CN1342724A - High-toughness polyamide and its preparing process - Google Patents
High-toughness polyamide and its preparing process Download PDFInfo
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- CN1342724A CN1342724A CN 00124703 CN00124703A CN1342724A CN 1342724 A CN1342724 A CN 1342724A CN 00124703 CN00124703 CN 00124703 CN 00124703 A CN00124703 A CN 00124703A CN 1342724 A CN1342724 A CN 1342724A
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Abstract
A high-toughness polyamide composition is prepared by mixing the rubber particles (grain size 20-200 mm) with polyamide in weight ratio of (0.5-50):(50-99.5). Its advantages are balance rigidity and toughness and stable performance.
Description
The present invention relates to a kind of high-toughness polyamide and preparation method thereof, say further, the present invention relates to utilize rubber and polyamide blended and high-toughness polyamide and this kind preparation of compositions method that make.
Polymeric amide is a kind of engineering plastics of high comprehensive performance, uses very extensive.But under many occasions, particularly under lower temperature, its low temperature impact properties is lower, therefore need carry out toughening modifying.In the prior art, typically using elastomerics carries out toughness reinforcing to polymeric amide.Used elastomerics generally is an olefin copolymer, as ethylene-propylene rubber(EPR), SBS etc.But, must improve consistency by carboxylic acid or acid anhydride-grafted elastomerics because the consistency of this type of elastomerics and polymeric amide is poor.At present, mainly use maleic anhydride modified.The like product that PA alloy as U.S. Dupont company---Zyte1801 and toray Co., Ltd. sell with trade(brand)name UTN all is the second third glue tenacity increased nylons with maleic anhydride graft.The relevant patent of maleic anhydride graft second third glue as the technology of polymeric amide toughner had: the patent JP127503/97 of the patent FR8519421 of French Atochem (FR) Cedex 22, 94091 Paris La Defense, France, FR8803877, FR9512701, FR9609148, Mitsui KCC and patent JP190634/97, the JP190635/97 etc. of Japanese Kishimoto Sangyo Co., Ltd.
Ooze theory according to the exceeding of plastic toughening that the Souheng Wu the eighties of du pont company proposes, point out that in rubber toughened plastics, dispersive rubber phase particle diameter is more little, the easy more generation brittle-ductile transition of toughened plastics.In the technology of existing toughened polyamide, be the grafting elastomerics as toughner and polyamide blended and obtain toughened polyamide.But elastomerics grafting cost is higher, and this grafting elastomerics and polyamide blended, also have the following disadvantages: (1) is under the blending condition of present rubber and plastic processing, elastomerics particle diameter as disperse phase is difficult to be controlled at small range, and average elastomerics particle dia is greater than 200nm.If will realize brittle-ductile transition, then need the elastomerics of big umber, thereby cause the toughened polyamide inflexible to reduce; (2) the particle diameter instability of elastomerics disperse phase, along with the variation of factors such as course of processing middle shear rate, the elastomerics disperse phase particle diameter in the toughened polyamide is always in variation; (3) elastomerics disperse phase particle diameter is very inhomogeneous; (4) elastomer content can not surpass 40%, otherwise is prone to " Hai-Hai " phase structure, even phase reversion occurs, makes the degradation of toughened polyamide.
Therefore, it is little to the purpose of this invention is to provide a kind of contained rubber phase median size, and even, the stable high-toughness polyamide of rubber size.Phase reversion also do not occur even its rubber content reaches 70%, rubber remains disperse phase.When having higher toughness, this high-toughness polyamide also has rigidity preferably.
Another object of the present invention provides the preparation method of described high-toughness polyamide, and this method technology is simple, easy handling.
High-toughness polyamide of the present invention is achieved in that
High-toughness polyamide of the present invention comprises following component blend and gets: polymeric amide and median size are the rubber particles of 20～200nm.Wherein the weight ratio of rubber particles and polymeric amide is 0.5: 99.5～50: 50, preferred 5: 95-30: 70.The median size of rubber particles is preferably between 50～150nm.This modified polyamide has good strong and unyielding equilibrated over-all properties.
In this high-toughness polyamide, can be selected from nylon 6, nylon 66, nylon 46 or nylon 1010 etc. as the polymeric amide of external phase.
In this high-toughness polyamide, be preferably the rubber particles of equal phase structure as the rubber particles of disperse phase, it is the cross-linked rubber particle of gel content 〉=60% preferably.This kind rubber particles can adopt according to the inventor in the prepared fully vulcanized powder rubber of the Chinese patent 99125530.5 of on December 3rd, 1999 application, comprises at least a of fully vulcanized powder rubbers such as form of finely divided powder, mehtod carboxylic styrene-butadiene rubber, form of finely divided powder, mehtod paracril, form of finely divided powder, mehtod carboxy nitrile rubber or form of finely divided powder, mehtod acrylic elastomer.This kind fully vulcanized powder rubber is meant that gel content reaches more than 60%, and need not with separant after the drying is free flowable rubber particle.This powdered rubber is with rubber particles particle diameter fixed by cross-linking radiation.
