CN101597384A - The composite antioxidant that is used for polyoxymethylene - Google Patents
The composite antioxidant that is used for polyoxymethylene Download PDFInfo
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- CN101597384A CN101597384A CNA2009100543990A CN200910054399A CN101597384A CN 101597384 A CN101597384 A CN 101597384A CN A2009100543990 A CNA2009100543990 A CN A2009100543990A CN 200910054399 A CN200910054399 A CN 200910054399A CN 101597384 A CN101597384 A CN 101597384A
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Abstract
The invention discloses a kind of composite antioxidant that is used for polyoxymethylene, this composite antioxidant is with 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene is main and mixes isoamyl tetrol-four (3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester, three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) three isocyanuric acid esters and β-(3,5-di-t-butyl-4-hydroxyl-phenyl) one or both in the propionic acid octadecyl ester are formed, and make an addition in the polyoxymethylene, to promote the thermostability of polyoxymethylene; The weight ratio of this composite antioxidant component is: 1,3, and 5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene with the ratio of another component or other two component sums is: 1～90: 99～10; Its addition is: 0.01%～5.0% of polyoxymethylene weight.The present invention has promoted the polyoxymethylene commercial performance greatly.
Description
Technical field
The invention belongs to polymkeric substance organic oxidation-resistant agent, specifically a kind of polyoxymethylene that is used for is to promote the composite antioxidant of polyoxymethylene thermostability.
Background technology
Polyoxymethylene be with-[CH2O]-serve as repeat the polymer of class unit, belong to the polymkeric substance of high crystalline high-melting-point.Because the relation of its molecular structure, so thermostability is relatively poor, can discharge formaldehyde or formic acid micromolecular quantity of material when being heated, and causes plastic cracking.Therefore, industry can adopt the method upgrading polyoxymethylene of copolyreaction sometimes, promotes its thermostability, for example can with cyclic ethers class such as oxyethane or dioxolane (1,3-dioxolane) copolymerization.Because a spot of carbon-to-carbon (C-C) copolymerization chain can promote the polyoxymethylene thermostability in the copolymer, therefore adopted by industry.Among the European patent EP .128739 (1984) with trioxa cyclohexane (trioxane) copolymerization.Second kind of upgrading mode can adopt the hydroxyl with the polyoxymethylene end to replace with ether or ester group, to reduce polyoxymethylene because of decomposes, for example has the scholar to use methoxyl group (methoxy) or ethanoyl (acetyl) to replace the hydroxyl of polyoxymethylene end.U.S. Pat 4097453 promptly is that the unstable hydroxyl etherificate (Etherification) of polyoxymethylene is reached stabilising effect.Yet no matter be to adopt first kind to replace more unsettled hydroxyl mode with methoxyl group or ethanoyl terminal group with copolymerization mode or second kind; still be subject to the molecular structure of polyoxymethylene own and be easy to generate oxicracking (autoxidation) voluntarily; especially the hydrogen atom on the methylene radical (methylene) is subject to the stabilizing effect influence of contiguous Sauerstoffatom and is subject to the free radical attack, causes oxicracking.Report as people J.Polym.Sci.Polym.Lett.Ed.16 (1967) p2277 such as Didina and to contain formaldehyde 80-90% in the main pyrolysis gasification product, formic acid 7-9% also detects a spot of carbon monoxide and carbonic acid gas and exists.Studies show that the major cause that freely is generated as the polyoxymethylene decomposes, therefore controlling the free radical generation also becomes one of important means of improving the polyoxymethylene heat-resistant quality.
