CN101508819A - Thermal stable polyoxymethylene containing high-efficiency anti-oxidant and method for producing the same - Google Patents
Thermal stable polyoxymethylene containing high-efficiency anti-oxidant and method for producing the same Download PDFInfo
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- CN101508819A CN101508819A CNA2009100586233A CN200910058623A CN101508819A CN 101508819 A CN101508819 A CN 101508819A CN A2009100586233 A CNA2009100586233 A CN A2009100586233A CN 200910058623 A CN200910058623 A CN 200910058623A CN 101508819 A CN101508819 A CN 101508819A
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Abstract
The invention discloses a thermally stable polyformaldehyde containing high-efficacy antioxidant and a preparation method thereof. The invention is characterized in that 100 parts of polyformaldehyde resin, 0.1 to 0.3 part of primary antioxidant, 0.1 to 0.3 part of complemental antioxidant 1, 0.05 to 0.5 part of complemental antioxidant 2, 0.05 to 2 parts of formaldehyde absorbent, 0.05 to 0.5 part of methanoic acid absorbent and 0.05 to 0.5 part of lubricant by part by weight are put into a high-speed mixer to be mixed and then are melted and mixed by an exhaust double-screw extruder to be extruded and granulated; the rotating speed of a screw is 30-150 revolution/minute, the temperature of a barrel is 140-230 DEG C; and the thermally stable polyformaldehyde is obtained.
Description
Technical field
The present invention relates to a kind of thermal stable polyoxymethylene that contains high-efficiency anti-oxidant and preparation method thereof, belong to field of high polymer material processing.
Background technology
Polyoxymethylene (POM) is with [CH
2-O-] be main chain, no branching, high-melting-point, high-density, high crystallization thermoplastic engineering plastics, have very high strength and stiffness, outstanding creep resistant, resistance to fatigue, intrinsic oilness, wearability and chemical proofing etc., be near the kind of metal in the engineering plastics, can be in order to non-ferrous metal and alloy products such as Alloy instead of Copper, aluminium, zinc, be widely used in fields such as electric, automobile, light industry, machinery, chemical industry, building materials.
POM is because the specific molecule structure, and its thermostability is relatively poor, thereby the thermostabilization of POM is most important, the most basic gordian technique in the synthetic or processed and applied process at it.Yu Jian etc., engineering plastics are used, and 2001,29 (4), 28-30 has described under the heat and oxygen effect of POM in the melt-processed process, and in a single day its molecule produces free radical, and chain rupture will take place, and successive piptonychia aldehyde reaction takes place then.And formaldehyde and will promote thermal decomposition process by the micro-formic acid that oxidation of formaldehyde generates quickens the piptonychia aldehyde reaction greatly, until the macromolecular chain decomposition of POM totally.Chinese patent CN1196073A discloses existing P OM resin can not satisfy the thermostability requirement, produces dirt settling on mould, and product surface is worsened.
Oxidation inhibitor is most important, the most basic thermal oxidation stability auxiliary agent of polymer materials.The oxidative degradation of polymkeric substance is an autoxidation chain reaction with chain initiation, chainpropagation, chain termination process, free polymer readical is cause its oxidative degradation basic, and removing free radical and hydroperoxide decomposition is the Basic Ways that suppresses polymkeric substance oxidative degradation.Oxidation inhibitor is to tie up to free radical that heat, oxygen effect produces down and interrupt whole system autoxidation working cycle and reach stable purpose by catching polymeric acceptor.It comprises primary antioxidants such as hindered phenol, arylamine, the main oxygen radical (HO, RO or ROO) that generates in the polymkeric substance thermal-oxidative ageing of catching; Thiopropionate class, phosphorous acid esters auxiliary antioxidant, main polymkeric substance hydroperoxide in order to generate in the decomposition heat deterioration by oxidation chain reaction; The carbon radicals trapping agent is mainly caught the alkyl diradical that generates in the thermo-oxidative ageing chain reaction, comprises aryl benzofuranone, diphenyl acrylate, hindered amine, azanol, tertiary amino oxides, quinones and benzo dithia cyclic cpds etc.
