CN102702674A - Polyformaldehyde composition and preparation method thereof - Google Patents
Polyformaldehyde composition and preparation method thereof Download PDFInfo
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- CN102702674A CN102702674A CN2012102223664A CN201210222366A CN102702674A CN 102702674 A CN102702674 A CN 102702674A CN 2012102223664 A CN2012102223664 A CN 2012102223664A CN 201210222366 A CN201210222366 A CN 201210222366A CN 102702674 A CN102702674 A CN 102702674A
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Abstract
The invention discloses a polyformaldehyde composition and a preparation method thereof. The polyformaldehyde composition contains by part of weight: 100 parts of acetal resins, 0.01-2 parts of oxidation inhibitors, 0.01-2 parts of formaldehyde catching agents, 0.01-2 parts of formic acid catching agents and 0.01-5 parts of crosslinking acetal resins. Compared with the prior art, the crosslinking acetal resins serve as nucleating agents and are obvious in nucleating effects, and a great number of crystal nucleuses are formed before crystallization of the acetal resins, so that crystallization of the acetal resin is induced, the number of the crystal nucleuses is improved, crystallization degree and temperature are improved, sphaerocrystal dimension is lowered, and accordingly crystallization structure of the acetal resin is improved. Further, due to the fact that the adding amount of the crosslinking acetal resins is small, and bad influence on mechanical property, thermal performance and surface morphology of the polyformaldehyde composition is avoided. Experiment results prove that the sphaerocrystal dimension of the polyformaldehyde composition is about 40 mu m, and the polyformaldehyde composition has good crystalline structure and good mechanical property.
Description
Technical field
The present invention relates to technical field of polymer materials, more particularly, relate to a kind of polyformaldehyde composition and preparation method thereof.
Background technology
(Polyoxymethylene POM) claims oxygen methyne polymkeric substance again to polyoxymethylene, is one of the world's five large-engineering plastics, and output is only second to nylon and polycarbonate, occupies the third place in the world.Because the difference of structure, polyoxymethylene can be divided into two big types: one type is acefal homopolymer, is developed by du pont company, and has realized suitability for industrialized production in nineteen fifty-nine, and commodity are called Delrin.Acefal homopolymer has good intensity, rigidity and fatigue resistance, and still, owing to acefal homopolymer all is made up of carbon-oxygen bond, thereby thermal property is relatively poor, adds to be prone to man-hour decompose.Another kind of is copolymerized methanal, is succeeded in developing and industriallization by U.S. Celanse company in 1961, and commodity are called Celcon.Copolymerized methanal is got by trioxymethylene and dioxolane ring-opening polymerization, has good thermostability and chemicalstability, and is easy to processing.
As a kind of engineering plastics, the molecular chain kindliness of polyoxymethylene (POM) is big, and the chain structure regularity is high, easy and crystalline, and percent crystallinity is high, can reach 60 ~ 80%.Above-mentioned particular structure characteristics have given polyoxymethylene good performance, and are big like hardness, modulus is high and dimensional stability is good etc., and therefore, the mechanical performance index of polyoxymethylene (POM) in five large-engineering plastics maintains the leading position.Wherein, the tensile strength of acefal homopolymer is 66Mpa, and tensile modulus is 2800Mpa; The tensile strength of copolymerized methanal is 60Mpa, and tensile modulus is 2600Mpa.
But the spherocrystal that polyoxymethylene itself forms is very big, and the polyoxymethylene spherocrystal of part trade mark grade can reach 500 μ m; The spherocrystal interface is fairly obvious; Stress concentration, thus cause the toughness of polyformaldehyde material relatively poor, particularly when forming thin wall parts, be prone to the phenomenon of material embrittlement; Yielding, cause demoulding difficulty.Therefore, research and development and improvement to the crystal property of polyoxymethylene have very important meaning in the practical application of polyformaldehyde material.
Summary of the invention
In view of this, the technical problem that the present invention will solve is to provide a kind of polyformaldehyde composition and preparation method thereof, and this polyformaldehyde composition has good crystalline texture, good mechanical properties.
In order to solve above technical problem, the present invention provides a kind of polyformaldehyde composition, comprises following composition:
Polyoxymethylene resin 100 weight parts;
Oxidation inhibitor 0.01 ~ 2 weight part;
Formaldehyde-trapping agent 0.01 ~ 2 weight part;
Formic acid trapping agent 0.01 ~ 2 weight part;
Cross-linked formaldehyde resin 0.01 ~ 5 weight part.
Preferably, said oxidation inhibitor is Hinered phenols antioxidant, phosphite ester kind antioxidant, contains in thioesters kind antioxidant and the metal passivation oxidation inhibitor one or more.
Preferably, said formaldehyde-trapping agent is one or more in trimeric cyanamide, Dyhard RU 100, methylol melamine, urea, guanidine compound, carbamide condenses, SEPIGEL 305 and the polymeric amide.