Usually the mode that adopts the adding antioxidant to come Mulberry Extract to generate is controlled the generation of free radical.Suppress free-radical oxidn as hindered phenol anti-oxidants (hindered phenolic antioxidants).Hinered phenols antioxidant commonly used has 1,1-two (3, the 5-tertiary butyl-2-hydroxy phenyl) ethane [(1,1-bis (3,5-tert-butyl-2-hydroxyphenyl) ethane)], (3-(3 for isoamyl tetrol four, the 5-di-tert-butyl-hydroxy phenyl) propionic ester) (CAS No.6683-19-8), triethylene glycol two [3-(the 3-tertiary butyl-5-methyl-4 hydroxy phenyl) propionic ester] (CAS No.36443-68-2), three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) three isocyanuric acid esters [1,3,5-tris (3,5-di-tert-butyl-4-hydroxy benzyl) isocyanurate], 1, (3-(3 for 6-hexa-methylene two, the 5-di-tert-butyl-hydroxy phenyl) propionic ester) [1,6-hexamethylene bis-3-(3,5-di-tert-butyl-4-hydroxyl phenyl) propionate], N, N-hexa-methylene two-3,5-di-t-butyl-4-hydroxyl hydrocinnamamide (CAS No.245-442-7), 4,4 '-methylene radical two (2, the 6-DI-tert-butylphenol compounds) [4,4 '-methylene (2,6-di-tert-butyl phenol)], β-(3,5-di-t-butyl-4-hydroxyl-phenyl) propionic acid octadecyl ester (CAS No.2082-79-3), 2,2 '-methylene radical-two (4-methyl-6-tert butyl phenol) [2,2 '-methylene-bis (4-methyl-6-tert-butyl phenol)], 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene [1,3,5-tris (3,5-di-tert-butyl-4-hydroxyphenyl) mesitylene], 1,1,3-three (5 '-tertiary butyl-4 '-hydroxyl-2 '-aminomethyl phenyl) butane [1,1,3-tris (5 '-tert-butyl-4 '-butane of hydroxy-2 '-methylphenyl)], 2, the 4 '-dimethyl-6 '-tert-butyl-phenyl-methylene radical-6-tertiary butyl-4-methyl-phenyl acrylate (CAS No.61167-58-6) etc.Above-mentioned phenol is that to be most commonly used to polyoxymethylene in the free radical scavenger be isoamyl methyl alcohol four (3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester and triethylene glycol two [two kinds of 3-(the 3-tertiary butyl-5-methyl-4-hydroxy phenyl) propionic esters.It is that class (hindered phenols) free radical scavenger improves the thermostability of polyoxymethylene that the resistance of use phenol is all arranged among Japanese Patent JP57179245 (1982), JP01275652 (1989), JP02028240 (1990), JP06240102 (1994), JP06207080 (1994) and the United States Patent (USP) U.S2004176508 (2004).Yet no matter polyoxymethylene is that automobile, aviation, precision instrument, industrial machine etc. need higher rigidity, intensity and thermostability, and adopts the oxidation inhibitor of above-mentioned single-component can't satisfy current social increasingly stringent requirement as engineering plastics.
Summary of the invention
A kind of composite antioxidant that is used for polyoxymethylene of providing at the deficiencies in the prior art is provided, this composite antioxidant is with 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene is main and mixes isoamyl tetrol-four (3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester, three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) three isocyanuric acid esters and β-(3,5-di-t-butyl-4-hydroxyl-phenyl) one or both in the propionic acid octadecyl ester are formed, and make an addition in the polyoxymethylene, to promote the thermostability of polyoxymethylene; The weight ratio of this composite antioxidant component is: 1,3, and 5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene with the ratio of another component or other two component sums is: 1～90: 99～10; Its addition is: 0.01%～5.0% of polyoxymethylene weight.
The weight ratio of described component is: 1,3, and 5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene with the ratio of another component or other two component sums is: 5～60: 95～40.
The weight ratio of described component is: 1,3, and 5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene with the ratio of another component or other two component sums is: 10～40: 90～60.
Described composite antioxidant is meant and all belongs to the hindered phenol type antioxidant.
It is in antioxidant, UV light absorber, formaldehyde-trapping agent, formic acid trapping agent and the mineral filler one or more that described composite antioxidant can add phosphorous antioxidant, ammonia in adding polyoxymethylene to the time simultaneously.
The present invention is directed to further strengthening of polyoxymethylene thermostability and propose a compositing formula, this prescription is with 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene is main and with isoamyl tetrol-four (3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester or three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) three isocyanuric acid esters or β-(3,5-di-t-butyl-4-hydroxyl-phenyl) composite antioxidant formed of propionic acid octadecyl ester is used for polyoxymethylene and promotes that it is thermally-stabilised qualitative.Studies show that, the industrial prescription that has used is compared with 1 at present, 3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene is that main above-mentioned composite antioxidant is when being used for polyoxymethylene, it is about 20% that its thermostability can significantly improve, the usefulness of the single-component oxidation inhibitor of being carried in the different background technology greatly, and can effectively reduce production costs.
