CN103992614A - Polyacetal resin composition and preparation method thereof - Google Patents
Polyacetal resin composition and preparation method thereof Download PDFInfo
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- CN103992614A CN103992614A CN201410252086.7A CN201410252086A CN103992614A CN 103992614 A CN103992614 A CN 103992614A CN 201410252086 A CN201410252086 A CN 201410252086A CN 103992614 A CN103992614 A CN 103992614A
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Abstract
The invention provides a polyacetal resin composition, which comprises the following components: 100 parts of polyacetal resin, 0.001-2.0 parts of antioxygen, 0.005-3.0 parts of formaldehyde absorbent, 0.002-2.0 parts of acid absorbent, 0.001-2.0 parts of processing stabilizer, 0.1-20 parts of modified inorganic filler, and 0.005-2.0 parts of dispersant, wherein the dispersant is one or more of mineral oil, oligomerization polyolefin, fatty acid of C12-C20, dimethyl polysiloxane and dimethyl polysiloxane obtained by using hydrogen, phenyl, halogenated phenyl, halogenated alkyl and fluorinated ester to replace methyl; and the modified inorganic filler is obtained by modifying an inorganic filler and a modifier at 10-100 DEG C at the rotation speed of 500-10000 rpm. On the premise of increasing the tensile strength, the toughness of the polyacetal resin composition is obviously increased; and furthermore, the notch impact strength and the breaking elongation are higher.
Description
Technical field
The present invention relates to rosin products field, particularly polyacetal resin composite and preparation method thereof.
Background technology
Polyacetal resin is a kind of high crystalline thermoplastic polymer, there is wear-resistant self-lubricating, oil-proofness, chemical proofing, creep resistance and low water absorption, can be in wide temperature range, there is higher mechanics, chemical property and electrical property conservation rate, be widely used in the industries such as automobile, electric, household electrical appliance, precision optical machinery and material of construction.
But due to polyacetal resin poor toughness, particularly, to breach sensitivity, notched Izod impact strength is low, has greatly limited its application.Publication number is that CN1025862C adds a kind of grafting in polyoxymethylene or crosslinked multipolymer, lubricant and average grain particle diameter diameter is 50 μ m or less inorganic powder, make a kind of polyacetal resin composite of wear resisting property excellence, but said composition has just improved the wear resisting property of polyacetal resin composite, the improvement of toughness is not taken effect really.
Publication number is that CN101724222A has invented a kind of polyformaldehyde compound, and this mixture is coordinated and formed by polyformaldehyde resin, Low Density Polyethylene, nano silicon, silicone oil, oxidation inhibitor and stablizer.The tensile strength of mixture is the highest can reach 72.1MPa, and notched Izod impact strength reaches as high as 9.8KJ/m
2but its elongation at break but only has 28%, and the production cost of product is very high.
Publication number is that CN1910233B Chinese patent discloses a kind of polyacetal resin composite being made up of polyacetal resin, the calcium carbonate with specific length-to-diameter ratio, specified particle diameter, organic acid and fatty acid ester, the balance that said composition has thermostability and can realize rigidity and toughness also has good creep resistance life-span, resistance to fatigue and acid resistance, but the tensile strength of this disclosure of the invention only has 40-55MPa, or lower than the intensity of general purpose grade polyacetal resin.
In sum, foregoing invention all, by adding mineral filler or elastomeric method to improve the toughness of polyacetal, still all can cause the reduction of product strength, and meanwhile, also can increase cost elastomeric adding.
Summary of the invention
The technical problem that the present invention solves is to provide a kind of polyacetal composition, improves under the condition of tensile strength ensureing, has obviously promoted toughness, and notched Izod impact strength and elongation at break all higher.
The invention discloses a kind of polyacetal resin composite, comprise the component of following weight part:
Described dispersion agent is the lipid acid, dimethyl polysiloxane of mineral oil, lower polyolefins, C12～C20 and by one or more in the dimethyl polysiloxane obtaining after hydrogen, phenyl, halogenophenyl, haloalkyl, fluorine ester group substituent methyl;
Described modified inorganic filler is 500～10000 revs/min by mineral filler and properties-correcting agent at rotating speed, and temperature is under the condition of 10～100 DEG C, to carry out modification to obtain.
Preferably, described dispersion agent is one or more in machine oil, gear oil, paraffin, polyethylene wax, alpha-olefin low polymers, lauric acid and stearic acid.
Preferably, described rotating speed is 1000～8000 revs/min.
Preferably, described mineral filler is aluminum oxide, zinc oxide, alumina, silicon-dioxide, titanium dioxide, calcium sulfate, magnesium sulfate, calcium carbonate, talcum, kaolin, diatomite, clay, molybdenumdisulphide, tungsten disulfide, silicon carbide or Graphite fluorination thing.
Preferably, described properties-correcting agent is stearic acid and salt, Aluminate, phosphoric acid ester, organosilane, organic titanium, organoaluminum, aluminium titanium mixture, aluminium zirconium complex or rare earth organic polymer.
Preferably, described oxidation inhibitor be Hinered phenols antioxidant, phosphite ester kind antioxidant, suffocated amine antioxidant, containing one or more in sulphur ester antioxidant and metal passivation oxidation inhibitor.
Preferably, described formaldehyde absorbent is one or more of trimeric cyanamide, Dyhard RU 100, methylol melamine, urea, guanidine class, carbamide condenses, hydrazine, hydrazides, polyacrylamide and polymeric amide.
Preferably, described acid absorber is one or more of oxyhydroxide, inorganic acid salt and soap of alkali or alkaline-earth metal.
Preferably, described processing stabilizers is one or more in long-chain or higher fatty acid or derivatives thereof, polyoxyalkylene glycol and silicone compounds.
The present invention also provides a kind of preparation method of polyacetal composition, comprises the following steps:
By 100 parts of polyacetal resins, 0.001～2.0 part of oxidation inhibitor, 0.005～3.0 part of formaldehyde absorbent, 0.002～2.0 part of acid absorber, 0.001～2.0 part of processing stabilizers, 0.1～20 part of modified inorganic filler, 0.005～2.0 part of dispersion agent melting mixing, obtains polyacetal composition;
Described dispersion agent is the lipid acid, dimethyl polysiloxane of mineral oil, lower polyolefins, C12～C20 and by one or more in the dimethyl polysiloxane obtaining after hydrogen, phenyl, halogenophenyl, haloalkyl, fluorine ester group substituent methyl;
Described modified inorganic filler is 500～10000 revs/min by mineral filler and properties-correcting agent at rotating speed, and temperature is under the condition of 10～100 DEG C, to carry out modification to obtain.
Compared with prior art, polyacetal resin composite of the present invention comprises: 100 parts of polyacetal resins, 0.001～2.0 part of oxidation inhibitor, 0.005～3.0 part of formaldehyde absorbent, 0.002～2.0 part of acid absorber, 0.001～2.0 part of processing stabilizers, 0.1～20 part of modified inorganic filler, 0.005～2.0 part of dispersion agent.Wherein, described dispersion agent is the lipid acid, dimethyl polysiloxane of mineral oil, lower polyolefins, C12～C20 and by one or more in the dimethyl polysiloxane obtaining after hydrogen, phenyl, halogenophenyl, haloalkyl, fluorine ester group substituent methyl; Modified inorganic filler is 500～10000 revs/min by mineral filler and properties-correcting agent at rotating speed, and temperature is under the condition of 10～100 DEG C, to carry out modification to obtain.
