CN1611549A - Polyamide composition and its preparing method - Google Patents
Polyamide composition and its preparing method Download PDFInfo
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- CN1611549A CN1611549A CN 200310101795 CN200310101795A CN1611549A CN 1611549 A CN1611549 A CN 1611549A CN 200310101795 CN200310101795 CN 200310101795 CN 200310101795 A CN200310101795 A CN 200310101795A CN 1611549 A CN1611549 A CN 1611549A
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- rubber
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- rubber latex
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- 239000000203 mixture Substances 0.000 title claims description 64
- 238000000034 method Methods 0.000 title claims description 24
- 239000004952 Polyamide Substances 0.000 title abstract description 14
- 229920002647 polyamide Polymers 0.000 title abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 100
- 239000002131 composite material Substances 0.000 claims abstract description 98
- 239000004927 clay Substances 0.000 claims abstract description 89
- 229920000126 latex Polymers 0.000 claims abstract description 86
- 229920001971 elastomer Polymers 0.000 claims abstract description 58
- 239000005060 rubber Substances 0.000 claims abstract description 58
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000004816 latex Substances 0.000 claims description 50
- 238000004132 cross linking Methods 0.000 claims description 46
- 239000002245 particle Substances 0.000 claims description 37
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 33
- 229920003656 Daiamid® Polymers 0.000 claims description 31
- 238000002360 preparation method Methods 0.000 claims description 30
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 27
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 24
- 239000010410 layer Substances 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 22
- 239000002002 slurry Substances 0.000 claims description 17
- 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 description 15
- 239000011734 sodium Substances 0.000 claims description 15
- 229910052708 sodium Inorganic materials 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 13
- 229920006174 synthetic rubber latex Polymers 0.000 claims description 11
- 239000000839 emulsion Substances 0.000 claims description 10
- 239000011229 interlayer Substances 0.000 claims description 10
- 229920002857 polybutadiene Polymers 0.000 claims description 10
- 241000446313 Lamella Species 0.000 claims description 9
- 229920000459 Nitrile rubber Polymers 0.000 claims description 8
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 7
- 229910001415 sodium ion Inorganic materials 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 6
- 230000005855 radiation Effects 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 229920013649 Paracril Polymers 0.000 claims description 4
- 239000005062 Polybutadiene Substances 0.000 claims description 4
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 229920002379 silicone rubber Polymers 0.000 claims description 4
- 150000003673 urethanes Chemical class 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 3
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 claims description 3
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052621 halloysite Inorganic materials 0.000 claims description 3
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 claims description 3
- 229910000271 hectorite Inorganic materials 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims description 3
- 238000004073 vulcanization Methods 0.000 claims description 3
- 229920002449 FKM Polymers 0.000 claims description 2
- 244000043261 Hevea brasiliensis Species 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- IRLQAJPIHBZROB-UHFFFAOYSA-N buta-2,3-dienenitrile Chemical compound C=C=CC#N IRLQAJPIHBZROB-UHFFFAOYSA-N 0.000 claims description 2
- 229920001973 fluoroelastomer Polymers 0.000 claims description 2
- 229920003052 natural elastomer Polymers 0.000 claims description 2
- 229920001194 natural rubber Polymers 0.000 claims description 2
- 229920006173 natural rubber latex Polymers 0.000 claims description 2
- 239000004945 silicone rubber Substances 0.000 claims description 2
- 239000002689 soil Substances 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 claims 1
- 229920003051 synthetic elastomer Polymers 0.000 claims 1
- 239000005061 synthetic rubber Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 3
- 150000001408 amides Chemical class 0.000 description 22
- 238000012360 testing method Methods 0.000 description 21
- 238000002347 injection Methods 0.000 description 17
- 239000007924 injection Substances 0.000 description 17
- 239000008188 pellet Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- 239000004677 Nylon Substances 0.000 description 13
- 229920001778 nylon Polymers 0.000 description 13
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 11
- 239000003112 inhibitor Substances 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- 230000004048 modification Effects 0.000 description 9
- 239000002114 nanocomposite Substances 0.000 description 9
- 229920003023 plastic Polymers 0.000 description 9
- 239000004033 plastic Substances 0.000 description 9
- 238000012986 modification Methods 0.000 description 8
- 238000012545 processing Methods 0.000 description 8
- 229920002292 Nylon 6 Polymers 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- 229910001414 potassium ion Inorganic materials 0.000 description 4
- 230000003014 reinforcing effect Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 229940059574 pentaerithrityl Drugs 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- -1 (methyl) Octyl Chemical group 0.000 description 2
- GUTLYIVDDKVIGB-OUBTZVSYSA-N Cobalt-60 Chemical compound [60Co] GUTLYIVDDKVIGB-OUBTZVSYSA-N 0.000 description 2
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 239000004258 Ethoxyquin Substances 0.000 description 1
- 229920003189 Nylon 4,6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- DECIPOUIJURFOJ-UHFFFAOYSA-N ethoxyquin Chemical compound N1C(C)(C)C=C(C)C2=CC(OCC)=CC=C21 DECIPOUIJURFOJ-UHFFFAOYSA-N 0.000 description 1
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- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012802 nanoclay Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
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- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a kind of polyamide combination and its manufacturing method, which involves in polyamide resin modifying technological field. The polyamide combination contains polyamide resin and composite powder. The weight ratio of composite powder and polyamide resin is (0.5-100) : 100. The composite powder contains argillic horizon and rubber globule with no organic faculty, which is manufactured by blending raw material containing rubber latex and clay sera with irradiation or no irradiation evenly and then drying. Using this composite powder to modify polyamide resin can improve the allround properties of polyamide; furthermore, it can improve heat resistance of polyamide resin while it has fine rigidity.
Description
Technical field
The present invention relates to a kind of polymeric amide of modification, say further, relate to Amilan polyamide resin composition of a kind of composite powder modification and preparation method thereof.
