CN100349976C - Rubber modified nylon composition - Google Patents
Rubber modified nylon composition Download PDFInfo
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- CN100349976C CN100349976C CNB2004100666358A CN200410066635A CN100349976C CN 100349976 C CN100349976 C CN 100349976C CN B2004100666358 A CNB2004100666358 A CN B2004100666358A CN 200410066635 A CN200410066635 A CN 200410066635A CN 100349976 C CN100349976 C CN 100349976C
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Abstract
The present invention relates to a rubber modified nylon composition which mainly solves the problems of difficult acquisition of compatibilizer, low content of MA in SAM, higher dosage of the SAM, complex working processes, unreasonable device selection, etc. The existing in prior art. The rubber modified nylon composition better solves the problems by adopting the technical scheme that the nylon composition is composed of 30 to 80% of PA6, 30 to 80% of ABS and 2 to 10% of the SAM, wherein PB accounts for 20 to 80%, AN accounts for 10 to 30% and MA accounts for 1 to 15%. The rubber modified nylon composition can be used for industrial production of nylon plastic alloy.
Description
Technical field
The present invention relates to the composition of a kind of nylon, rubber and polystyrene terpolymer, particularly about the multipolymer (ABS) that contains nylon 6 (PA6), acrylonitrile-butadiene-styrene and the polymeric composition of vinylbenzene-vinyl cyanide-MALEIC ANHYDRIDE (cis-butenedioic anhydride) multipolymer (SAM) blend gained.
Background technology
Nylon (PA) becomes class engineering resin quite popular to people because of use temperature with excellent intensity, hardness, low-friction coefficient, broad, chemicals-resistant and characteristic such as wear-resistant.Yet the high notch sensitivity of this resinoid inherent promptly, when non-notch, is showed the ductility one side, when jagged, shows as brittle rupture; And under the loading condiction of low temperature and harshness, show the brittle rupture feature.Yet the contained chemical functional group of PA molecular end (amino and carboxyl) has brought facility for its modification.
The PA/ABS alloy is the thermoplastic compounds of extensively being paid close attention to, and can be used for making trolley part, as: collision bumper, splash pan, front bumper, dashboard, door inner panel, switchboard.But regrettably PA and ABS do not hold (JP23476-1963) mutually, and both phenomenon of phase separation occurs easily without the formed blend of increase-volume, thereby cause the blend mechanical property impaired.
There is number of ways to impel and carries out the reaction in increase-volume between PA and the ABS.Wherein, comparatively effectively adopt a kind of can with PA terminal amino group reaction again can be compatible with SAN among the ABS expanding material, as amidated acrylate copolymer (IA) [Majumdar B, Keskkula H, Paul D R.Polymer 1994,35 (25): 5453-5467; Kudva R A, Keskkula H, Paul D R.Polymer 2000,41 (1): 225-237].People's such as D.R.Paul result of study shows that adding IA obviously diminishes the ABS microcell, and when PA6/ABS=1/1,5 weight %IA just can make the crisp-tough transition temperature of this alloy sharply drop to subzero 45 ℃.Though the IA compatibilization effect is obvious, but its complicated process of preparation, no commercial prod, and be unable to undergo repeatedly to melt extrude test [the Kudva R A of processing with the PA6/ABS/IA alloy mechanical property that it makes, KeskkulaH, Paul D R.Polymer 2000,41 (1): 239-258], unfavorable to the recycling of environmental protection and material.
D.R.Paul etc. [Majumdar B, Keskkula H, Paul D R.Polymer 1994,35 (15): 3164-3172] once used vinylbenzene-cis-butenedioic anhydride multipolymer (SMA) (25% cis-butenedioic anhydride) as expanding material development PA6/ABS (60/40) alloy.The result shows that alloy socle girder notched Izod impact strength is very responsive to the SMA consumption.Maximum value appears in this alloy shock strength when adding 1.6 weight %SMA.PA6 and ABS do not form common external phase when adding SMA, and ABS becomes disperse phase and SMA dosage rising ABS phase microcell diminishes when adding SMA.After analyzing relatively, they think that SMA and PA6 overreaction cause SMA that the affinity of SAN is reduced.In addition, they are to the PA6/ABS of Bayer company alloy Triax
TM1120 studies show that PA6 and ABS form common external phase.Table 1 has been listed Bayer company's T riax
TM1120 is the PA6/ABS alloy of two kinds of brands.Their composition, promptly used compatibilizing method and expanding material are not reported.