Preferably, one or more in the soap of said formic acid trapping agent be alkali-metal oxyhydroxide, earth alkali metal oxyhydroxide, alkali-metal inorganic acid salt, the inorganic acid salt of earth alkali metal, alkali-metal soap and earth alkali metal.
Preferably, the melting index of said cross-linked formaldehyde resin is 1 ~ 70g/10min.
Preferably, the melting index of said cross-linked formaldehyde resin is 1 ~ 27g/10min.
Preferably, said cross-linked formaldehyde is 0.1 ~ 1 weight part.
Preferably, also comprise:
Auxiliary nucleator 0.01 ~ 2 weight part.
Preferably, said auxiliary nucleator is TiO
2, CaO, SiO
2, A1
2O
3, MgO, BaSO
4, in talcum powder, zeyssatite, organo montmorillonite, nano-calcium carbonate, BN, organic carboxylate, trimeric cyanamide formal, polymeric amide and the acefal homopolymer one or more.
Accordingly, the present invention also provides a kind of preparation method of polyformaldehyde composition, may further comprise the steps:
With the polyoxymethylene resin of 100 weight parts, the oxidation inhibitor of 0.01 ~ 2 weight part, the formaldehyde-trapping agent of 0.01 ~ 2 weight part, the formic acid trapping agent of 0.01 ~ 2 weight part and cross-linked formaldehyde resin fusion in twin screw extruder under 160 ~ 250 ℃ of 0.01 ~ 5 weight part, obtain polyformaldehyde composition after extruding.
The present invention provides a kind of polyformaldehyde composition and preparation method thereof, comprises following composition: polyoxymethylene resin 100 weight parts; Oxidation inhibitor 0.01 ~ 2 weight part; Formaldehyde-trapping agent 0.01 ~ 2 weight part; Formic acid trapping agent 0.01 ~ 2 weight part; Cross-linked formaldehyde resin 0.01 ~ 5 weight part.Compared with prior art, the present invention is a nucleator with the cross-linked formaldehyde resin, and the cross-linked formaldehyde nucleating effect of adding is obvious; Before the polyoxymethylene resin crystallization, form a large amount of nucleus; Cause the polyoxymethylene resin crystallization thereby induce, improved the nucleus number of polyoxymethylene resin, improved percent crystallinity and Tc; Reduce spherulite size, thereby improved the crystalline texture of polyoxymethylene resin.Secondly, because the addition of cross-linked formaldehyde resin is less, thereby avoided the disadvantageous effect of mechanical property, thermal property and configuration of surface to polyformaldehyde composition.Once more, the oxidation inhibitor of interpolation, formaldehyde-trapping agent and formic acid trapping agent, stable and improved the thermal property of the process systems of polyformaldehyde composition.Experimental result shows that the spherulite size of the polyformaldehyde composition of the present invention's preparation is about 40 μ m, has good crystalline texture, and good mechanical properties.
Description of drawings
Fig. 1 is the spherocrystal polarisation photo (200 *) of the polyformaldehyde composition of the embodiment of the invention 1 preparation;
The spherocrystal polarisation photo (200 *) of the pure polyoxymethylene that Fig. 2 provides for comparative example 2 of the present invention.
Embodiment
Carry out clear, intactly description in the face of the technical scheme in the embodiment of the invention down, obviously, described embodiment only is the present invention's part embodiment, rather than whole embodiment.Based on the embodiment among the present invention, those of ordinary skills are not making the every other embodiment that is obtained under the creative work prerequisite, all belong to the scope of the present invention's protection.
The invention discloses a kind of polyformaldehyde composition, comprise following composition: polyoxymethylene resin 100 weight parts; Oxidation inhibitor 0.01 ~ 2 weight part; Formaldehyde-trapping agent 0.01 ~ 2 weight part; Formic acid trapping agent 0.01 ~ 2 weight part; Cross-linked formaldehyde resin 0.01 ~ 5 weight part.
In mentioned component, said polyoxymethylene resin comprises with-[CH
2O]-be the acefal homopolymer of main repeating unit or with-[CH
2O]-with-[CH
2-CH
2O]-be the copolymerized methanal of main repeating unit.Polyoxymethylene resin has good resistance to fatigue, creep resistance and self-lubricating property, is widely used at aspects such as aviation, automobile, precise electronic, machinery and buildings.The present invention is to the said polyoxymethylene resin trade mark and manufacturer and have no special requirements, and can adopt the compsn of polyoxymethylene of polyoxymethylene or several kinds of trades mark of all on the market known brands.The melting index of said polyoxymethylene resin under standard conditions is preferably 1 ~ 70g/min, more preferably 1 ~ 27g/min; Molecular weight is preferably 20,000 ~ 7,000,000, and more preferably 100,000 ~ 5,000,000, more preferably 500,000 ~ 3,000,000.
