CN102888092B - Quickly crystallized nylon compound and preparation method thereof - Google Patents
Quickly crystallized nylon compound and preparation method thereof Download PDFInfo
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- CN102888092B CN102888092B CN201210022412.6A CN201210022412A CN102888092B CN 102888092 B CN102888092 B CN 102888092B CN 201210022412 A CN201210022412 A CN 201210022412A CN 102888092 B CN102888092 B CN 102888092B
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Abstract
The invention relates to a nylon compound. The nylon compound comprises a nylon substrate and an organic nucleating agent and is characterized in that the organic nucleating agent is micromolecular amide. Meanwhile, the invention also relates to a preparation method for the nylon compound.
Description
technical field:
The present invention relates to a kind of nylon composite and preparation method thereof, relate in particular to one and obtain nylon composite and preparation method thereof by rapid crystallization.
background technology:
As far back as the 1950's, nylon-type product is just developed and produces injection-molded item, the requirement that meets the lightweight of downstream industry goods, reduces costs with substituted metal.Because nylon has nontoxic, light weight, good physical strength, wear resistance and erosion resistance preferably, at aspects such as automobile, electric installation, Machinery Ministry structure, transportation equipment, weaving, papermaking equipments, be used widely.
But when nylon is used as engineering plastics, in molding process, exist the shortcoming that crystallization rate is slow, injection molding temperature is high, molding cycle is long, this has had a strong impact on the forming process efficiency of nylon always.
For this problem, conventional solution mainly contains following several at present: 1. utilize kaolin to carry out melt blending to nylon, obtain nylon composite materials; 2. utilize polynite to carry out melt blending to nylon, obtain nano level nylon composite materials; 3. utilize organo-clay and nylon melt blending by a certain percentage, the nylon/clay nano polymer composites obtaining; 4. in nylon matrix, add inorganic nucleator, as talcum powder, nano silicon, nano titanium oxide, Neodymium trioxide, nano-calcium carbonate etc., obtain nylon composite materials; 5. by melt blending, obtain Polyphenylene Sulfide/Polyamide blend; 6. by melt blending, obtain carbon fiber/blend of nylon.Although these methods have been accelerated the crystallization rate of nylon in forming process, have shortened molding cycle, inorganic nucleator add the impelling strength that has reduced material, make the mechanical property variation of material.Organic nucleating agent is mainly phenyl sodium hypophosphite, phenyl zinc hypophosphite etc., although these nucleators and nylon compatibility are better, nucleating effect is bad, and price is relatively high.Therefore, improve forming process efficiency, can not affect again the mechanical property of nylon itself simultaneously, control cost, the nylon material of developing a kind of rapid crystallization becomes very urgent.
summary of the invention:
Scope of the present invention, only by appended claim book defined, is not limit by the statement of this joint summary of the invention in any degree.
The object of the invention is to provide that a kind of rapid crystallization, shaping cycle are short, the nylon composite of good combination property and preparation method thereof.
On the one hand, the invention provides a kind of nylon composite, comprise nylon matrix and organic nucleating agent, wherein said organic nucleating agent is small molecules acid amides.Preferably, described small molecules acid amides is naphthalene-ring containing small molecules acid amides, and more preferably, described naphthalene-ring containing small molecules acid amides is NDA Cyclohexamide.
Wherein, the massfraction that described naphthalene-ring containing small molecules acid amides accounts for nylon matrix is 0.001%～5%, and preferably, the massfraction that described naphthalene-ring containing small molecules acid amides accounts for nylon matrix is 0.01%～1%.
Wherein, above-mentioned nylon composite can also comprise processing aid, and described processing aid can be selected from a kind of or its combination in pigment, softening agent, toughener, opening agent, slipping agent.Preferably, described processing aid is selected from a kind of or its combination in silicon-dioxide, ethylene bis stearamide, erucicamide.
Wherein, described nylon matrix is selected from following one or a combination set of: nylon-6, nylon-66, nylon-1010, nylon-11, PA-12, nylon-8, nylon-9, nylon-6 12, nylon-610 or various aromatic nylon.
On the other hand, the present invention also provides a kind of preparation method of nylon composite, comprises the following steps: a) using nylon matrix, mix as the small molecules acid amides of organic nucleating agent; B) add melting mixing equipment to carry out melting mixing in the mixture of described nylon matrix and described small molecules acid amides; C) by the said mixture after melting mixing from the discharging of melting mixing equipment, and decrease temperature crystalline.
Wherein, described small molecules acid amides is naphthalene-ring containing small molecules acid amides, is preferably NDA Cyclohexamide.