The preparation method of high-toughness polyamide of the present invention is: with polymeric amide and median size is that the rubber particles of 20～200nm makes high-toughness polyamide by blend.The median size of rubber particles is preferably between 100～200nm.This kind rubber particles is preferably the rubber particles of equal phase structure, and it is the cross-linked rubber particle of gel content 〉=60% preferably.The weight ratio of rubber particles and polymeric amide is 0.5: 99.5-70: 30, preferred 5: 95-50: 50.
When preparation high-toughness polyamide of the present invention, polymeric amide can be selected from nylon 6, nylon 66, nylon 46 or nylon 1010 etc.
Rubber particles can adopt according to the inventor in the prepared fully vulcanized powder rubber of the Chinese patent 99125530.5 of on December 3rd, 1999 application in present method, and it comprises at least a of fully vulcanized powder rubbers such as form of finely divided powder, mehtod carboxylic styrene-butadiene rubber, form of finely divided powder, mehtod paracril, form of finely divided powder, mehtod carboxy nitrile rubber or form of finely divided powder, mehtod acrylic elastomer.This kind fully vulcanized powder rubber is meant that gel content reaches more than 60%, and need not with separant after the drying is free flowable rubber particle.This powdered rubber is with rubber particles particle diameter fixed by cross-linking radiation.When fully vulcanized powder rubber mixed with polymeric amide, these particles were dispersed in the polymeric amide very easily uniformly and stably, were difficult for cohesion, can keep the particle diameter of the preceding powdered rubber of blend substantially.
Fully vulcanized powder rubber can add or add with undried crosslinked emulsions form with the crosslinked powder morphology of exsiccant.
In preparation process, the blending temperature of material is used blending temperature in the common polymeric amide processing, can decide according to the melt temperature of the concrete material of polymeric amide, should select not only guaranteeing the complete fusion of base polyamide material but also can not make in the scope of its decomposition.In 230～250 ℃ scope, and the blending temperature of nylon 66 is generally in 250～275 ℃ scope as the blending temperature of nylon 6.In addition, according to the processing needs, can in the blend material, add the conventional auxiliary agent and the expanding material of plastic working in right amount.
The employed blending equipment of present method is the general blending equipment in the rubber and plastic processing industry, can be mill, Banbury mixer, single screw extrusion machine or twin screw extruder etc.
High-toughness polyamide of the present invention, contained rubber phase particle diameter is little, and particle diameter is even, stable, also is easy to reach high rubber and plastic ratio; It has high-rigidity high-toughness and good processing forming, is applicable to very extensive fields.
Simple, the easy handling of method technology for preparing high-toughness polyamide of the present invention.
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.
Accompanying drawing 1 is embodiment 3 gained sample atoms force microscope photos, and magnification is about 40,000 times.
Embodiment 1-5:
(trade mark of producing in Yanshan Petrochemical is in the XSBRL-54B1 carboxyl styrene-butadiene emulsion with the form of finely divided powder, mehtod carboxylic styrene-butadiene rubber, after sneaking into the crosslinking coagent Isooctyl acrylate monomer by 3% of the dried glue weight of carboxyl styrene-butadiene emulsion, carry out radiation vulcanization, irradiation dose is 2.5Mrad, spray-dried obtaining, median size is 150nm, and gel content is 92.6%) and nylon 6 (trade mark 1013B of Co., Ltd. of Ube Industries Ltd.) and calcium stearate (the long Yang Huagongchang production in Beijing chemical pure) and superfine talcum powder (the He Beilu county produces 1250 orders) uniform mixing.Adopt the ZSK-25 twin screw extruder blend granulation of German WP company, each section of forcing machine temperature is respectively: 230 ℃, 235 ℃, 240 ℃, 245 ℃, 240 ℃ and 235 ℃ (head temperature).Concrete prescription sees Table 1, and wherein the component concentration of form of finely divided powder, mehtod carboxylic styrene-butadiene rubber and nylon 6 is all in parts by weight, and other auxiliary agent is to account for the weight percentage of each component summation.The pellet oven dry is carried out every Mechanics Performance Testing after injection moulding is made the standard batten.Testing standard and results of property are as shown in table 1.The atomic force microscope photo of embodiment 3 samples as shown in Figure 1, wherein partly for being dispersed in the particle of the form of finely divided powder, mehtod carboxylic styrene-butadiene rubber in the nylon 6, its median size is about 150nm to black shade.
Comparative Examples 1:
After twin screw extruder blend granulation, all the other conditions are identical with embodiment 1 with the nylon among the embodiment 16 and calcium stearate and superfine talcum powder uniform mixing.Concrete prescription, testing standard and results of property are as shown in table 1.