As macromolecular compound, polyoxymethylene resin is prone to take place the thermal-oxidative degradation reaction, and therefore, the present invention passes through to add the premium properties that oxidation inhibitor keeps macromolecular material, increases the service life.The oxidation inhibitor that the present invention adopts is preferably Hinered phenols antioxidant, phosphite ester kind antioxidant, contain in thioesters kind antioxidant and the metal passivation oxidation inhibitor one or more.Wherein, said Hinered phenols antioxidant is preferably four [methyl-β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester (being antioxidant 1010) and/or 2,2 methylene radical two (4-methyl-6-tert butyl phenol) (being oxidation inhibitor 245); Said phosphite ester kind antioxidant is preferably tricresyl phosphite (nonyl phenyl) (being oxidation inhibitor TNPP) and/or tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester (being oxidation inhibitor 168).Above-mentioned oxidation inhibitor all can be avoided the reaction of polyoxymethylene resin generation thermal-oxidative degradation, keeps the premium properties of macromolecular material, prolongs the work-ing life of material.
Since polyoxymethylene resin deposit with the course of processing in possibly be decomposed into free formaldehyde, therefore, said polyformaldehyde composition adopts formaldehyde-trapping agent.The present invention can adopt commercial formaldehyde-trapping agent for the trade mark and the manufacturer and unrestricted of said formaldehyde-trapping agent.As preferably; Said formaldehyde-trapping agent is one or more in trimeric cyanamide, Dyhard RU 100, methylol melamine, urea, guanidine compound, carbamide condenses, SEPIGEL 305 and the polymeric amide, more preferably one or more in trimeric cyanamide, Dyhard RU 100, urea and the trimeric cyanamide-formal.
Simultaneously; Free formaldehyde is prone to be oxidized to formic acid in air; Therefore the present invention preferably adds the formic acid trapping agent; Said formic acid trapping agent is preferably one or more in the soap of the inorganic acid salt of the oxyhydroxide of alkali-metal oxyhydroxide, earth alkali metal, alkali-metal inorganic acid salt, earth alkali metal, alkali-metal soap and earth alkali metal, more preferably one or more in the soap of the soap of the soap of the soap of the soap of sodium hydroxide, Pottasium Hydroxide, Marinco H, calcium hydroxide, zinc hydroxide, yellow soda ash, salt of wormwood, magnesiumcarbonate, lime carbonate, zinc carbonate, sodium, potassium, magnesium, calcium and zinc.
Above-mentioned formaldehyde-trapping agent and formic acid trapping agent have reached the purpose of removing free formaldehyde or formic acid through physics or chemical action, have guaranteed the cleaning of environment.Simultaneously, the present invention stablizes and has improved the thermal property of the process systems of polyformaldehyde composition through adding oxidation inhibitor, formaldehyde-trapping agent and formic acid trapping agent.The consumption of compositions such as oxidation inhibitor, formaldehyde-trapping agent and formic acid trapping agent has tangible influence to said polyformaldehyde composition performance in the polyformaldehyde composition, and wherein, said oxidation inhibitor is preferably 0.1 ~ 1 weight part, more preferably 0.3 ~ 0.5 weight part; Said formaldehyde-trapping agent is preferably 0.03 ~ 1 weight part, more preferably 0.05 ~ 0.1 weight part; Said formic acid trapping agent is preferably 0.05 ~ 1 weight part, more preferably 0.1 ~ 0.0.5 weight part.The too high levels of above-mentioned oxidation inhibitor, formaldehyde-trapping agent and formic acid trapping agent will exert an influence to mechanical property, thermal property and the configuration of surface etc. of the polyformaldehyde composition that forms.
According to the present invention, said cross-linked formaldehyde resin is meant the cross-linked formaldehyde with crosslinking structure that adopts copolymerization, adds methods formation such as linking agent or cross-linking radiation, comprises the grafting class polyoxymethylene that forms through the same manner simultaneously, uses as main nucleator.The melting index of said cross-linked formaldehyde resin is the important factor that influences the nucleation performance, and the melting index of said cross-linked formaldehyde resin is preferably 1 ~ 70g/10min, 1 ~ 27g/10min more preferably, and more preferably 1 ~ 9g/10min most preferably is 1 ~ 3g/10min.The present invention is through adding a spot of cross-linked formaldehyde resin; Give the change that brings of microcosmic polymer molecular chain state of aggregation; The structure that helps refinement polymer aggregational attitude is improved the polyoxymethylene crystal property, reduces its notch sensitivity; Increase to hinder the ability of crack propagation, increase polyformaldehyde composition simultaneously and prepare meticulous controllability and actual operational capacity during with thin wall parts.