Through the mineral filler of modification, particle surface transfers lipophilicity to by wetting ability, thereby the consistency in polyacetal resin composite matrix improves; Dispersion agent is oil-soluble substance, there is better consistency with the mineral filler after modification, thereby modified inorganic filler can be enriched near dispersion agent in a large number, dispersion agent fusing point is well below polyacetal resin simultaneously, can before polyacetal resin melting prerequisite, melt, melt the viscosity of rear dispersion agent well below the melt viscosity of polyacetal resin, thereby can in extrusion, be disperseed uniformly.Being enriched in modified inorganic filler in dispersion agent can be along with the Uniform Flow of dispersion agent in extruder screw and further disperseed, in composition crystallisation process, play the effect of heterogeneous nucleation, reduce crystalline core size, thereby the intensity of the polyacetal composition obtaining and toughness are obviously improved.Add separately modified inorganic filler or dispersion agent and can not play the object that tensile strength, elongation at break and notched Izod impact strength all increase.In addition, polyacetal composition cost of the present invention is extremely low.Experimental result shows, the tensile strength of polyacetal composition of the present invention is 67～70MPa, and notched Izod impact strength is 7.5～9KJ/m
2, elongation at break is 62%～80%.
Brief description of the drawings
Fig. 1 is the polarisation picture of the polyacetal composition prepared of embodiment 2;
Fig. 2 is the polarisation picture of the polyacetal composition prepared of comparative example 1;
Fig. 3 is the polarisation picture of the polyacetal composition prepared of comparative example 2.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these are described is for further illustrating the features and advantages of the present invention, instead of limiting to the claimed invention.
The embodiment of the invention discloses a kind of polyacetal resin composite, comprise the component of following weight part:
Described dispersion agent is the lipid acid, dimethyl polysiloxane of mineral oil, lower polyolefins, C12～C20 and by one or more in the dimethyl polysiloxane obtaining after hydrogen, phenyl, halogenophenyl, haloalkyl, fluorine ester group substituent methyl;
Described modified inorganic filler is 500～10000 revs/min by mineral filler and properties-correcting agent at rotating speed, and temperature is under the condition of 10～100 DEG C, to carry out modification to obtain.
According to the present invention, polyacetal composition comprises polyacetal resin, oxidation inhibitor, formaldehyde absorbent, acid absorber, processing stabilizers, modified inorganic filler and dispersion agent.
Described polyacetal resin is with-[CH
2o]-be the macromolecular compound of main repeating unit, can be by oxidation MU (methylene unit)-[CH
2o]-acefal homopolymer, can be also any one in the multipolymer that oxidation contains other a small amount of structural units methylene radical, polynary random copolymers, polynary segmented copolymer, be preferably polyoxymethylene.The molecular structure of described polyacetal resin is not limited only to linearity, also can contain crosslinked or esterification structure.The present invention is not particularly limited the polymerization degree of described polyacetal.The present invention is also not particularly limited for the source of polyacetal, can be buied by market, also can be according to method preparation well known to those skilled in the art.The content of described polyacetal resin is 100 weight parts.
Described oxidation inhibitor is preferably Hinered phenols antioxidant, phosphite ester kind antioxidant, suffocated amine antioxidant, containing one or more in sulphur ester antioxidant and metal passivation oxidation inhibitor, more preferably four [methyl-β-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester] one or more of pentaerythritol ester, triglycol-bis--3-(hydroxyl-5, the 3-tertiary butyl-4 aminomethyl phenyl) propionic ester, tricresyl phosphite (nonyl phenyl) and tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester.The present invention is not particularly limited the source of described oxidation inhibitor, commercially available prod.The content of described oxidation inhibitor is 0.001～2.0 weight part, is preferably 0.1～1 weight part.When the content of described oxidation inhibitor is during lower than 0.01 weight part, the thermostability of polyacetal resin composite improves not remarkable; When the content of described oxidation inhibitor higher than 1 weight part is, the configuration of surface benzylalcohol of polyacetal resin composite molding converted products, physicals reduces.
Described formaldehyde absorbent is preferably one or more of trimeric cyanamide, Dyhard RU 100, methylol melamine, urea, guanidine class, carbamide condenses, hydrazine, hydrazides, polyacrylamide and polymeric amide, more preferably one or more in trimeric cyanamide, Dyhard RU 100, hydrazine, hydrazides, urea and trimeric cyanamide-formal.The present invention is not particularly limited the source of described formaldehyde absorbent, commercially available prod.The content of described formaldehyde absorbent is 0.005～3.0 weight part, is preferably 0.01～2 weight part.In the time that described formaldehyde absorbent consumption is less than 0.01 weight part, goods formaldehyde odor is obvious.In addition, when described formaldehyde absorbent consumption is during higher than 2 weight part, can make the configuration of surface variation of polyacetal resin composite molding converted products, physicals reduces.
Described acid absorber is preferably one or more of oxyhydroxide, inorganic acid salt and soap of alkali or alkaline-earth metal, the more preferably oxyhydroxide of sodium, potassium, magnesium, calcium, zinc, one or more of carbonate and soap, most preferably are one or more in magnesium hydroxide, calcium stearate, Magnesium Stearate and calcium carbonate.The present invention is not particularly limited the source of described acid absorber, commercially available prod.The content of described acid absorber is 0.002～2.0 weight part, is preferably 0.01～1 weight part.In the time that described acid absorber consumption is less than 0.01 weight part, improve not remarkable to the thermostability of polyacetal resin composite product.In addition, when described acid absorber consumption is during higher than 1 weight part, can make the configuration of surface variation of polyacetal resin composite molding converted products, physicals reduces.
Described processing stabilizers is preferably one or more in long-chain or higher fatty acid or derivatives thereof, polyoxyalkylene glycol and silicone compounds, more preferably in stearic acid, lauric acid, the stearic pentaerythritol ester of Dan Zhisi, capric acid acidamide and polydimethylsiloxane one or more.Taking polyacetal resin as 100 weight parts, the content of described processing stabilizers is 0.001～2.0 weight part, is preferably 0.01～1 weight part.In the time that described processing stabilizers consumption is less than 0.01 weight part, improve not remarkable to the processing characteristics of polyacetal resin composite product.In addition,, when described processing stabilizers consumption is during higher than 1 weight part, can make polyacetal resin composite physicals reduce.
Described mineral filler is 500～10000 revs/min by mineral filler and properties-correcting agent at rotating speed, and temperature is under the condition of 10～100 DEG C, to carry out modification to obtain.Described mineral filler is particulate filler independent or combination, as oxide compound, vitriol, carbonate, silicate, sulfide, carbide etc., be preferably aluminum oxide, zinc oxide, alumina, silicon-dioxide, titanium dioxide, calcium sulfate, magnesium sulfate, calcium carbonate, talcum, kaolin, diatomite, clay, molybdenumdisulphide, tungsten disulfide, silicon carbide or Graphite fluorination thing, more preferably one or more in zinc oxide, silicon-dioxide, titanium dioxide and calcium carbonate.The particle diameter of described mineral filler is preferably 0.03-20 μ m, more preferably 0.05-15 μ m.The particle of described mineral filler can obviously affect toughness and the intensity of polyacetal resin composite of the present invention.When mineral filler particle diameter is less than 0.05 μ m, particle aggregation is obvious, disperses inequality in polyacetal resin matrix, causes strength degradation, toughness to decline; When mineral filler size is greater than 15 μ m, intensity and toughness degradation.
