CN106810715A - A kind of nucleating agent compositions and its application - Google Patents
A kind of nucleating agent compositions and its application Download PDFInfo
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- CN106810715A CN106810715A CN201510848913.3A CN201510848913A CN106810715A CN 106810715 A CN106810715 A CN 106810715A CN 201510848913 A CN201510848913 A CN 201510848913A CN 106810715 A CN106810715 A CN 106810715A
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- nucleating agent
- carboxylate
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- 239000000203 mixture Substances 0.000 title claims abstract description 34
- 239000002667 nucleating agent Substances 0.000 title claims abstract description 25
- -1 aliphatic carboxylate Chemical class 0.000 claims abstract description 41
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 27
- 229920000642 polymer Polymers 0.000 claims abstract description 23
- 239000011347 resin Substances 0.000 claims abstract description 9
- 229920005989 resin Polymers 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 239000011575 calcium Substances 0.000 claims abstract description 6
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 6
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 6
- 239000011734 sodium Substances 0.000 claims abstract description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 4
- 239000011591 potassium Substances 0.000 claims abstract description 4
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 4
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 150000002367 halogens Chemical class 0.000 claims abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 3
- 229910052701 rubidium Inorganic materials 0.000 claims abstract description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims abstract description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000004743 Polypropylene Substances 0.000 claims description 16
- 229920001155 polypropylene Polymers 0.000 claims description 16
- 239000004925 Acrylic resin Substances 0.000 claims description 5
- 229920000178 Acrylic resin Polymers 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 3
- QXJSBBXBKPUZAA-CMDGGOBGSA-N (e)-octadec-10-enoic acid Chemical class CCCCCCC\C=C\CCCCCCCCC(O)=O QXJSBBXBKPUZAA-CMDGGOBGSA-N 0.000 claims description 2
- 241000208317 Petroselinum Species 0.000 claims description 2
- ZQPPMHVWECSIRJ-MDZDMXLPSA-N elaidic acid Chemical class CCCCCCCC\C=C\CCCCCCCC(O)=O ZQPPMHVWECSIRJ-MDZDMXLPSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-M hexadecanoate Chemical compound CCCCCCCCCCCCCCCC([O-])=O IPCSVZSSVZVIGE-UHFFFAOYSA-M 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 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
- OYHQOLUKZRVURQ-AVQMFFATSA-N linoelaidic acid Chemical class CCCCC\C=C\C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-AVQMFFATSA-N 0.000 claims description 2
- 229940049918 linoleate Drugs 0.000 claims description 2
- 229940040452 linolenate Drugs 0.000 claims description 2
- DTOSIQBPPRVQHS-PDBXOOCHSA-M linolenate Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC([O-])=O DTOSIQBPPRVQHS-PDBXOOCHSA-M 0.000 claims description 2
- KEMQGTRYUADPNZ-UHFFFAOYSA-M margarate Chemical compound CCCCCCCCCCCCCCCCC([O-])=O KEMQGTRYUADPNZ-UHFFFAOYSA-M 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- 229940049964 oleate Drugs 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N palmitic acid group Chemical group C(CCCCCCCCCCCCCCC)(=O)O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-M 9-cis,12-cis-Octadecadienoate Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC([O-])=O OYHQOLUKZRVURQ-HZJYTTRNSA-M 0.000 claims 1
- 235000021314 Palmitic acid Nutrition 0.000 claims 1
- VZCCETWTMQHEPK-QNEBEIHSSA-N gamma-linolenic acid Chemical class CCCCC\C=C/C\C=C/C\C=C/CCCCC(O)=O VZCCETWTMQHEPK-QNEBEIHSSA-N 0.000 claims 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 claims 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims 1
- 239000002994 raw material Substances 0.000 claims 1
- 238000002425 crystallisation Methods 0.000 abstract description 7
- 230000008025 crystallization Effects 0.000 abstract description 7
- 239000003595 mist Substances 0.000 abstract description 6
- 230000003287 optical effect Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 20
- 238000012360 testing method Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- 238000000227 grinding Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000001125 extrusion Methods 0.000 description 9
- 239000000654 additive Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 7
- GJAPSKMAVXDBIU-UHFFFAOYSA-L zinc;hexadecanoate Chemical class [Zn+2].CCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCC([O-])=O GJAPSKMAVXDBIU-UHFFFAOYSA-L 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- QSAWQNUELGIYBC-OLQVQODUSA-N (1s,2r)-cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)[C@H]1CCCC[C@H]1C(O)=O QSAWQNUELGIYBC-OLQVQODUSA-N 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 4