Because the nucleating effect of the cross-linked formaldehyde that the present invention adds is obvious; Before the polyoxymethylene resin crystallization, can form a large amount of nucleus; Cause the polyoxymethylene resin crystallization thereby induce, improved the nucleus number of polyoxymethylene resin, improved percent crystallinity and Tc; Reduce spherulite size, thereby improved the crystalline texture of polyoxymethylene resin.Secondly, because the addition of cross-linked formaldehyde resin is less, thereby avoided the disadvantageous effect of mechanical property, thermal property and configuration of surface to polyformaldehyde composition.
In the present invention, said polyformaldehyde composition also preferably includes auxiliary nucleator 0.01 ~ 2 weight part, and said auxiliary nucleator is preferably inorganic nucleator and/or organic nucleating agent, more preferably TiO
2, CaO, SiO
2, A1
2O
3, MgO, BaSO
4, in talcum powder, zeyssatite, organo montmorillonite, nano-calcium carbonate, BN, organic carboxylate, trimeric cyanamide formal, polymeric amide and the acefal homopolymer one or more.
Said auxiliary nucleator and the acting in conjunction of cross-linked formaldehyde resin; Make it in the molten polyformaldehyde process, before the crystallization of polyoxymethylene matrix, form a large amount of nucleus, cause the polyoxymethylene crystallization thereby induce; Improve the nucleus number of polyoxymethylene; Percent crystallinity and Tc reduce its spherulite size, and then play the purpose of improving polyoxymethylene crystalline texture.Simultaneously, cross-linked formaldehyde resin and above-mentioned auxiliary nucleator are used, and the cross-linked formaldehyde resin of employing and the addition of above-mentioned auxiliary nucleator are all less, have avoided other performances such as mechanical property, thermal property and the configuration of surface of system are exerted an influence; And, reasonably combined through the ratio of two kinds of nucleators, improve the mechanical property of system largely.
According to the present invention, the consumption of said cross-linked formaldehyde resin is the important factor that influences the polyformaldehyde composition performance equally, and the addition of this cross-linked formaldehyde resin is crossed the crystal property of the polyformaldehyde composition that causes at least forming etc. and can not get improving; Otherwise mechanical property, thermal property and the configuration of surface of the polyformaldehyde composition that the addition of cross-linked formaldehyde resin is too high then to be caused forming are affected.Said cross-linked formaldehyde resin is preferably 0.01 ~ 3 weight part, 0.01 ~ 1 weight part more preferably, and more preferably 0.01 ~ 0.5 weight part most preferably is 0.03 ~ 0.5 weight part.Therefore, polyformaldehyde composition provided by the invention has good crystalline texture, and good mechanical properties, mainly is applicable to automobile component, and machinery, electronics, electrical equipment or the like need the Application Areas of the accurate product of injection moulding.
Accordingly; The present invention also provides a kind of preparation method of polyformaldehyde composition; May further comprise the steps:, obtain polyformaldehyde composition after extruding the polyoxymethylene resin of 100 weight parts, the oxidation inhibitor of 0.01 ~ 2 weight part, the formaldehyde-trapping agent of 0.01 ~ 2 weight part, the formic acid trapping agent of 0.01 ~ 2 weight part and cross-linked formaldehyde resin fusion in twin screw extruder under 160 ~ 250 ℃ of 0.01 ~ 5 weight part.
The present invention serves as the preparation raw material with polyoxymethylene resin, oxidation inhibitor, formaldehyde-trapping agent, formic acid trapping agent and cross-linked formaldehyde resin, and wherein, said polyoxymethylene resin is with-[CH
2O]-be the acefal homopolymer of main repeating unit or with-[CH
2O]-with-[CH
2-CH
2O]-be the copolymerized methanal of main repeating unit.The melting index of said polyoxymethylene resin under standard conditions is preferably 1 ~ 70g/min, more preferably 1 ~ 27g/min; Molecular weight is preferably 20,000 ~ 7,000,000, and more preferably 100,000 ~ 5,000,000, more preferably 500,000 ~ 3,000,000.
As macromolecular compound, polyoxymethylene resin is prone to take place the thermal-oxidative degradation reaction, and therefore, the present invention passes through to add the premium properties that oxidation inhibitor keeps macromolecular material, increases the service life.The oxidation inhibitor that the present invention adopts is preferably Hinered phenols antioxidant, phosphite ester kind antioxidant, contain in thioesters kind antioxidant and the metal passivation oxidation inhibitor one or more.Wherein, said Hinered phenols antioxidant to be preferably four [methyl-β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester be antioxidant 1010) and/or 2,2 methylene radical two (4-methyl-6-tert butyl phenol) (being oxidation inhibitor 245); Said phosphite ester kind antioxidant is preferably tricresyl phosphite (nonyl phenyl) (being oxidation inhibitor TNPP) and/or tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester (being oxidation inhibitor 168).