Described properties-correcting agent is preferably stearic acid and salt, Aluminate, phosphoric acid ester, organosilane, organic titanium, organoaluminum, aluminium titanium mixture, aluminium zirconium complex or rare earth organic polymer.Described stearic acid and salt thereof are preferably stearic acid, calcium stearate, Zinic stearas, lead stearate or sodium stearate; Described organosilicon is preferably γ-aminopropyl triethoxysilane, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-methacryloxypropyl trimethoxy silane, γ-divinyl triammonium base propyl trimethoxy silicane or β-(3,4 epoxycyclohexyl)-ethyl triethoxysilane; Described organic titanium is preferably sec.-propyl three (dodecyl benzenesulfonyl) titanic acid ester, bis(acetylacetonate) titanium acid diisopropyl ester or two (methyl aceto acetate) metatitanic acid diisopropyl ester; Described organoaluminum is preferably methyl aceto acetate aluminium diisopropyl ester.Described properties-correcting agent is one or more in calcium stearate, γ-aminopropyl triethoxysilane, γ-methacryloxypropyl trimethoxy silane, sec.-propyl three (dodecyl benzenesulfonyl) titanic acid ester and aluminium titanium mixture more preferably.Described modifier content is preferably 0.01～10wt% of described mineral filler addition, more preferably 0.1～5wt%.When modifier content is less than described mineral filler 0.1wt%, mineral filler can not obtain abundant modification, adds in polyacetal resin composite and can not play and strengthen toughness reinforcing effect; Modifier content is greater than described mineral filler 5wt%, and product properties is reduced.
The modified technique of described modified inorganic filler is most important for described modified effect, and wherein, rotating speed and temperature are even more important.In the condition of described modification, rotating speed is 500～10000 revs/min, is preferably 1000～8000 revs/min; Temperature is 10～100 DEG C, is preferably 20～80 DEG C.Modification rotating speed is less than 1000 revs/min, and mineral filler modification is incomplete, makes polyacetal resin composite intensity, toughness drop, modification rotating speed is greater than 8000 revs/min, mineral filler size decreases, reunites again, makes polyacetal resin composite intensity, toughness drop; Modification temperature is lower than 20 DEG C, and properties-correcting agent activity is low, and modification is incomplete, make polyacetal resin composite (intensity, toughness drop, modification temperature is higher than 80 DEG C, properties-correcting agent generation decomposed, modified effect reduces, polyacetal resin composite performance reduces.
Taking polyacetal resin composite as 100 weight parts, the content of described modified inorganic filler is 0.1～20 weight part, preferably 1.0～15 weight parts.In the time that described modified inorganic filler content is less than 1.0 weight part, improve not remarkable to the toughness of polyacetal resin composite product.In addition, when described modified inorganic filler content is during higher than 15 weight part, can make the configuration of surface variation of polyacetal resin composite molding converted products, physicals reduces.
Described dispersion agent is oil-soluble substance, there is good consistency with modified inorganic filler, modified inorganic filler is enriched in around described dispersion agent, dispersion agent fusing point is well below polyacetal resin simultaneously, can before polyacetal resin melting prerequisite, melt, melt the viscosity of rear dispersion agent well below the melt viscosity of polyacetal resin, thereby can in extrusion, be disperseed uniformly.Being enriched in modified inorganic filler in dispersion agent can be along with the Uniform Flow of dispersion agent in extruder screw and further disperseed, can in polyacetal resin composite crystallisation process, play better the effect of heterogeneous nucleation, crystalline core size obviously reduces, and intensity and toughness obviously improve.
Described dispersion agent is the lipid acid, dimethyl polysiloxane of mineral oil, lower polyolefins, C12～C20 and by one or more in the dimethyl polysiloxane obtaining after hydrogen, phenyl, halogenophenyl, haloalkyl, fluorine ester group substituent methyl; Be preferably one or more in machine oil, gear oil, paraffin, polyethylene wax, alpha-olefin low polymers, lauric acid and stearic acid; More preferably one or more in machine oil, whiteruss and stearic acid.Taking polyacetal resin composite as 100 weight parts, the consumption of described dispersion agent is 0.005～2.0 part, preferably 0.1～1, part.In the time that described dispersant dosage is less than 0.1 part, improve not remarkable to the toughness of polyacetal resin composite product.In addition, when described dispersant dosage is during higher than 1 part, can make the configuration of surface variation of polyacetal resin composite molding converted products, bring difficulty to processing.
The present invention also provides a kind of preparation method of polyacetal composition, comprises the following steps:
By 100 parts of polyacetal resins, 0.001～2.0 part of oxidation inhibitor, 0.005～3.0 part of formaldehyde absorbent, 0.002～2.0 part of acid absorber, 0.001～2.0 part of processing stabilizers, 0.1～20 part of modified inorganic filler, 0.005～2.0 part of dispersion agent melting mixing, obtains polyacetal composition; Described dispersion agent is the lipid acid, dimethyl polysiloxane of mineral oil, lower polyolefins, C12～C20 and by one or more in the dimethyl polysiloxane obtaining after hydrogen, phenyl, halogenophenyl, haloalkyl, fluorine ester group substituent methyl;
Described modified inorganic filler is 500～10000 revs/min by mineral filler and properties-correcting agent at rotating speed, and temperature is under the condition of 10～100 DEG C, to carry out modification to obtain.
According to the present invention, after various raw materials are mixed, through melting mixing, can obtain polyacetal resin composite.The present invention is preferably 10KPa for the pressure of melting mixing, and temperature is preferably 170～220 DEG C.After mixing, preferably pass through granulating and forming, obtain the moulding product of polyacetal composition.
Intensity to polyacetal composition of the present invention and toughness polarity test, testing method is:
(1) tensile strength is according to ISO527 standard test, the draw speed 50mm/min of employing;
(2) simply supported beam notched Izod impact strength is according to ISO179/1eA standard test.
(3) mineral filler evaluation of modification effect standard is activation efficiency: take the mineral filler of 1g modification, join in 100mL distilled water, after using ultra-sonic oscillation 30min, leave standstill 1h, then take out the floating powder drying in upper strata and weigh, calculating the activation efficiency of modified inorganic filler according to formula below:
Experimental result shows, the tensile strength of polyacetal composition of the present invention is 67～70MPa, and notched Izod impact strength is 7.5～9KJ/m
2, elongation at break is 62%～80%.
In order further to understand the present invention, below in conjunction with embodiment, polyacetal composition provided by the invention and preparation method thereof is described, protection scope of the present invention is not limited by the following examples.