At present, the normal phenolic antioxidant that adopts Irganox259 and Irganox245 in the POM production application both at home and abroad, experimental results show that this kind antioxidant has significant thermostable effect to POM, can increase substantially the thermal stability of POM, be the oxidation inhibitor that is fit to the excellent property of POM, but its large usage quantity, price are expensive, have become one of principal element that influences the POM production cost.Wang Kezhi, Speciality Petrochemicals, 1993 (3): 46-52 describes anti-oxidant Irganox 1010, Irganox1076 is cheap, but venerates the quinones coloring material and cause material color to change owing to being easy to for symmetric form hindered phenol structure produce.Numerous results of study show that the Irganox1010 of higher dosage can cause POM goods jaundice variable color.Therefore, research and development POM high-efficiency anti-oxidant system reduces the oxidation inhibitor consumption, and it is significant to the POM industrial development to reduce its production cost.
Summary of the invention
The objective of the invention is provides a kind of high-efficiency anti-oxidant to stablize POM and preparation method thereof at the deficiencies in the prior art, be characterized in the compound use of main and auxiliary oxidation inhibitor, effectively catch alkoxy free group RO, the peroxy radical ROO, hydroperoxide ROOH and the alkyl diradical R that generate in the POM thermal-oxidative ageing chain reaction, constitute the thermal oxidation stability three lines of defence, effectively improve the POM thermostability, reduce the oxidation inhibitor consumption, reduce its production cost.
Purpose of the present invention is realized that by following technical measures wherein said raw material mark is parts by weight except that specified otherwise.
The starting raw material of thermostability POM that contains high-efficiency anti-oxidant is composed of the following components:
100 parts of POM melting index 9-27g/10min
0.1～0.3 part of primary antioxidant
1 0.1～0.3 part of auxiliary antioxidant
2 0.05～0.5 part of auxiliary antioxidant
0.05～2 part in formaldehyde absorption agent
0.05～0.5 part in formic acid absorption agent
0.05～0.5 part of lubricant
Wherein, primary antioxidant is four [β-(3; the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (that is: Irganox1010); N; N '-two-[3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl] hexanediamine (that is: Irganox1098), β-(4-hydroxyl-3; the 5-di-tert-butyl-phenyl) any in propionic acid stearyl alcohol ester (that is: Irganox 1076) or the 2,6 di tert butyl 4 methyl phenol (that is: BHT (264)).
The formaldehyde absorption agent is any in trimeric cyanamide, Dyhard RU 100, urea or the hydrazides.
The formic acid absorption agent is any in magnesium oxide, Calucium Silicate powder, neurosin, magnesium hydroxide or the lime carbonate.
Lubricant is any in Zerol, two hard esteramides or the tetramethylolmethane tristearate.
The preparation method who contains the thermostability POM of high-efficiency anti-oxidant:
100 parts of POM resins are added in the high-speed mixer with 0.1～0.3 part of primary antioxidant, 10.1～0.3 parts of auxiliary antioxidants, 20.05～0.5 parts of auxiliary antioxidants, 0.05～2 part in formaldehyde absorption agent, formic acid absorption agent 0.05-0.5 part and lubricant 0.05-0.5 part mix, use exhaust twin screw extruder melting mixing again, extruding pelletization; Screw speed 30-150 rev/min, barrel temperature 140-230 ℃, obtain thermostability POM product.
The formaldehyde absorption agent that the present invention is used, formic acid absorption agent and lubricant are known technologies well known to those skilled in the art, and its prerequisite is that the adding of these additives does not have a negative impact to obtaining of excellent technique effect of the present invention.
Thermostability POM performance:
The POM thermal weight loss rate that is added with new antioxidant systems Irganox1010/Irgafos168/BMA is starkly lower than traditional Irganox1010/Irgafos168 system, a little less than Irganox245; And increase with the BMA consumption and to reduce.See for details shown in Figure 1.
The POM thermal weight loss speed that is added with Irganox1010/Irgafos168/BMA is starkly lower than traditional Irganox1010/Irgafos168 system, and is suitable with Irganox245; It is more mild that higher dosage BMA descends POM thermal weight loss rate.See for details shown in Fig. 2 and the table 1.
The POM burst size of methanal that is added with new antioxidant systems Irganox1010/Irgafos168/BMA is starkly lower than traditional Irganox1010/Irgafos168 system, and is suitable with Irganox245; And with its consumption increase, the POM burst size of methanal obviously reduces.See for details shown in Figure 3.
The aerial TG curve of POM is simple S shape, illustrates that the decomposition course of POM system roughly has only a step.Rising with temperature, the sample residual mass reduces, under uniform temp, traditional Irganox1010/Irgafos168 system and the Irganox245 of the residual mass ratio of POM that is added with Irganox1010/Irgafos168/BMA wants big, its Thermal Decomposition Characteristics temperature is higher, even is higher than 8～16 ℃ of traditional systems (seeing Table 1).Show that the adding of new antioxidant systems can effectively improve the thermostability of POM, particularly can be more effective under the high temperature process condition degraded of inhibition POM, its heat stabilization is better than Irganox245.See for details shown in Figure 4.