The table 1 Bayer PA6/ABS of company alloy property
*
| The trade mark | Tensile strength MPa | Elongation at break % | The socle girder notched Izod impact strength | Flexural strength MPa | |
| The normal temperature joules per meter | -40 ℃ of joules per meter | ||||
| Triax TM 1120 Triax TM 1220S | 40 37 | 290 90 | 800 900 | 80 100 | 57 61 |
*Data are picked up from http://www.matweb.com
Usefulness SAM such as D.R.Paul (contain 33 weight % vinyl cyanide, 1.3 weight % cis-butenedioic anhydrides, Bayer company provides) show that as expanding material development PA6/ABS/SAM alloy extruding the processing number of times does not almost have obvious influence to the socle girder notched Izod impact strength.In addition, the SAM consumption increases ABS phase microcell and diminishes, and the super toughness of low temperature improves and is irrelevant with processing history.After rheological analysis, electron microscopic observation and compatibility test, they think among SAM and the ABS SAN mutually affinity and not exclusively consistency not change with processing history be that the PA6/ABS/SAM alloy shows one of super flexible reason of excellent low temperature.And thereby IA and PA6 have experienced interaction that degree of depth branching reaction changed IA and SAN, have reduced both affinities [Kitayama N, Keskkula H, Paul D R.Polymer 2000,41 (22): 8053-8060] with processing number of times increase.
[Padwa A R such as A.R.Padwa, Lavengood R E.Polym.Prepr.1992,33 (2): 600-601] research 50 weight %PA6,6/6, point out behind 44 weight %ABS and the 6 weight %SAM alloys among the SAM cis-butenedioic anhydride content at 0.36～0.99 weight % for well, and the difference of the vinyl cyanide weight percentage of SAN is less than 5% among acrylonitrile content and the ABS.But the above-mentioned result of study of D.R.Paul shows that both differences of acrylonitrile content are greater than 5%.
Introduced PA6 in the U.S. Pat 4713415, the 6-A6/ABS/SAM alloy preparation method based on ABS component (〉=50 weight %).Cis-butenedioic anhydride among the employed SAM (MA) content is 0.3～1.5 mole of %, its preparation method the unknown, and its usage quantity in alloy is 6 weight %.The content of polyhutadiene glue (PB) is 40 weight % among the used ABS.The preparation technology of alloy be earlier with ABS, SMA and oxidation inhibitor premix, extrude, after the granulation, again with nylon blending, extrude, granulation makes alloy.Forcing machine is a single screw extrusion machine.The normal temperature socle girder notched Izod impact strength of alloy can be greater than 800 joules per meter.
Introduced PA6 in the U.S. Pat 4777211,6-A6/ABS/ ethylene-methyl methacrylate methyl terpolymer/SAM alloy.Cis-butenedioic anhydride among the SAM (MA) content is the about 30 weight % of 0.9 mole of %, vinyl cyanide (AN) content, and its usage quantity in alloy is 3～6 weight %.The content of poly-butadiene-acrylonitrile rubber is 40 weight % among the ABS.The preparation technology of alloy and above-mentioned patent are similar.The normal temperature socle girder notched Izod impact strength of alloy can be greater than 800 joules per meter, the most about 1160 joules per meter.
Having introduced with butanone solution method synthetic SAM in the U.S. Pat 4987185 is that expanding material prepares the PA6/ABS/SAM alloy.Cis-butenedioic anhydride among the SAM (MA) content is the about 30 weight % of 0.83 or 0.94 weight %, vinyl cyanide (AN) content, and its usage quantity in alloy is 3～6 weight %.The content of poly-butadiene-styrene rubber (SB) is 55 weight % among the ABS, 0.38 micron of average rubber particle size.About 750 joules per meter when about 900 joules per meter of normal temperature socle girder notched Izod impact strength of alloy, low temperature-20 ℃.
Also introduced among the European patent EP 0785234A1 with butanone solution method synthetic SAM and be expanding material, prepare the PA6/ABS/SAM alloy based on ABS component (＞50 weight %).Cis-butenedioic anhydride among the SAM (MA) content is the about 30 weight % of 0.5～1.1 mole of %, vinyl cyanide (AN) content, and its usage quantity in alloy is 6 weight %.The content of PB is 40 weight % among the ABS.Forcing machine is a single screw extrusion machine.The about 79.2 kilojoule/rice of the normal temperature socle girder notched Izod impact strength of alloy
2, about 50.4 kilojoule/rice during low temperature-20 ℃
2
In sum, selection [the LacasseC. of the selection of expanding material and use, processing units in the preparation process of PA/ABS alloy, Favis B.D.Adv.Polym.Techn.1999,18 (3): 255-265], the selection of ABS and PA and use, complete processing etc. all exert an influence to the performance of alloy.Particularly the expanding material type selecting directly has influence on the final use value of alloy.And IA that in the past mentioned in the document or SAM synthetic method are uneconomical and do not have a commercial prod.
