all from commercial product.
Table 3 provides modified oxidized constructed of aluminium used in the embodiment of the present invention
The modified oxidized constructed of aluminium of table 3
Embodiment 1
The preparation of modified aluminas A
In three mouthfuls of reaction kettles equipped with blender, charging hopper and condenser, 6g aluminum oxide nanoparticle first is added,
100cm3Toluene, stirring.Then under stiring, 4.16g benzoic acid is added, after 90 DEG C of reaction 6h, filters, with ethanol washing, 40
DEG C it is dried to obtain white powder.The sample is denoted as BA-Al2O3。
Embodiment 2
The preparation of modified aluminas B
In three mouthfuls of reaction kettles equipped with blender, charging hopper and condenser, 6g aluminum oxide nanoparticle first is added,
100cm3Toluene, stirring.Then under stiring, 5.25g p-methylbenzoic acid is added, after 90 DEG C of reaction 8h, filters, is washed with ethyl alcohol
It washs, 40 DEG C are dried to obtain white powder.The sample is denoted as PTA-Al2O3。
Embodiment 3
The preparation of modified aluminas C
In three mouthfuls of reaction kettles equipped with blender, charging hopper and condenser, 6g aluminum oxide nanoparticle first is added,
100cm3Ortho-xylene, stirring.Then under stiring, 4.27g P-hydroxybenzoic acid is added, after 120 DEG C of reaction 10h, filtering, use
Isopropanol washing, 80 DEG C are dried to obtain white powder.The sample is denoted as PHBA-Al2O3。
Embodiment 4
The preparation of modified aluminas D
In three mouthfuls of reaction kettles equipped with blender, charging hopper and condenser, 6g aluminum oxide nanoparticle first is added,
100cm3Ortho-xylene, stirring.Then under stiring, 5.60g p-aminobenzoic acid is added, after 120 DEG C of reaction 12h, filtering, use
Isopropanol and ethyl alcohol wash respectively, and 80 DEG C are dried to obtain white powder.The sample is denoted as PABA-Al2O3。
Embodiment 5
The preparation of modified aluminas E
In three mouthfuls of reaction kettles equipped with blender, charging hopper and condenser, 6g aluminum oxide nanoparticle second is added,
100cm3Dimethylbenzene, stirring.Then under stiring, 4.89g 2- naphthoic acid is added, after 120 DEG C of reaction 8h, filters, uses isopropanol
It is washed respectively with ethyl alcohol, 90 DEG C are dried to obtain white powder.The sample is denoted as NA-Al2O3。
Embodiment 6
The preparation of modified aluminas F
In three mouthfuls of reaction kettle equipped with blender, charging hopper and condenser, 6g aluminium oxide is added and receives nano particle second,
100cm3Dimethylbenzene, stirring.Then under stiring, 5.75g 2- hydroxyl -3- naphthoic acid is added, after 120 DEG C of reaction 10h, filters,
It is washed respectively with isopropanol and ethyl alcohol, 90 DEG C are dried to obtain white powder.The sample is denoted as HNA-Al2O3。
Embodiment 7
The preparation of modified aluminas G
In three mouthfuls of reaction kettles equipped with blender, charging hopper and condenser, 6g aluminum oxide nanoparticle second is added,
100cm3Dimethylbenzene, stirring.Then under stiring, the bromo- 2- naphthoic acid of 3.89g 6- is added, after 120 DEG C of reaction 12h, filtering, use
Isopropanol and ethyl alcohol wash respectively, and 90 DEG C are dried to obtain white powder.The sample is denoted as BNA-Al2O3。
The preparation of polypropylene resin composite
Table 4 provides polypropylene and nucleating agent used in inventive embodiments 8-42, comparative example 1-7 and nucleating agent weight hundred
Score, wherein polypropylene, using common homopolypropylene and block polypropylene.Lanzhou Petrochemical is respectively adopted in embodiment
T30S, Dushanzi petrochemical industry K9928H be explained experiment effect, but polypropylene is not limited in T30S and K9928H.