Embodiment 1
The trioxymethylene of 100 weight parts and 3.5 weight parts as the DOX of comonomer at BF
3-ether catalyzer carries out polymerization under existing, and uses methylal as chain-transfer agent, then makes catalyst deactivation with triethylamine solution, obtains polyacetal copolymer, and the melting index (190 DEG C, measure under 2.16kg) of its melt is 2.0-30.0g/10min.
Embodiment 2
3000 revs/min of modification rotating speeds, 50 DEG C of modification temperatures, sec.-propyl three (dodecyl benzenesulfonyl) titanic acid ester addition is weight of calcium carbonate 2.0%, obtains modified calcium carbonate.
In the 100 weight part polymethanal polymers of preparing in preparation example 1, add four [methyl-β-(3 of 0.4 weight part, 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, the trimeric cyanamide of 0.2 weight part, the calcium stearate of 0.1 weight part, 0.2 weight part pentaerythritol stearate, the above-mentioned modified calcium carbonate of 5 weight part, 0.5 weight part dimethyl siloxane, fully mix, then under 10KPa reduced pressure, in 210 DEG C, with the granulating and forming after 0.5 minute of the twin screw extruder melting mixing with venting port, pellet is dried 3 hours at 140 DEG C, obtain the polyacetal composition of stabilization.
Fig. 1 is the polarisation picture of the polyacetal composition prepared of embodiment 2, as shown in Figure 1, adds the polyacetal composition nucleus obtaining after modified inorganic filler and dispersion agent minimum.
Embodiment 3
Modification rotating speed, 3000 revs/min, 50 DEG C of modification temperatures, sec.-propyl three (dodecyl benzenesulfonyl) titanic acid ester addition is weight of calcium carbonate 1.0%, obtains modified calcium carbonate.
In the 100 weight part polymethanal polymers of preparing in preparation example 1, add four [methyl-β-(3 of 0.4 weight part, 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, the trimeric cyanamide of 0.2 weight part, the calcium stearate of 0.1 weight part, 0.2 weight part pentaerythritol stearate, the above-mentioned modified calcium carbonate of 5 weight part, 0.5 weight part stearic acid fully mixes, then under 10KPa reduced pressure, in 210 DEG C, with the granulating and forming after 0.5 minute of the twin screw extruder melting mixing with venting port, pellet is dried 3 hours at 140 DEG C, obtain the polyacetal composition of stabilization.
Embodiment 4
3000 revs/min of modification rotating speeds, 50 DEG C of modification temperatures, sec.-propyl three (dodecyl benzenesulfonyl) titanic acid ester addition is weight of calcium carbonate 4.0%, obtains modified calcium carbonate.
In the 100 weight part polymethanal polymers of preparing in preparation example 1, add four [methyl-β-(3 of 0.4 weight part, 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, the trimeric cyanamide of 0.2 weight part, the calcium stearate of 0.1 weight part, 0.2 weight part pentaerythritol stearate, the above-mentioned modified calcium carbonate of 5 weight part, 0.5 weight part dimethyl siloxane fully mixes, then under 10KPa reduced pressure, in 210 DEG C, with the granulating and forming after 0.5 minute of the twin screw extruder melting mixing with venting port, pellet is dried 3 hours at 140 DEG C, obtain the polyacetal composition of stabilization.
Embodiment 5
1000 revs/min of modification rotating speeds, 50 DEG C of modification temperatures, sec.-propyl three (dodecyl benzenesulfonyl) titanic acid ester addition is weight of calcium carbonate 2.0%, obtains modified calcium carbonate.
In the 100 weight part polymethanal polymers of preparing in preparation example 1, add four [methyl-β-(3 of 0.4 weight part, 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, the trimeric cyanamide of 0.2 weight part, the calcium stearate of 0.1 weight part, 0.2 weight part pentaerythritol stearate, 5 weight part modified calcium carbonates, 0.5 weight part dimethyl siloxane fully mixes, then under 10KPa reduced pressure, in 210 DEG C, with the granulating and forming after 0.5 minute of the twin screw extruder melting mixing with venting port, pellet is dried 3 hours at 140 DEG C, obtain the polyacetal composition of stabilization.
Embodiment 6
5000 revs/min of modification rotating speeds, 50 DEG C of modification temperatures, sec.-propyl three (dodecyl benzenesulfonyl) titanic acid ester addition is weight of calcium carbonate 2.0%, obtains modified calcium carbonate.
In the 100 weight part polymethanal polymers of preparing in preparation example 1, add four [methyl-β-(3 of 0.4 weight part, 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, the trimeric cyanamide of 0.2 weight part, the calcium stearate of 0.1 weight part, 0.2 weight part pentaerythritol stearate, 5 weight part modified calcium carbonates, 0.5 weight part dimethyl siloxane fully mixes, then under 10KPa reduced pressure, in 210 DEG C, with the granulating and forming after 0.5 minute of the twin screw extruder melting mixing with venting port, pellet is dried 3 hours at 140 DEG C, obtain the polyacetal composition of stabilization.
Embodiment 7
3000 revs/min of modification rotating speeds, 20 DEG C of modification temperatures, sec.-propyl three (dodecyl benzenesulfonyl) titanic acid ester addition is weight of calcium carbonate 2.0%, obtains modified calcium carbonate.
In the 100 weight part polymethanal polymers of preparing in preparation example 1, add four [methyl-β-(3 of 0.4 weight part, 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, the trimeric cyanamide of 0.2 weight part, the calcium stearate of 0.1 weight part, 0.2 weight part pentaerythritol stearate, 5 weight part modified calcium carbonates, 0.5 weight part dimethyl siloxane fully mixes, then under 10KPa reduced pressure, in 210 DEG C, with the granulating and forming after 0.5 minute of the twin screw extruder melting mixing with venting port, pellet is dried 3 hours at 140 DEG C, obtain the polyacetal composition of stabilization.
Embodiment 8
3000 revs/min of modification rotating speeds, 80 DEG C of modification temperatures, sec.-propyl three (dodecyl benzenesulfonyl) titanic acid ester addition is weight of calcium carbonate 2.0%, obtains modified calcium carbonate.
In the 100 weight part polymethanal polymers of preparing in preparation example 1, add four [methyl-β-(3 of 0.4 weight part, 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, the trimeric cyanamide of 0.2 weight part, the calcium stearate of 0.1 weight part, 0.2 weight part pentaerythritol stearate, 5 weight part modified calcium carbonates, 0.5 weight part machine oil fully mixes, then under 10KPa reduced pressure, in 210 DEG C, with the granulating and forming after 0.5 minute of the twin screw extruder melting mixing with venting port, pellet is dried 3 hours at 140 DEG C, obtain the polyacetal composition of stabilization.
Embodiment 9
3000 revs/min of modification rotating speeds, 50 DEG C of modification temperatures, sec.-propyl three (dodecyl benzenesulfonyl) titanic acid ester addition is weight of calcium carbonate 2.0%, obtains modified calcium carbonate.
In the 100 weight part polymethanal polymers of preparing in preparation example 1, add four [methyl-β-(3 of 0.4 weight part, 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, the trimeric cyanamide of 0.2 weight part, the calcium stearate of 0.1 weight part, 0.2 weight part pentaerythritol stearate, 10 weight part modified calcium carbonates, 0.5 weight part whiteruss fully mixes, then under 10KPa reduced pressure, in 210 DEG C, with the granulating and forming after 0.5 minute of the twin screw extruder melting mixing with venting port, pellet is dried 3 hours at 140 DEG C, obtain the polyacetal composition of stabilization.