Summary of the invention
Technical problem to be solved by this invention be had in the past that expanding material is difficult for obtaining in the document, MA content is low among the SAM, the SAM consumption is higher, the course of processing is complicated and equipment is selected technical problems such as unreasonable.Thereby PA, rubber and polystyrene terpolymer alloy comprehensive mechanical property and economy are reasonably improved, a kind of new PA, rubber and SAM alloy are provided.This alloy has the characteristics of better comprehensive mechanical property and cost advantage.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of nylon composite of modified rubber comprises following component by weight percentage:
A) 40～70% nylon 6;
B) 40～70% acrylonitrile-butadiene-styrene copolymer, polybutadiene content is 20～80% by weight percentage in the multipolymer;
C) styrene-acrylonitrile-maleic anhydride copolymer of 2～10%, in the multipolymer by weight percentage acrylonitrile content be 10～30%, MALEIC ANHYDRIDE content is 1～15%.
In the technique scheme, the molecular weight preferable range of PA6 is 1.5 * 10
4～2.5 * 10
4In acrylonitrile-butadiene-styrene (ABS) multipolymer polyhutadiene (PB) content by weight percentage preferable range be 40～75%.Vinylbenzene-vinyl cyanide-MALEIC ANHYDRIDE (SAM) multipolymer consumption preferable range is 3～8% by weight percentage, wherein by weight percentage, the acrylonitrile content preferable range is 15～25%, and MALEIC ANHYDRIDE (MA) content preferable range is 3～10%.
Used ABS is the product that blending method or grafting method are produced in the blend of the present invention.Preferred grafting method product, PB content 55～75 weight %.The technology of producing this kind product can be:
1, chemical graft process comprises letex polymerization grafting method, emulsion-mass polymerization grafting method, body-suspension polymerization grafting method and continuous bulk polymerization grafting method;
2, chemical graft blending method comprises that the poly-grafted ABS latex of breast+the poly-SAN latex of breast condenses altogether, breast gathers grafted ABS powder+suspension polymerization SAN pellet blend, the poly-grafted ABS powder of breast+mass polymerization SAN pellet blend.
The used SAM of the present invention is substance law production, has only a second-order transition temperature.Cis-butenedioic anhydride among the SAM and vinyl cyanide weight content require respectively 1～15% and 10～30%, and preferred cis-butenedioic anhydride and acrylonitrile content are respectively 3～10% and 15～25%.
The used PA6 of the present invention is that hexanolactam forms through hydrolysis, polymerization, casting, section, aftertreatment in the presence of water and acid etc.Its embrittlement temperature is-20～-30 ℃; Relative viscosity is greater than 3.0 (sulfuric acid solvent ,/100 milliliters of strength of solution 1 grams); Molecular weight is greater than 19800.
Polyblend of the present invention is a kind of thermoplastic material of easy processing.The implication of " easily processing " is that the polyblend injection adds the injection pressure in man-hour and is lower than 90MPa, 3～4 seconds inject time, 245～250 ℃ of injection temperatures.In addition, polyblend is presenting excellent characteristic aspect heat-resisting, shock resistance and other mechanical performance index.Notched Izod impact strength at least 300 joules per meter for example are generally greater than 900 joules per meter.
Polyblend preparation method of the present invention mixes above-mentioned each polymeric components, again predetermined plasticization temperature to the material of premix plastify, knead, extrude, pelletizing.Extrusion equipment is that Germany makes Leistritz AG Mic-27 parallel dual-screw extruding machine.
Except above-mentioned polymeric components, adding some auxiliary agents also is necessary sometimes.Auxiliary agent has stablizer, fluidizer, oxidation inhibitor, fire retardant and colour batch etc.Identical when adding the method for auxiliary agent and preparing the PA6 blend usually.
