CN1526763A - Antioxidant nylon-66 resin and its prepn - Google Patents
Antioxidant nylon-66 resin and its prepn Download PDFInfo
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- CN1526763A CN1526763A CNA031263755A CN03126375A CN1526763A CN 1526763 A CN1526763 A CN 1526763A CN A031263755 A CNA031263755 A CN A031263755A CN 03126375 A CN03126375 A CN 03126375A CN 1526763 A CN1526763 A CN 1526763A
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- nylon
- oxidation inhibitor
- antioxidant
- oxidant
- compound
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Abstract
The present invention discloses antioxidant nylon-66 resin and its preparation process. The material includes mainly nylon-66 salt and antioxidant added during the later stage of nylon-66 polymerization and dispersed under the action of polymerizing heat and stirring. After polymerization and adding the antioxidant, the mixture is discharged, cut into grain and blow dried at 100 deg.c in nitrogen atmosphere to obtain nylon-66 resin. The technological process is simple, easy to embody, pollution-free and suitable for industrial production, and the antioxidant nylon-66 resin has excellent antioxidant performance, raised physical and mechanical performance and good machinability.
Description
Technical field:
The present invention relates to a kind of novel nylon 66 resins---anti-oxidant Nylon 66 and preparation method thereof, be specifically related to a kind of anti-oxidant Nylon 66 of making by nylon 66 and oxidation inhibitor and preparation method thereof.
Background technology:
E.I.Du Pont Company had at first applied for the polymeric amide patent in 1931, nineteen thirty-seven discloses this patent (USP2130948), built the pilot plant that is used to produce monofilament and sheet material simultaneously, developed nylon 66 kinds in 1938, and be made into women socks with it and in the world, the New York trade fair of nineteen thirty-nine and Chicago trade fair, put on display, obtained immense success, nylons were formally sold on American market in 1940, and present the gesture that supply falls short of demand rapidly, set up a lot of nylon 66 and fiber production device thereof rapidly in the many areas of the U.S. subsequently.
Nylon 66 beginnings in 1956 are used as engineering plastics, because its excellent mechanical property, wear resistance, self lubricity, erosion resistance etc., replacing steady growth always aspect traditional structural metallic materials, obtained widespread use in fields such as trolley part, mechanical part, electronic apparatus, tackiness agent and wrapping material.But nylon 66 in use also exists many weak points, and long as shaping cycle, demolding performace is poor, the size instability, easily brittle failure, poor heat resistance, resistance to impact shock is low under dry state and low temperature, water-intake rate is big, and dimensional stability and poor electrical performance are opaque in addition, poorly soluble etc.Therefore, the research to nylon 66 modifications gets more and more people's extensive concerning.The modification of the nylon 66 of domestic and foreign literature report mainly concentrates on preparation high tensile, transparent engineering plastics or improves performances such as its flame retardant resistance, static resistance, germ resistance, ageing resistance, wear resistance, improves its antioxidant property aspect but relate to.The present invention mainly from improving its antioxidant property, improves the over-all properties of nylon 66, and it is more widely used.
Summary of the invention:
Exist not sludge proof problem in order to overcome Nylon 66, the purpose of this invention is to provide that a kind of antioxygen property is good, the anti-oxidant Nylon 66 of excellent combination property.
Technical scheme of the present invention realizes in the following manner:
A kind of anti-oxidant Nylon 66 mainly combines with nylon 66 and oxidation inhibitor, it is characterized in that: each component according to weight part is:
Nylon 66 monomers or nylon 66 powder 100 (part)
Oxidation inhibitor 1 * 10
-4～5 * 10
-2(part)
Said nylon 66 monomers are nylon salt.
Said oxidation inhibitor is: one or more in the mixture of (1) mantoquita and halogen-containing or P contained compound, (2) phosphorus compound, (3) hindered phenol compound, (4) hindered amine compound.