Wherein, the massfraction that described naphthalene-ring containing small molecules acid amides accounts for nylon matrix is 0.001%～5%, and preferably, the massfraction that described naphthalene-ring containing small molecules acid amides accounts for nylon matrix is: 0.01%～1%.
Wherein, in step a), can also add processing aid, described processing aid is selected from a kind of or its combination in pigment, softening agent, toughener, opening agent, slipping agent, preferably, described processing aid is selected from a kind of or its combination in silicon-dioxide, ethylene bis stearamide, erucicamide.
Wherein, described nylon matrix is selected from following one or a combination set of: nylon-6, nylon-66, nylon-1010, nylon-11, PA-12, nylon-8, nylon-9, nylon-6 12, nylon-610 or various aromatic nylon.
In molding process, crystallization rate is fast, injection molding temperature is low, molding cycle is short for nylon composite of the present invention, and have that modulus is little, tensile strength is large, elongation at break is high, impelling strength is good and in certain temperature range the high feature of thermostability, can be widely used in the component of manufacturing electronic apparatus, machine machinery, household electrical appliances etc.
Meanwhile, its preparation only needs to use conventional melting mixing equipment, and industry preparation is simple.
accompanying drawing explanation:
Fig. 1 (a) is the nylon composite of the embodiment 3 polarizing microscope photo in the time of 260 ℃;
Fig. 1 (b) is the nylon composite of the embodiment 3 polarizing microscope photo in the time of 210 ℃;
Fig. 1 (c) is the nylon composite of the embodiment 3 polarizing microscope photo in the time of 200 ℃;
Fig. 2 is that the pure nylon of comparative example is at the polarizing microscope photo of 200 ℃;
Fig. 3 is the TGA figure of the nylon composite of embodiment 3 and the pure nylon of comparative example;
Fig. 4 is the DMA figure of the nylon composite of embodiment 3 and the pure nylon of comparative example.
embodiment:
Below in conjunction with the drawings and specific embodiments, elaborate the present invention, but do not limit the present invention in the scope of described embodiment.
In the present embodiment, nylon composite of the present invention, comprises nylon matrix and organic nucleating agent, and wherein said organic nucleating agent is small molecules acid amides, is preferably naphthalene-ring containing small molecules acid amides.So-called small molecules, refers to the molecule that molecular weight is less than 1000.The small molecules acid amides using in present embodiment, at the mixture from itself and the maintenance molten state of above-mentioned nylon matrix after melting mixing, form in the temperature-fall period of above-mentioned nylon composite, can from the product of above-mentioned maintenance molten state after melting mixing, crystallize out prior to above-mentioned nylon matrix, form needle-like crystal.Because small molecules acid amides is similar to the molecular structure of nylon, therefore at high temperature the consistency of itself and nylon matrix is good.Especially for naphthalene-ring containing small molecules acid amides, due to the interaction between the contained naphthalene nucleus of small molecules acid amides, at mixture from melt state temperature-fall period, first nucleator crystallizes out from the melt of nylon, form needle-like crystal, while continuing cooling, nylon based is known from experience the crystallization of growing nonparasitically upon another plant on the surface of needle-like crystal, thereby accelerate the crystallisation process of nylon, improve the mechanical property of material simultaneously.
Above-mentioned more preferably NDA Cyclohexamide of naphthalene-ring containing small molecules acid amides, its molecular weight is 378, structural formula is as follows.
In the above-described embodiment, the massfraction that accounts for above-mentioned nylon matrix as the above-mentioned small molecules acid amides of organic nucleating agent can be 0.001%～5%, and the massfraction that preferably accounts for described nylon matrix is 0.01%～1%.That is: in described nylon composite, the nylon matrix of 100 parts is corresponding to the organic nucleating agent of 0.001～5 part, is preferably the nylon matrix of 100 parts corresponding to the organic nucleating agent of 0.01～1 part.
In the above-described embodiment, described nylon matrix can be selected from one of following or its arbitrary combination: nylon-6, nylon-66, nylon-1010, nylon-11, PA-12, nylon-8, nylon-9, nylon-6 12, nylon-610, or various aromatic nylon.
In the present embodiment, in above-mentioned nylon composite, can add according to actual needs other processing aids, it can be one of pigment, softening agent, toughener, opening agent, slipping agent or their arbitrary combination.And above-mentioned other processing aids can be preferably one of following or their arbitrary combination: silicon-dioxide, ethylene bis stearamide (EBS), erucicamide.