As preferably; Said formaldehyde-trapping agent is one or more in trimeric cyanamide, Dyhard RU 100, methylol melamine, urea, guanidine compound, carbamide condenses, SEPIGEL 305 and the polymeric amide, more preferably one or more in trimeric cyanamide, Dyhard RU 100, urea and the trimeric cyanamide-formal.Said formic acid trapping agent is preferably one or more in the soap of the inorganic acid salt of the oxyhydroxide of alkali-metal oxyhydroxide, earth alkali metal, alkali-metal inorganic acid salt, earth alkali metal, alkali-metal soap and earth alkali metal, more preferably one or more in the soap of the soap of the soap of the soap of the soap of sodium hydroxide, Pottasium Hydroxide, Marinco H, calcium hydroxide, zinc hydroxide, yellow soda ash, salt of wormwood, magnesiumcarbonate, lime carbonate, zinc carbonate, sodium, potassium, magnesium, calcium and zinc.
According to the present invention, said cross-linked formaldehyde resin is meant the cross-linked formaldehyde with crosslinking structure that adopts copolymerization, adds methods formation such as linking agent or cross-linking radiation, comprises the grafting class polyoxymethylene that forms through the same manner simultaneously.The melting index of said cross-linked formaldehyde resin is preferably 1 ~ 70g/10min, 1 ~ 27g/10min more preferably, and more preferably 1 ~ 9g/10min most preferably is 1 ~ 3g/10min.In the preparation process, melt temperature is preferably 180 ~ 230 ℃ in the said twin screw extruder, more preferably 180 ~ 210 ℃; The residence time is preferably 2 ~ 3min; The feeding revolution is preferably 15 ~ 25 to be changeed; The screw rod revolution is preferably 150 ~ 300.
In sum, polyformaldehyde composition provided by the invention and preparation method thereof has following characteristics: 1, the addition of cross-linked formaldehyde resin is few, and nucleating effect is obvious, makes the spherulite size of polyoxymethylene resin be decreased to 40 μ m from 400 μ m; 2, cross-linked formaldehyde resin and auxiliary nucleator are used; The addition of cross-linked formaldehyde resin and auxiliary nucleator is all less; Can other performances such as mechanical property, thermal property and the configuration of surface etc. of system not exerted an influence; Reasonably combined through two kinds of nucleators improves the mechanical property of system; 3, preparing method's technology of polyformaldehyde composition provided by the invention is simple, easy to implement.Experimental result shows that the polyformaldehyde composition that the present invention obtains has good thermal property, mechanical property and crystalline texture.
According to following method polyformaldehyde composition provided by the invention is carried out performance measurement, wherein table 1 is the testing standard of the formaldehyde compsn of the present invention's employing.
The testing standard of the polyformaldehyde composition that table 1 the present invention adopts
The TGA thermal property is estimated
Constant temperature is estimated: the heat-up rate with 40 ℃/min is raised to 220 ℃ fast, and constant temperature under this temperature is when the polyoxymethylene sample quality stops experiment during with a toll of prescribed value, usually with the sample 5% o'clock required time t (unit: min) as evaluation index that degrades.Atmosphere is air.
Polarizing properties is estimated
Adopt constant heating and cooling program: the temperature rise rate with 40 ℃/min is rapidly heated 200 ℃, stablizes 3min, and the rate of temperature fall with 20 ℃/min reduces the temperature to 160 ℃ then, and then drops to 145 ℃ with the rate of temperature fall of 5 ℃/min.In the process of cooling, observe the crystallization onset temperature of polyoxymethylene, nucleus is counted out, the final spherulite size size that forms.
In order to further specify technical scheme of the present invention; Below in conjunction with embodiment the preferred embodiment of the invention is described; Describe just to further specifying feature and advantage of the present invention but should be appreciated that these, rather than to the restriction of claim of the present invention.
The chemical reagent that the embodiment of the invention adopts is commercial.
Embodiment 1
With polyoxymethylene 100 weight parts, oxidation inhibitor 2450.3 weight parts, trimeric cyanamide 0.05 weight part, calcium stearate 0.1 weight part; Cross-linked formaldehyde 0.1 weight part, nano-calcium carbonate 0.05 weight part prepares in proportion, in high mixer, stirs and adopts twin screw extruder to carry out extruding pelletization in 3 minutes, obtains polyformaldehyde composition; Concrete complete processing is: temperature: 175 ℃ in a district, 180 ℃ in two districts, 185 ℃ in three districts, 190 ℃ in four districts; 190 ℃ in five districts, 190 ℃ in six districts, 190 ℃ in seven districts; 190 ℃ in eight districts, 190 ℃ in nine districts, 190 ℃ of heads; Feeding revolution 15; Screw rod revolution 200.