Said mantoquita is a neutralized verdigris, and halogen-containing or P contained compound is one or more of potassiumiodide, Repone K, potassiumphosphate, sodium-chlor, sodium phosphate and sodium hypophosphite etc.; Phosphorus compound is a kind of in sodium phosphate, sodium hypophosphite and the sodium phosphite etc.; Hindered phenol compound is a kind of in antioxidant 1010, antioxidant 2246, antioxidant 1076, the antioxidant 300 etc.; (4) hindered amine compound is N, a kind of in N`-hexa-methylene-two-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid amide, oxidation inhibitor DNP, oxidation inhibitor H and the oxidation inhibitor 4010 etc.
The preparation method of above-mentioned anti-oxidant Nylon 66 realizes in the following manner:
Nylon 66 monomers are added polymeric kettle, before the polymerization later stage discharging of nylon 66, add oxidation inhibitor, under the effect of heat of polymerization and stirring, it is uniformly dispersed, discharging then, pelletizing, 80～110 ℃ of forced air dryings promptly got anti-oxidant Nylon 66 in 2～20 hours in nitrogen atmosphere.
The consumption of oxidation inhibitor is 1 * 10 of nylon 66 weight
-4～5 * 10
-2Part.
The preparation method of above-mentioned anti-oxidant Nylon 66 can also realize in the following manner:
A pours nylon 66 powder forced air drying 2～20 hours or 80～110 ℃ of vacuum-drying 18～24 hours under nitrogen protection into the high speed kneader with itself and one in oxidation inhibitor, stirs fast 10～15 minutes, and discharging promptly gets nylon 66 powder I.
B is nylon 66 powder I twin screw extruder extruding pelletizations, and the particle that obtains forced air drying 2～20 hours or 80～110 ℃ of vacuum-drying 18～24 hours under nitrogen protection promptly get anti-oxidant Nylon 66.
Said oxidation inhibitor is: one or more in the mixture of (1) mantoquita and halogen-containing or P contained compound, (2) phosphorus compound, (3) hindered phenol compound, (4) hindered amine compound.
Said mantoquita is a neutralized verdigris, and halogen-containing or P contained compound is one or more of potassiumiodide, Repone K, potassiumphosphate, sodium-chlor, sodium phosphate and sodium hypophosphite etc.; Phosphorus compound is a kind of in sodium phosphate, sodium hypophosphite and the sodium phosphite etc.; Hindered phenol compound is a kind of in antioxidant 1010, antioxidant 2246, antioxidant 1076, the antioxidant 300 etc.; (4) hindered amine compound is N, a kind of in N`-hexa-methylene-two-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid amide, oxidation inhibitor DNP, oxidation inhibitor H and the oxidation inhibitor 4010 etc.
Inventive point of the present invention is: selected good antioxidant and consumption thereof, adopted respectively and made raw material and made raw material and corresponding prepared thereof that to go out antioxidant property good with nylon 66 monomers, the anti-oxidant Nylon 66 of high comprehensive performance with nylon 66 powder.
The used nylon 66 of the present invention is the Industrial products grade nylon 66, can select the different trades mark for use according to purposes.
Oxidation inhibitor preferably is crushed to suitable particle diameter, and available ball mill, vibration mill, jet mill etc. are ground into desirable particle size to oxidation inhibitor, and general particle diameter should be between 0.1～50 μ.
The consumption of used oxidation inhibitor is 1 * 10
-4～5 * 10
-2Part.When content is lower than 1 * 10
-4Part, oxidation inhibitor is not enough to produce antioxygenation; When content is higher than 5 * 10
-2During part, too much oxidation inhibitor plays the effect of impurity in nylon 66 molding process, influence the physical and mechanical properties of nylon 66.In the present invention, the optimum content scope of oxidation inhibitor is 100～1000ppm.