Composite antioxidant component proposed by the invention is Hinered phenols antioxidant, wherein (3-(3 for isoamyl tetrol-four, the 5-di-tert-butyl-hydroxy phenyl) propionic ester or three (3, the 5-di-tert-butyl-hydroxy phenyl) three isocyanuric acid esters or β-(3,5-di-t-butyl-4-hydroxyl-phenyl) propionic acid octadecyl ester content is more than 10%, 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene content is more than 1%, and two component recipe ingredient ratios are between 99/1 to 10/90, and effect formula rate preferably is 95/5 to 40/60, if consider polyoxymethylene production cost and usefulness simultaneously, then oxidation inhibitor agent best group is proportional is 90/10 to 60/40.
It is 0.01-3.0 (with respect to the polyoxymethylene of 100 weight parts) that antioxidant is used for the polyoxymethylene addition.Composite antioxidant proposed by the invention be except that forming the oxidation inhibitor with above-mentioned hindered phenol type antioxidant, simultaneously can and with phosphorous antioxidant or UV light absorber or formaldehyde-trapping agent or formic acid trapping agent or mineral filler etc.
Phosphorous antioxidant commonly used has triphenyl phosphite, tricresyl phosphite (2, the 4-di-tert-butyl) ester (CAS No.31570-04-4), four (2, the 4-di-tert-butyl-phenyl)-4,4 '-xenyl biphosphonate (PEP-Q), tetramethylolmethane diphosphite two (2,4-di-tert-butyl phenyl) ester (CAS No.26741-53-7) and tetramethylolmethane diphosphite (18) ester (CAS No.3806-34-6) etc.
Oxidation inhibitor used in the present invention and UV light absorber are also with also improving the polyoxymethylene weather resisteant, UV light absorber commonly used is based on benzotriazole, this compounds has 2-(2 '-hydroxyl-the 3 '-tertiary butyl-5 '-aminomethyl phenyl)-5-chlorinated benzotriazole (CAS No.3896-11-5), 2-(2 hydrogen-benzotriazole-2-yl)-4,6-di-tert-pentyl phenol (CAS No.25973-55-1), 2-(2 '-hydroxy-5-methyl base phenyl) benzotriazole (CAS No.2440-22-4), 2 benzotriazole-2-base-4,6-DI-tert-butylphenol compounds (CAS No.3846-71-7), 2-(2 hydrogen-benzotriazole-2-hydroxyl)-4-(tertiary butyl-6-sec-butyl) phenol (CAS No.36437-37-3), 2-(2 '-hydroxyl-5 '-uncle's octyl phenyl) benzotriazole (CAS No.3147-75-9), 2-(2 hydrogen-benzotriazole-2-hydroxyl)-4,6-two (1-methyl isophthalic acid-phenylethyl) phenol (CAS No.70321-86-7), 2-2 '-methylene-bis (6-(2 hydrogen-benzotriazole-2-yl)-4-(1,1,3, the 3-tetramethyl butyl)) phenol (CAS No.103597-45-1), 2-(2 hydrogen-benzotriazole-2-yl)-6-dodecyl-4-methylphenol (CAS No.23328-53-2) and 2-(2 '-hydroxyl-3 '-cumyl-5 '-uncle's octyl phenyl) benzotriazole (CAS No.73936-91-1) etc., but the also UV light absorber of available non-benzotriazole, as N-(2-ethoxyl phenenyl)-N '-(2-ethylphenyl) oxalic acid diamide (Sanduvor VSU), 2-(4,6-phenylbenzene-1,3,5-triazine-2-hydroxyl)-5-hexyloxy phenol (Tinuvin 1577), 2-(4,6-two (2, the 4-xylyl)-2-(1,3, the 5-triazinyl)) 5-octyl group oxygen base phenol (Cytec UV-1164), or poly--((6-(1,1,3, the 3-tetramethyl butyl)-and imino-)-1,3,5-triazine-2,4-two bases)-(2-(2,2,6,6-tetramethyl-piperidinyl)-amino)-hexylidene-(4-(2,2,6,6-tetramethyl-piperidinyl))-imino-(CAS No.71878-19-8) etc.