Polyformaldehyde composition to the present embodiment preparation carries out tensile strength, tensile modulus, elongation at break, notch shock and the Performance Detection of weightless 5% time respectively, and the result is as shown in table 2.
Polyformaldehyde composition to the present embodiment preparation carries out the polarizing properties detection, and Fig. 2 is the spherocrystal polarisation photo of the polyformaldehyde composition of present embodiment preparation.
Embodiment 2
With polyoxymethylene 100 weight parts, oxidation inhibitor 2450.3 weight parts, trimeric cyanamide 0.05 weight part, calcium stearate 0.1 weight part; Cross-linked formaldehyde 0.1 weight part, nano-calcium carbonate 0.05 weight part prepares in proportion, in high mixer, stirs and adopts twin screw extruder to carry out extruding pelletization in 3 minutes, obtains polyformaldehyde composition; Concrete complete processing is: 195 ℃ in a district, 200 ℃ in two districts, 205 ℃ in three districts, 210 ℃ in four districts; 210 ℃ in five districts, 210 ℃ in six districts, 210 ℃ in seven districts; 210 ℃ in eight districts, 210 ℃ in nine districts, 210 ℃ of heads; Feeding revolution 15; Screw rod revolution 200.
Polyformaldehyde composition to the present embodiment preparation carries out tensile strength, tensile modulus, elongation at break, notch shock and the Performance Detection of weightless 5% time respectively, and the result is as shown in table 2.
Embodiment 3
With polyoxymethylene 100 weight parts, oxidation inhibitor 2450.3 weight parts, trimeric cyanamide 0.05 weight part, calcium stearate 0.1 weight part; Cross-linked formaldehyde 0.1 weight part, nano-calcium carbonate 0.05 weight part prepares in proportion, in high mixer, stirs and adopts twin screw extruder to carry out extruding pelletization in 3 minutes, obtains polyformaldehyde composition; Concrete complete processing is: temperature: 175 ℃ in a district, 180 ℃ in two districts, 185 ℃ in three districts, 190 ℃ in four districts; 190 ℃ in five districts, 190 ℃ in six districts, 190 ℃ in seven districts; 190 ℃ in eight districts, 190 ℃ in nine districts, 190 ℃ of heads; Feeding revolution 20; Screw rod revolution 280.
Polyformaldehyde composition to the present embodiment preparation carries out tensile strength, tensile modulus, elongation at break, notch shock and the Performance Detection of weightless 5% time respectively, and the result is as shown in table 2.
Embodiment 4
With polyoxymethylene 100 weight parts, oxidation inhibitor 2450.3 weight parts, trimeric cyanamide 0.05 weight part, calcium stearate 0.1 weight part; Cross-linked formaldehyde 0.01 weight part, nano-calcium carbonate 0.05 weight part prepares in proportion, in high mixer, stirs and adopts twin screw extruder to carry out extruding pelletization in 3 minutes, obtains polyformaldehyde composition; Concrete complete processing is: temperature: 175 ℃ in a district, 180 ℃ in two districts, 185 ℃ in three districts, 190 ℃ in four districts; 190 ℃ in five districts, 190 ℃ in six districts, 190 ℃ in seven districts; 190 ℃ in eight districts, 190 ℃ in nine districts, 190 ℃ of heads; Feeding revolution 15; Screw rod revolution 200.
Polyformaldehyde composition to the present embodiment preparation carries out tensile strength, tensile modulus, elongation at break, notch shock and the Performance Detection of weightless 5% time respectively, and the result is as shown in table 2.
Embodiment 5
With polyoxymethylene 100 weight parts, oxidation inhibitor 2450.3 weight parts, trimeric cyanamide 0.05 weight part, calcium stearate 0.1 weight part; Cross-linked formaldehyde 0.05 weight part, nano-calcium carbonate 0.05 weight part prepares in proportion, in high mixer, stirs and adopts twin screw extruder to carry out extruding pelletization in 3 minutes, obtains polyformaldehyde composition; Concrete complete processing is: temperature: 175 ℃ in a district, 180 ℃ in two districts, 185 ℃ in three districts, 190 ℃ in four districts; 190 ℃ in five districts, 190 ℃ in six districts, 190 ℃ in seven districts; 190 ℃ in eight districts, 190 ℃ in nine districts, 190 ℃ of heads; Feeding revolution 15; Screw rod revolution 200.
Polyformaldehyde composition to the present embodiment preparation carries out tensile strength, tensile modulus, elongation at break, notch shock and the Performance Detection of weightless 5% time respectively, and the result is as shown in table 2.