Embodiment 10
3000 revs/min of modification rotating speeds, 50 DEG C of modification temperatures, sec.-propyl three (dodecyl benzenesulfonyl) titanic acid ester addition is weight of calcium carbonate 2.0%, obtains modified calcium carbonate.
In the 100 weight part polymethanal polymers of preparing in preparation example 1, add four [methyl-β-(3 of 0.4 weight part, 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, the trimeric cyanamide of 0.2 weight part, the calcium stearate of 0.1 weight part, 0.2 weight part pentaerythritol stearate, 12 weight part modified calcium carbonates, 0.5 weight account polyethylene wax fully mixes, then under 10KPa reduced pressure, in 210 DEG C, with the granulating and forming after 0.5 minute of the twin screw extruder melting mixing with venting port, pellet is dried 3 hours at 140 DEG C, obtain the polyacetal composition of stabilization.
Embodiment 11
3000 revs/min of modification rotating speeds, 50 DEG C of modification temperatures, sec.-propyl three (dodecyl benzenesulfonyl) titanic acid ester addition is silica weight 2.0%, obtains improved silica.
In the 100 weight part polymethanal polymers of preparing in preparation example 1, add four [methyl-β-(3 of 0.4 weight part, 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, the trimeric cyanamide of 0.2 weight part, the calcium stearate of 0.1 weight part, 0.2 weight part pentaerythritol stearate, 5 weight part improved silicas, 0.5 weight part dimethyl siloxane fully mixes, then under 10KPa reduced pressure, in 210 DEG C, with the granulating and forming after 0.5 minute of the twin screw extruder melting mixing with venting port, pellet is dried 3 hours at 140 DEG C, obtain the polyacetal composition of stabilization.
Embodiment 12
3000 revs/min of modification rotating speeds, 50 DEG C of modification temperatures, sec.-propyl three (dodecyl benzenesulfonyl) titanic acid ester addition is 2.0% of titanium dioxide weight, obtains modifying titanium dioxide.
In the 100 weight part polymethanal polymers of preparing in preparation example 1, add four [methyl-β-(3 of 0.4 weight part, 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, the trimeric cyanamide of 0.2 weight part, the calcium stearate of 0.1 weight part, 0.2 weight part pentaerythritol stearate, 5 weight part modifying titanium dioxides, 0.5 weight part dimethyl siloxane fully mixes, then under 10KPa reduced pressure, in 210 DEG C, with the granulating and forming after 0.5 minute of the twin screw extruder melting mixing with venting port, pellet is dried 3 hours at 140 DEG C, obtain the polyacetal composition of stabilization.
Embodiment 13
3000 revs/min of modification rotating speeds, under 50 DEG C of conditions of modification temperature, select γ-aminopropyl triethoxysilane to add calcium carbonate is carried out to modification, obtain the right sour calcium of modification; γ-aminopropyl triethoxysilane addition is 2.0% of weight of calcium carbonate.
In the 100 weight part polymethanal polymers of preparing in preparation example 1, add four [methyl-β-(3 of 0.4 weight part, 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, the trimeric cyanamide of 0.2 weight part, the calcium stearate of 0.1 weight part, 0.2 weight part pentaerythritol stearate, 5 weight part modified calcium carbonates, 0.5 weight part dimethyl siloxane fully mixes, then under 10KPa reduced pressure, in 210 DEG C, with the granulating and forming after 0.5 minute of the twin screw extruder melting mixing with venting port, pellet is dried 3 hours at 140 DEG C, obtain the polyacetal composition of stabilization.
Embodiment 14
Under following modified condition, calcium carbonate is being carried out to modification: 3000 revs/min of modification rotating speeds, 50 DEG C of modification temperatures, calcium stearate addition is weight of calcium carbonate 2.0%.
In the 100 weight part polymethanal polymers of preparing in preparation example 1, add four [methyl-β-(3 of 0.4 weight part, 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, the trimeric cyanamide of 0.2 weight part, the calcium stearate of 0.1 weight part, 0.2 weight part pentaerythritol stearate, 5 weight part modified calcium carbonates, 0.5 weight part dimethyl siloxane fully mixes, then under 10KPa reduced pressure, in 210 DEG C, with the granulating and forming after 0.5 minute of the twin screw extruder melting mixing with venting port, pellet is dried 3 hours at 140 DEG C, obtain the polyacetal composition of stabilization.
Embodiment 15
At following modified condition, calcium carbonate is carried out to modification: 3000 revs/min of modification rotating speeds, 50 DEG C of modification temperatures, sec.-propyl three (dodecyl benzenesulfonyl) titanic acid ester addition is weight of calcium carbonate 2.0%.
In the 100 weight part polymethanal polymers of preparing in preparation example 1, add four [methyl-β-(3 of 0.8 weight part, 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, the trimeric cyanamide of 0.2 weight part, the calcium stearate of 0.1 weight part, 0.2 weight part pentaerythritol stearate, 5 weight part modified calcium carbonates, 0.5 weight part dimethyl siloxane fully mixes, then under 10KPa reduced pressure, in 210 DEG C, with the granulating and forming after 0.5 minute of the twin screw extruder melting mixing with venting port, pellet is dried 3 hours at 140 DEG C, obtain the polyacetal composition of stabilization.
Embodiment 16
At following modified condition, calcium carbonate is carried out to modification: 3000 revs/min of modification rotating speeds, 50 DEG C of modification temperatures, sec.-propyl three (dodecyl benzenesulfonyl) titanic acid ester addition is weight of calcium carbonate 2.0%.
In the 100 weight part polymethanal polymers of preparing in preparation example 1, add four [methyl-β-(3 of 0.2 weight part, 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, the trimeric cyanamide of 0.2 weight part, the calcium stearate of 0.1 weight part, 0.2 weight part pentaerythritol stearate, 5 weight part modified calcium carbonates, 0.5 weight part dimethyl siloxane fully mixes, then under 10KPa reduced pressure, in 210 DEG C, with the granulating and forming after 0.5 minute of the twin screw extruder melting mixing with venting port, pellet is dried 3 hours at 140 DEG C, obtain the polyacetal composition of stabilization.
Embodiment 17
At following modified condition, calcium carbonate is carried out to modification: 2000 revs/min of modification rotating speeds, 50 DEG C of modification temperatures, sec.-propyl three (dodecyl benzenesulfonyl) titanic acid ester addition is weight of calcium carbonate 2.0%.
In the 100 weight part polymethanal polymers of preparing in preparation example 1, add triglycol-bis--3-(hydroxyl-5, the 3-tertiary butyl-4 aminomethyl phenyl) propionic ester of 0.4 weight part, the trimeric cyanamide of 0.2 weight part, the calcium stearate of 0.1 weight part, 0.2 weight part pentaerythritol stearate, 5 weight part modified calcium carbonates, 0.5 weight part dimethyl silica fully mixes, then under 10KPa reduced pressure, in 210 DEG C, with the granulating and forming after 0.5 minute of the twin screw extruder melting mixing with venting port, pellet is dried 3 hours at 140 DEG C, obtain the polyacetal composition of stabilization.