In the present invention, the production technique of above-mentioned nylon composite is as follows:
First, using above-mentioned nylon matrix with as the above-mentioned small molecules acid amides of organic nucleating agent, evenly mix, preferably can also add according to actual needs other processing aids and mix, thereby obtain corresponding mixture.Then, obtained mixture is added in melting mixing equipment, wherein above-mentioned melting mixing equipment does not have special requirement, it can be the various industrial conventional melting mixing devices such as Banbury mixer, single screw extrusion machine, twin screw extruder or injector, and those skilled in the art's public affairs are also known the use-pattern of above-mentioned melting mixing equipment.Then, according to the melting temperature of each raw material, set suitable smelting temperature, and carry out the product of the maintenance molten state of melting mixing acquisition after melting mixing.Wherein, when melting mixing, more than the smelting temperature in equipment is set in the melt temperature of all raw materials conventionally, but should be lower than the thermal degradation temperature of nylon matrix, thereby make all raw materials keep molten states.Finally, by the product of above-mentioned maintenance molten state after melting mixing discharging decrease temperature crystalline from above-mentioned melting mixing equipment, form nylon composite.Wherein, from the product of the maintenance molten state after melting mixing, form in the temperature-fall period of above-mentioned nylon composite, above-mentioned organic nucleating agent (small molecules acid amides) first crystallizes out from the product of above-mentioned maintenance molten state after melting mixing, form needle-like crystal, then continue cooling, above-mentioned nylon based is known from experience the crystallization of growing nonparasitically upon another plant on above-mentioned needle-like crystal surface, finally obtains above-mentioned nylon composite.
In actual applications, above-mentioned product after melting mixing can be prepared corresponding nylon composite articles, such as film, pipe, rod, fiber yarn, plastic components etc. by various forming technologies (as extrusion moulding, injection molding, blow molding or calendering formation etc.) according to actual needs.Above-mentioned nylon composite articles not only can be used as wrapping material, building material, and can be used as the fields such as building materials, electronics, appliance material.
Below take nylon-6 as nylon matrix as example illustrates the present invention.
In the present embodiment and comparative example thereof, all use nylon-6 as nylon matrix, this nylon-6 is that DSM produces, and trade name is Akulon F128.
The organic nucleating agent that used is in the present embodiment NDA Cyclohexamide.
Embodiment 1-5
Nylon-6 (PA6) and organic nucleating agent 2, 6-naphthalic acid Cyclohexamide is dry after 24 hours in 80 ℃ of vacuum drying ovens respectively, take nylon 6(PA6) certain mass, by with nylon 6 mass ratioes be 0.001%(embodiment 1), 0.01%(embodiment 2), 0.5%(embodiment 3), 1%(embodiment 4), 5%(embodiment 5) ratio add organic nucleating agent, under room temperature, after mix and blend, add in Banbury mixer, Banbury mixer temperature is 260 ℃, when screw speed is 20rpm/min, banburying 3 minutes, adjusting screw speed is 50rpm/min again, banburying discharging after 5 minutes.
Comparative example
Nylon-6 (PA6) is dry in 80 ℃ of vacuum drying ovens to be taken nylon-6 (PA6) 50.25g and adds in Banbury mixer after 24 hours, and Banbury mixer temperature is 260 ℃, when screw speed is 20rpm/min, banburying 3 minutes, then to adjust screw speed be 50rpm/min, banburying discharging after 5 minutes.
Gained sample in embodiment 1-5 and comparative example is hot pressed into the sheet that thickness is 0.31mm in the thermocompressor of 260 ℃, with standard dumbbell shape punching press cutter preparation standard test batten.Test condition: be 25 ℃ in temperature, the environment that relative humidity is 27%, is used instrument to be: Instron Universal Testing Machine.Use dumbbell shape sample, by GB/T-1042-92 standard, in rate of extension, be respectively under 10mm/min and 200mm/min and carry out Mechanics Performance Testing, relevant mechanical performance index result is displayed in Table 1.
Get appropriate embodiment 1-5 and the made sample of comparative example and carry out differential calorimetric analysis (DSC) test, test condition is: initial temperature is 30 ℃, with 10 ℃/min, is warmed up to 260 ℃.With 10 ℃/min, cool to 30 ℃ again.Finally with 10 ℃/min, be warmed up to 260 ℃.Testing tool is: TA Instruments Q2000 Differential Scanning Calorimeter.The crystal property that detects sample, result is as shown in table 1.
The performance comparison table of table 1 nylon composite and pure nylon
As shown in Table 1, the crystallization initiation temperature of nylon composite of the present invention is than the height of pure nylon, and the flexible chain of nylon composite of the present invention to compare pure nylon short, illustrate that this complex crystallization speed is fast, molding cycle is short.