Embodiment 6
With polyoxymethylene 100 weight parts, oxidation inhibitor 2450.3 weight parts, trimeric cyanamide 0.05 weight part, calcium stearate 0.1 weight part; Cross-linked formaldehyde 0.3 weight part, nano-calcium carbonate 0.05 weight part prepares in proportion, in high mixer, stirs and adopts twin screw extruder to carry out extruding pelletization in 3 minutes, obtains polyformaldehyde composition; Concrete complete processing is: temperature: 175 ℃ in a district, 180 ℃ in two districts, 185 ℃ in three districts, 190 ℃ in four districts; 190 ℃ in five districts, 190 ℃ in six districts, 190 ℃ in seven districts; 190 ℃ in eight districts, 190 ℃ in nine districts, 190 ℃ of heads; Feeding revolution 15; Screw rod revolution 200.
Polyformaldehyde composition to the present embodiment preparation carries out tensile strength, tensile modulus, elongation at break, notch shock and the Performance Detection of weightless 5% time respectively, and the result is as shown in table 2.
Embodiment 7
With polyoxymethylene 100 weight parts, oxidation inhibitor 2450.3 weight parts, trimeric cyanamide 0.05 weight part, calcium stearate 0.1 weight part; Cross-linked formaldehyde 0.5 weight part, nano-calcium carbonate 0.05 weight part prepares in proportion, in high mixer, stirs and adopts twin screw extruder to carry out extruding pelletization in 3 minutes, obtains polyformaldehyde composition; Concrete complete processing is: temperature: 175 ℃ in a district, 180 ℃ in two districts, 185 ℃ in three districts, 190 ℃ in four districts; 190 ℃ in five districts, 190 ℃ in six districts, 190 ℃ in seven districts; 190 ℃ in eight districts, 190 ℃ in nine districts, 190 ℃ of heads; Feeding revolution 15; Screw rod revolution 200.
Polyformaldehyde composition to the present embodiment preparation carries out tensile strength, tensile modulus, elongation at break, notch shock and the Performance Detection of weightless 5% time respectively, and the result is as shown in table 2.
Embodiment 8
With polyoxymethylene 100 weight parts, oxidation inhibitor 2450.3 weight parts, trimeric cyanamide 0.05 weight part, calcium stearate 0.1 weight part; Cross-linked formaldehyde 0.1 weight part, nano-calcium carbonate 0.3 weight part prepares in proportion, in high mixer, stirs and adopts twin screw extruder to carry out extruding pelletization in 3 minutes, obtains polyformaldehyde composition; Concrete complete processing is: temperature: 175 ℃ in a district, 180 ℃ in two districts, 185 ℃ in three districts, 190 ℃ in four districts; 190 ℃ in five districts, 190 ℃ in six districts, 190 ℃ in seven districts; 190 ℃ in eight districts, 190 ℃ in nine districts, 190 ℃ of heads; Feeding revolution 15; Screw rod revolution 200.
Polyformaldehyde composition to the present embodiment preparation carries out tensile strength, tensile modulus, elongation at break, notch shock and the Performance Detection of weightless 5% time respectively, and the result is as shown in table 2.
Embodiment 9
With polyoxymethylene 100 weight parts, oxidation inhibitor 2450.3 weight parts, trimeric cyanamide 0.05 weight part, calcium stearate 0.1 weight part; Cross-linked formaldehyde 0.1 weight part, nanometer BN 0.05 weight part prepares in proportion, in high mixer, stirs and adopts twin screw extruder to carry out extruding pelletization in 3 minutes, obtains polyformaldehyde composition; Concrete complete processing is: temperature: 175 ℃ in a district, 180 ℃ in two districts, 185 ℃ in three districts, 190 ℃ in four districts; 190 ℃ in five districts, 190 ℃ in six districts, 190 ℃ in seven districts; 190 ℃ in eight districts, 190 ℃ in nine districts, 190 ℃ of heads; Feeding revolution 15; Screw rod revolution 200.
Polyformaldehyde composition to the present embodiment preparation carries out tensile strength, tensile modulus, elongation at break, notch shock and the Performance Detection of weightless 5% time respectively, and the result is as shown in table 2.
Embodiment 10
With polyoxymethylene 100 weight parts, oxidation inhibitor 2450.3 weight parts, trimeric cyanamide 0.05 weight part, calcium stearate 0.1 weight part; Cross-linked formaldehyde 0.1 weight part, nanometer BN 0.3 weight part prepares in proportion, in high mixer, stirs and adopts twin screw extruder to carry out extruding pelletization in 3 minutes, obtains polyformaldehyde composition; Concrete complete processing is: temperature: 175 ℃ in a district, 180 ℃ in two districts, 185 ℃ in three districts, 190 ℃ in four districts; 190 ℃ in five districts, 190 ℃ in six districts, 190 ℃ in seven districts; 190 ℃ in eight districts, 190 ℃ in nine districts, 190 ℃ of heads; Feeding revolution 15; Screw rod revolution 200.