Background technology
Polymeric amide is as a kind of engineering plastics, and it has good wear resistance, self lubricity and thermotolerance, and its oil-proofness is good, physical strength height, advantages such as easy machine-shaping.But because the strong polar characteristics of polymeric amide cause its water-intake rate big, suction back intensity and Young's modulus descend more.And the heat-drawn wire of polymeric amide is low, is unsuitable for the application that temperature is had higher requirements.The shock strength of polymeric amide when dry state and low temperature is lower in addition, shows shortcomings such as tangible notch sensitivity.Therefore be very necessary to toughness reinforcing, the enhancing of polymeric amide and the modification of thermotolerance aspect.
At present, the toughness reinforcing employing elastomerics of polyamide resin comes modification usually.Used elastomerics generally is an olefin copolymer, as ethylene-propylene rubber(EPR), SBS etc.But because the consistency of this type of elastomerics and polymeric amide is poor, must improve consistency by carboxylic acid or acid anhydride-grafted elastomerics, maleic anhydride commonly used carries out modification.The introducing of maleic anhydride can cause environmental pollution and production cost higher.In addition,, can cause intensity, the rigidity of material, the greater loss of heat-drawn wire simultaneously, limit the practical application of material so greatly though traditional elastomerics can improve the toughness of polymeric amide greatly.
From the tough angle of elastomerics, applicant of the present invention provides a kind of in the Chinese patent application of submitting on September 13rd, 2,000 00124703.4 (CN 1342724A) be the toughness reinforcing polymeric amide of rubber particles of 0.02 μ m～0.2 μ m by median size.Because it is very little to be used for toughness reinforcing rubber particles particle diameter, has brought the effect different with conventional elastic body toughening, the strong and unyielding balance of the daiamid composition that makes therefrom, stable performance.But this daiamid composition, heat-drawn wire incurs loss behind toughening modifying.
The development of the nanometer composite polyamide-clay material that utilizes nanoclay material to improve the rigidity of polymeric amide at present and obtain is very rapid (as " polymkeric substance-inorganic nano composite material ", Chemical Industry Press 2002.12 publishes nano material and utilisation technology book series).The clay that is used to prepare nanometer composite polyamide-clay material is generally laminated clay.This laminated clay has the laminated structure of nano level yardstick, is natural nano material, is very suitable for preparing nano composite material.But because the sheet interlayer spacing of laminated clay is very little, and contained be mineral ion, the interlayer that organic polymer can't enter into clay layer makes it peel off into the disperse phase of nano-grade size.So before this polymer clay nanocomposites of preparation, need handle to clay, surface-treated clay and various organism to be replaced, the nanometer persursor material that obtains containing organo-functional group is used for further nano combined.The process of preparation nanometer persursor material also becomes the clay processing that organises.Organise clay after handling, the lamella interlayer is replaced as organo-functional group such as organic positively charged ion etc., makes polymer monomer or polymer macromolecule be easy to insert (seeing " polymkeric substance-inorganic nano composite material " the 21st～22 page).Adopt intercalation compounding laminated clay can be scattered in the form of nanometer lamella to the clay after organising and make composite nano polymer/clay material in the polymeric matrix, characteristics such as that this nano composite material has is high-strength, Gao Mo, high heat distortion temperature.Chinese patent CN1055706C and CN1081207C have reported respectively by in-situ inserted polymerization and melt intercalated method and have prepared nanometer composite polyamide-clay material, these two kinds of methods all need polynite is organised processing so that intercalation is compound, but make that the preparation process of matrix material is complicated.At present,, and directly utilize natural earth synthetic polymer/clay nanocomposites, then can reduce cost greatly, also have important industrialization and commercial value if can make clay need not pass through the preparation process of any organic modification.Recently, Polymer 44 (2002) 2933～2937: reported in " Nylon 6/Na-montmorillonite nanocomposites prepared bycompounding Nylon 6 with Na-montmorillonite slurry " literary composition that Japanese Toyota research centre adopts a kind of recombining process of novelty, being that raw material can successfully prepare nanometer composite polyamide-clay material without clay slurry and the polymeric amide of handling that organise.This method biggest advantage do not need to be the clay processing that organises just can obtain the nano composite material of separability, and the mechanical property of matrix material is improved greatly.But this technology is very harsh for the requirement of equipment, and industrialization truly has certain difficulty, and particularly the discharge to moisture requires very strict.
More than these technology of utilizing clay material to come modified polyamide, the rigidity of polymeric amide is improved, but simultaneously makes the shock resistance of polymeric amide be subjected to bigger loss.
Summary of the invention
The applicant provides a kind of composite powder that includes rubber particles and inorganic particulate in the Chinese patent application 03109108.3 of application on April 3rd, 2003.This composite powder is by will be through irradiation or without the rubber latex of irradiation and inorganic particulate slurries etc., and even by the mixed of required dry weight, drying is prepared then.
As everyone knows, clay mineral such as sodium-based montmorillonite etc. can be peeled off into lamella fully in water, and clay layer is dispersed in and forms clay slurry (clay dispersion) in the water.In addition, most of rubber all exist with the emulsion form of oneself.The contriver finds according to the method that provides in the Chinese patent application 03109108.3, with clay slurry with mix through irradiation or without the irradiation rubber latex, clay layer and latex particle will intert and isolate mutually.Carry out spraying drying this moment, and both microcosmic nano composite structures just can be preserved, and theoretically, montmorillonite layer is peeled away fully in the composite powder that obtains, and keeps its nano-scale.
Therefore, on this basis, the inventor has developed the daiamid composition with the composite powder modification that includes rubber particles and clay layer.This composite powder with the polyamide blended composition that obtains in, rubber particles and clay layer homodisperse in matrix, clay layer can be peeled off in matrix fully.Weight ratio by rubber and clay in the adjusting composite powder can realize improving the said composition flexible and keep higher rigidity simultaneously, also can realize improving its inflexible and keep high toughness simultaneously, can also obtain high heat-drawn wire simultaneously.
In preparation toughening polyamide combination process of the present invention, used clay does not need to carry out any processing that organises of the prior art just can peel off into lamella, the simple easy handling of technology fully in plastic substrate.
Therefore, the purpose of this invention is to provide a kind of daiamid composition that contains rubber particles and clay layer.It has favorable rigidity, toughness and thermotolerance.
Another object of the present invention provides the preparation method of described daiamid composition.