Embodiment 18
At following modified condition, calcium carbonate is carried out to modification: 3000 revs/min of modification rotating speeds, 50 DEG C of modification temperatures, sec.-propyl three (dodecyl benzenesulfonyl) titanic acid ester addition is weight of calcium carbonate 2.0%.
In the 100 weight part polymethanal polymers of preparing in preparation example 1, add four [methyl-β-(3 of 0.4 weight part, 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, the trimeric cyanamide of 0.5 weight part, the calcium stearate of 0.1 weight part, 0.2 weight part pentaerythritol stearate, 5 weight part modified calcium carbonates, 0.5 weight part dimethyl silica fully mixes, then under 10KPa reduced pressure, in 210 DEG C, with the granulating and forming after 0.5 minute of the twin screw extruder melting mixing with venting port, pellet is dried 3 hours at 140 DEG C, obtain the polyacetal composition of stabilization.
Embodiment 19
At following modified condition, calcium carbonate is carried out to modification: 3000 revs/min of modification rotating speeds, 50 DEG C of modification temperatures, sec.-propyl three (dodecyl benzenesulfonyl) titanic acid ester addition is weight of calcium carbonate 2.0%.
In the 100 weight part polymethanal polymers of preparing in preparation example 1, add four [methyl-β-(3 of 0.4 weight part, 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, the trimeric cyanamide of 1.0 weight parts, the calcium stearate of 0.1 weight part, 0.2 weight part pentaerythritol stearate, 5 weight part modified calcium carbonates, 0.5 weight part dimethyl silica fully mixes, then under 10KPa reduced pressure, in 210 DEG C, with the granulating and forming after 0.5 minute of the twin screw extruder melting mixing with venting port, pellet is dried 3 hours at 140 DEG C, obtain the polyacetal composition of stabilization.
Embodiment 20
At following modified condition, calcium carbonate is carried out to modification: 3000 revs/min of modification rotating speeds, 50 DEG C of modification temperatures, sec.-propyl three (dodecyl benzenesulfonyl) titanic acid ester addition is weight of calcium carbonate 2.0%.
In the 100 weight part polymethanal polymers of preparing in preparation example 1, add four [methyl-β-(3 of 0.4 weight part, 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, the Dyhard RU 100 of 0.2 weight part, the calcium stearate of 0.1 weight part, 0.2 weight part pentaerythritol stearate, 5 weight part modified calcium carbonates, 0.5 weight part dimethyl silica fully mixes, then under 10KPa reduced pressure, in 210 DEG C, with the granulating and forming after 0.5 minute of the twin screw extruder melting mixing with venting port, pellet is dried 3 hours at 140 DEG C, obtain the polyacetal composition of stabilization.
Embodiment 21
At following modified condition, calcium carbonate is carried out to modification: 3000 revs/min of modification rotating speeds, 50 DEG C of modification temperatures, sec.-propyl three (dodecyl benzenesulfonyl) titanic acid ester addition is weight of calcium carbonate 2.0%.
In the 100 weight part polymethanal polymers of preparing in preparation example 1, add four [methyl-β-(3 of 0.4 weight part, 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, the trimeric cyanamide of 0.2 weight part, the calcium stearate of 0.3 weight part, 0.2 weight part pentaerythritol stearate, 5 weight part modified calcium carbonates, 0.5 weight part dimethyl silica fully mixes, then under 10KPa reduced pressure, in 210 DEG C, with the granulating and forming after 0.5 minute of the twin screw extruder melting mixing with venting port, pellet is dried 3 hours at 140 DEG C, obtain the polyacetal composition of stabilization.
Embodiment 22
At following modified condition, calcium carbonate is carried out to modification: 3000 revs/min of modification rotating speeds, 50 DEG C of modification temperatures, sec.-propyl three (dodecyl benzenesulfonyl) titanic acid ester addition is weight of calcium carbonate 2.0%.
In the 100 weight part polymethanal polymers of preparing in preparation example 1, add four [methyl-β-(3 of 0.4 weight part, 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, the trimeric cyanamide of 0.2 weight part, the calcium stearate of 0.5 weight part, 0.2 weight part pentaerythritol stearate, 5 weight part modified calcium carbonates, 0.5 weight part dimethyl silica fully mixes, then under 10KPa reduced pressure, in 210 DEG C, with the granulating and forming after 0.5 minute of the twin screw extruder melting mixing with venting port, pellet is dried 3 hours at 140 DEG C, obtain the polyacetal composition of stabilization.
Embodiment 23
At following modified condition, calcium carbonate is carried out to modification: 3000 revs/min of modification rotating speeds, 50 DEG C of modification temperatures, sec.-propyl three (dodecyl benzenesulfonyl) titanic acid ester addition is weight of calcium carbonate 2.0%.
In the 100 weight part polymethanal polymers of preparing in preparation example 1, add four [methyl-β-(3 of 0.4 weight part, 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, the trimeric cyanamide of 0.2 weight part, the magnesium hydroxide of 0.1 weight part, 0.2 weight part pentaerythritol stearate, 5 weight part modified calcium carbonates, 0.5 weight part dimethyl silica fully mixes, then under 10KPa reduced pressure, in 210 DEG C, with the granulating and forming after 0.5 minute of the twin screw extruder melting mixing with venting port, pellet is dried 3 hours at 140 DEG C, obtain the polyacetal composition of stabilization.
Embodiment 24
At following modified condition, calcium carbonate is carried out to modification: 3000 revs/min of modification rotating speeds, 50 DEG C of modification temperatures, sec.-propyl three (dodecyl benzenesulfonyl) titanic acid ester addition is weight of calcium carbonate 2.0%.
In the 100 weight part polymethanal polymers of preparing in preparation example 1, add four [methyl-β-(3 of 0.4 weight part, 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, the trimeric cyanamide of 0.2 weight part, the calcium stearate of 0.1 weight part, 0.2 weight part stearic acid, 5 weight part modified calcium carbonates, 0.5 weight part dimethyl silica fully mixes, then under 10KPa reduced pressure, in 210 DEG C, with the granulating and forming after 0.5 minute of the twin screw extruder melting mixing with venting port, pellet is dried 3 hours at 140 DEG C, obtain the polyacetal composition of stabilization.
Embodiment 25
At following modified condition, calcium carbonate is carried out to modification: 3000 revs/min of modification rotating speeds, 50 DEG C of modification temperatures, sec.-propyl three (dodecyl benzenesulfonyl) titanic acid ester addition is weight of calcium carbonate 2.0%.
In the 100 weight part polymethanal polymers of preparing in preparation example 1, add four [methyl-β-(3 of 0.4 weight part, 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, the trimeric cyanamide of 0.2 weight part, the calcium stearate of 0.1 weight part, 0.4 weight part pentaerythritol stearate, 5 weight part modified calcium carbonates, 0.5 weight part dimethyl silica fully mixes, then under 10KPa reduced pressure, in 210 DEG C, with the granulating and forming after 0.5 minute of the twin screw extruder melting mixing with venting port, pellet is dried 3 hours at 140 DEG C, obtain the polyacetal composition of stabilization.