4 acrylic resin of table, nucleating agent and additive amount
| Number | Polypropylene | Nucleating agent | Additive amount wt% |
| Embodiment 8 | T30S | BA-Al2O3 | 0.05 |
| Embodiment 9 | T30S | BA-Al2O3 | 0.1 |
| Embodiment 10 | T30S | BA-Al2O3 | 0.2 |
| Embodiment 11 | K9928H | BA-Al2O3 | 0.5 |
| Embodiment 12 | K9928H | BA-Al2O3 | 1.0 |
| Embodiment 13 | T30S | PTA-Al2O3 | 0.05 |
| Embodiment 14 | T30S | PTA-Al2O3 | 0.1 |
| Embodiment 15 | T30S | PTA-Al2O3 | 0.2 |
| Embodiment 16 | K9928H | PTA-Al2O3 | 0.5 |
| Embodiment 17 | K9928H | PTA-Al2O3 | 1.0 |
| Embodiment 18 | T30S | PHBA-Al2O3 | 0.05 |
| Embodiment 19 | T30S | PHBA-Al2O3 | 0.1 |
| Embodiment 20 | T30S | PHBA-Al2O3 | 0.2 |
| Embodiment 21 | K9928H | PHBA-Al2O3 | 0.5 |
| Embodiment 22 | K9928H | PHBA-Al2O3 | 1.0 |
| Embodiment 23 | T30S | PABA-Al2O3 | 0.05 |
| Embodiment 24 | T30S | PABA-Al2O3 | 0.1 |
| Embodiment 25 | T30S | PABA-Al2O3 | 0.2 |
| Embodiment 26 | K9928H | PABA-Al2O3 | 0.5 |
| Embodiment 27 | K9928H | PABA-Al2O3 | 1.0 |
| Embodiment 28 | T30S | NA-Al2O3 | 0.05 |
| Embodiment 29 | T30S | NA-Al2O3 | 0.1 |
| Embodiment 30 | T30S | NA-Al2O3 | 0.2 |
| Embodiment 31 | K9928H | NA-Al2O3 | 0.5 |
| Embodiment 32 | K9928H | NA-Al2O3 | 1.0 |
| Embodiment 33 | T30S | HNA-Al2O3 | 0.05 |
| Embodiment 34 | T30S | HNA-Al2O3 | 0.1 |
| Embodiment 35 | T30S | HNA-Al2O3 | 0.2 |
| Embodiment 36 | K9928H | HNA-Al2O3 | 0.5 |
| Embodiment 37 | K9928H | HNA-Al2O3 | 1.0 |
| Embodiment 38 | T30S | BNA-Al2O3 | 0.05 |
| Embodiment 39 | T30S | BNA-Al2O3 | 0.1 |
| Embodiment 40 | T30S | BNA-Al2O3 | 0.2 |
| Embodiment 41 | K9928H | BNA-Al2O3 | 0.5 |
| Embodiment 42 | K9928H | BNA-Al2O3 | 1.0 |
| Comparative example 1 | T30S | Al2O3First | 0.05 |
| Comparative example 2 | T30S | Al2O3First | 0.1 |
| Comparative example 3 | T30S | Al2O3First | 0.2 |
| Comparative example 4 | K9928H | Al2O3Second | 0.5 |
| Comparative example 5 | K9928H | Al2O3Second | 1.0 |
| Comparative example 6 | T30S | — | 0 |
| Comparative example 7 | K9928H | — | 0 |
Embodiment 8-12
The modified oxidized of the method for the present invention preparation is added by the additive amount in table 4 in the acrylic resin of 100 mass parts
Aluminium (embodiment 1), the two is uniformly mixed, be then added in blender in double screw extruder, is joined according to the technique of table 1
Number is squeezed out, and is prepared containing BA-Al2O3Then the polypropylene resin composite of nucleating agent is infused according to 2 technological parameter of table
It is moulded into standard batten (ASTM standard), is tested using preceding method, properties are listed in table 5.
Embodiment 13-17
The modified oxidized of the method for the present invention preparation is added by the additive amount in table 4 in the acrylic resin of 100 mass parts
Aluminium (embodiment 2), the two is uniformly mixed, be then added in blender in double screw extruder, is joined according to the technique of table 1
Number is squeezed out, and is prepared containing PTA-Al2O3Then the polypropylene resin composite of nucleating agent is infused according to 2 technological parameter of table
It is moulded into standard batten (ASTM standard), is tested using preceding method, properties are listed in table 5.