The daiamid composition of a kind of modification of the present invention is characterized in that including in this kind resin combination the following component of blend: polyamide resin and composite powder.The weight ratio of composite powder and polyamide resin is (0.5～100): 100, preferred (1～50): 100, more preferably (1～40): 100.
Polyamide resin among the present invention in the composition comprises the disclosed various types of polyamide resins of prior art, comprises nylon 6, nylon 66, nylon 46 or nylon 1010 etc.
Composite powder described in the present composition includes rubber particles and clay layer, and wherein the weight ratio of rubber particles and clay layer is 99: 1～20: 80, is preferably 95: 5～40: 60.
Himself gel content of the rubber particles that contains in the above-described composite powder is 60% weight or higher, preferred 75% weight or higher.The median size of rubber particles is 20～2000nm, is preferably 30～1500nm, more preferably 50～500nm.The kind of described rubber particles is selected from least a in the following rubber kind: natural rubber, styrene-butadiene rubber(SBR), carboxylic styrene-butadiene rubber, paracril, carboxy nitrile rubber, polybutadiene rubber, chloroprene rubber, silicon rubber, esters of acrylic acid rubber, vinylpyridiene-styrene-butadiene rubber, Acrylester Butadiene Rubber, urethanes or viton etc.
The clay that composite powder contains in the present composition is the clay with laminate structure, comprises natural and/or the synthetic clay, and it exists with the nanometer sheet form of peeling away in composite powder.The laminated clay that the present invention relates to can be dispersed into suspension in water, it is selected from one of following material or its combination: green stone, polynite, talcum powder, beidellite, hectorite, silica, halloysite.Be easier to be dispersed in the water because the clay layer interlayer cation is the clay of sodium ion, potassium ion, the clay that relates among the present invention is preferably the clay that interlayer cation is sodium ion or potassium ion, more preferably interlayer cation is the clay of sodium ion, as sodium-based montmorillonite.The mean thickness of the contained clay layer of composite powder is 0.5～100nm in daiamid composition provided by the invention, is preferably 0.8～50nm.Clay in the composite powder involved in the present invention is handled without of the prior art organising (functionalized), so this clay does not contain organo-functional group.
Above-described composite powder can adopt 03109108.3 kind of method that provides of Chinese patent application of submitting on April 3rd, 2003 according to the applicant to prepare.
Composite powder in this patent application (03109108.3) is by will be through irradiated or without irradiated rubber latex and inorganic particulate slurries etc., by required dry weight mixed and stir, and the prepared composite powder of drying then.In the present invention, the inorganic particulate slurries adopt clay slurry, and specifically, composite powder of the present invention is got by the method preparation that comprises one of following steps:
A. with clay slurry, mix, obtain mixed emulsion, again with this mixed emulsion drying with the cross-linking type synthetic rubber latex;
B. after adding or not adding under the situation of crosslinking coagent, adopting the high-energy radiation line source to carry out radiation vulcanization rubber latex, again with clay slurry, mix with rubber latex behind the irradiation, obtain mixed emulsion, again with this mixed emulsion drying;
Clay slurry in the preparation method of described composite powder is the suspension of laminated clay in water, can directly adopt commercial slurries product, with need before rubber latex is mixed to disperse through common dispersing apparatus (as high-shearing dispersion emulsifying machine, colloidal mill etc.), with guarantee clay layer in the slurries can be in water homodisperse.If clay does not have the slurries of commercial grade, also can make by oneself, promptly adopt common dispersing apparatus to make clay and an amount of water formation steady suspension, and then mix with rubber latex.
Laminated clay in the present composition among the composite powder preparation method comprises natural and/or the synthetic clay.Laminated clay of the present invention can be dispersed into suspension in water, it is selected from one of following material or its combination: green stone, polynite, talcum powder, beidellite, hectorite, silica, halloysite.Be easier to be dispersed in the water because the lamella interlayer cation is the clay of sodium ion, potassium ion, the clay that relates among the present invention is preferably the clay that interlayer cation is sodium ion or potassium ion, more preferably interlayer cation is the clay of sodium ion, as sodium-based montmorillonite.Its mean thickness of single lamella that above-mentioned laminated clay suspends in water is 0.5～100nm, is preferably 0.8～50nm.Clay in the composite powder involved in the present invention is handled without of the prior art organising (functionalized), so this clay does not contain organo-functional group.
In this patent application in rubber latex described in the preparation method of composite powder or the crosslinking-type rubber emulsion in the weight of contained rubber (being the solid content of rubber latex dry weight or rubber latex) and the clay slurry ratio of the weight (dry weight of clay slurry) of institute's argillaceous be 99: 1～20: 80, be preferably 95: 5～40: 60.
In the above-described method, can make it to mix through fully stirring in the rubber latex or crosslinking-type rubber latex behind the equilateral stirring of the clay slurry limit adding irradiation.Solid content (drc) to rubber latex is not particularly limited, and is generally 20～70% weight, is preferably 30～60% weight, more preferably 40～50% weight.For clay is fully peeled off in water, the concentration of clay slurry is suitable, should not surpass the critical gel strength of this clay.Drying means when preparing fully vulcanized powder rubber in the Chinese patent 00109217.0 of the drying means that is adopted in the described drying process with Chinese patent application 99125530.5 (publication number of its international patent application is WO01/40356) and application on June 15th, 2000, be that drying process can be carried out with spray-dryer, inlet temperature can be controlled at 100～200 ℃, and temperature out can be controlled at 20～80 ℃.Consistent with the gel content of cross-linking type synthetic rubber latex in step a by the rubber content that the composite powder of above two kinds of method gained is contained, consistent with the gel content of rubber latex behind the irradiation in step b.