- 239000012496 blank sample Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical class OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- NDJKXXJCMXVBJW-UHFFFAOYSA-N heptadecane Chemical compound CCCCCCCCCCCCCCCCC NDJKXXJCMXVBJW-UHFFFAOYSA-N 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 2
- 235000010234 sodium benzoate Nutrition 0.000 description 2
- 239000004299 sodium benzoate Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- AMGRXJSJSONEEG-UHFFFAOYSA-L strontium dichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Sr]Cl AMGRXJSJSONEEG-UHFFFAOYSA-L 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001507939 Cormus domestica Species 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical class OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000010102 injection blow moulding Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002942 palmitic acid derivatives Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229940012185 zinc palmitate Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/017—Additives being an antistatic agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
-
- 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
- C08L2205/24—Crystallisation aids
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 present invention relates to a kind of nucleating agent compositions, including the ring-type organic carboxylate shown in Formulas I and aliphatic carboxylate,In formula, M1Selected from the one kind in potassium, sodium, rubidium and caesium, M2Selected from strontium or calcium, R1、R2、R3、R4、R5、R6、R7、R8、R9、R10Independently selected from hydrogen, C1-C10Alkyl, C1-C9Alkyl amino, halogen, phenyl, hydroxyl, C1-C9Alkoxy, C2-C9Alkenyloxy group and amino.The nucleating agent compositions are good with resin compatible, are uniformly dispersed in resin, are difficult to reunite or separate out.By adding above-mentioned nucleating agent compositions, crystallization temperature, heat resistance, rigidity, the toughness of polymer product can be significantly improved, and improve its optical property, such as mist degree, yellow colour index, with preferable prospects for commercial application and economic worth.
Description
Technical field
The present invention relates to polymer processing aidses field, and in particular to a kind of nucleating agent compositions and contain the nucleation
The polymer product of agent composition.
Background technology
Polypropylene be in current five big general synthetic resins the most fast kind of concerned growth rate, but poly- third
There is the low shortcoming of poor rigidity, poor toughness, transparency in alkene.Nucleator can promote non-crystalline type or imperfect crystal
Type polymer crystallization simultaneously makes grainiess miniaturization, so as to improve the crystallinity of polymer.By adding nucleator
Method be also greatly improved polypropylene articles stretching, bending and shock resistance.Further, since nucleator
The size of polypropylene crystals is set to diminish, so as to dissipating on the crystalline portion and amorphous fraction interface that reduce crystal
Penetrate, thus be remarkably improved the polyacrylic transparency.
Polypropylene nucleater chemically can be divided into inorganic nucleator and the class of organic nucleating agent two in structure.It is inorganic into
Core agent mainly has talcum powder, titanium dioxide, nano silicon etc., and this kind of nucleator abundance is inexpensive easy
, but to product the transparency and lustrous surface have a certain impact, using effect is poor, and range of application is subject to
Limitation.
Organic nucleating agent mainly has phosphate metal salt, carboxylic metallic salt and glucitol derivative and other macromolecules
Nucleator etc..Organic nucleating agent has good compatibility with fluoropolymer resin, can significantly improve the saturating of product
Bright property and lustrous surface.For example, the compound 1,3 of Milliken exploitations:Double (3,4- dimethyl benzylidenes) sorbs of 2,4-
Sugar alcohol improves the transparency of polymer product, but the shortcoming of the nucleator is addition high, and processing temperature is high,
There is peculiar smell in process, easily separated out in product.Additionally, nucleator need when in use it is certain uniform
Dispersiveness, therefore generally exist with powder-form, but powdery nucleator is typically easy to the moisture absorption and influences nucleation performance.
The content of the invention
In view of above-mentioned the deficiencies in the prior art, present inventor has done numerous studies to polypropylene nucleater simultaneously
Have been surprisingly found that, specific ring-type organic carboxylate and aliphatic carboxylate are coordinated and is used as nucleator, itself and resin
Compatibility and favorable dispersibility, and the crystallization temperature of polymer product, heat resistance, just can be significantly improved
Property, toughness, and improve its transparency.