Positively effect of the present invention is:
1, anti-oxidant Nylon 66 of the present invention, its physical and mechanical properties improves a lot.This raising can improve nylon 66 owing to the adding of oxidation inhibitor easily oxidized in molding process, causes the weakness of degradation.
2, the preparation method of anti-oxidant Nylon 66 provided by the invention, technology is simple, easily implements, and is pollution-free, realizes industrialization easily.
3, the preparation method of anti-oxidant Nylon 66 provided by the invention, the yellowness index of the Nylon 66 that makes, end amido and end carboxyl, black grain number and water content are all far below the pure Nylon 66 that does not add oxidation inhibitor, and viscosity then is higher than pure Nylon 66.
4, the preparation method of anti-oxidant Nylon 66 provided by the invention, the Nylon 66 antioxygen property excellence that makes heats in 80 ℃ of following air conditions, not variable color still in 54 hours.
5, the preparation method of anti-oxidant Nylon 66 provided by the invention shows as pseudoplastic fluid under the Nylon 66 high temperature that makes.Compare its η with pure nylon 66
aSusceptibility to shearing force descends, and can obtain in the range of shear rate of relative broad than steady flow under the steady temperature; The susceptibility of temperature also reduces, and can obtain more stable flowing in the wide temperature range relatively under the permanent shearing rate.
6, heat resisting temperature improves, and whiteness significantly improves, more easy-formation processing.
Embodiment:
Embodiment:
Press formula ratio respectively in the polymerization later stage of nylon 66 and add three kinds of oxidation inhibitor, the effect of heat of polymerization and stirring is uniformly dispersed it, discharging then, pelletizing, and 100 ℃ of forced air dryings promptly get three kinds of anti-oxidant Nylon 66s in nitrogen atmosphere, are labeled as AO respectively
1, AO
2And AO
3, pure nylon 66 identified as samples are designated as AO
0
Test the physicochemical property of anti-oxidant Nylon 66, the result is as shown in table 1.The end amido of company standard regulation Nylon 66 premium grads is 50 ± 4meg/kg, and the end carboxyl is 75 ± 4meg/kg, black grain number≤0.017%, water content≤900mg/kg.As seen sample AO
1Performance more meet the requirement of Nylon 66 premium grads.
The physicochemical property of the anti-oxidant Nylon 66 of table 1
The several 100 ℃ of water content of sample end amido end carboxyl stain
(mng/kg)????(mng/kg)????(％)????????(mg/kg)
AO
0???????55.6????????70.0???????0.016????????695
AO
1???????54.9????????77.9???????0.009????????686
AO
2???????57.6????????83.9???????0.101????????680
AO
3???????66.2????????54.8???????0.009????????621
With AO
0And AO
1Sample is injection molding in injector, tests its stretching, bending, impact and thermal deformation behavior, and data are as shown in table 2.As can be seen from Table 2, with pure nylon 66 AO
0Compare AO
1Tensile strength and modulus, flexural strength and modulus all increase, heat-drawn wire also increases to some extent.Wherein, tensile strength has increased by 7.0%, and Young's modulus has increased by 11.8%, and flexural strength has increased by 18.5%, and modulus in flexure has increased by 12.1%.
The mechanics of each sample of table 2 and thermal characteristics table
| Sample | Tensile strength (MPa) | Young's modulus (MPa * 10 3) | Elongation at break (%) | Flexural strength (MPa) | Modulus in flexure (MPa * 10 3) | Notched Izod impact strength (kJ/m 2) | Heat-drawn wire (℃) |
| AO 0AO 1 | ????71.6 ????77.3 | ????2.46 ????2.79 | 90.9 92.3 | ??81.7 ??100.3 | ????2.23 ????2.50 | ????6.9 ????4.9 | ????61.7 ????64.2 |
For comparing AO
1With the antioxygen property of external nylon 66 samples, with AO
1, AO
0Nylon 66 samples of producing with a U.S. Monsanto Company heat in 80 ℃ of following air conditions, respectively take out certain sample at regular intervals, relatively its color and luster.Found that pure nylon 66 sample AO
0After 1 hour, begin jaundice, prolong in time, the yellow intensification; All sample some milky whites that became since 4 hours of Meng Shan, but also not flavescence up to 54 hours, just some intensification of oyster white; And AO
1Sample is not variable color still up to 54 hours.AO is described
1Antioxidant property improve much than the pure sample product, and be better than external similar sample.