In the preparation method's of described composite powder step a, cross-linking type synthetic rubber latex described in the Chinese patent application 00130386.4 that the cross-linking type synthetic rubber latex that uses is submitted on November 3rd, 2000 as the applicant, the gel content of this cross-linking type synthetic rubber latex (cross-linking type synthetic rubber latex) should be 80% weight or higher, is preferably 85% weight or higher.For this cross-linking type synthetic rubber latex,, need not further cross-linking radiation and get final product drying and obtain rubber powder because the crosslinking degree of self is higher.The kind of cross-linking type synthetic rubber latex is selected from cross-linking type butylbenzene rubber latex, cross-linking type carboxylic styrene-butadiene rubber latex, cross-linking type content of polybutadiene rubber latex, crosslinking butadiene nitrile rubber latex, cross-linking type carboxy nitrile rubber latex, cross-linking type chloroprene rubber latex, crosslinking acrylate rubber latex etc.
Among the preparation method's of described composite powder the step b, to used rubber latex raw material without any restriction, rubber latex with preparation fully vulcanized powder rubber in the Chinese patent 00109217.0 of Chinese patent application 99125530.5 (publication number of its international patent application is WO01/40356) and application on June 15th, 2000 can be selected from natural rubber latex; styrene butadiene rubber latex; carboxylic styrene-butadiene rubber latex; paracril latex; carboxy nitrile rubber latex; content of polybutadiene rubber latex; chloroprene rubber latex; silicone rubber latex; the esters of acrylic acid rubber latex; vinylpyridiene-styrene-butadiene rubber latex; Acrylester Butadiene Rubber latex; urethanes latex and fluoroelastomer latex etc.
In fact used rubber latex comprises the crosslinking-type rubber latex among the above-described step a among the described composite powder preparation process b, that is to say that crosslinking-type rubber latex can prepare composite powder of the present invention (as described in step a) without irradiation, also can prepare composite powder of the present invention (as step b) through irradiation.Just the gel content of the composite powder kind rubber that obtains of the latter is higher than the former.
Among preparation method's step b of described composite powder, to the irradiance method of the irradiance method of rubber latex (comprise energetic ray line source that crosslinking coagent, irradiation dose, irradiation are used etc.) with preparation fully vulcanized powder rubber in the Chinese patent 00109217.0 of Chinese patent application 99125530.5 (publication number of its international patent application is WO01/40356) and application on June 15th, 2000.Crosslinking coagent can be do not used at rubber latex, also crosslinking coagent can be used.Used crosslinking coagent is selected from simple function group crosslinking coagent, two functional group's crosslinking coagents, trifunctional crosslinking coagent, four-functional group crosslinking coagent or polyfunctional group crosslinking coagent and arbitrary combination thereof.The example of described simple function group crosslinking coagent includes, but is not limited to: (methyl) Octyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) glycidyl acrylate; The example of described two functional group's crosslinking coagents includes, but is not limited to: 1,4-butyleneglycol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, Diethylene Glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, Vinylstyrene; The example of described trifunctional crosslinking coagent includes, but is not limited to: trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate; The example of described four-functional group crosslinking coagent includes, but is not limited to: tetramethylolmethane four (methyl) acrylate, ethoxyquin tetramethylolmethane four (methyl) acrylate; The example of described polyfunctional group crosslinking coagent includes, but is not limited to: Dipentaerythritol five (methyl) acrylate.In this article, " (methyl) acrylate " refers to acrylate or methacrylic ester.These crosslinking coagents can use in the mode of arbitrary combination, as long as they help sulfuration under irradiation.
The add-on of the above crosslinking coagent is generally 0.1～10% weight of dried glue weight in the latex with the kind and different variation of prescription of rubber latex.Be preferably 0.5～9% weight, more preferably 0.7～7% weight.
The energetic ray source is selected from cobalt source, ultraviolet or high-energy electron accelerator among preparation method's step b of described composite powder rubber, preferred cobalt source.The dosage of irradiation can be 0.1～30Mrad, preferred 0.5～20Mrad.The dosage of irradiation is relevant with prescription with the kind of rubber latex.Generally speaking, irradiation dose should make the gel content behind the rubber latex radiation vulcanization reach 60% weight or higher, preferred 75% weight or higher, more preferably 80% weight or higher.
This composite powder that above method is prepared, in the composition that itself and polyamide resin blends obtain, composite powder is dispersed in the polyamide resin as disperse phase, rubber particles is dispersed in the polymeric amide in this disperse phase, clay layer is peeled off in polyamide substrate fully simultaneously, both can produce certain synergistic effect, obtain effect preferably.Can realize improving the said composition flexible and keep higher rigidity simultaneously, also can realize improving its inflexible and keep high toughness simultaneously, can also obtain high heat-drawn wire simultaneously.The composition that composite powder and polyamide resin blends are obtained solidifies the back section, and direct viewing can obtain reflecting rubber particles and the clay layer dispersion state (as Fig. 1) in matrix under transmission electron microscope.As seen rubber particles and clay dispersion are even, and clay layer is peeled off in polyamide substrate fully simultaneously.So homodisperse rubber particles and clay layer also can keep its original size respectively in the composition, be the particle diameter that the median size of rubber particles can keep latex particle in the rubber latex, and the clay particle also can keep its original nano-grade size in aqueous dispersions.
The preparation method of modified polyamide resin of the present invention is: the daiamid composition that polymeric amide and above-described composite powder is made modification by melt blending.The weight ratio of composite powder and polyamide resin is (0.5～100): 100, preferred (1～50): 100, more preferably (1～40): 100.
In preparation process, the blending temperature of material is the temperature that polyamide plastics is processed used melt blending in the prior art, can decide according to the melt temperature of base polyamide, select in the scope that should not only guarantee the complete fusion of polyamide plastics but also polymeric amide is decomposed.In addition, according to the processing needs, can in the blend material, add the conventional auxiliary agent and the expanding material of polyamide plastics processing in right amount.The employed melt blending equipment of present method is the general blending equipment of rubber and plastic processing industry kind, can make mill, Banbury mixer, single screw extrusion machine or twin screw extruder etc.
Daiamid composition of the present invention owing to rubber phase and clay composition homodisperse in matrix in the composite powder, can have good strong and unyielding balance and obtain high heat-drawn wire simultaneously.Be fit to require polymeric amide to have the Application Areas of good over-all properties, especially be fit to the goods that preparation is applied to the comparatively high temps occasion.Make that the Application Areas of polymeric amide is more extensive.
Preparation method that must this daiamid composition provided by the present invention, the clay of employing does not carry out any processing that organises of the prior art, and this method technology is simple, easy handling.