Embodiment 18-22
The modified oxidized of the method for the present invention preparation is added by the additive amount in table 4 in the acrylic resin of 100 mass parts
Aluminium (embodiment 3), the two is uniformly mixed, be then added in blender in double screw extruder, is joined according to the technique of table 1
Number is squeezed out, and is prepared containing PHBA-Al2O3The polypropylene resin composite of nucleating agent, then according to 2 technological parameter of table
It is molded into standard batten (ASTM standard), is tested using preceding method, properties are listed in table 5.
Embodiment 23-27
The modified oxidized of the method for the present invention preparation is added by the additive amount in table 4 in the acrylic resin of 100 mass parts
Aluminium (embodiment 4), the two is uniformly mixed, be then added in blender in double screw extruder, is joined according to the technique of table 1
Number is squeezed out, and is prepared containing PABA-Al2O3The polypropylene resin composite of nucleating agent, then according to 2 technological parameter of table
It is molded into standard batten (ASTM standard), is tested using preceding method, properties are listed in table 5.
Embodiment 28-32
The modified oxidized of the method for the present invention preparation is added by the additive amount in table 4 in the acrylic resin of 100 mass parts
Aluminium (embodiment 5), the two is uniformly mixed, be then added in blender in double screw extruder, is joined according to the technique of table 1
Number is squeezed out, and is prepared containing NA-Al2O3Then the polypropylene resin composite of nucleating agent is infused according to 2 technological parameter of table
It is moulded into standard batten (ASTM standard), is tested using preceding method, properties are listed in table 5.
Embodiment 33-37
The modified oxidized of the method for the present invention preparation is added by the additive amount in table 4 in the acrylic resin of 100 mass parts
Aluminium (embodiment 6), the two is uniformly mixed, be then added in blender in double screw extruder, is joined according to the technique of table 1
Number is squeezed out, and is prepared containing HNA-Al2O3Then the polypropylene resin composite of nucleating agent is infused according to 2 technological parameter of table
It is moulded into standard batten (ASTM standard), is tested using preceding method, properties are listed in table 5.
Embodiment 38-42
The modified oxidized of the method for the present invention preparation is added by the additive amount in table 4 in the acrylic resin of 100 mass parts
Aluminium (embodiment 7), the two is uniformly mixed, be then added in blender in double screw extruder, is joined according to the technique of table 1
Number is squeezed out, and is prepared containing BNA-Al2O3Then the polypropylene resin composite of nucleating agent is infused according to 2 technological parameter of table
It is moulded into standard batten (ASTM standard), is tested using preceding method, properties are listed in table 5.
Comparative example 1-3
Unmodified aluminum oxide nanoparticle first is added by the additive amount in table 4 in the acrylic resin of 100 mass parts,
The two is uniformly mixed in blender, is then added in double screw extruder, is squeezed out according to the technological parameter of table 1,
The polypropylene resin composite containing unmodified aluminum oxide nanoparticle first is prepared, is then molded into according to 2 technological parameter of table
Standard batten (ASTM standard), is tested using preceding method, and properties are listed in table 5.
Comparative example 4-5
Unmodified aluminum oxide nanoparticle second is added by the additive amount in table 4 in the acrylic resin of 100 mass parts,
The two is uniformly mixed in blender, is then added in double screw extruder, is squeezed out according to the technological parameter of table 1,
The polypropylene resin composite containing unmodified aluminum oxide nanoparticle second is prepared, is then molded into according to 2 technological parameter of table
Standard batten (ASTM standard), is tested using preceding method, and properties are listed in table 5.
Comparative example 6-7
Comparative example 6 directlys adopt polypropylene T30S, and comparative example 7 directlys adopt polypropylene K9928H.
Table 5 provides embodiment 8-42, the crystallization temperature of comparative example 1-7, bending modulus and tensile strength.
5 embodiment 8-42 of table, comparative example 1-7 polypropylene resin composite performance
Either homopolypropylene or block polypropylene as can be seen from Table 5, in the table prepared using the method for the present invention
Under face modified alumina particles are modified, all there is good crystal property and mechanical property；Simultaneously as can be seen that the modified oxygen in surface
Changing alumina particles can use in the level of only 0.1wt%, still show the crystal property observed with higher level, mechanical property
Improve.
Furthermore it can be seen that comparison with comparative example 1-5, add the knot of the polypropylene resin composite of unmodified aluminium oxide
It is smaller that the indexs such as brilliant temperature, mechanical property improve range；And, crystallization temperature and mechanical property modified by aromatic carboxylic acid
It is obvious compared with unmodified aluminium oxide to rise.