The repeatedly processing characteristics of material can be used for characterizing its processing heat stability and can reply use properties.Result of study shows, the initial melting index of POM/Irganox1010/Irgafos168/BMA and POM/Irganox245 is close, later expect machining experiment through 5 times, the POM melting index that contains Irganox245 has increased by 27.3%, the POM that contains new antioxidant systems only increases by 13.3%, show that its molecular degradation is few, show higher thermostability.The two yellowness index is close.Aspect mechanical property, the POM that contains new antioxidant systems Irganox1010/Irgafos168/BMA is close with the POM mechanical property that contains Irganox245, even has slightly high toughness.Therefore, new antioxidant systems has the thermally-stabilised efficient suitable with Irganox245 to POM, and is repeatedly keeping more stable thermal stability and mechanical property in the processing.
Long-term thermal stability can be at a certain temperature, the situation that material property changes with digestion time.Result of study shows, in the long-term aging process, the YI that adds the POM sample of new antioxidant systems Irganox1010/Irgafos168/BMA is lower than Irganox245, MI is suitable with it, the two mechanical property is close, show that new antioxidant systems and Irganox245 are suitable to the POM thermostable effect, can effectively prolong long term thermal, the oxygen life-span of POM goods.
The present invention has following advantage:
The present invention is directed in the present POM industrial production Irganox259 that generally adopts and Irganox245 high-efficient phenol antioxidant consumption is big, cost is high, traditional economical and practical can cause in high temperature process or life-time service process, the turn to be yellow problem of variable color of material as the monobasic of primary antioxidant representative or binary antioxidant systems and use separately with Irganox1010, by to the technical study of compoundization of antioxidant systems, research and development high-efficiency anti-oxidant system is used for POM, has following characteristics:
1, with primary antioxidant, auxiliary antioxidant 1, auxiliary antioxidant 2 compound use, effectively catch alkoxy free group RO, the peroxy radical ROO, hydroperoxide ROOH and the alkyl diradical R that generate in the POM thermal-oxidative ageing chain reaction, constitute thermally-stabilised three lines of defence, effectively improve the POM thermostability, its heat stabilization obviously is better than monobasic or the binary antioxidant systems that Irganox1010 is the primary antioxidant representative, meets or exceeds the stabilising effect of Irganox245 to POM.
2,, can obviously improve the problem that antioxidant systems such as independent use Irganox1010 can cause POM jaundice variable color by the complex role between each component of antioxidant system and the reduction of consumption thereof.
3, owing to select lower-cost primary antioxidant such as Irganox1010 for use, the overall consumption of oxidation inhibitor also reduces to some extent, thereby can reduce the POM production cost.
Description of drawings
Fig. 1 contains the thermal weight loss rate of different antioxidant systems POM
Fig. 2 contains the POM thermal weight loss speed of different antioxidant systems POM
Fig. 3 contains the burst size of methanal of different antioxidant systems POM
Fig. 4 contains the thermogravimetric analysis of different antioxidant systems POM
Embodiment
Below by embodiment the present invention is carried out concrete description; be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment to the present invention according to the content of the invention described above.
With POM resin 10Kg and four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 30g, three (2,4,-di-tert-butyl-phenyl) phosphorous acid ester 10g, chavicol 10g, trimeric cyanamide 20g, lime carbonate 20g, Zerol 10g add in the high-speed mixer and mix, use exhaust twin screw extruder melting mixing again, extruding pelletization.Screw speed, 50 rev/mins; Barrel temperature, 140-190 ℃.
With POM resin 10Kg and N; N '-two-[3-(3; the 5-di-tert-butyl-hydroxy phenyl) propionyl] hexanediamine 40g, two sulfurous acid (18) the ester 30g of tetramethylolmethane; azanol 30g, Dyhard RU 100 10g, magnesium oxide 10g, two hard esteramides 20g add in the high-speed mixer and mix; use exhaust twin screw extruder melting mixing again, extruding pelletization.Screw speed, 90 rev/mins; Barrel temperature, 150-200 ℃.
With POM resin 10Kg and N; N '-two-[3-(3; the 5-di-tert-butyl-hydroxy phenyl) propionyl] hexanediamine 20g, tetramethylolmethane diphosphite two (2; the 4-di-tert-butyl-phenyl) ester 20g, diphenyl acrylate 10g, urea 70g, Calucium Silicate powder 7g, tetramethylolmethane tristearate 10g add in the high-speed mixer and mix; use exhaust twin screw extruder melting mixing again, extruding pelletization.Screw speed, 150 rev/mins; Barrel temperature, 170-230 ℃.
