CN102516706A - Polyformaldehyde resin composite nucleating agent as well as polyformaldehyde resin complex and preparation method thereof - Google Patents
Polyformaldehyde resin composite nucleating agent as well as polyformaldehyde resin complex and preparation method thereof Download PDFInfo
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- CN102516706A CN102516706A CN2011103701419A CN201110370141A CN102516706A CN 102516706 A CN102516706 A CN 102516706A CN 2011103701419 A CN2011103701419 A CN 2011103701419A CN 201110370141 A CN201110370141 A CN 201110370141A CN 102516706 A CN102516706 A CN 102516706A
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Abstract
The invention provides a polyformaldehyde resin composite nucleating agent which is composed of 90-95wt% of polyamide and 5-10wt% of nano silicon dioxide. The invention also provides a polyformaldehyde resin complex comprising the composite nucleating agent and a preparation method thereof. The composite nucleating agent provided by the invention can be used for improving the crystallization properties of polyformaldehyde resin, so as to obtain high crystallization temperature and high crystallization rate as well as maintain or improve the mechanical properties of polyformaldehyde materials. The polyformaldehyde resin complex provided by the invention has the advantages of high crystallization temperature, high crystallization rate, high strength, high rigidity, shock resistance, good fluidity, easiness in processing and shaping, smooth and uniform surface and the like. The preparation method has the advantages of simple and continuous flow, high production efficiency and stable product quality.
Description
Technical field
The present invention relates to macromolecular material and forming process field thereof, be specifically related to a kind of polyoxymethylene resin composite nucleating agent, contain polyoxymethylene resin mixture of said nucleator and preparation method thereof.
Background technology
Since the U.S. Du Pont homopolymerization POM of company, the copolymerization POM of the Celanese company success industriallization of last century 50, the sixties; The POM resin through the nineties in 20th century in one period relatively stably in early days after; Getting into the fast-developing new stage in recent years, its production capacity and the market requirement are all more and more powerful.Polyoxymethylene resin has special mechanical properties; Very high rigidity and hardness; Fabulous resistance to fatigue, oil-proofness, chemical resistant properties, low water absorbable and good heat, electrical property and wear resistance; Less creep properties, dimensional stability and chemicalstability preferably, be in the engineering plastics mechanical property near the material of metal; Especially decrease characteristic and outstanding fatigue performance with its good self-lubricating abrasion-resistant; Be widely used in fields such as machinery, automobile, precision instrument, drive bearing parts and electronics, as non-ferrous metal and the alloy replacing thing of making parts such as bearing, gear, automobile instrument panel, pump leaf impeller.
Yet; Because polyoxymethylene percent crystallinity is high, in molding process, very easily forms larger-size spherocrystal, these larger-size spherocrystals receive at material and form focal point of stress when impacting easily; Cause the destruction of material; So the polyoxymethylene resin notch sensitivity is big, notched Izod impact strength is low, and this has limited the development and the application of polyoxymethylene resin greatly.Therefore need the crystallization behavior of polyoxymethylene resin is intervened, improve its Tc, accelerate its crystallization velocity, thereby reduce its spherulite size to adapt to the requirement of precise forming.Adding nucleator is the controlling polymers spherulite size, improves the simple and practical method of polymer crystallization speed.Traditionally; The nucleator that can be used for regulating and control the copolymerized methanal crystal property is divided into organic low molecular classes such as trimeric cyanamide formal; Three types of systems such as high score subclass such as inorganic mineral classes such as talcum powder, zeyssatite and SP 1 and polymeric amide; Although these several types of nucleators all can improve the crystal property of polyoxymethylene resin, the use of the nucleator of single kind tends to cause other shortcoming, and for example: organic low molecular class fusing point is low, poor stability in the course of processing; Inorganic mineral class and polymer phase capacitive are poor, and it is bad dispersibility in resin; The high score subclass falls between, but often causes the decline of polyoxymethylene resin mechanical property.Therefore need the multi-functional composite nucleating agent of development of new, when obtaining excellent crystal property, keep or improve its mechanical property.