Furthermore it can be seen that comparison with comparative example 6-7, be not added with the blank acrylic resin of modified aluminas and be added to
The polypropylene resin composite of aromatic carboxylic acid modified aluminas is compared, and crystal property and mechanical property are all poor.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and modifications, but these corresponding changes and modifications can be made according to the present invention by knowing those skilled in the art
It all should belong to the protection scope of the claims in the present invention.
Claims (14)
1. a kind of method of modifying of aluminium oxide, which is characterized in that in the reactor under stirring condition, by aromatic carboxylic acid and oxygen
Change alumina particles to be added in organic solvent, 2-12h is reacted at 90 DEG C -130 DEG C, products therefrom is washed, is dried to obtain surface virtue
The fragrant carboxyl acid modified aluminium oxide of race.
2. the method for modifying of aluminium oxide according to claim 1, which is characterized in that 100 mass parts alumina particles are based on,
The aromatic carboxylic acid additive amount is 50 to 100 mass parts.
3. the method for modifying of aluminium oxide according to claim 1, which is characterized in that the aromatic carboxylic acid includes benzene first
Acid, p-methylbenzoic acid, o-toluic acid, m-methyl benzoic acid, p-ethylbenzoic acid, p-tert-butyl benzoic acid, tertiary fourth
Yl benzoic acid, to vinyl benzoic acid, P-methoxybenzoic acid, P-hydroxybenzoic acid, septichen, parachlorobenzoic-acid,
M-bromobenzoic acid, p-aminobenzoic acid, terephthalic acid (TPA), 1- naphthoic acid, 2- naphthoic acid, 4- methyl-1-naphthoic acid, 4- methoxy
Base -1- naphthoic acid, 2- hydroxyl -3- naphthoic acid, the bromo- 2- naphthoic acid of 6-.
4. the method for modifying of aluminium oxide according to claim 1, which is characterized in that the alumina particle is nanoscale oxygen
Change alumina particles.
5. the method for modifying of aluminium oxide according to claim 1, which is characterized in that the alumina particle is received for 1-100
The aluminum oxide nanoparticle of rice.
6. the method for modifying of aluminium oxide according to claim 1, which is characterized in that when aromatic carboxylic acid is benzoic acids
When, the surface aromatic carboxylic acid modified aluminas has the structure of logical formula (I),
Wherein, R11, R12, R13, R14And R15Each independently represent hydrogen atom, C1-C10Alkyl, C2-C10Alkenyl, C2-C10
Alkoxy or hydroxyl, halogen, amino.
7. the method for modifying of aluminium oxide according to claim 1, which is characterized in that when aromatic carboxylic acid is naphthoic acid class
When, the surface aromatic carboxylic acid modified aluminas has the structure of general formula (II),
Wherein, general formula (II) R21, R22, R23, R24, R25, R26And R27Each independently represent hydrogen atom, C1-C10Alkyl, C2-
C10Alkenyl, C2-C10Alkoxy or hydroxyl, halogen, amino.
8. alumina modified method according to claim 6 or 7, which is characterized in that in the logical formula (I) or general formula (II)
C1-C10Alkyl include methyl, ethyl, propyl, isopropyl, butyl or cyclopropyl.
9. alumina modified method according to claim 6 or 7, it is characterised in that in the logical formula (I) or general formula (II)
C2-C10Alkenyl include vinyl, acrylic, allyl, 1- n-butene base.
10. alumina modified method according to claim 6 or 7, which is characterized in that the logical formula (I) or general formula (II)
Middle C2-C10Alkoxy include methoxyl group, ethyoxyl, propoxyl group, isopropoxy, cyclopropyl oxygroup.
11. alumina modified method according to claim 6 or 7, which is characterized in that the halogen includes fluorine, chlorine, bromine.
12. the method for modifying of aluminium oxide according to claim 1, which is characterized in that the surface aromatic carboxylic acid is modified
Aluminium oxide can be used as nucleating agent application.
13. the method for modifying of aluminium oxide according to claim 12, which is characterized in that the surface aromatic carboxylic acid is modified
Aluminium oxide is as nucleating agent, and on the basis of base resin quality, additive amount is 0.01wt% to 1wt%.
14. the method for modifying of aluminium oxide according to claim 13, which is characterized in that the base resin is polypropylene tree
Rouge.
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