With POM resin 10Kg and β-(4-hydroxyl-3, the 5-di-tert-butyl-phenyl) propionic acid stearyl alcohol ester 10g, three (2,4,-di-tert-butyl-phenyl) phosphorous acid ester 20g, chavicol 20g, hydrazides 180g, neurosin 10g, two hard esteramides 30g add in the high-speed mixer and mix, use exhaust twin screw extruder melting mixing again, extruding pelletization.Screw speed, 90 rev/mins; Barrel temperature, 170-230 ℃.
Embodiment 5
With POM resin 10Kg and 2,6-di-tert-butyl-4-methy phenol 30g, thiopropionate 10g, diphenyl acrylate 20g, trimeric cyanamide 10g, magnesium hydroxide 7g, tetramethylolmethane tristearate 20g add in the high-speed mixer and mix, use exhaust twin screw extruder melting mixing again, extruding pelletization.Screw speed, 120 rev/mins; Barrel temperature, 140-220 ℃.
Comparison example 1
[3-(the 3-tertiary butyl-5-methyl-4-hydroxy phenyl) propionic acid triethylene Glycol ester 50g, trimeric cyanamide 10g, lime carbonate 20g, Zerol 10g add in the high-speed mixer and mix with POM resin 10Kg and two, use exhaust twin screw extruder melting mixing again, extruding pelletization.Screw speed, 50 rev/mins; Barrel temperature, 180-220 ℃.
Comparison example 2
With POM resin 10Kg and four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 20g, three (2,4,-di-tert-butyl-phenyl) phosphorous acid ester 20g, trimeric cyanamide 10g, lime carbonate 20g, Zerol 10g add in the high-speed mixer and mix, use exhaust twin screw extruder melting mixing again, extruding pelletization.Screw speed, 150 rev/mins; Barrel temperature, 180-220 ℃.
Table 1 is for containing the thermogravimetric analysis characterization parameter of different antioxidant systems POM
Claims (5)
1, a kind of thermal stable polyoxymethylene that contains high-efficiency anti-oxidant is characterized in that the raw material of this heat-stabilised poly formaldehyde is composed of the following components, is by weight:
100 parts of molten polyformaldehyde index 9-27g/10min
0.1～0.3 part of primary antioxidant
1 0.1～0.3 part of auxiliary antioxidant
2 0.05～0.5 part of auxiliary antioxidant
0.05～2 part in formaldehyde absorption agent
0.05～0.5 part in formic acid absorption agent
0.05～0.5 part of lubricant.
2, the thermal stable polyoxymethylene that contains high-efficiency anti-oxidant according to claim 1; it is characterized in that primary antioxidant is four [β-(3; the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester; N; N '-two-[3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl] hexanediamine, β-(4-hydroxyl-3; the 5-di-tert-butyl-phenyl) any in propionic acid stearyl alcohol ester or the 2,6 di tert butyl 4 methyl phenol.
3, the thermal stable polyoxymethylene that contains high-efficiency anti-oxidant according to claim 1, it is characterized in that auxiliary antioxidant 1 is three (2,4,-di-tert-butyl-phenyl) phosphorous acid ester, tetramethylolmethane diphosphite two (2, the 4-di-tert-butyl-phenyl) ester, any in two sulfurous acid (18) esters of tetramethylolmethane or the thiopropionate.
4, the thermal stable polyoxymethylene that contains high-efficiency anti-oxidant according to claim 1 is characterized in that auxiliary antioxidant 2 is any in chavicol, diphenyl acrylate (that is: BMA) or the azanol.
5, as containing the preparation method of the heat-stabilised poly formaldehyde of high-efficiency anti-oxidant as described in one of claim 1-4, it is characterized in that this method may further comprise the steps:
Polyformaldehyde resin 100 weight parts and primary antioxidant 0.1～0.3 weight part, auxiliary antioxidant 10.1～0.3 weight parts, auxiliary antioxidant 20.05～0.5 weight parts, formaldehyde absorption agent 0.05～2 weight part, formic acid absorption agent 0.05-0.5 weight part and lubricant 0.05-0.5 weight part added in the high-speed mixer mix, use exhaust twin screw extruder melting mixing again, extruding pelletization; Screw speed 30-150 rev/min, barrel temperature 140-230 ℃, obtain heat-stabilised poly formaldehyde.
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