Nanoparticle is because size is little, and specific surface area is big, and its surperficial atomicity is many, Atomic coordinate is not enough, thereby surfactivity is very big.With polymkeric substance compound after; Easily with forming physics or chemical action between the macromolecular chain; Thereby the reactive force between the change macromolecular chain; Play the effect of physical crosslinking point, the interface binding intensity between particle and matrix is increased, strengthened intensity, toughness and the wear resisting property etc. of matrix material simultaneously.Nano silicon with its have that chemical purity height, dispersing property are good, thermal resistance and resistive performance is excellent and superior stability, enhanced and thixotropy etc. become and important nano inorganic novel material; And be widely used in the polymer modification system; Disclose " nano silicon comes modified polypropene and preparation method thereof " like patent CN 101302317A, the nano-silicon dioxide modified Vestolen PP 7052 tensile strength and the flexural strength of its acquisition are greatly enhanced; Patent CN 1834151A discloses a kind of " preparation method of nano SiO 2/boron bakelite resin nano composite material ", and the nano composite material compressive strength of its acquisition can improve 5-6 doubly; Patent CN 1493611A discloses a kind of " bismaleimides-polyetherimide-silica ternary hybrid nano-material and preparation method thereof "; This hybrid material is along with the introducing of nanoscale silicon-dioxide, and the mechanical property and the thermal property of material all are greatly improved; " engineering plastics application " (Wu Runde etc., 2003,31 (11), p15) in report, Wu Runde etc. carry out modification with nano silicon to Vestolen PP 7052, make polyacrylic tensile strength improve 10%, modulus in tension improves 30%; " matrix material journal " (Liu Feng etc., 2006,23 (6), p57) in report, Liu Feng etc. strengthen Zylox with nano silicon, and tensile strength, tear strength and the elongation at break of Zylox all are significantly increased.
Summary of the invention
The objective of the invention is to overcome the shortcoming that present polyoxymethylene resin Tc is low, crystallization rate is slow, a kind of composite nucleating agent of polyoxymethylene resin is provided.
Another object of the present invention provide a kind of contain nucleator according to the invention, have high crystallization temperature, fast crystallization rate, and good fluidity, be easy to the polyoxymethylene resin mixture of machine-shaping.
Another object of the present invention is to provide the method that a kind of flow process is simple, continuous, production efficiency is high, constant product quality prepares above-mentioned polyoxymethylene resin mixture.
Polyoxymethylene resin composite nucleating agent of the present invention is grouped into by following one-tenth by weight:
Polymeric amide: 90～95%;
Nano silicon: 5～10%.
Said polymeric amide is one or more in nylon 6, nylon 1010, the NYLON610.
The selection of said nano silicon must consider that itself and resin should have good consistency, and nano silicon will have good dispersion in material matrix simultaneously.Nano silicon according to the invention is selected from one or more in the nano silicon of the nano silicon of surperficial unmodified nano silicon, surface amino groups modification, surperficial epoxide group modification.
The particle diameter of said nano silicon is 10～100nm.
Above-mentioned nano silicon, polymeric amide all can be selected the existing or commercial product in this area for use; The product that preferably is usually used in nucleator.
Polyoxymethylene resin mixture of the present invention comprises polyoxymethylene resin and nucleator, and said nucleator is the described composite nucleating agent of each technical scheme of the present invention.
Said polyoxymethylene resin mixture also comprises oxidation inhibitor and stablizer, forms by following weight part:
95～100 parts of polyoxymethylene resins;
0～1.5 part of nucleator;
0.2～1 part in oxidation inhibitor;
0.2～1 part of stablizer;
Wherein, the weight of said nucleator is not 0.
Said polyoxymethylene resin mixture is further preferred to be formed by following weight part:
97～99.5 parts of polyoxymethylene resins;
0.3～1.2 part of nucleator;
0.2～0.8 part in oxidation inhibitor;
0.2～0.8 part of stablizer.
Said polyoxymethylene resin is that melting index is the copolymerized methanal resin between 1g/10min～70g/10min.Said polyoxymethylene resin can use a kind of polyoxymethylene resin of independent melting index, also can select the mixture of the polyoxymethylene resin of multiple different melting index for use.
Said oxidation inhibitor is phenolic antioxidant, phosphite ester kind antioxidant, contain in thioesters kind antioxidant, the metal passivator one or more.
Wherein, as optimized technical scheme, phenolic antioxidant has four [methyl-β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester (antioxidant 1010), 2,2 methylene-biss (4-methyl-6-tert butyl phenol) (antioxidant 2246) etc.; Phosphite ester kind antioxidant has tricresyl phosphite (nonyl phenyl) (oxidation inhibitor TNPP) or tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) esters (oxidation inhibitor 168); Contain the thioesters kind antioxidant Tyox B (anti-oxidant DLTP) is arranged.
Said stablizer is one or more in trimeric cyanamide, Dyhard RU 100, methylol melamine, carbamide condenses, urea, SEPIGEL 305, the polymeric amide.Further preferred one or more the mixture that adopts trimeric cyanamide, carbamide condenses, Dyhard RU 100.