Owing in PA6 and ABS, add the SAM component, make between rubber among PA6, SAM and the ABS and the SAN all might exist mutually among the present invention, form three thing phases at least with thing independent, that can debate.Rubber exists with disperse phase, and SAM is present in the interface of PA6 and SAN, has played expanding material effect preferably, has reduced interfacial tension, has improved interfacial adhesion.Adopting less SAM consumption and containing the polybutadiene rubber weight content is 40～75% ABS, more strengthened the compatibilization of above-mentioned PA6 and ABS, thereby make PA6, the ABS and the SAM alloy notch shock strength that make can reach 1000 joules per meter, elongation at break reaches 249% simultaneously, yield tensile strength reaches 58MPa, heat-drawn wire reaches 71 ℃, has obtained better technical effect.
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1]
The granular exsiccant PA6 of 57.6 weight parts, 38.4 weight part powdery ABS (wherein the PB weight content is 70%) and the granular SAM of 4 weight parts (wherein cis-butenedioic anhydride and vinyl cyanide weight content are respectively 6% and 18%) are put into a container, stir up and down repeatedly, mix.Again this Preblend is sent into Germany and made Leistritz AG Mic-27 parallel dual-screw extruding machine, service temperature (from the spout to the die head): 200/220/230/245/250/250/255/255/255/250 ℃.Material finally is cut into granular (diameter is 3 millimeters, and length is 3～4 millimeters) through plastifying, knead, extruding.About 20 seconds of material residence time in forcing machine, screw speed is 150 rev/mins.The pellet that makes is injected into type for stretching and impacting batten at 245～250 ℃.These battens are used for the physicals of test material, heat-resisting and impact resistance.Every test result sees Table 1 numbering, 1 sample.
In order to further specify the present invention,, change SAM and make different polyblends with PA6 content with same method.Every test result sees Table 1.
[embodiment 2]
Press each Step By Condition of embodiment 1, just changing the PA6 parts by weight is 48.5; The ABS parts by weight are 48.5; The SAM parts by weight are 3, and its alloy test result sees Table 1.
[embodiment 3]
Press each Step By Condition of embodiment 1, just changing the PA6 parts by weight is 67.2; The ABS parts by weight are 28.8; The SAM parts by weight are 4, and its alloy test result sees Table 1.
[embodiment 4]
Press each Step By Condition of embodiment 1, just changing the PA6 parts by weight is 55.8, and the ABS parts by weight are 37.2 parts, and the SAM parts by weight are 7, and its alloy test result sees Table 1.
[comparative example 1]
With the operating method among the embodiment 1, with the granular PA6 of 50 weight parts, 50 weight part powdery ABS, hybrid process and test performance.Every test result sees Table 1.
[comparative example 2]
With the operating method among the embodiment 1, with the granular PA6 of 58.5 weight parts, the granular ABS of 38.5 weight parts (wherein the PB weight content is 20%), the granular SAM of 3 weight parts, hybrid process and test performance.Every test result sees Table 1.
[comparative example 3]
With the operating method among the embodiment 1, with the granular PA6 of 58 weight parts, 38 weight part powdery ABS, the granular vinylbenzene of 4 weight parts-cis-butenedioic anhydride multipolymer (SMA) (18% cis-butenedioic anhydride), hybrid process and test performance.Every test result sees Table 1.
Table 1
| Numbering | Form (parts by weight) | Yield tensile strength MPa | Elongation at break % | The notched Izod impact strength joules per meter | Heat-drawn wire ℃ | Flexural strength MPa | ||
| PA6 | ABS | SAM | ||||||
| Embodiment 1 embodiment 2 embodiment 3 embodiment 4 | 57.6 48.5 67.2 55.8 | 38.4 48.5 28.8 37.2 | 4.0 3.0 4.0 7.0 | 53 46 58 54 | 178 249 99 135 | 1004 902 985 347 | 67 71 69 68 | 60 52 65 64 |
| Comparative example 1 comparative example 2 comparative examples 3 | 50.0 58.5 58.0 | 50.0 38.5 38.0 | 0.0 3.0 4.0 | 45 70 69 | 74 46 76 | 96 73 138 | 62 79 65 | 49 78 77 |
| Testing method | GB/T1040 | GB/T1040 | GB/T1043 | GB/T1633 | GB/T9341 | |||
Claims (5)
1, a kind of nylon composite of modified rubber comprises following component by weight percentage:
A) 40～70% nylon 6;
B) 40～70% acrylonitrile-butadiene-styrene copolymer, polybutadiene content is 20～80% by weight percentage in the multipolymer;
C) styrene-acrylonitrile-maleic anhydride copolymer of 2～10%, in the multipolymer by weight percentage acrylonitrile content be 10～30%, MALEIC ANHYDRIDE content is 1～15%.