Comparative Examples 2
After twin screw extruder blend granulation, all the other conditions are identical with embodiment 1 with the nylon among the embodiment 16 and the calcium stearate described in acrylic elastomer (du pont company Lucite44-N) and the embodiment 1 and superfine talcum powder uniform mixing.Concrete prescription sees Table 1, and wherein the component concentration of acrylic elastomer and nylon 6 is all in parts by weight, and other auxiliary agent is to account for the weight percentage of each component summation.Testing standard and results of property are as shown in table 1.
Comparative Examples 3
After twin screw extruder blend granulation, all the other conditions are identical with embodiment 1 with the POE (being that the POE-g-MAH U.S. connection UCC of C.-Chem AG produces trade mark DFDA1373) of the nylon among the embodiment 16 and maleic anhydride graft and the calcium stearate described in the embodiment 1 and superfine talcum powder uniform mixing.Concrete prescription sees Table 1, and wherein the component concentration of the POE of maleic anhydride graft and nylon 6 is all in parts by weight, and other auxiliary agent is to account for the weight percentage of each component summation.Testing standard and results of property are as shown in table 1.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 | Unit | Standard | |
| Nylon 6 | ?90 | ??85 | ?80 | ??75 | ?70 | ?100 | ?80 | ??80 | —— | ?—— |
| The form of finely divided powder, mehtod carboxylic styrene-butadiene rubber | ?10 | ??15 | ?20 | ??25 | ?30 | ??- | ?- | ??- | - | ?- |
| Acrylic elastomer | ?- | ??- | ?- | ??- | ?- | ??- | ?20 | ??- | - | ?- |
| ????POE-g-MAH | ?- | ??- | ?- | ??- | ?- | ??- | ?- | ??20 | —— | ?—— |
| Calcium stearate | ?0.6％ | ??0.6％ | ?0.6％ | ??0.6％ | ?0.6％ | ??0.6％ | ?0.6％ | ??0.6％ | —— | ?—— |
| Superfine talcum powder | ?0.8％ | ??0.8％ | ?0.8％ | ??0.8％ | ?0.8％ | ??0.8％ | ?0.8％ | ??0.8％ | - | ?- |
| Tensile strength | ?62.6 | ??56.1 | ?51.5 | ??43.6 | ?39.7 | ??72 | ?52.1 | ??53.2 | MPa | ?ASTM ?D638 |
| Elongation at break | ?75 | ??135 | ?175 | ??205 | ?220 | ??60 | ?120 | ??135 | ％ | ?ASTM ?D638 |
| Flexural strength | ?72.8 | ??63.4 | ?56.6 | ??49.7 | ?43.8 | ??80.5 | ?57.2 | ??55.6 | MPa | ?ASTM ?D790 |
| Modulus in flexure | ?1.97 | ??1.81 | ?1.72 | ??1.56 | ?1.38 | ??2.2 | ?1.78 | ??1.75 | GPa | ?ASTM ?D790 |
| The socle girder notched Izod impact strength | ?176 | ??428 | ?665 | ??708 | ?785 | ??45 | ?325 | ??409 | J/m | ?ASTM ?D256 |
| Heat-drawn wire (1.82MPa) | ?64.2 | ??62.7 | ?61.8 | ??57.1 | ?54.6 | ??68.5 | ?59.8 | ??59.6 | ℃ | ?ASTM ?D648 |
Embodiment 6-10:
With form of finely divided powder, mehtod carboxylic styrene-butadiene rubber (with embodiment 1) and nylon 66 (the Japanese trade mark 1300s of Asahi Kasei Corporation) and calcium stearate (the long Yang Huagongchang production in Beijing chemical pure) and superfine talcum powder (the He Beilu county produces 1250 orders) uniform mixing.Adopt the ZSK-25 twin screw extruder blend granulation of German WP company, each section of forcing machine temperature is respectively: 255 ℃, 260 ℃, 265 ℃, 270 ℃, 270 ℃ and 265 ℃ (head temperature).Concrete prescription sees Table 2, and wherein the component concentration of form of finely divided powder, mehtod carboxylic styrene-butadiene rubber and nylon 66 is all in parts by weight, and other auxiliary agent is to account for the weight percentage of each component summation.The pellet oven dry is carried out every Mechanics Performance Testing after injection moulding is made the standard batten.Testing standard and results of property such as table 2 are not.
Comparative Examples 4:
After twin screw extruder blend granulation, all the other conditions are identical with embodiment 6 with the nylon among the embodiment 6 66 and calcium stearate and superfine talcum powder uniform mixing.Concrete prescription, testing standard and results of property are as shown in table 2.