The preparation method of polyoxymethylene resin mixture of the present invention may further comprise the steps: at first raw material polyoxymethylene resin, nucleator, oxidation inhibitor and stablizer are mixed to evenly; Adopting forcing machine under 150～240 ℃, to carry out extruding pelletization mixed raw material then forms.
Above-mentioned preparation process further is preferably: at first raw material polyoxymethylene resin, nucleator, oxidation inhibitor and stablizer are mixed in high-speed mixer and stir; Then with mixed raw material put into twin screw extruder carry out fusion, mixing, extrude, tie rod, cooling, drying, pelletizing promptly get; Wherein, the rate of feeding of said twin screw extruder is 5～10rpm/min, and screw speed is 200～400rpm/min, and each subregion temperature of barrel remains between 150～240 ℃.
Among the above-mentioned preparation method, said high-speed mixer, twin screw extruder are the existing installation of this area; Said fusion, mixing, extrude, process step such as tie rod, cooling, drying, pelletizing all adopts the existing technology of this area.
Composite nucleating agent provided by the invention has been selected polymeric amide and nano silicon for use; The two compound working in coordination with can be carried out the crystal property modification to polyoxymethylene resin; When obtaining high crystallization temperature, fast crystallization rate; Can keep or improve the mechanical property of polyformaldehyde material again, thereby enlarge the range of application of polyformaldehyde material.
Polyoxymethylene resin mixture provided by the invention is compared with common polyoxymethylene (POM) resin; Polyoxymethylene resin mixture of the present invention is owing to added polymeric amide and nano silicon in composite body system; Have high crystallization temperature, fast crystallization rate, high-strength, high rigidity, shock-resistant, good fluidity, be easy to characteristics such as machine-shaping, but also have smooth surface, advantage such as even.Be highly suitable for making the wear part of aspects such as automobile, food machinery, papermaking, agricultural machine, wide application prospect is arranged.
The method for preparing the polyoxymethylene resin mixture provided by the invention adopts the twin screw extrusion technique device, have flow process simple, continuously, the advantage of high, the constant product quality of production efficiency.
Embodiment
Following examples further specify content of the present invention, but should not be construed as limitation of the present invention.Under the situation that does not deviate from the present invention's spirit and essence, modification or replacement to the inventive method, step or condition are done all belong to scope of the present invention.If do not specialize the conventional means that used technique means is well known to those skilled in the art among the embodiment.
The acetal resin that adopts among the embodiment is that the melt index that Shanghai blue star new chemical materials factory produces is the polyformaldehyde of 9g/10min, and the trade mark is M90; Polyamide is PA6
7301NC010, PA1010
RSLC1000BK385, PA610
RSLC3090NC010 that du pont company is produced; Nano silicon is that the particle diameter that German DEGUSSA company produces is the A200 of 20nm and RNS-A, the RNS-E of the particle diameter 15-25nm of Beijing Zhongbona Science And Technology Co., Ltd's production; IRGANOX1010 and IRGAFOS168 that antioxidant is produced for CIBA company; Melamine, carbamide condensation product and dicyandiamide that stabilizing agent is produced for Beijing chemical reagents corporation.
Embodiment 1
Press POM 98.45 quality %, PA6 0.5 quality %, nano silicon A200 0.05 quality %, IRGANOX1010 0.3 quality %, IRGAFOS168 0.3 quality %, trimeric cyanamide 0.4 quality %.Take by weighing after raw material mixes in high-speed mixer, drop into the twin screw extruder extruding pelletization.Processing temperature is set first section 150 ℃, second section 170 ℃, the 3rd section 190 ℃, the 4th section 210 ℃, the 5th section 230 ℃, the 6th section 220 ℃, the 7th section 210 ℃, the 8th section 190 ℃, the 9th section 175 ℃, 170 ℃ of die head temperatures; Tie rod is crossed the water pelletizing.
Wherein, the rate of feeding of twin screw extruder is that 5rpm/min, screw speed are 400rpm/min.
Embodiment 2
Press POM 98.12 quality %, PA6 0.8 quality %, nano silicon A200 0.08 quality %, IRGANOX1010 0.3 quality %, IRGAFOS168 0.3 quality %, carbamide condenses 0.4 quality %.Take by weighing after raw material mixes in high-speed mixer, drop into the twin screw extruder extruding pelletization.Processing temperature is set first section 150 ℃, second section 170 ℃, the 3rd section 190 ℃, the 4th section 210 ℃, the 5th section 230 ℃, the 6th section 220 ℃, the 7th section 210 ℃, the 8th section 190 ℃, the 9th section 175 ℃, 170 ℃ of die head temperatures; Tie rod is crossed the water pelletizing.