Polyformaldehyde composition to the present embodiment preparation carries out tensile strength, tensile modulus, elongation at break, notch shock and the Performance Detection of weightless 5% time respectively, and the result is as shown in table 2.
Comparative example 1
With polyoxymethylene 100 weight parts, oxidation inhibitor 2450.3 weight parts, trimeric cyanamide 0.05 weight part, calcium stearate 0.1 weight part prepares in proportion; In high mixer, stir and adopted twin screw extruder to carry out extruding pelletization in 3 minutes, obtain polyformaldehyde composition, concrete complete processing is: temperature: 175 ℃ in a district, 180 ℃ in two districts; 185 ℃ in three districts, 190 ℃ in four districts, 190 ℃ in five districts, 190 ℃ in six districts; 190 ℃ in seven districts, 190 ℃ in eight districts, 190 ℃ in nine districts, 190 ℃ of heads; Feeding revolution 15; Screw rod revolution 200.
Polyformaldehyde composition to the preparation of this comparative example carries out tensile strength, tensile modulus, elongation at break, notch shock and the Performance Detection of weightless 5% time respectively, and the result is as shown in table 2.
Comparative example 2
Pure polyoxymethylene is provided, it is carried out polarizing properties detect.The spherocrystal polarisation photo of the pure polyoxymethylene that Fig. 1 provides for this comparative example.
Can find out that by Fig. 1 and Fig. 2 the nucleating effect of cross-linked formaldehyde is obvious, the spherulite size that adds the polyformaldehyde composition that forms behind the cross-linked formaldehyde can be reduced to 40 μ m from 400 μ m.
The mechanical property and the thermal property of the polyformaldehyde composition of table 2 embodiment of the invention and comparative example preparation
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be conspicuous concerning those skilled in the art, and defined General Principle can realize under the situation that does not break away from the spirit or scope of the present invention in other embodiments among this paper.Therefore, the present invention will can not be restricted to these embodiment shown in this paper, but will meet and principle disclosed herein and features of novelty the wideest corresponding to scope.
Claims (10)
1. a polyformaldehyde composition is characterized in that, comprises following composition:
Polyoxymethylene resin 100 weight parts;
Oxidation inhibitor 0.01 ~ 2 weight part;
Formaldehyde-trapping agent 0.01 ~ 2 weight part;
Formic acid trapping agent 0.01 ~ 2 weight part;
Cross-linked formaldehyde resin 0.01 ~ 5 weight part.
2. polyformaldehyde composition according to claim 1 is characterized in that, said oxidation inhibitor is Hinered phenols antioxidant, phosphite ester kind antioxidant, contain in thioesters kind antioxidant and the metal passivation oxidation inhibitor one or more.
3. polyformaldehyde composition according to claim 1; It is characterized in that said formaldehyde-trapping agent is one or more in trimeric cyanamide, Dyhard RU 100, methylol melamine, urea, guanidine compound, carbamide condenses, SEPIGEL 305 and the polymeric amide.
4. polyformaldehyde composition according to claim 1; It is characterized in that one or more in the soap of the inorganic acid salt of the oxyhydroxide that said formic acid trapping agent is alkali-metal oxyhydroxide, earth alkali metal, alkali-metal inorganic acid salt, earth alkali metal, alkali-metal soap and earth alkali metal.
5. polyformaldehyde composition according to claim 1 is characterized in that, the melting index of said cross-linked formaldehyde resin is 1 ~ 70g/10min.
6. polyformaldehyde composition according to claim 5 is characterized in that, the melting index of said cross-linked formaldehyde resin is 1 ~ 27g/10min.
7. polyformaldehyde composition according to claim 1 is characterized in that, said cross-linked formaldehyde is 0.1 ~ 1 weight part.
8. polyformaldehyde composition according to claim 1 is characterized in that, also comprises:
Auxiliary nucleator 0.01 ~ 2 weight part.
9. said according to Claim 8 polyformaldehyde composition is characterized in that said auxiliary nucleator is TiO
2, CaO, SiO
2, A1
2O
3, MgO, BaSO
4, in talcum powder, zeyssatite, organo montmorillonite, nano-calcium carbonate, BN, organic carboxylate, trimeric cyanamide formal, polymeric amide and the acefal homopolymer one or more.
10. the preparation method of a polyformaldehyde composition is characterized in that, may further comprise the steps:
With the polyoxymethylene resin of 100 weight parts, the oxidation inhibitor of 0.01 ~ 2 weight part, the formaldehyde-trapping agent of 0.01 ~ 2 weight part, the formic acid trapping agent of 0.01 ~ 2 weight part and cross-linked formaldehyde resin fusion in twin screw extruder under 160 ~ 250 ℃ of 0.01 ~ 5 weight part, obtain polyformaldehyde composition after extruding.
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