First implementation method of the invention is to provide a kind of nucleating agent compositions, including the ring-type shown in Formulas I
Organic carboxylate and aliphatic carboxylate,
In formula, M1Selected from the one kind in potassium, sodium, rubidium and caesium, M2It is strontium or calcium, R1、R2、R3、R4、
R5、R6、R7、R8、R9、R10Independently selected from hydrogen, C1-C10Alkyl, C1-C9Alkyl amino, halogen,
Phenyl, hydroxyl, C1-C9Alkoxy, C2-C9Alkenyloxy group and amino.
According to the present invention, if R1-R10When being alkyl, the alkyl on any two ortho position or same carbon can be tied
Close the carbocyclic ring for forming up to six carbon atom.
Inventor has found that the ring-type organic carboxylate shown in the Formulas I has group when placing at normal temperatures under study for action
Poly- phenomenon, disperses uneven in resin process, thus influence crystallization effect；Add aliphatic monocarboxylic acid
Salt can improve the dispersive property of the ring-type organic carboxylate, it is dispersed in polymer product, no
Easily separate out.The nucleating agent compositions coordinated by ring-type organic carboxylate and aliphatic monocarboxylic acid salt, can
Significantly improve the mechanical performance of polymer product, additionally it is possible to reduce the mist degree and yellow colour index of polymer product, change
It is apt to its transparency and lustrous surface, and it does not react with the acid scavenger being widely used in polymerisation,
Compatibility is good.
One of the invention preferred embodiment in, the gross weight with nucleating agent compositions as calculating benchmark, institute
The content for stating ring-type organic carboxylate is 10-70 weight %, preferably 30-70 weight %；The aliphatic carboxylic acid
Salt is 10-70 weight %, preferably 20-50 weight %.
Within the above range, the nucleating agent compositions are uniformly dispersed, and do not have agglomeration, compatible with resin
Property and favorable dispersibility, help to form the polymer product of high-quality.
One of the invention preferred embodiment in, according to actual needs, above-mentioned nucleating agent compositions
Also include additive, the additive may be selected from dispersant, stabilizer, antioxidant, antistatic additive, ultraviolet
At least one in light absorbers and other additives commonly used in the art, wherein, the stabilizer is preferred
It is steric hindrance amine light stabilizer, the antioxidant is preferably phosphorus antioxidants and phenol antioxidant, described
Antistatic additive is preferably fatty acid ester antistatic additive.
According to the present invention, above-mentioned additive can be added to nucleator group in any appropriate form such as powder, particle
In compound.
It is of the invention another preferred embodiment in, the ring-type organic carboxylate be cis ring-type it is organic
Carboxylate.
It is of the invention another preferred embodiment in, the R1、R2、R3、R4、R5、R6、R7、
R8、R9、R10Independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl,
Isobutyl group, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl, neopentyl, n-hexyl, 2- methyl amyls, 3-
Methyl amyl, 2,3- dimethylbutyls and 2, the one kind in 2 '-dimethylbutyl, more preferably hydrogen, M1For potassium or
Sodium, M2It is calcium.
One of the invention preferred embodiment in, the aliphatic carboxylate be C12-C29Aliphatic carboxylic
Hydrochlorate, preferably C14-C20Aliphatic carboxylate, more preferably margarate, stearate, palmitic acid
Salt, petroselinum hydrochlorate, oleate, elaidic acid salt, isooleic acid salts, for example, linoleate, linolelaidic acid salt, γ-flax
One or more in hydrochlorate, linolenate and ricinate.
One of the invention preferred embodiment in, the aliphatic carboxylate be palmitate, heptadecane
One or more in hydrochlorate and 12- hydroxyl stearates.
Another embodiment of the invention is the preparation method for providing above-mentioned nucleating agent compositions, including：Will
The ring-type organic carboxylate and aliphatic carboxylate's grinding, mixing.
According to the present invention, the Ginding process and mixed method can be any methods commonly used in the art, grinding
Process and mixed process can be carried out simultaneously, it is also possible to which first carry out process of lapping carries out mixed process again.