Wherein, the rate of feeding of twin screw extruder is that 10rpm/min, screw speed are 300rpm/min.
Embodiment 3
Press POM 97.9 quality %, PA61 quality %, nano silicon A200 0.1 quality %, IRGANOX1010 0.3 quality %, IRGAFOS168 0.3 quality %, Dyhard RU 100 0.4 quality %.Take by weighing after raw material mixes in high-speed mixer, drop into the twin screw extruder extruding pelletization.Processing temperature is set first section 150 ℃, second section 170 ℃, the 3rd section 190 ℃, the 4th section 210 ℃, the 5th section 230 ℃, the 6th section 220 ℃, the 7th section 210 ℃, the 8th section 190 ℃, the 9th section 175 ℃, 170 ℃ of die head temperatures; Tie rod is crossed the water pelletizing.
Wherein, the rate of feeding of twin screw extruder is that 7rpm/min, screw speed are 200rpm/min.
Embodiment 4
Press POM 98.45 quality %, PA1010 0.5 quality %, nano silicon RNS-A0.05 quality %, IRGANOX1010 0.3 quality %, IRGAFOS168 0.3 quality %, trimeric cyanamide 0.4 quality %.Take by weighing after raw material mixes in high-speed mixer, drop into the twin screw extruder extruding pelletization.Processing temperature is set first section 150 ℃, second section 170 ℃, the 3rd section 190 ℃, the 4th section 210 ℃, the 5th section 230 ℃, the 6th section 220 ℃, the 7th section 210 ℃, the 8th section 190 ℃, the 9th section 175 ℃, 170 ℃ of die head temperatures; Tie rod is crossed the water pelletizing.
Wherein, the rate of feeding of twin screw extruder is that 5rpm/min, screw speed are 400rpm/min.
Embodiment 5
Press POM 98.45 quality %, PA610 0.5 quality %, nano silicon RNS-E0.05 quality %, IRGANOX1010 0.3 quality %, IRGAFOS168 0.3 quality %, trimeric cyanamide 0.4 quality %.Take by weighing after raw material mixes in high-speed mixer, drop into the twin screw extruder extruding pelletization.Processing temperature is set first section 150 ℃, second section 170 ℃, the 3rd section 190 ℃, the 4th section 210 ℃, the 5th section 230 ℃, the 6th section 220 ℃, the 7th section 210 ℃, the 8th section 190 ℃, the 9th section 175 ℃, 170 ℃ of die head temperatures; Tie rod is crossed the water pelletizing.
Wherein, the rate of feeding of twin screw extruder is that 5rpm/min, screw speed are 400rpm/min.
Comparative Examples 1
Press POM 99 quality %, IRGANOX1010 0.3 quality %, IRGAFOS168 0.3 quality %, trimeric cyanamide 0.4 quality %.Take by weighing after raw material mixes in high-speed mixer, drop into the twin screw extruder extruding pelletization.Processing temperature is set first section 150 ℃, second section 170 ℃, the 3rd section 190 ℃, the 4th section 210 ℃, the 5th section 230 ℃, the 6th section 220 ℃, the 7th section 210 ℃, the 8th section 190 ℃, the 9th section 175 ℃, 170 ℃ of die head temperatures; Tie rod is crossed the water pelletizing.
Wherein, the rate of feeding of twin screw extruder is that 5rpm/min, screw speed are 400rpm/min.
Comparative Examples 2
Press POM 98.5 quality %, PA6 0.5 quality %, IRGANOX1010 0.3 quality %, IRGAFOS168 0.3 quality %, trimeric cyanamide 0.4 quality %.Take by weighing after raw material mixes in high-speed mixer, drop into the twin screw extruder extruding pelletization.Processing temperature is set first section 150 ℃, second section 170 ℃, the 3rd section 190 ℃, the 4th section 210 ℃, the 5th section 230 ℃, the 6th section 220 ℃, the 7th section 210 ℃, the 8th section 190 ℃, the 9th section 175 ℃, 170 ℃ of die head temperatures; Tie rod is crossed the water pelletizing.
Wherein, the rate of feeding of twin screw extruder is that 5rpm/min, screw speed are 400rpm/min.
Comparative Examples 3
Press POM 98.5 quality %, nano silicon A200 0.5 quality %, IRGANOX1010 0.3 quality %, IRGAFOS168 0.3 quality %, trimeric cyanamide 0.4 quality %.Take by weighing after raw material mixes in high-speed mixer, drop into the twin screw extruder extruding pelletization.Processing temperature is set first section 150 ℃, second section 170 ℃, the 3rd section 190 ℃, the 4th section 210 ℃, the 5th section 230 ℃, the 6th section 220 ℃, the 7th section 210 ℃, the 8th section 190 ℃, the 9th section 175 ℃, 170 ℃ of die head temperatures; Tie rod is crossed the water pelletizing.