As shown in Table 1, in embodiment 1-5, the tensile strength of nylon composite of the present invention and elongation at break be than the height of pure nylon, illustrates that mechanical property will get well.
Lower mask body illustrates the performance of the nylon composite that the present invention obtained with embodiment 3.
By embodiment 3 and comparative example gained sample crystallisation by cooling and use polarizing microscope to observe.Experiment condition is: initial temperature is 25 ℃, with 30 ℃/min, is warmed up to 260 ℃.With 10 ℃/min, cool to 220 ℃ again.Finally with 2 ℃/min, cool to 200 ℃, keep 30min.Polarizing microscope used is Olympus polarization microscope.Acquired results is as shown in Fig. 1 (a), Fig. 1 (b), Fig. 1 (c) and Fig. 2.
Fig. 1 (a), Fig. 1 (b) and Fig. 1 (c) are the nylon composite materials of the embodiment 3 polarizing microscope photo under differing temps.In 260 ℃ (Fig. 1 (a)), system is homogeneous state, illustrates that nucleator and nylon matrix consistency are good, and when being cooled to 210 ℃, (Fig. 1 (b)), can see strip crystal, and this crystal is nucleator crystal.Nylon matrix is now still melt state, and while continuing to be cooled to 200 ℃ (Fig. 1 (c)), nylon becomes very little crystal in needle-like crystal surface growth.And under identical crystallization condition, do not contain the pure nylon spherulite size large (Fig. 2) of nucleator.The nucleogenesis that nucleator in embodiment 3 is described is remarkable.
Get appropriate embodiment 3 and the made sample of comparative example and carry out thermal weight loss (TGA) test, test condition is: initial temperature is 40 ℃, with 20 ℃/min, is warmed up to 650 ℃.Testing tool is: TA Instruments Q500 Thermo Gravimetric Analyzer.Result as shown in Figure 3.As shown in Figure 3, the heat decomposition temperature of nylon composite of the present invention is than the height of pure nylon, and the thermostability that this nylon composite is described is better than pure nylon.
Get appropriate embodiment 3 and the made sample of comparative example and carry out dynamic mechanical (DMA) test, test condition is: initial temperature is 40 ℃, with 3 ℃/min, is warmed up to 220 ℃, and frequency is 5 hertz.Testing tool is: TA Instruments DMA Q800 Dynamic Mechanical Analyzer.Result as shown in Figure 4.As shown in Figure 4, when temperature is less than 70 ℃, the storage modulus of pure nylon is high; When temperature is greater than 70 ℃, the storage modulus of nylon composite of the present invention is high.
Claims (10)
1. a nylon composite, comprises nylon matrix and organic nucleating agent, it is characterized in that: described organic nucleating agent is small molecules acid amides, wherein said small molecules acid amides is 2,6-naphthalic acid Cyclohexamide, the massfraction that described NDA Cyclohexamide accounts for nylon matrix is 0.5%.
2. nylon composite according to claim 1, is characterized in that: can also comprise processing aid.
3. nylon composite according to claim 2, is characterized in that: described processing aid is selected from a kind of or its combination in pigment, softening agent, toughener, opening agent, slipping agent.
4. nylon composite according to claim 2, is characterized in that: described processing aid is selected from a kind of or its combination in silicon-dioxide, ethylene bis stearamide, erucicamide.
5. nylon composite according to claim 2, is characterized in that: described nylon matrix is selected from following one or a combination set of: nylon-6, nylon-66, nylon-1010, nylon-11, PA-12, nylon-8, nylon-9, nylon-6 12, nylon-610 or various aromatic nylon.
6. a preparation method for nylon composite, comprises the following steps:
A) the NDA Cyclohexamide as organic nucleating agent that is 0.5% using nylon matrix and the massfraction that accounts for nylon matrix mixes;
B) add melting mixing equipment to carry out melting mixing in the mixture of described nylon matrix and described NDA Cyclohexamide;
C) by the said mixture after melting mixing from the discharging of melting mixing equipment, and decrease temperature crystalline.
7. preparation method according to claim 6, is characterized in that: in step a), can also add processing aid.
8. preparation method according to claim 7, is characterized in that: described processing aid is selected from a kind of or its combination in pigment, softening agent, toughener, opening agent, slipping agent.
9. preparation method according to claim 7, is characterized in that: described processing aid is selected from a kind of or its combination in silicon-dioxide, ethylene bis stearamide, erucicamide.
10. preparation method according to claim 7, is characterized in that: described nylon matrix is selected from following one or a combination set of: nylon-6, nylon-66, nylon-1010, nylon-11, PA-12, nylon-8, nylon-9, nylon-6 12, nylon-610 or various aromatic nylon.
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