Description of drawings
Fig. 1 is the transmission electron microscope photo of the daiamid composition section of embodiment 6.Circular dash area is the vinylpyridiene-styrene-butadiene rubber particle among the figure, and the dash area of bar shaped is a sodium-based montmorillonite, and visible rubber particles and polynite are uniformly dispersed, and montmorillonite layer is peeled off in polyamide substrate fully simultaneously.
Embodiment
Further describe the present invention below in conjunction with embodiment, scope of the present invention is not subjected to the restriction of these embodiment.Scope of the present invention proposes in claims.
One, the preparation of composite powder
Embodiment 1
Sodium-based montmorillonite (chemical plant, Qinghe, Zhangjiakou, Hebei produces, and the lamella mean thickness is 1.0nm) is mixed by the concentration of 5% weight with water, disperse, place for some time through the high-shear dispersion machine.With solid content is that (Cixi City prosperous extra large latex company limited in Zhejiang produces for the commercially available vinylpyridiene-styrene-butadiene rubber latex of 40% weight, the trade mark 5555) 5Kg places container, under the stirring of limit, drip Viscoat 295 100g, after being added dropwise to complete, continue to stir one hour.Use cobalt-60 radiosterilize afterwards, dosage is 2.5Mrad, and dose rate is 50Gy/min.After the irradiation in the latex gel content of rubber particles be 87%, average particle size is 100nm.Latex behind the irradiation and sodium-based montmorillonite slurries cooperate in 95: 5 ratios of dry weight separately, stirred one hour, then mixed solution is passed through the spray-dryer spraying drying, the inlet temperature of spray-dryer is 140～160 ℃, temperature out is 40～60 ℃, the dried vinylpyridiene-styrene-butadiene rubber montmorillonite Composite powder of collection in cyclonic separator (
Composite powder 1).
Embodiment 2
Except described vinylpyridiene-styrene-butadiene rubber latex and sodium-based montmorillonite slurries by 80: 20 of dry weight separately, all the other conditions are all with embodiment 1.Spray-dried vinylpyridiene-styrene-butadiene rubber montmorillonite Composite powder (
Composite powder 2).
Embodiment 3
Except described vinylpyridiene-styrene-butadiene rubber latex and sodium-based montmorillonite slurries by 20: 80 of dry weight separately, all the other conditions are all with embodiment 1.Spray-dried vinylpyridiene-styrene-butadiene rubber montmorillonite Composite powder (
Composite powder 3).
Embodiment 4
Except described vinylpyridiene-styrene-butadiene rubber latex and sodium-based montmorillonite slurries by 50: 50 of dry weight separately, all the other conditions are all with embodiment 1.Spray-dried vinylpyridiene-styrene-butadiene rubber montmorillonite Composite powder (
Composite powder 4).
Embodiment 5
Sodium-based montmorillonite (chemical plant, Qinghe, Zhangjiakou, Hebei produces, and the lamella mean thickness is 1.0nm) is mixed by the concentration of 5% weight with water, disperse, place for some time through the high-shear dispersion machine.With solid content is commercially available carboxylic styrene-butadiene rubber latex (the latex factory of Qilu Petrochemical Qi Xiang industrial and trading company of 46.5% weight, the trade mark: XSBRL45B) 5Kg places container, under the stirring of limit, drip Viscoat 295 70g, after being added dropwise to complete, continue to stir one hour.Use cobalt-60 radiosterilize afterwards, dosage is 6KGy, and dose rate is 50Gy/min.After the irradiation in the latex gel content of rubber particles be 88%, average particle size is 150nm.Latex behind the irradiation and sodium-based montmorillonite slurries cooperate in 83: 17 ratios of dry weight separately, stirred one hour, then mixed solution is passed through the spray-dryer spraying drying, the inlet temperature of spray-dryer is 140～160 ℃, temperature out is 40～60 ℃, the dried carboxylic styrene-butadiene rubber montmorillonite Composite powder of collection in cyclonic separator (
Composite powder 5).
Embodiment 6
Except described carboxylic styrene-butadiene rubber latex and sodium-based montmorillonite slurries by 67: 33 of dry weight separately, all the other conditions are all with embodiment 5.Spray-dried carboxylic styrene-butadiene rubber montmorillonite Composite powder (
Composite powder 6).
Comparative example 1
Vinylpyridiene-styrene-butadiene rubber latex behind the irradiation among the embodiment 1 is not sneaked into montmorillonite slurry, directly by the spray-dryer spraying drying, the inlet temperature of spray-dryer is 140～160 ℃, and temperature out is 40～60 ℃, the dried vinylpyridiene-styrene-butadiene rubber powder of collection in cyclonic separator (
Powdered rubber 1).
Comparative example 2
Carboxylic styrene-butadiene rubber latex behind the irradiation among the embodiment 5 is not sneaked into montmorillonite slurry, directly by the spray-dryer spraying drying, the inlet temperature of spray-dryer is 140～160 ℃, and temperature out is 40～60 ℃, the dried vinylpyridiene-styrene-butadiene rubber powder of collection in cyclonic separator (
Powdered rubber 2).
Two, the preparation of daiamid composition
Embodiment 7
With preparation-obtained among the embodiment 1
Composite powder 1With nylon 6 (Ube company produce, trade mark 1013B) and antioxidant 1010 (Switzerland's vapour crust adds machine production) mix, be 100 parts in the weight fraction of plastics, it specifically consists of: 100 parts of nylon,
Composite powder 115 parts, 0.3 part in oxidation inhibitor.Adopt the ZSK-25 twin screw extruder blend granulation of German WP company, each section of forcing machine temperature is respectively: 220 ℃, 235 ℃, 235 ℃, 235 ℃, 235 ℃ and 235 ℃ (head temperature).Pellet is made the standard batten through injection, carries out every Mechanics Performance Testing, and its result is as shown in table 1.
Embodiment 8
Remove among the embodiment 7
Composite powder 1Change into
Composite powder 2Outward, all the other conditions are identical with embodiment 7.The pellet that melt blending obtains is made the standard batten through injection, carries out various Mechanics Performance Testings, the results are shown in table 1.