Wherein, the rate of feeding of twin screw extruder is that 5rpm/min, screw speed are 400rpm/min.
Performance Detection
The concrete material formula of each embodiment and Comparative Examples sees that shown in the table 1, crystal property is seen table 2, and physicals is seen table 3.The mixture of each embodiment preparation is injection molded into the standard batten of testing usefulness by standard size, and physicals is tested by China's national standard, sees table 4.
Compare with Comparative Examples; Polyformaldehyde compound is after adding polymeric amide and nano silicon among each embodiment; The Tc of material obviously improves, the hypocrystalline time significantly shortens, the crystallization peak width at half significantly narrows, and mechanics such as tensile strength, flexural strength and shock resistance also all are greatly improved, and this makes material when keeping and improving mechanical property; Its crystal property has obtained significantly to improve, and has the characteristics of high crystallization temperature, fast crystallization rate.
Each embodiment component concentration of table 1 polyformaldehyde compound
Each embodiment crystal property of table 2 polyformaldehyde compound
Annotate: adopt DSC to record with the nonisothermal crystallization method, Φ is a rate of temperature fall in the table, t
1/2Be the hypocrystalline time, Tp is a Tc, and WHH is the crystallization peak width at half.
Each embodiment physicals of table 3 polyformaldehyde compound
Each embodiment physicals testing standard of table 4 polyformaldehyde compound
Claims (10)
1. a polyoxymethylene resin composite nucleating agent is characterized in that, is grouped into by following one-tenth by weight:
Polymeric amide: 90～95%;
Nano silicon: 5～10%.
2. composite nucleating agent according to claim 1 is characterized in that, said polymeric amide is one or more in nylon 6, nylon 1010, the NYLON610.
3. composite nucleating agent according to claim 1; It is characterized in that said nano silicon is one or more in the nano silicon of the nano silicon of surperficial unmodified nano silicon, surface amino groups modification, surperficial epoxide group modification.
4. composite nucleating agent according to claim 3 is characterized in that, the particle diameter of said nano silicon is 10～100nm.
5. a polyoxymethylene resin mixture is characterized in that, comprises each described nucleator of polyoxymethylene resin and claim 1-4.
6. polyoxymethylene resin mixture according to claim 5 is characterized in that, said polyoxymethylene resin mixture also comprises oxidation inhibitor and stablizer, forms by following weight part:
95～100 parts of polyoxymethylene resins;
0～1.5 part of nucleator;
0.2～1 part in oxidation inhibitor;
0.2～1 part of stablizer;
Wherein, the weight of said nucleator is not 0;
Said polyoxymethylene resin mixture is preferably formed by following weight part:
97～99.5 parts of polyoxymethylene resins;
0.3～1.2 part of nucleator;
0.2～0.8 part in oxidation inhibitor;
0.2～0.8 part of stablizer.
7. according to claim 5 or 6 described polyoxymethylene resin mixtures, it is characterized in that said polyoxymethylene resin is the copolymerized methanal resin of melting index between 1～70g/10min.
8. according to claim 5 or 6 described polyoxymethylene resin mixtures, it is characterized in that said oxidation inhibitor is phenolic antioxidant, phosphite ester kind antioxidant, contain in the thioesters kind antioxidant one or more.
9. according to claim 5 or 6 described polyoxymethylene resin mixtures, it is characterized in that said stablizer is one or more in trimeric cyanamide, Dyhard RU 100, methylol melamine, carbamide condenses, urea, SEPIGEL 305, the polymeric amide.
10. the preparation method of each said polyoxymethylene resin mixture of claim 5-9 is characterized in that, may further comprise the steps: at first raw material polyoxymethylene resin, nucleator, oxidation inhibitor and stablizer are mixed to evenly; Adopting forcing machine under 150～240 ℃, to carry out extruding pelletization mixed raw material then forms.
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| CN113150540A (en) * | 2021-04-21 | 2021-07-23 | 深圳市高科塑化有限公司 | Nylon carbon fiber composite material for improving waterproofness and preparation method thereof |
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| CN103497484A (en) * | 2013-09-06 | 2014-01-08 | 开滦能源化工股份有限公司 | High-modulus high-strength high-heatproofnesspolyoxymethylene composite material and preparation method thereof |
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| CN113150540A (en) * | 2021-04-21 | 2021-07-23 | 深圳市高科塑化有限公司 | Nylon carbon fiber composite material for improving waterproofness and preparation method thereof |
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