Table 2
| Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Comparative Examples 4 | Unit | Standard | |
| Nylon 66 | ??90 | ??85 | ??80 | ??75 | ??70 | ??100 | ??—— | ??—— |
| The form of finely divided powder, mehtod carboxylic styrene-butadiene rubber | ??10 | ??15 | ??20 | ??25 | ??30 | ??—— | ??—— | ??—— |
| Calcium stearate | ??0.4％ | ??0.4％ | ??0.4％ | ??0.4％ | ??0.4％ | ??0.4％ | ??—— | ??—— |
| Superfine talcum powder | ??0.5％ | ??0.5％ | ??0.5％ | ??0.5％ | ??0.5％ | ??0.5％ | ??—— | ??—— |
| Tensile strength | ??72.1 | ??63.5 | ??58.9 | ??51.1 | ??43.8 | ??78.4 | ??MPa | ??ASTM ??D638 |
| Elongation at break | ??62 | ??85 | ??102 | ??120 | ??135 | ??48 | ??％ | ??ASTM ??D638 |
| Flexural strength | ??102.6 | ??93.2 | ??82.1 | ??73.3 | ??62.2 | ??113.5 | ??MPa | ??ASTM ??D790 |
| Modulus in flexure | ??2.47 | ??2.12 | ??1.88 | ??1.67 | ??1.43 | ??2.65 | ??GPa | ??ASTM ??D790 |
| The socle girder notched Izod impact strength | ??106 | ??210 | ??469 | ??545 | ??609 | ??41.2 | ??J/m | ??ASTM ??D256 |
| Heat-drawn wire (1.82MPa) | ??68.3 | ??65.2 | ??62.8 | ??61.5 | ??59.6 | ??71.5 | ??℃ | ??ASTM ??D648 |
Claims (11)
1. high-toughness polyamide, it is characterized in that this kind high-toughness polyamide is to comprise following component blend and get: polymeric amide and median size are the rubber particles of 20～200nm, and the weight ratio of rubber particles and polymeric amide is 0.5: 99.5～50: 50.
2. high-toughness polyamide according to claim 1 is characterized in that described polymeric amide comprises nylon 6, nylon 66, nylon 46 or nylon 1010.
3. high-toughness polyamide according to claim 1, the average particle size range that it is characterized in that described rubber particles is 50～150nm.
4. high-toughness polyamide according to claim 1 is characterized in that described rubber particles is the rubber particles of equal phase structure.
5. high-toughness polyamide according to claim 4 is characterized in that described rubber particles is the cross-linked rubber particle of gel content 〉=60%.
6. high-toughness polyamide according to claim 5 is characterized in that described rubber is fully vulcanized powder rubber.
7. high-toughness polyamide according to claim 6 is characterized in that described fully vulcanized powder rubber comprises at least a of following fully vulcanized powder rubber: form of finely divided powder, mehtod carboxylic styrene-butadiene rubber, form of finely divided powder, mehtod paracril, form of finely divided powder, mehtod carboxy nitrile rubber or form of finely divided powder, mehtod acrylic elastomer.
8. high-toughness polyamide according to claim 1, the weight ratio that it is characterized in that described rubber and polymeric amide is 1: 99～30: 70.
9. method for preparing each described high-toughness polyamide of claim 1-8, it is characterized in that with polymeric amide and median size being that the rubber particles blend of 20～200nm makes high-toughness polyamide, the weight ratio of rubber particles and polymeric amide is 0.5: 99.5～50: 50.
10. preparation method according to claim 9 is characterized in that described rubber particles is a fully vulcanized powder rubber.
11., it is characterized in that described fully vulcanized powder rubber adds with crosslinked powder morphology of exsiccant or undried crosslinked emulsions form according to each described preparation method of claim 10.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101418091B (en) * | 2007-10-26 | 2011-07-06 | 中国石油化工股份有限公司 | Laser marked plastic and preparation method thereof |
| CN112708260A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Nylon 6 composite material, preparation method and application |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4743670A (en) * | 1986-09-22 | 1988-05-10 | Toray Silicone Co., Ltd. | Method for producing silicone rubber powder |
| US4803247A (en) * | 1987-10-27 | 1989-02-07 | Allied-Signal Inc. | Polyamide compositions having nitrile rubber and copolymer of ethylene and alpha-olefin therein |
| JP2717229B2 (en) * | 1988-06-21 | 1998-02-18 | 旭化成工業株式会社 | Rubber particles for resin reinforcement and reinforcing resin composition |
| BE1010820A3 (en) * | 1996-12-23 | 1999-02-02 | Dsm Nv | Flexible composition polyamide. |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101418091B (en) * | 2007-10-26 | 2011-07-06 | 中国石油化工股份有限公司 | Laser marked plastic and preparation method thereof |
| CN112708260A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Nylon 6 composite material, preparation method and application |
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| CN1112406C (en) | 2003-06-25 |
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