The grinding for being used and/or mixer, can specifically be enumerated as mortar, ball mill, roller mill, hammer-mill,
Grinding mill, taper grinding machine, vibrator, rod mill, tube mill, Hai Siwen ball mills, colloidal mill,
General class mayer colloidal mill, jet-O-Mizer, ultra tiny metal grinding machine, injector-type mill, nanometer bradawl
Head, fine grinding machine, micron grinding machine, charlotte colloid mill machine, rotation stage property, two-dimentional batch mixer and other tools
There is the instrument of grinding and/or immixture.
One of the invention preferred embodiment in, by the ring-type organic carboxylate and aliphatic carboxylate
Mixed in two-dimentional batch mixer again after being ground in ball mill.
The time of mixed grinding can be according to the species of the grinder for using and model, severity of grind, material powder
Species etc. is selected, usually -10 hours 5 minutes, preferably 0.5-2 hours, more preferably 1 hour.
Yet further embodiment of the invention is to provide a kind of polymer product, including above-mentioned nucleator combination
Thing.
According to the present invention, the polymer product includes such as polyolefin such as polypropylene, polyethylene, also including polyester.
Polymer product of the present invention is added in polymer by by above-mentioned nucleating agent compositions, and by this
Any appropriate mode in field mixes, and by any appropriate mode in this area be processed into the mixture by continuation
Type, obtains the polymer product,
According to the present invention, the method for the machine-shaping, including but not limited to stretch-blow, extrusion, extrusion are blown
Modeling, film extrusion, foam extrusion, injection-blow molding, injection moulding, injection rotational forming, cast film extrusion,
Thermoforming, thin plate injection moulding and its similar approach.
In one of the invention preferred implementation method, the polymer product is with acrylic resin as former
The polypropylene articles of material.
According to the present invention, the polypropylene articles include acrylic resin and above-mentioned nucleating agent compositions, relative to
The acrylic resin of 100 weight portions, the content of the nucleating agent compositions is 0.01-2.0 weight portions, preferably
0.04-1 weight portions.
Nucleating agent compositions in above range, compatibility and favorable dispersibility with acrylic resin, Neng Gouyou
Effect improves rigidity, impact resistance, heat resistance and the transparency of polypropylene articles.
The beneficial effects of the present invention are the nucleating agent compositions are good with resin compatible, divide in resin
Dissipate it is uniform, be difficult to reunite or separate out.By adding above-mentioned nucleating agent compositions, polymer system can be significantly improved
The crystallization temperature of product, heat resistance, rigidity, toughness, and improve its optical property, such as mist degree, yellow colour index,
With preferable prospects for commercial application and economic worth.
Specific embodiment
The following example is only used for that the present invention is described in detail, it will be appreciated that the scope of the present invention is not
It is limited to these embodiments.
In the examples below that, the various reagents for being used are for purchased in market；Ball mill is frequency conversion type ball mill XQM-2,
Nanjing Kexi Inst. of Experiment Instrument；Two-dimentional batch mixer is KH-5, the prompt beautiful really limited public affairs of plant equipment of Beijing Kun
Department.
Embodiment 1
At room temperature, 4.0 grams of 16.6 grams of cis hexahydrophthalic acid and NaOH are added equipped with agitator and
In the flask of thermometer, distilled water 150mL is added, start to be stirred and heated to 50 DEG C.Heating stirring 1
After hour, to addition 3.7 grams of (cis hexahydrophthalic acids of calcium hydroxide in reaction system:NaOH:Hydrogen-oxygen
The mol ratio for changing calcium is 1:1:0.5), continue to stir 4 hours.Product to obtaining carries out suction filtration, is used in combination
Appropriate distillation water washing, suction filtration, filter cake is dried in drying box again, obtains cis hexahydrophthalic acid
Sodium calcium, i.e. ring-type organic carboxylate I1。
By 58wt% ring-type organic carboxylates I1, 38wt% zinc palmitates and 4wt% fatty acid esters be placed in ball mill
Mixed grinding 1 hour, then mixes 30 minutes in two-dimentional batch mixer, and nucleator 1 is obtained.