Embodiment 26
At following modified condition, calcium carbonate is carried out to modification: 3000 revs/min of modification rotating speeds, 50 DEG C of modification temperatures, sec.-propyl three (dodecyl benzenesulfonyl) titanic acid ester addition is weight of calcium carbonate 2.0%.
In the 100 weight part polymethanal polymers of preparing in preparation example 1, add four [methyl-β-(3 of 0.4 weight part, 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, the trimeric cyanamide of 0.2 weight part, the calcium stearate of 0.1 weight part, 0.6 weight part pentaerythritol stearate, 5 weight part modified calcium carbonates, 0.5 weight part dimethyl silica fully mixes, then under 10KPa reduced pressure, in 210 DEG C, with the granulating and forming after 0.5 minute of the twin screw extruder melting mixing with venting port, pellet is dried 3 hours at 140 DEG C, obtain the polyacetal composition of stabilization.
Embodiment 27
At following modified condition, calcium carbonate is carried out to modification: 3000 revs/min of modification rotating speeds, 50 DEG C of modification temperatures, sec.-propyl three (dodecyl benzenesulfonyl) titanic acid ester addition is weight of calcium carbonate 2.0%.
In the 100 weight part polymethanal polymers of preparing in preparation example 1, add four [methyl-β-(3 of 0.4 weight part, 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, the trimeric cyanamide of 0.2 weight part, the calcium stearate of 0.1 weight part, 0.2 weight part pentaerythritol stearate, 5 weight part modified calcium carbonates, 0.1 weight part dimethyl siloxane fully mixes, then under 10KPa reduced pressure, in 210 DEG C, with the granulating and forming after 0.5 minute of the twin screw extruder melting mixing with venting port, pellet is dried 3 hours at 140 DEG C, obtain the polyformaldehyde composition of stabilization.
Embodiment 28
At following modified condition, calcium carbonate is carried out to modification: 3000 revs/min of modification rotating speeds, 50 DEG C of modification temperatures, sec.-propyl three (dodecyl benzenesulfonyl) titanic acid ester addition is weight of calcium carbonate 2.0%.
In the 100 weight part polymethanal polymers of preparing in preparation example 1, add four [methyl-β-(3 of 0.4 weight part, 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, the trimeric cyanamide of 0.2 weight part, the calcium stearate of 0.1 weight part, 0.2 weight part pentaerythritol stearate, 5 weight part modified calcium carbonates, 0.8 weight part dimethyl siloxane fully mixes, then under 10KPa reduced pressure, in 210 DEG C, with the granulating and forming after 0.5 minute of the twin screw extruder melting mixing with venting port, pellet is dried 3 hours at 140 DEG C, obtain the polyformaldehyde composition of stabilization.
Embodiment 29
At following modified condition, calcium carbonate is carried out to modification: 3000 revs/min of modification rotating speeds, 50 DEG C of modification temperatures, sec.-propyl three (dodecyl benzenesulfonyl) titanic acid ester addition is weight of calcium carbonate 2.0%.
In the 100 weight part polymethanal polymers of preparing in preparation example 1, add four [methyl-β-(3 of 0.4 weight part, 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, the trimeric cyanamide of 0.2 weight part, the calcium stearate of 0.1 weight part, 0.2 weight part pentaerythritol stearate, 5 weight part modified calcium carbonates, 0.5 weight part whiteruss fully mixes, then under 10KPa reduced pressure, in 210 DEG C, with the granulating and forming after 0.5 minute of the twin screw extruder melting mixing with venting port, pellet is dried 3 hours at 140 DEG C, obtain the polyformaldehyde composition of stabilization.
Embodiment 30
At following modified condition, calcium carbonate is carried out to modification: 3000 revs/min of modification rotating speeds, 50 DEG C of modification temperatures, sec.-propyl three (dodecyl benzenesulfonyl) titanic acid ester addition is weight of calcium carbonate 2.0%.
In the 100 weight part polymethanal polymers of preparing in preparation example 1, add four [methyl-β-(3 of 0.4 weight part, 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, the trimeric cyanamide of 0.2 weight part, the calcium stearate of 0.1 weight part, 0.2 weight part pentaerythritol stearate, 5 weight part modified calcium carbonates, 0.5 weight part machine oil fully mixes, then under 10KPa reduced pressure, in 210 DEG C, with the granulating and forming after 0.5 minute of the twin screw extruder melting mixing with venting port, pellet is dried 3 hours at 140 DEG C, obtain the polyformaldehyde composition of stabilization.
Comparative example 1
In the 100 weight part polymethanal polymers of preparing in preparation example 1, add four [methyl-β-(3 of 0.4 weight part, 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, the trimeric cyanamide of 0.2 weight part, the calcium stearate of 0.1 weight part, 0.2 weight part pentaerythritol stearate, fully mix, then under 10KPa reduced pressure, in 210 DEG C, with the granulating and forming after 0.5 minute of the twin screw extruder melting mixing with venting port, pellet is dried 3 hours at 140 DEG C, obtains the polyacetal composition of stabilization.
Fig. 2 is the polarisation picture of the polyacetal composition prepared of comparative example 1, as shown in Figure 2, does not add the polyacetal composition nucleus obtaining after modified inorganic filler large.
Comparative example 2
At following modified condition, calcium carbonate is carried out to modification: 3000 revs/min of modification rotating speeds, 50 DEG C of modification temperatures, sec.-propyl three (dodecyl benzenesulfonyl) titanic acid ester addition is weight of calcium carbonate 2.0%.
In the 100 weight part polymethanal polymers of preparing in preparation example 1, add four [methyl-β-(3 of 0.4 weight part, 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, the trimeric cyanamide of 0.2 weight part, the calcium stearate of 0.1 weight part, 0.2 weight part pentaerythritol stearate, 5 weight part modified calcium carbonates, fully mix, then under 10KPa reduced pressure, in 210 DEG C, with the granulating and forming after 0.5 minute of the twin screw extruder melting mixing with venting port, pellet at 140 DEG C dry 3 hours, obtains the polyacetal composition of stabilization.
Fig. 3 is the polarisation picture of the polyacetal composition prepared of comparative example 2, as shown in Figure 2, does not add the polyacetal composition obtaining after dispersion agent, and nucleus is less than the polyacetal resin composite that does not add mineral filler.
Comparative example 3
In the 100 weight part polymethanal polymers of preparing in preparation example 1, add the trimeric cyanamide of 0.2 weight part, the calcium stearate of 0.1 weight part, 0.2 weight part pentaerythritol stearate, 0.5 weight part dimethyl siloxane fully mixes, then under 10KPa reduced pressure, in 210 DEG C, with the granulating and forming after 0.5 minute of the twin screw extruder melting mixing with venting port, pellet is dried 3 hours at 140 DEG C, obtains the polyacetal composition of stabilization.
Comparative example 4
At following modified condition, calcium carbonate is carried out to modification: 3000 revs/min of modification rotating speeds, 50 DEG C of modification temperatures, sec.-propyl three (dodecyl benzenesulfonyl) titanic acid ester addition is weight of calcium carbonate 2.0%.