2, according to the nylon composite of the described modified rubber of claim 1, the molecular weight that it is characterized in that nylon 6 is 1.5 * 10
4～2.5 * 10
4
3,, it is characterized in that in the acrylonitrile-butadiene-styrene copolymer that polybutadiene content is 40～75% by weight percentage according to the nylon composite of the described modified rubber of claim 1.
4,, it is characterized in that the consumption of styrene-acrylonitrile-maleic anhydride copolymer is 3～8% by weight percentage according to the nylon composite of the described modified rubber of claim 1.
5, according to the nylon composite of the described modified rubber of claim 1, it is characterized in that in styrene-acrylonitrile-maleic anhydride copolymer that the content of vinyl cyanide is 15～25% by weight percentage, MALEIC ANHYDRIDE content is 3～10%.
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|---|---|---|---|
| CNB2004100666358A CN100349976C (en) | 2004-09-24 | 2004-09-24 | Rubber modified nylon composition |
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|---|---|---|---|
| CNB2004100666358A CN100349976C (en) | 2004-09-24 | 2004-09-24 | Rubber modified nylon composition |
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| CN100349976C true CN100349976C (en) | 2007-11-21 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| TWI642688B (en) * | 2014-09-02 | 2018-12-01 | 日商電化股份有限公司 | Copolymer for optical film |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6248177B2 (en) * | 1979-06-19 | 1987-10-13 | Ricoh Kk | |
| US4740552A (en) * | 1986-02-14 | 1988-04-26 | Borg-Warner Chemicals, Inc. | Alloys of styrenic resins and polyamides |
| CN1032941A (en) * | 1987-11-02 | 1989-05-17 | 斯塔米卡本公司 | Thermoplastic elastomer mixture |
| SU1482928A1 (en) * | 1987-05-25 | 1989-05-30 | Минское Экспериментально-Конструкторское Технологическое Бюро Кожгалантерейной И Фурнитурной Промышленности | Polymeric composition |
| EP0400964A2 (en) * | 1989-05-30 | 1990-12-05 | Hoechst Celanese Corporation | Heat and impact resistant polyamide compositions |
| WO1991013939A1 (en) * | 1990-03-12 | 1991-09-19 | The Dow Chemical Company | Rubber modified nylon composition |
| US5482997A (en) * | 1988-06-23 | 1996-01-09 | Stamicarbon B.V. | Polyamide compositions |
| CN1430648A (en) * | 2000-04-12 | 2003-07-16 | 罗狄亚塑料工程股份有限公司 | Thermoplastic polymeric compositions |
| JP2007277278A (en) * | 2005-03-30 | 2007-10-25 | Tokai Rubber Ind Ltd | Semiconductive composition for electrophotographic apparatus, and semiconductive member for electrophotographic apparatus using the same |
-
2004
- 2004-09-24 CN CNB2004100666358A patent/CN100349976C/en not_active Expired - Fee Related
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6248177B2 (en) * | 1979-06-19 | 1987-10-13 | Ricoh Kk | |
| US4740552A (en) * | 1986-02-14 | 1988-04-26 | Borg-Warner Chemicals, Inc. | Alloys of styrenic resins and polyamides |
| SU1482928A1 (en) * | 1987-05-25 | 1989-05-30 | Минское Экспериментально-Конструкторское Технологическое Бюро Кожгалантерейной И Фурнитурной Промышленности | Polymeric composition |
| CN1032941A (en) * | 1987-11-02 | 1989-05-17 | 斯塔米卡本公司 | Thermoplastic elastomer mixture |
| US5482997A (en) * | 1988-06-23 | 1996-01-09 | Stamicarbon B.V. | Polyamide compositions |
| EP0400964A2 (en) * | 1989-05-30 | 1990-12-05 | Hoechst Celanese Corporation | Heat and impact resistant polyamide compositions |
| WO1991013939A1 (en) * | 1990-03-12 | 1991-09-19 | The Dow Chemical Company | Rubber modified nylon composition |
| CN1430648A (en) * | 2000-04-12 | 2003-07-16 | 罗狄亚塑料工程股份有限公司 | Thermoplastic polymeric compositions |
| JP2007277278A (en) * | 2005-03-30 | 2007-10-25 | Tokai Rubber Ind Ltd | Semiconductive composition for electrophotographic apparatus, and semiconductive member for electrophotographic apparatus using the same |
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