Embodiment 2
At room temperature, 11.3 grams of 34.8 grams of cis hexahydrophthalic acid and potassium hydroxide are added and is furnished with agitator
In the flask of thermometer, distilled water 250mL is added, start to be stirred and heated to 40 DEG C.Heating stirring 2
70 DEG C are warming up to after hour, to addition 7.5 grams of (cis hexahydrophthalic acids of calcium hydroxide in reaction system:
Potassium hydroxide:The mol ratio of calcium hydroxide is 1:1:0.5), continue to stir 6 hours.Product to obtaining is entered
Row suction filtration, and water washing is distilled with appropriate, suction filtration, filter cake is dried in drying box again, obtains cis six
Hydrogen phthalic acid potassium calcium, i.e. ring-type organic carboxylate I2。
By 80wt% ring-type organic carboxylates I2It is small mixed grinding 1 in ball mill to be placed in 20wt% zinc palmitates
When, then mix 30 minutes in two-dimentional batch mixer, nucleator 2 is obtained.
Embodiment 3
At room temperature, 6.5 grams of 28 grams of cis hexahydrophthalic acid and NaOH are added and is furnished with agitator and temperature
Spend in the flask of meter, add distilled water 150mL, start to be stirred and heated to 50 DEG C.Heating stirring 2 hours
After be warming up to 85 DEG C, in reaction system add Strontium dichloride hexahydrate 21.65g (cis hexahydrophthalic acids:
NaOH:The mol ratio of Strontium dichloride hexahydrate 21.65g is 1:1:0.5), continue to stir 5 hours.To obtaining
Product carry out suction filtration, and with appropriate distillation water washing, suction filtration, filter cake is dried in drying box again,
Obtain cis hexahydrophthalic acid strontium sodium, i.e. ring-type organic carboxylate I3。
By 70wt% ring-type organic carboxylates I3It is small mixed grinding 1 in ball mill to be placed in 30wt% zinc palmitates
When, then mix 30 minutes in two-dimentional batch mixer, nucleator 3 is obtained.
The nucleator composition of the embodiment 1-3 of table 1
| Sequence number | Ring-type organic carboxylate and content | Aliphatic carboxylate and content | Additive |
| Embodiment 1 | 38wt% zinc palmitates | 4wt% fatty acid esters | |
| Embodiment 2 | 20wt% zinc palmitates | / | |
| Embodiment 3 | 30wt% zinc palmitates | / |
Comparative example 1
By by the ring-type organic carboxylate I of 100wt%1The nucleator of composition as a comparison case 1.
Comparative example 2
The nucleator that will be made up of the Sodium Benzoate of 100wt% as a comparison case 2.
Comparative example 3
The nucleator that will be made up of the Sodium Benzoate of 58wt% and the zinc palmitate of 42wt% as a comparison case 3.
Test example 1
Take respectively polypropylene (melt mass flow rate MFR be 2-3g/10min (according to GB/T 3682-2000,
At 230 DEG C, 2.16Kg conditions are measured) HOPP) each 100 weight portion, with 0.2 weight portion into
After core agent sample is well mixed in super mixer, by four heating in TE-34 type double screw extruders
Area carries out melting mixing, extrusion, and extrusion temperature is 220 DEG C, is then molded through injector (ST125 types),
Injection temperature is 230 DEG C, is made sample；The polypropylene of nucleator will be added without through same treatment, as blank
Sample.
Sample to obtaining carries out mist degree, light transmittance and tests (by GB/T 2410-2008 testing standards) and yellow
Index tests (pressing HG/T 3862-2006 testing standards), and test result is shown in Table 2.
The Polymer optical the performance test results of table 2
| Nucleator | Blank | Nucleator 1 | Nucleator 2 | Nucleator 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Mist degree (%) | 55.6 | 39.8 | 40.0 | 40.9 | 49.8 | 60.0 | 61.5 |
| Light transmittance (%) | 88.3 | 90.0 | 89.6 | 89.7 | 89.1 | 89.1 | 89.2 |
| Yellow colour index | 7.78 | 6.14 | 5.97 | 6.08 | 7.06 | 7.28 | 7.16 |
As can be seen from Table 2, by using nucleator 1-3 of the invention, compared to comparative example, blank sample,
The mist degree and yellow colour index of polypropylene articles can be made to be significantly reduced, and increased the transparency of product, and improve it
Light transmittance.