Can learn AO by rheological test
1Show as pseudoplastic fluid under the high-temperature sample.Compare its apparent viscosity η with pure nylon 66
aSusceptibility to temperature also reduces, and can obtain more stable flowing in the wide temperature range relatively under the permanent shearing rate.Table 3 is AO
0And AO
1Non-newtonian index n value under the sample differing temps.AO
0Non-newtonian index n raise along with temperature and increase, and AO
1When temperature was higher than 277 ℃, its non-newtonian index n was almost constant, and latter n value is little than the former all the time.This shows AO
1Sample is than AO
0Non-Newtonianism strong.The non-Newtonianism that the n value is reflected, essence are apparent viscosity η
aTo the shearing force sensitive question.The n value is big more, η
aResponsive more to shearing force.Therefore the adding of oxidation inhibitor makes η
aSusceptibility to shearing force descends.Can in the range of shear rate of relative broad, obtain under the steady temperature than steady flow.
Table 3 AO
0And AO
1The non-newtonian index n value of sample differing temps
Temperature (℃) 275 277 280 283
AO
0??????0.8????10.83???0.93?????0.94
AO
1??????0.77???0.79????0.79?????0.79
By above discussion as can be known, the physicochemical property of anti-oxidant nylon 66, antioxygen property, physical and mechanical properties and rheological property all are greatly improved.
Claims (9)
1, a kind of anti-oxidant Nylon 66 mainly combines with nylon 66 and oxidation inhibitor, it is characterized in that: each component according to weight part is:
Nylon 66 monomers or nylon 66 powder 100 (part)
Oxidation inhibitor 1 * 10
-4～5 * 10
-2(part)
2, anti-oxidant Nylon 66 according to claim 1 is characterized in that: said nylon 66 monomers are nylon salt.
3, anti-oxidant Nylon 66 according to claim 2, it is characterized in that: said oxidation inhibitor is: one or more in the mixture of (1) mantoquita and halogen-containing or P contained compound, (2) phosphorus compound, (3) hindered phenol compound, (4) hindered amine compound.
4, anti-oxidant Nylon 66 according to claim 3 is characterized in that: said mantoquita is a neutralized verdigris, and halogen-containing or P contained compound is one or more of potassiumiodide, Repone K, potassiumphosphate, sodium-chlor, sodium phosphate and sodium hypophosphite etc.; Phosphorus compound is a kind of in sodium phosphate, sodium hypophosphite and the sodium phosphite etc.; Hindered phenol compound is a kind of in antioxidant 1010, antioxidant 2246, antioxidant 1076, the antioxidant 300 etc.; (4) hindered amine compound is N, a kind of in N`-hexa-methylene-two-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid amide, oxidation inhibitor DNP, oxidation inhibitor H and the oxidation inhibitor 4010 etc.
5, a kind of preparation method according to the described any anti-oxidant Nylon 66 of claim 1-4, it is characterized in that: nylon 66 monomers are added polymeric kettle, before the polymerization later stage discharging of nylon 66, add oxidation inhibitor, under the effect of heat of polymerization and stirring, it is uniformly dispersed, discharging then, pelletizing, 80-110 ℃ of forced air drying promptly got anti-oxidant Nylon 66 in 2～20 hours in nitrogen atmosphere.
6, the preparation method of anti-oxidant Nylon 66 according to claim 5 is characterized in that: the consumption of oxidation inhibitor is 1 * 10 of nylon 66 weight
-4～5 * 10
-2Part.