Comparative example 3
Remove among the embodiment 7
Composite powder 1Change into
Powdered rubber 1Outward, all the other conditions are identical with embodiment 7.The pellet that melt blending obtains is made the standard batten through injection, carries out various Mechanics Performance Testings, the results are shown in table 1.
Comparative example 4
After nylon pellet among the embodiment 7 and oxidation inhibitor mixed, through with identically among the embodiment 7 extrude, the injection technique condition makes the standard batten, carries out various Mechanics Performance Testings, the results are shown in table 1.
Table 1
| Project | Polymeric amide | Composite powder (rubber: clay) | Powdered rubber | Tensile strength MPa | Tension fracture elongation rate % | Socle girder notched Izod impact strength (23 ℃) J/m | Socle girder notched Izod impact strength (20 ℃) J/m | Flexural strength MPa | Modulus in flexure GPa | Heat-drawn wire ℃ |
| Embodiment 7 | ?100 | ??15 ??(95∶5) | ?- | ??60.8 | ??25 | ??116 | ??90.1 | ??85.7 | ??2.01 | ??69.2 |
| Embodiment 8 | ?100 | ??15 ??(80∶20) | ?- | ??65.2 | ??20 | ??99.8 | ??71.3 | ??91.0 | ??2.15 | ??76.8 |
| Comparative example 3 | ?100 | ??-- | ?15 | ??56.2 | ??40 | ??107 | ??61.5 | ??79.8 | ??1.83 | ??66.5 |
| Comparative example 4 | ?100 | ??-- | ?- | ??82.4 | ??16 | ??34.4 | ??29.8 | ??111 | ??2.41 | ??67.4 |
| Testing standard | ?- | ??-- | ?- | ??ASTM ??D-638 | ??ASTM ??D-638 | ??ASTM ??D-256 | ??ASTM ??D-256 | ??ASTM ??D-790 | ??ASTM ??D-790 | ??ASTM ??D-648 |
Annotate: each component content is parts by weight in the table 1
Embodiment 9
With preparation-obtained among the embodiment 3
Composite powder 3With nylon 6 (Yueyang petrochemical iy produced, trade mark YH800) and antioxidant 1010 (Switzerland's vapour crust adds machine production) mix, be 100 parts in the parts by weight of plastics, it specifically consists of: 100 parts of nylon,
Composite powder 33.75 part, 0.3 part in oxidation inhibitor.Adopt the ZSK-25 twin screw extruder blend granulation of German WP company, each section of forcing machine temperature is respectively: 220 ℃, 230 ℃, 230 ℃, 235 ℃, 235 ℃ and 235 ℃ (head temperature).Pellet is made the standard batten through injection, carries out every Mechanics Performance Testing, and its result is as shown in table 2.
Embodiment 10
With the nylon pellet among the embodiment 9 with
Composite powder 4And the antioxidant 1010 mixing, it specifically consists of: 100 parts of nylon,
Composite powder 46 parts, 0.3 part in oxidation inhibitor, through with embodiment 9 identical extrude, the injection technique condition makes the standard batten, carries out various Mechanics Performance Testings, the results are shown in table 2.
Comparative example 5
With the nylon pellet among the embodiment 9,
Powdered rubber 1, sodium-based montmorillonite (with embodiment 1) and antioxidant 1010 mix, it specifically consists of: 100 parts of nylon,
Powdered rubber 13 parts, 3 parts of sodium-based montmorillonites, oxidation inhibitor are 0.3 part, through with embodiment 9 identical extrude, the injection technique condition makes the standard batten, carries out various Mechanics Performance Testings, the results are shown in table 2.
Comparative example 6
After nylon pellet among the embodiment 9 and oxidation inhibitor mixed, through with identically among the embodiment 9 extrude, the injection technique condition makes the standard batten, carries out various Mechanics Performance Testings, the results are shown in table 2.
Table 2
| Project | Polymeric amide | Composite powder (rubber: clay) | Powdered rubber | Clay | Tensile strength MPa | Tension fracture elongation rate % | Socle girder notched Izod impact strength (23 ℃) J/m | Flexural strength MPa | Modulus in flexure GPa | Heat-drawn wire ℃ |
| Embodiment 9 | ?100 | ??3.75 ??(20∶80) | ??- | ??64.5 | ??8 | ??78.2 | ??92.4 | ??2.52 | ??82.1 | |
| Embodiment 10 | ?100 | ??6 ??(50∶50) | ??- | ??68.3 | ??10 | ??90.3 | ??88.6 | ??2.36 | ??67.8 | |
| Comparative example 5 | ?100 | ??-- | ??3 | ??3 | ??68.3 | ??11 | ??83.3 | ??85.3 | ??2.28 | ??64.4 |
| Comparative example 6 | ?100 | ??-- | ??- | ??- | ??60.8 | ??12 | ??81.6 | ??76.1 | ??2.10 | ??60.3 |
| Testing standard | ?- | ??-- | ??- | ??- | ??ASTM ??D-638 | ??ASTM ??D-638 | ??ASTM ??D-256 | ??ASTM ??D-790 | ??ASTM ??D-790 | ??ASTM ??D-648 |
Annotate: each component content is parts by weight in the table 2
Embodiment 11
With preparation-obtained among the embodiment 2
Composite powder 2With nylon 6 (Ube company produce, trade mark 1015B) and antioxidant 1010 (Switzerland's vapour crust adds machine production) mix, be 100 parts in the weight fraction of plastics, it specifically consists of: 100 parts of nylon,
Composite powder 25 parts, 0.3 part in oxidation inhibitor.Adopt the ZSK-25 twin screw extruder blend granulation of German WP company, each section of forcing machine temperature is respectively: 215 ℃, 230 ℃, 230 ℃, 235 ℃, 235 ℃ and 235 ℃ (head temperature).Pellet is made the standard batten through injection, carries out every Mechanics Performance Testing, and its result is as shown in table 3.
Embodiment 12
Remove among the embodiment 11
Composite powder 2Consumption change 10 into especially, all the other conditions are identical with embodiment 11.The pellet that melt blending obtains is made the standard batten through injection, carries out various Mechanics Performance Testings, the results are shown in table 3.