Formaldehyde-trapping agent of the present invention is trimeric cyanamide, hydrazine hydrate derivative; As 1, two (the N of 6-hexa-methylene, N-dimethylamino urea) [1,6-hexamethylene bis (N, N-dimethylsemicarbazide)] (CAS No.69938-76-7) or 1,1,1 ', 1 '-tetramethyl--4,4 '-(methylenediphenyl) diaminourea [1,1,1 ', 1 '-tetramethyl-4,4 '-(methylene-di-phenylene) disemi-carbazide] (CAS No.85095-61-0) etc. or urea, Dyhard RU 100, trimeric cyanamide, aniline, anils is as 4,4 '-two uncle's octyl group phenylbenzene phenol (4,4 '-di-tert-octyldiphenylamine), formaldehyde condensation products, one or more mixtures in polyacrylamide or the polymeric amide, wherein trimeric cyanamide, urea, anils or hydrazine hydrate derivative are preferred formaldehyde-trapping agent.
Then preferably adopt the oxyhydroxide or the mineral acid salt of basic metal or alkaline-earth metal as for the formic acid trapping agent, as the oxyhydroxide of sodium, potassium, magnesium, calcium, zinc or above-mentioned as described in the inorganic acid salt of alkaline-earth metal.Mineral filler also can be dosed increases its intensity in polyoxymethylene, mineral filler described here can be talcum powder, molybdenumdisulphide or boron nitride or natural montmorillonite or zeolite etc.
Proposed by the invention with 1,3,5-trimethylammonium-2,4,6-two (3, the 5-di-tert-butyl-hydroxy phenyl) benzene is main composite antioxidant, the preparation method who is used for polyoxymethylene is: with polyformaldehyde resin 100 weight parts, 1,3,5-trimethylammonium-2,4,6-two (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene 0.01-2.0 weight part, isoamyl tetrol-four (3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester or three (3, the 5-di-tert-butyl-hydroxy phenyl) three isocyanuric acid esters or β-(3,5-two uncles) propionic acid octadecyl ester 0.01-3.0 weight part base-4-hydroxyl-phenyl), formaldehyde-trapping agent 0.01-2.0 weight part, formic acid trapping agent 0.01-2.0 weight part, mineral filler 0.01-10.0 weight part, after mixing machine mixes, squeeze out through list or twin screw extruder machine in proportion, extrusion temperature is 180-260 ℃, melting mixing, preferred temperature is 220-230 ℃, extrudes the back granulation and promptly gets required polyformaldehyde resin, gets about 20 milligrams sample and measures its processing stability in thermogravimetric amount loss determinator.Polyoxymethylene heat-resistant quality test of the present invention is with capable again compressing tablet of the polyoxymethylene after granulating or ejection formation, and sample is placed 140 ℃ of hot-air ovens, observes the required time of 2% weight loss.
Polyoxymethylene used in the present invention is the POM-M90 (tensile strength: 62Mpa) of being produced based on Taiwan Bao Li company, oxidation inhibitor, UV light absorber is produced by the two key chemical companies in Taiwan, in the formaldehyde-trapping agent 1, two (the N of 6-hexa-methylene, N-dimethylamino urea) [1,6-hexamethylenebis (N, N-dimethyl semicarbaz-ide)] (CAS No.69938-76-7) and 1,1,1 ', 1 '-tetramethyl--4,4 '-(methylenediphenyl) diaminourea [1,1,1 ', 1 '-tetra methyl-4,4 '-(methylene-di-phenylene) disemicarbazide] (CASNo.85095-61-0) produce by the two key chemical companies in Taiwan, all the other formaldehyde-trapping agents, formic acid trapping agent and mineral filler then obtain by commercial, extruder size SHJ-20 is made by Nanjing Jie Ente company, Jet forming machine type Y-450-1S-p then reaches company by Taiwan Troubleshoot, and weather resistance test machine (QUV) type is that QUV accelerated weathering tester is made by Q-PANEL.
The test result of embodiments of the invention that table 1 is classified as and comparative example, show in the table that be used in the polyoxymethylene composite antioxidant more can improve polyoxymethylene than single-component oxidation inhibitor and be subjected to thermostability, studies show that 1,3,5-trimethylammonium-2,4,6-two (3, the 5-di-tert-butyl-4-hydroxyl benzyl) the high more then polyoxymethylene of benzene addition heat-resistant quality good more (embodiment 1,2 and 3), interpolation is total to tranquilizer such as UV light absorber (embodiment 7) can further be strengthened weathering resistance.And the gained result obviously is better than the oxidation inhibitor (comparative example 8,9,10) of existing industrial use among the embodiment, promotes the polyoxymethylene commercial performance greatly.