7, a kind of preparation method of anti-oxidant Nylon 66 according to claim 1; it is characterized in that: a is with nylon 66 powder forced air drying 2～20 hours or 80～110 ℃ of vacuum-drying 18～24 hours under nitrogen protection; pour itself and one in oxidation inhibitor into the high speed kneader; stirred 10～15 minutes fast; discharging promptly gets nylon 66 powder I.
B is nylon 66 powder I twin screw extruder extruding pelletizations, and the particle that obtains forced air drying 2～20 hours or 80～110 ℃ of vacuum-drying 18～-24 hour under nitrogen protection promptly get anti-oxidant Nylon 66.
8, the preparation method of anti-oxidant Nylon 66 according to claim 7 is characterized in that: said oxidation inhibitor is: one or more in the mixture of (1) mantoquita and halogen-containing or P contained compound, (2) phosphorus compound, (3) hindered phenol compound, (4) hindered amine compound.
9, the preparation method of anti-oxidant Nylon 66 according to claim 8, it is characterized in that: said mantoquita is a neutralized verdigris, and halogen-containing or P contained compound is one or more of potassiumiodide, Repone K, potassiumphosphate, sodium-chlor, sodium phosphate and sodium hypophosphite etc.; Phosphorus compound is a kind of in sodium phosphate, sodium hypophosphite and the sodium phosphite etc.; Hindered phenol compound is a kind of in antioxidant 1010, antioxidant 2246, antioxidant 1076, the antioxidant 300 etc.; (4) hindered amine compound is N, a kind of in N`-hexa-methylene-two-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid amide, oxidation inhibitor DNP, oxidation inhibitor H and the oxidation inhibitor 4010 etc.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03126375 CN1252183C (en) | 2003-09-23 | 2003-09-23 | Antioxidant nylon-66 resin and its prepn |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03126375 CN1252183C (en) | 2003-09-23 | 2003-09-23 | Antioxidant nylon-66 resin and its prepn |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1526763A true CN1526763A (en) | 2004-09-08 |
| CN1252183C CN1252183C (en) | 2006-04-19 |
Family
ID=34285962
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03126375 Expired - Fee Related CN1252183C (en) | 2003-09-23 | 2003-09-23 | Antioxidant nylon-66 resin and its prepn |
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| Country | Link |
|---|---|
| CN (1) | CN1252183C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102115596A (en) * | 2010-12-31 | 2011-07-06 | 马艳荣 | Nylon composite material for wire and cable sheaths |
| CN113423275A (en) * | 2018-12-11 | 2021-09-21 | X-茵菲克斯有限公司 | Polyamide composition biocide, preparation method and use thereof |
-
2003
- 2003-09-23 CN CN 03126375 patent/CN1252183C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102115596A (en) * | 2010-12-31 | 2011-07-06 | 马艳荣 | Nylon composite material for wire and cable sheaths |
| CN113423275A (en) * | 2018-12-11 | 2021-09-21 | X-茵菲克斯有限公司 | Polyamide composition biocide, preparation method and use thereof |
| CN113423275B (en) * | 2018-12-11 | 2023-08-08 | X-茵菲克斯有限公司 | Polyamide composition biocide, method for the production and use thereof |
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| Publication number | Publication date |
|---|---|
| CN1252183C (en) | 2006-04-19 |
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| ASS | Succession or assignment of patent right |
Owner name: CHINA SHENMA GROUP CO.,LTD. Effective date: 20050311 |
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Effective date of registration: 20050311 Address after: 450052 University Road, Henan, Zhengzhou 75 Applicant after: Zhengzhou University Co-applicant after: China Shenma Group Co., Ltd. Address before: 450052 University Road, Henan, Zhengzhou 75 Applicant before: Zhengzhou University |
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Granted publication date: 20060419 Termination date: 20091023 |