CN1066280A - The polyacetal resin that contains cellulose stabiliser - Google Patents
The polyacetal resin that contains cellulose stabiliser Download PDFInfo
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- CN1066280A CN1066280A CN92102673A CN92102673A CN1066280A CN 1066280 A CN1066280 A CN 1066280A CN 92102673 A CN92102673 A CN 92102673A CN 92102673 A CN92102673 A CN 92102673A CN 1066280 A CN1066280 A CN 1066280A
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Abstract
In polyacetal molding composition, mix 0.05-5% (weight) certain crystallite or fibrous cellulose, the result has improved the thermostability of said composition.
Description
The present invention relates to certain polyacetal composition, it is characterized in that having improved stability during processing, the described stability of having improved is owing to mix due at least a crystallite or the fibrous cellulose stablizer in the said composition.
Polyacetal composition is generally understood as homopolymer and the cyclic oligomer of formaldehyde or formaldehyde and the composition of other monomeric multipolymer that comprises based on formaldehyde, the end group of described homopolymer is end capped by esterification or etherificate institute, described monomer will be in main chain at least two adjacent carbonss produce oxyalkylene groups, the end group of multipolymer may be hydroxy terminal or may be by esterification or etherified sealed end.The ratio of comonomer can be up to 20%(weight).With quite high number-average molecular weight (as 10,000 to 100,000) polyacetal is the composition on basis, is using the normally used any processing technology of thermoplastic material, for example compression moulding, injection moulding is extruded, blowing, rotational molding, melt-spinning, punching press and thermoforming are of great use in work in-process that prepare and the finished product.The finished product of being made by said composition has physical properties desired, comprises high rigidity, intensity, low coefficient of friction and good solvent resistance.
But, in some applications, wish work in-process than presumable common polyacetal composition so far or even the polyacetal composition that contains common stablizer have higher stability.Crystallite of the present invention or fibrous cellulose stablizer can make the stability of polyacetal resin be improved.
The crystallite or the fibrous cellulose stablizer that are used in the present composition are to be got by naturally occurring cellulose-derived, and are not fusible at the polyacetal melt processing temperature.The average particle size particle size of Microcrystalline Cellulose stablizer is 100 microns or littler.
United States Patent (USP) 4722662 discloses the manufacture method of thermal destruction being carried out the stabilization copolyoxymethylenes, this method is included in heating multipolymer in the water-bearing media that contains water and disubstituted ether of cellulose so that the formaldehyde terminal of hydrolytically unstable is separated described copolyoxymethylenes from described the containing of containing two substituted cellulose ethers then the hydrolyte.Two substituted celluloses are known thermoplasticss.
United States Patent (USP) 4 111,887 disclose the polyoxymethylene moulding compositions that improves physical properties, and said composition comprises a kind of polymethanal polymer, the mixture of fibrous stiffeners (may comprise cellulosic fibre) and polycarbodiimide.
United States Patent (USP) 3406129 discloses the fusion adulterant of mouldable cellulose polymer compound, and this polymkeric substance contains free hydroxyl group and up to 50% acetal polymer.United States Patent (USP) 3,406,130 disclose the colloidal dispersions of certain solvent of this adulterant and cellulose polymer compound.It is said that composition has improved melt strength and elongation.United States Patent (USP) 3,406,129 special events use greater than 50%(weight) polyacetal is unfavorable to the fusion adulterant.In addition, disclosed Mierocrystalline cellulose in these Patent datas is not neither crystallite is again fibrous mouldable Mierocrystalline cellulose, and therefore it is fusible when the polyacetal melt processing temperature.
Disclose in above-mentioned some patent reference materials of discussing some specialty fibers element has been mixed in the polyacetal composition, the Mierocrystalline cellulose that openly is not used for present composition specific type does not openly mix the plain accident of described types of fibers and has improved gained polyacetal composition stability.