Embodiment
Embodiment 1
With 100 weight part polyoxymethylene (tensile strength: 62Mpa) with by 0.2 weight part 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, 0.3 (3-(3 for weight part isoamyl tetrol-four, the 5-di-tert-butyl-hydroxy phenyl) 1 of the diradical trapping agent of propionic ester composition and 0.15 weight part, 6-hexa-methylene two (N, N-dimethylamino urea), the lime carbonate of 0.3 weight part, 0.3 the weight part zeolite is sent into exhaust duplex bar extrusion machine after mixing machine mixes, barrel temperature is under 220 ℃ the condition after the mixing extrusion granulation of fusing, makes standard test piece through Jet forming machine again and measures its performance, and measurement result is as shown in table 1.
Embodiment 2
Prescription is formed with embodiment 1 but with 1 of 0.2 weight part, 3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene change reduce to 0.05 weight part and the isoamyl tetrol-four of 0.3 weight part (3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester then increases to 0.45 weight part, after mixing, mixing machine sends into exhaust duplex bar extrusion machine, barrel temperature is under 220 ℃ the condition after the mixing extrusion granulation of fusing, make standard test piece through Jet forming machine again and measure its performance, measurement result is as shown in table 1.
Embodiment 3
Prescription is formed with embodiment 1 but with 1 of 0.2 weight part, 3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene changes and increases to 0.3 weight part, and the isoamyl tetrol-four of 0.3 weight part (3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester is then reduced to 0.2 weight part, after mixing, mixing machine sends into exhaust duplex bar extrusion machine, barrel temperature is under 220 ℃ the condition after the mixing extrusion granulation of fusing, makes standard test piece through Jet forming machine again and measures its performance, and measurement result is as shown in table 1.
Embodiment 4
Prescription is formed with embodiment 1 but only (3-(3 with the isoamyl tetrol-four of 0.3 weight part, the 5-di-tert-butyl-hydroxy phenyl) propionic ester changes with three (3 of 0.3 weight part, the 5-di-tert-butyl-hydroxy phenyl) three isocyanuric acid esters substitute, after mixing, mixing machine sends into exhaust duplex bar extrusion machine, barrel temperature is under 220 ℃ the condition after the mixing extrusion granulation of fusing, make standard test piece through Jet forming machine again and measure its performance, measurement result is as shown in table 1.
Embodiment 5
Prescription is formed with embodiment 1 but only (3-(3 with the isoamyl tetrol-four of 0.3 weight part, the 5-di-tert-butyl-hydroxy phenyl) propionic ester changes the β-(3 with 0.3 weight part, 5-di-t-butyl-4-hydroxyl-phenyl) the propionic acid octadecyl ester substitutes, after mixing, mixing machine sends into exhaust duplex bar extrusion machine, barrel temperature is under 220 ℃ the condition after the mixing extrusion granulation of fusing, make standard test piece through Jet forming machine again and measure its performance, measurement result is as shown in table 1.
Embodiment 6
With 100 weight part polyoxymethylene (tensile strength: 62Mpa) with by 0.1 weight part 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, 0.1 three (3 of weight part, the 5-di-tert-butyl-hydroxy phenyl) three isocyanuric acid esters, 0.3 (3-(3 for weight part isoamyl tetrol-four, the 5-di-tert-butyl-hydroxy phenyl) propionic ester three is formed 1 of part free radical scavenger and 0.15 weight part, 6-hexa-methylene two (N, N-dimethylamino urea), the lime carbonate of 0.3 weight part, 0.3 the weight part zeolite is sent into exhaust duplex bar extrusion machine after mixing machine mixes, barrel temperature is under 220 ℃ the condition after the mixing extrusion granulation of fusing, makes standard test piece through Jet forming machine again and measures its performance, and measurement result is as shown in table 1.
Embodiment 7
Prescription is formed with embodiment 1, other adds 2-(2 '-hydroxy-5-methyl base phenyl) benzotriazole (CAS No.2440-22-4) UV light absorber of 0.3 weight part, after mixing, mixing machine sends into exhaust duplex bar extrusion machine, barrel temperature is under 220 ℃ the condition after the mixing extrusion granulation of fusing, make standard test piece through Jet forming machine again and measure its performance, measurement result is as shown in table 1.