Embodiment 13
Remove among the embodiment 11
Composite powder 2Consumption change 25 into especially, all the other conditions are identical with embodiment 11.The pellet that melt blending obtains is made the standard batten through injection, carries out various Mechanics Performance Testings, the results are shown in table 3.
Embodiment 14
Remove among the embodiment 11
Composite powder 2Consumption change 35 into especially, all the other conditions are identical with embodiment 11.The pellet that melt blending obtains is made the standard batten through injection, carries out various Mechanics Performance Testings, the results are shown in table 3.
Comparative example 7
After nylon pellet among the embodiment 11 and oxidation inhibitor mixed, through with identically among the embodiment 11 extrude, the injection technique condition makes the standard batten, carries out various Mechanics Performance Testings, the results are shown in table 3.
Embodiment 15
With preparation-obtained among the embodiment 5
Composite powder 5With nylon 6 (Yangzhou Organic Chemical Plant product) and antioxidant 1010 (Switzerland's vapour crust adds machine production) mix, be 100 parts in the weight fraction of plastics, it specifically consists of: 100 parts of nylon,
Composite powder 512 parts, 0.3 part in oxidation inhibitor.Adopt the ZSK-25 twin screw extruder blend granulation of German WP company, each section of forcing machine temperature is respectively: 220 ℃, 235 ℃, 235 ℃, 235 ℃, 235 ℃ and 235 ℃ (head temperature).Pellet is made the standard batten through injection, carries out every Mechanics Performance Testing, and its result is as shown in table 4.
Embodiment 16
Remove among the embodiment 15
Composite powder 5Change into
Composite powder 6, and umber changes into beyond 15 parts, all the other conditions are identical with embodiment 15.The pellet that melt blending obtains is made the standard batten through injection, carries out various Mechanics Performance Testings, the results are shown in table 4.
Comparative example 8
Remove among the embodiment 15
Composite powder 5Change into
Powdered rubber 2, and umber change 10 into especially, all the other conditions are identical with embodiment 15.The pellet that melt blending obtains is made the standard batten through injection, carries out various Mechanics Performance Testings, the results are shown in table 4.
Comparative example 9
After nylon pellet among the embodiment 15 and oxidation inhibitor mixed, through with identically among the embodiment 15 extrude, the injection technique condition makes the standard batten, carries out various Mechanics Performance Testings, the results are shown in table 4.
Table 3
| Project | Polymeric amide | ??? Compound??? Powder????2 | Tensile strength MPa | Tension fracture elongation rate % | Socle girder notched Izod impact strength (23 ℃) J/m | Socle girder notched Izod impact strength (20 ℃) J/m | Flexural strength MPa | Modulus in flexure GPa | Heat-drawn wire ℃ |
| Embodiment 11 | ?100 | ????5 | ????67.9 | ????11 | ??72.1 | ??58.6 | ??96.6 | ??2.56 | ??68.6 |
| Embodiment 12 | ?100 | ????10 | ????62.3 | ????17 | ??87.3 | ??77.6 | ??92.2 | ??2.49 | ??71.3 |
| Embodiment 13 | ?100 | ????25 | ????51.4 | ????21 | ??148 | ??98.9 | ??75.5 | ??2.12 | ??70.0 |
| Embodiment 14 | ?100 | ????35 | ????43.9 | ????25 | ??161 | ??120 | ??67.0 | ??1.96 | ??66.1 |
| Comparative example 7 | ?100 | ????-- | ????60.3 | ????15 | ??64.5 | ??55.0 | ??95.2 | ??2.45 | ??62.2 |
| Testing standard | ?- | ????-- | ????ASTM ????D-638 | ????ASTM ????D-638 | ??ASTM ??D-256 | ??ASTM ??D-256 | ??ASTM ??D-790 | ??ASTM ??D-790 | ??ASTM ??D-648 |
Annotate: each component content is parts by weight in the table 3
Table 4
| Project | Polymeric amide | Composite powder (rubber: clay) | Powdered rubber | Tensile strength MPa | Tension fracture elongation rate % | Socle girder notched Izod impact strength (23 ℃) J/m | Socle girder notched Izod impact strength (20 ℃) J/m | Flexural strength MPa | Modulus in flexure GPa | Heat-drawn wire ℃ |
| Embodiment 15 | ?100 | ????12 ????(83∶17) | ??- | ??73.6 | ????26 | ????58.5 | ??45.5 | ????94.5 | ??2.52 | ??64.2 |
| Embodiment 16 | ?100 | ????15 ????(67∶33) | ??- | ??54.7 | ????120 | ????102 | ??25.7 | ????75.4 | ??2.03 | ??59.0 |
| Comparative example 8 | ?100 | ????-- | ??10 | ??55.1 | ????102 | ????105 | ??78.1 | ????73.2 | ??1.98 | ??56.9 |
| Comparative example 9 | ?100 | ????-- | ??- | ??55.5 | ????86 | ????115 | ??76.2 | ????77.4 | ??2.15 | ??61.1 |
| Testing standard | ?- | ????-- | ??- | ??ASTM ??D-638 | ????ASTM ????D-638 | ????ASTM ????D-256 | ??ASTM ??D-256 | ????ASTM ????D-790 | ??ASTM ??D-790 | ??ASTM ??D-648 |
Annotate: each component content is parts by weight in the table 4
Claims (17)
1. daiamid composition includes the following component of blend: polyamide resin and composite powder; The ratio of composite powder gross weight and polyamide resin gross weight is (0.5～100): 100; It is the rubber particles of 20～2000nm that wherein said composite powder includes clay layer and the median size that mean thickness is 0.5～100nm, and described clay is not for containing the clay with laminate structure of organic functional group; The weight ratio of described rubber particles and clay layer is 99: 1～20: 80.
2. daiamid composition according to claim 1 is characterized in that the ratio of described composite powder gross weight and polyamide resin gross weight is (1～50): 100.
3. daiamid composition according to claim 1 is characterized in that the weight ratio of contained rubber particles and clay layer is 95: 5～40: 60 in the described composite powder.