In the 100 weight part polymethanal polymers of preparing in preparation example 1, add the trimeric cyanamide of 0.2 weight part, the calcium stearate of 0.1 weight part, 0.2 weight part pentaerythritol stearate, 5 weight part modified calcium carbonates, 0.5 weight part dimethyl siloxane fully mixes, then under 10KPa reduced pressure, in 210 DEG C, with the granulating and forming after 0.5 minute of the twin screw extruder melting mixing with venting port, pellet at 140 DEG C dry 3 hours, obtains the polyacetal composition of stabilization.
Comparative example 5
At following modified condition, calcium carbonate is carried out to modification: 3000 revs/min of modification rotating speeds, 50 DEG C of modification temperatures, sec.-propyl three (dodecyl benzenesulfonyl) titanic acid ester addition is weight of calcium carbonate 2.0%.
In the 100 weight part polymethanal polymers of preparing in preparation example 1, add four [methyl-β-(3 of 0.4 weight part, 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, the calcium stearate of 0.1 weight part, 0.2 weight part pentaerythritol stearate, 5 weight part modified calcium carbonates, 0.5 weight part dimethyl siloxane fully mixes, then under 10KPa reduced pressure, in 210 DEG C, with the granulating and forming after 0.5 minute of the twin screw extruder melting mixing with venting port, pellet is dried 3 hours at 140 DEG C, obtains the polyacetal composition of stabilization.
Comparative example 6
In the 100 weight part polymethanal polymers of preparing in preparation example 1, add four [methyl-β-(3 of 0.4 weight part, 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, the trimeric cyanamide of 0.2 weight part, 0.2 weight part pentaerythritol stearate, (modified condition is 5 weight part modified calcium carbonates: 3000 revs/min of modification rotating speeds, 50 DEG C of modification temperatures, sec.-propyl three (dodecyl benzenesulfonyl) titanic acid ester addition is weight of calcium carbonate 2.0%), 0.5 weight part dimethyl siloxane fully mixes, then under 10KPa reduced pressure, in 210 DEG C, with the granulating and forming after 0.5 minute of the twin screw extruder melting mixing with venting port, pellet is dried 3 hours at 140 DEG C, obtain the polyformaldehyde composition of stabilization.
Comparative example 7
In the 100 weight part polymethanal polymers of preparing in preparation example 1, add four [methyl-β-(3 of 0.4 weight part, 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, the trimeric cyanamide of 0.2 weight part, the calcium stearate of 0.1 weight part, (modified condition is 5 weight part modified calcium carbonates: 3000 revs/min of modification rotating speeds, 50 DEG C of modification temperatures, sec.-propyl three (dodecyl benzenesulfonyl) titanic acid ester addition is weight of calcium carbonate 2.0%), 0.5 weight part dimethyl siloxane fully mixes, then under 10KPa reduced pressure, in 210 DEG C, with the granulating and forming after 0.5 minute of the twin screw extruder melting mixing with venting port, pellet is dried 3 hours at 140 DEG C, obtain the polyformaldehyde composition of stabilization.
Intensity and the toughness of the polyacetal composition that embodiment and comparative example are obtained are tested, and result is as shown in table 1.
The polyacetal composition performance comparison of table 1 embodiment and comparative example
The explanation of above embodiment is just for helping to understand method of the present invention and core concept thereof.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of the claims in the present invention.
To the above-mentioned explanation of the disclosed embodiments, make professional and technical personnel in the field can realize or use the present invention.To be apparent for those skilled in the art to the multiple amendment of these embodiment, General Principle as defined herein can, in the situation that not departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (10)
1. a polyacetal resin composite, comprises the component of following weight part:
Described dispersion agent is the lipid acid, dimethyl polysiloxane of mineral oil, lower polyolefins, C12～C20 and by one or more in the dimethyl polysiloxane obtaining after hydrogen, phenyl, halogenophenyl, haloalkyl, fluorine ester group substituent methyl;
Described modified inorganic filler is 500～10000 revs/min by mineral filler and properties-correcting agent at rotating speed, and temperature is under the condition of 10～100 DEG C, to carry out modification to obtain.
2. polyacetal resin composite according to claim 1, is characterized in that, described dispersion agent is one or more in machine oil, gear oil, paraffin, polyethylene wax, alpha-olefin low polymers, lauric acid and stearic acid.
3. polyacetal resin composite according to claim 2, is characterized in that, described rotating speed is 1000～8000 revs/min.
4. polyacetal resin composite according to claim 1, it is characterized in that, described mineral filler is aluminum oxide, zinc oxide, alumina, silicon-dioxide, titanium dioxide, calcium sulfate, magnesium sulfate, calcium carbonate, talcum, kaolin, diatomite, clay, molybdenumdisulphide, tungsten disulfide, silicon carbide or Graphite fluorination thing.
5. polyacetal resin composite according to claim 1, is characterized in that, described properties-correcting agent is stearic acid and salt, Aluminate, phosphoric acid ester, organosilane, organic titanium, organoaluminum, aluminium titanium mixture, aluminium zirconium complex or rare earth organic polymer.
6. polyacetal resin composite according to claim 1, is characterized in that, described oxidation inhibitor is Hinered phenols antioxidant, phosphite ester kind antioxidant, suffocated amine antioxidant, containing one or more in sulphur ester antioxidant and metal passivation oxidation inhibitor.
7. polyacetal resin composite according to claim 1, it is characterized in that, described formaldehyde absorbent is one or more of trimeric cyanamide, Dyhard RU 100, methylol melamine, urea, guanidine class, carbamide condenses, hydrazine, hydrazides, polyacrylamide and polymeric amide.
8. polyacetal resin composite according to claim 1, is characterized in that, described acid absorber is one or more of oxyhydroxide, inorganic acid salt and soap of alkali or alkaline-earth metal.
9. polyacetal resin composite according to claim 1, is characterized in that, described processing stabilizers is one or more in long-chain or higher fatty acid or derivatives thereof, polyoxyalkylene glycol and silicone compounds.
10. a preparation method for polyacetal composition, comprises the following steps:
By 100 parts of polyacetal resins, 0.001～2.0 part of oxidation inhibitor, 0.005～3.0 part of formaldehyde absorbent, 0.002～2.0 part of acid absorber, 0.001～2.0 part of processing stabilizers, 0.1～20 part of modified inorganic filler, 0.005～2.0 part of dispersion agent melting mixing, obtains polyacetal composition;
Described dispersion agent is the lipid acid, dimethyl polysiloxane of mineral oil, lower polyolefins, C12～C20 and by one or more in the dimethyl polysiloxane obtaining after hydrogen, phenyl, halogenophenyl, haloalkyl, fluorine ester group substituent methyl;
Described modified inorganic filler is 500～10000 revs/min by mineral filler and properties-correcting agent at rotating speed, and temperature is under the condition of 10～100 DEG C, to carry out modification to obtain.
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| CN109721943A (en) * | 2017-10-27 | 2019-05-07 | 旭化成株式会社 | Polyacetal resin composite |
| CN112724593A (en) * | 2020-12-30 | 2021-04-30 | 甘肃泰尔精细化工有限公司 | Thermal-oxidative-aging-resistant polyformaldehyde |
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| CN109721943B (en) * | 2017-10-27 | 2021-11-09 | 旭化成株式会社 | Polyacetal resin composition |
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