Embodiment 8
Prescription is formed with embodiment 1 but with 1 of 0.2 weight part, 3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene change reduce to 0.01 weight part and the isoamyl tetrol-four of 0.3 weight part (3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester then increases to 0.49 weight part, after mixing, mixing machine sends into exhaust duplex bar extrusion machine, barrel temperature is under 220 ℃ the condition after the mixing extrusion granulation of fusing, make standard test piece through Jet forming machine again and measure its performance, measurement result is as shown in table 1.
Embodiment 9
Prescription is formed with embodiment 1 but with 1 of 0.2 weight part, 3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene change rise to 0.45 weight part and the isoamyl tetrol-four of 0.3 weight part (3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester is then reduced to 0.05 weight part, after mixing, mixing machine sends into exhaust duplex bar extrusion machine, barrel temperature is under 220 ℃ the condition after the mixing extrusion granulation of fusing, make standard test piece through Jet forming machine again and measure its performance, measurement result is as shown in table 1.
Embodiment 10
Prescription is formed with embodiment 1 but with 1 of 0.2 weight part, 3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene change rise to 0.5 weight part and the isoamyl tetrol-four of 0.3 weight part (3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester then rises to 4.5 weight parts, after mixing, mixing machine sends into exhaust duplex bar extrusion machine, barrel temperature is under 220 ℃ the condition after the mixing extrusion granulation of fusing, make standard test piece through Jet forming machine again and measure its performance, measurement result is as shown in table 1.
Embodiment 11
Prescription is formed with embodiment 1 but with 1 of 0.2 weight part, 3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene change reduce to 0.005 weight part and the isoamyl tetrol-four of 0.3 weight part (3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester is then reduced to 0.005 weight part, after mixing, mixing machine sends into exhaust duplex bar extrusion machine, barrel temperature is under 220 ℃ the condition after the mixing extrusion granulation of fusing, make standard test piece through Jet forming machine again and measure its performance, measurement result is as shown in table 1.
Comparative example 12
(tensile strength: 62Mpa) (3-(3 with 0.5 weight part isoamyl tetrol-four with 100 weight part polyoxymethylene, the 5-di-tert-butyl-hydroxy phenyl) 1 of single free radical scavenger of propionic ester and 0.15 weight part, two (the N of 6-hexa-methylene, N-dimethylamino urea), 0.3 the lime carbonate of weight part, 0.3 the weight part zeolite is sent into exhaust duplex bar extrusion machine after mixing machine mixes, barrel temperature is under 220 ℃ the condition after the mixing extrusion granulation of fusing, make standard test piece through Jet forming machine again and measure its performance, measurement result is as shown in table 1.
Comparative example 13
Prescription is formed with comparative example 8 but only (3-(3 with the isoamyl tetrol-four of 0.5 weight part, the 5-di-tert-butyl-hydroxy phenyl) [3-(the 3-tertiary butyl-5-methyl-4 hydroxy phenyl) propionic ester substitutes propionic ester with 0.5 weight part triethylene glycol two, after mixing, mixing machine sends into exhaust duplex bar extrusion machine, barrel temperature is under 220 ℃ the condition after the mixing extrusion granulation of fusing, make standard test piece through Jet forming machine again and measure its performance, measurement result is as shown in table 1.
Comparative example 14
Prescription is formed with comparative example 8 but only (3-(3 with the isoamyl tetrol-four of 0.5 weight part, the 5-di-tert-butyl-hydroxy phenyl) propionic ester is with the β-(3 of 0.5 weight part, 5-di-t-butyl-4-hydroxyl-phenyl) the propionic acid octadecyl ester substitutes, after mixing, mixing machine sends into exhaust duplex bar extrusion machine, barrel temperature is under 220 ℃ the condition after the mixing extrusion granulation of fusing, make standard test piece through Jet forming machine again and measure its performance, measurement result is as shown in table 1.