4. daiamid composition according to claim 1, the mean thickness that it is characterized in that described composite powder medium clay soil lamella is 0.8～50nm.
5. daiamid composition according to claim 1, it is characterized in that described clay comprises natural clay and/or synthesis of clay, it is selected from one of following material or its combination: green stone, polynite, talcum powder, beidellite, hectorite, silica, halloysite.
6. daiamid composition according to claim 5 is characterized in that described clay is that sheet interlayer positively charged ion is the clay of sodium ion.
7. daiamid composition according to claim 6 is characterized in that described clay is a sodium-based montmorillonite.
8. daiamid composition according to claim 1, the gel content that it is characterized in that the rubber particles in the described composite powder is 60% weight or higher.
9. daiamid composition according to claim 8, the gel content that it is characterized in that the rubber particles in the described composite powder is 75% weight or higher.
10. daiamid composition according to claim 1, the median size that it is characterized in that the rubber particles in the described composite powder is 30～1500nm.
11. daiamid composition according to claim 1, the kind that it is characterized in that the rubber particles in the described composite powder are selected from least a in the following rubber kind: natural rubber, styrene-butadiene rubber(SBR), carboxylic styrene-butadiene rubber, paracril, carboxy nitrile rubber, polybutadiene rubber, chloroprene rubber, silicon rubber, esters of acrylic acid rubber, vinylpyridiene-styrene-butadiene rubber, Acrylester Butadiene Rubber, urethanes or viton.
12. daiamid composition according to claim 11, it is characterized in that in the described composite powder rubber particles for vinylpyridiene-styrene-butadiene rubber particle or carboxylic styrene-butadiene rubber particle.
13., it is characterized in that described composite powder is got by the method preparation that includes one of following steps according to the described daiamid composition of one of claim 1～12:
A. with the slurries of clay, mix, obtain mixed emulsion, again with this mixed emulsion drying with cross-linking type synthetic rubber latex;
B. after adding or not adding under the situation of crosslinking coagent, adopting the energetic ray source to carry out radiation vulcanization rubber latex, again with the slurries of clay, mix with rubber latex behind the irradiation, obtain mixed emulsion, again with this mixed emulsion drying;
Above-described clay slurry is not for containing the suspension of laminated clay in water of organic functional group, and wherein the mean thickness of clay layer is 0.1～100nm;
In described rubber latex or the cross-linking type synthetic rubber latex in the weight of contained rubber and the clay slurry weight ratio of institute's argillaceous be 99: 1～20: 80.
14. daiamid composition according to claim 13, the gel content that it is characterized in that the cross-linking type synthetic rubber latex described in the step a among the described composite powder preparation method is 80% weight or higher.
15. daiamid composition according to claim 14 is characterized in that the described cross-linking type synthetic rubber of step a latex is selected from cross-linking type butylbenzene rubber latex, cross-linking type carboxylic styrene-butadiene rubber latex, cross-linking type content of polybutadiene rubber latex, crosslinking butadiene nitrile rubber latex, cross-linking type carboxy nitrile rubber latex, cross-linking type chloroprene rubber latex or crosslinking acrylate rubber latex among the described composite powder preparation method.
16. daiamid composition according to claim 13 is characterized in that the described rubber latex of step b is selected from natural rubber latex, styrene butadiene rubber latex, carboxylic styrene-butadiene rubber latex, paracril latex, carboxy nitrile rubber latex, content of polybutadiene rubber latex, chloroprene rubber latex, silicone rubber latex, esters of acrylic acid rubber latex, vinylpyridiene-styrene-butadiene rubber latex, Acrylester Butadiene Rubber latex, urethanes latex or fluoroelastomer latex among the described composite powder preparation method.
17. a preparation method who prepares the described daiamid composition of one of claim 1～16 is characterized in that described polyamide resin and described composite powder melt blending are made daiamid composition.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102321281A (en) * | 2011-08-09 | 2012-01-18 | 上海华明高技术（集团）有限公司 | Composition of calcium carbonate and organic elastomer and preparation method thereof |
| CN101696282B (en) * | 2009-10-23 | 2012-06-20 | 蚌埠市瑞洁科技有限责任公司 | Reinforcing filler used for rubber latex product, preparation method thereof and application thereof |
| CN107043534A (en) * | 2017-04-07 | 2017-08-15 | 北京隆轩橡塑有限公司 | A kind of polyamide 66 composite material of high-strength toughness reinforcing and preparation method thereof |
| CN107189424A (en) * | 2017-05-17 | 2017-09-22 | 马鞍山瑞美塑业有限公司 | A kind of preparation method of the heatproof polyamide manufactured for automotive seat backplate |
| CN108841153A (en) * | 2018-07-02 | 2018-11-20 | 江南大学 | A kind of high-ductility, high heat distortion temperature poly (lactic acid) composition and preparation method thereof |
-
2003
- 2003-10-29 CN CN 200310101795 patent/CN1257939C/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101696282B (en) * | 2009-10-23 | 2012-06-20 | 蚌埠市瑞洁科技有限责任公司 | Reinforcing filler used for rubber latex product, preparation method thereof and application thereof |
| CN102321281A (en) * | 2011-08-09 | 2012-01-18 | 上海华明高技术（集团）有限公司 | Composition of calcium carbonate and organic elastomer and preparation method thereof |
| CN107043534A (en) * | 2017-04-07 | 2017-08-15 | 北京隆轩橡塑有限公司 | A kind of polyamide 66 composite material of high-strength toughness reinforcing and preparation method thereof |
| CN107189424A (en) * | 2017-05-17 | 2017-09-22 | 马鞍山瑞美塑业有限公司 | A kind of preparation method of the heatproof polyamide manufactured for automotive seat backplate |
| CN108841153A (en) * | 2018-07-02 | 2018-11-20 | 江南大学 | A kind of high-ductility, high heat distortion temperature poly (lactic acid) composition and preparation method thereof |
| CN108841153B (en) * | 2018-07-02 | 2020-10-30 | 江南大学 | High-toughness and high-heat-deformation-temperature polylactic acid composition and preparation method thereof |
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| CN1257939C (en) | 2006-05-31 |
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