Test example 2
(melt mass flow rate MFR is 0.2-0.5g/10min (according to GB/T to take polypropylene respectively
3682-2000, measures in 230 DEG C, 2.16Kg conditions) COPP) each 100 weight portion, with 0.06
After the nucleator sample of parts by weight is well mixed in super mixer, carried out using above-mentioned same extruder
Melting mixing, extrusion, extrusion temperature are 210 DEG C, are then molded through injector (ST125 types), injection temperature
It is 230 DEG C to spend, and is made sample；The polypropylene of nucleator will be added without through same treatment, as blank sample.
Sample to obtaining carries out bending modulus test (by GB/T 9341-2008 testing standards), cantilever beam and lacks
Mouth impact strength test (pressing GB/T 1843-2008 testing standards, tested under the conditions of 23 DEG C), heat become
Shape temperature test (pressing GB/T 1634.2-2004 testing standards) and crystallization temperature (Tc) test (heat up, drop
Warm speed is 10 DEG C/min), test result is shown in Table 3.
The mechanical properties of polymer test result of table 3
From table 3 it can be seen that compared with blank sample and comparative example, using nucleator 1-3 of the invention, energy
Polypropylene articles heat distortion temperature, crystallization temperature (Tc), bending modulus and impact strength are enough significantly improved, from
And realize processing characteristics higher, heat resistance and more excellent mechanical performance.
It should be noted that embodiment described above is only used for explaining the present invention, do not constitute to this hair
Bright any limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that its
In word used be descriptive and explanatory vocabulary, rather than limited vocabulary.Can be by regulation at this
The present invention is modified in the range of invention claim, and without departing substantially from the scope of the present invention and essence
The present invention is revised in god.Although the present invention described in it is related to specific method, material and reality
Example is applied, it is not intended that the present invention is limited to wherein disclosed particular case, conversely, the present invention is expansible
To other all methods and applications with identical function.
Claims (10)
1. a kind of nucleating agent compositions, including the ring-type organic carboxylate shown in Formulas I and aliphatic carboxylate,
In formula, M1Selected from the one kind in potassium, sodium, rubidium and caesium, M2It is strontium or calcium, R1、R2、R3、R4、
R5、R6、R7、R8、R9、R10Independently selected from hydrogen, C1-C10Alkyl, C1-C9Alkyl amino, halogen,
Phenyl, hydroxyl, C1-C9Alkoxy, C2-C9Alkenyloxy group and amino.
2. composition according to claim 1, it is characterised in that gross weight with nucleating agent compositions is to count
Benchmark is calculated, the content of the ring-type organic carboxylate is 10-70 weight %, preferably 30-70 weight %；It is described
Aliphatic carboxylate is 10-70 weight %, preferably 20-50 weight %.
3. composition according to claim 1 and 2, it is characterised in that the ring-type organic carboxylate
It is cis ring-type organic carboxylate.
4. the composition according to any one of claim 1-3, it is characterised in that the R1、R2、
R3、R4、R5、R6、R7、R8、R9、R10Independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl
Base, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl, neopentyl, just
One kind in hexyl, 2- methyl amyls, 3- methyl amyls, 2,3- dimethylbutyls and 2,2 '-dimethylbutyl.
5. the composition according to claim any one of 1-4, it is characterised in that the aliphatic carboxylate
It is C12-C29Aliphatic carboxylate, preferably C14-C20Aliphatic carboxylate, more preferably Heptadecanoic acide
Salt, stearate, palmitate, petroselinum hydrochlorate, oleate, elaidic acid salt, isooleic acid salts, for example, linoleate,
One or more in linolelaidic acid salt, gamma-Linolenic acid salt, linolenate and ricinate.
6. composition according to claim 5, it is characterised in that the aliphatic carboxylate is palmitic acid
One or more in salt, margarate and 12- hydroxyl stearates.
7. the preparation method of a kind of composition according to claim any one of 1-6, including：By the ring
Shape organic carboxylate and aliphatic carboxylate grind, are mixed into powder.
8. the nucleating agent compositions any one of a kind of polymer product, including claim 1-6.
9. polymer product according to claim 8, it is characterised in that the polymer product is with poly-
Allyl resin is the polypropylene articles of raw material.
10. polymer product according to claim 9, it is characterised in that relative to 100 weight portions
Acrylic resin, the content of the nucleating agent compositions is 0.01-2.0 weight portions, preferably 0.04-1 weight portions.
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