Table 1: polyoxymethylene (POM) test piece heat-resistant quality test----thermogravimeter (TGA) (under 220 ℃ of air) and oven ageing test
| Thermogravimeter 10% weight loss required time (minute) | Oven ageing (140 ℃) 2% weight loss required time (fate) | The QUV irradiation (50 ℃) in 200 hours of xanthochromia index (YI) value | |
| Embodiment 1 | 132 | 94 | 12.5 |
| Embodiment 2 | 125 | 87 | 21.4 |
| Embodiment 3 | 134 | 96 | 12.3 |
| Embodiment 4 | 123 | 84 | 15.6 |
| Embodiment 5 | 116 | 82 | 21.4 |
| Embodiment 6 | 129 | 89 | 14.4 |
| Embodiment 7 | 132 | 95 | 11.6 |
| Embodiment 8 | 107 | 76 | 26.3 |
| Embodiment 9 | 145 | 101 | 10.7 |
| Embodiment 10 | 142 | 100 | 10.6 |
| Embodiment 11 | 72 | 66 | 31.2 |
| Comparative example 12 | 75 | 66 | 29.9 |
| Comparative example 13 | 108 | 79 | 23.4 |
| Comparative example 14 | 64 | 66 | 44.1 |
Claims (5)
1, a kind of composite antioxidant that is used for polyoxymethylene, it is characterized in that this composite antioxidant is with 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene is main and mixes isoamyl tetrol-four (3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester, three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) three isocyanuric acid esters and β-(3,5-di-t-butyl-4-hydroxyl-phenyl) one or both in the propionic acid octadecyl ester are formed, and make an addition in the polyoxymethylene, to promote the thermostability of polyoxymethylene; The weight ratio of this composite antioxidant component is: 1,3, and 5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene with the ratio of another component or other two component sums is: 1～90: 99～10; Its addition is: 0.01%～5.0% of polyoxymethylene weight.
2, composite antioxidant according to claim 1 is characterized in that the weight ratio of described component is: 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene with the ratio of another component or other two component sums is: 5～60: 95～40.
3, composite antioxidant according to claim 1 is characterized in that the weight ratio of described component is: 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene with the ratio of another component or other two component sums is: 10～40: 90～60.
4, composite antioxidant according to claim 1 is characterized in that described composite antioxidant is meant and all belongs to the hindered phenol type antioxidant.
5, composite antioxidant according to claim 1 is characterized in that can adding simultaneously when this composite antioxidant is in adding polyoxymethylene to phosphorous antioxidant, ammonia and is in antioxidant, UV light absorber, formaldehyde-trapping agent, formic acid trapping agent and the mineral filler one or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100543990A CN101597384A (en) | 2009-07-03 | 2009-07-03 | The composite antioxidant that is used for polyoxymethylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100543990A CN101597384A (en) | 2009-07-03 | 2009-07-03 | The composite antioxidant that is used for polyoxymethylene |
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| Publication Number | Publication Date |
|---|---|
| CN101597384A true CN101597384A (en) | 2009-12-09 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2009100543990A Pending CN101597384A (en) | 2009-07-03 | 2009-07-03 | The composite antioxidant that is used for polyoxymethylene |
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| Country | Link |
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| CN (1) | CN101597384A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105001590A (en) * | 2014-04-18 | 2015-10-28 | 奕益实业有限公司 | Melamine-free composite additive for polyoxymethylene |
| CN107629403A (en) * | 2017-10-09 | 2018-01-26 | 四川大学 | A kind of preparation method and applications of the soft melamino-formaldehyde foam of low formaldehyde emission |
| CN114350022A (en) * | 2021-12-03 | 2022-04-15 | 国家能源集团宁夏煤业有限责任公司 | Anti-yellowing antioxidant and application thereof, anti-yellowing polyolefin composition and application thereof, anti-yellowing polyolefin and preparation method and application thereof |
-
2009
- 2009-07-03 CN CNA2009100543990A patent/CN101597384A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105001590A (en) * | 2014-04-18 | 2015-10-28 | 奕益实业有限公司 | Melamine-free composite additive for polyoxymethylene |
| CN105001590B (en) * | 2014-04-18 | 2017-10-20 | 奕益实业有限公司 | Melamine-free composite additive for polyoxymethylene |
| CN107629403A (en) * | 2017-10-09 | 2018-01-26 | 四川大学 | A kind of preparation method and applications of the soft melamino-formaldehyde foam of low formaldehyde emission |
| CN114350022A (en) * | 2021-12-03 | 2022-04-15 | 国家能源集团宁夏煤业有限责任公司 | Anti-yellowing antioxidant and application thereof, anti-yellowing polyolefin composition and application thereof, anti-yellowing polyolefin and preparation method and application thereof |
| CN114350022B (en) * | 2021-12-03 | 2023-12-22 | 国家能源集团宁夏煤业有限责任公司 | Anti-yellowing antioxidant and application thereof, anti-yellowing polyolefin composition and application thereof, anti-yellowing polyolefin and preparation method and application thereof |
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Open date: 20091209 |