The present invention relates to 0.05 to 5%(weight) at least a crystallite or certain stable polyacetal composition of fibrous cellulose stablizer, this crystallite or fibrous cellulose stablizer all are not fusible when the polyacetal melt processing temperature, all get from naturally occurring Mierocrystalline cellulose again.Above-mentioned weight percentage is that weight with cellulose stabiliser and polyacetal polymer is benchmark.
The feature of the present composition has been improved thermostability.As everyone knows, polyacetal polymer is heat-labile when no stablizer exists.In order to relax this problem, the commercially available typical polyacetal composition in market is all with polymeric amide stable (for example United States Patent (USP) 2,993,025).But have found that polymeric amide in the course of processing can with the formaldehyde reaction that discharges, the reaction product of generation and/or degradation production pollute moulded parts.Therefore, need continually develop the efficient stable agent of polyacetal composition.
Having found that polyacetal can be prepared burden with crystallite or fibrous cellulose stablizer has become to improve the composition of thermostability.The said composition feature has been improved thermostability, hangs down as discharging amount with formaldehyde and weighs.Crystallite and fibrous cellulose stablizer all get from naturally occurring Mierocrystalline cellulose, both are not fusible at the polyacetal melt processing temperature, find that they are used in easy degraded unlike common polymeric amide (or nylon) stablizer in the composition of the present invention.
When mixing in polyacetal as stablizer crystallite or fibrous cellulose, reached above-mentioned improvement.Composition of the present invention is basically by (a) 0.05 to 5%(weight) Microcrystalline Cellulose or fibrous cellulose and (b) 95 to 99.95%(weight) polyacetal polymer forms.Preferred compositions is basically by 0.05 to 2%(weight) crystallite or fibrous cellulose stablizer and 98 to 99.95%(weight) polyacetal polymer forms.Most preferred composition is basically by (a) 0.05 to 1%(weight) crystallite or fibrous cellulose stablizer and 99.0 to 99.95%(weight) polyacetal polymer forms.Above-mentioned all wt percentage ratio is all only based on crystallite or fibrous cellulose stablizer and polyacetal polymer.
Should be understood that composition of the present invention except that comprising polyacetal and stablizer, also comprise other component, properties-correcting agent and additive (as being generally used in the polyacetal mold resin), comprise that promptly co-stabilizer is (for example at United States Patent (USP) 3,960,984,4098, disclosed in 843 and 4766,168), oxidation inhibitor, pigment, tinting material, UV stablizer, toughner, toughener, hindered amine, stablizer, lubricant, glass fibre, nucleator and filler.Should be understood that also some pigment and tinting material itself may have a negative impact to the stability of polyacetal composition.
Polyacetal polymer
Used term polyacetal comprises the homopolymer of the cyclic oligomer of formaldehyde or formaldehyde in the literary composition, and its end group is end capped by esterification or etherificate institute; Formaldehyde or formaldehyde cyclic oligomer and other monomeric multipolymer, described monomer will be in main chain at least two adjacent carbonss produce oxyalkylene groups, the end group of multipolymer may be hydroxy terminal or may be by esterification or etherified sealed end.
In the present composition used polyacetal may be branching or line style, its number-average molecular weight is generally 10,000 to 100,000, preferably 20,000 to 75,000.Molecular weight with gel permeation chromatography-to be furnished with nominal pore size in 160 ℃ of uses in the cresols be 60 and 1, supporting can conveniently measurement of Du pont psm bimodal column of 000A.According to desired physical properties and processing characteristics, although can use higher or than the polyacetal of low average molecular weight, the optimum balance of well blend when but the polyacetal of above-mentioned molecular-weight average preferably provides each component melts is blended into composition, thereby has the physicals combination that needs most by the moulded parts that said composition is made.
As above indication, polyacetal be homopolymer both, multipolymer, their mixture again.Multipolymer can contain one or more comonomers, for example generally is used for preparing those comonomers of polyacetal component.More generally used comonomer comprises the cyclic addition product of the alkylene oxide of 2-12 carbon atom and they and formaldehyde.The amount of comonomer will be not more than 20%(weight), preferably be not more than 15%(weight), most preferably be about 2%(weight).Most preferred comonomer is an oxyethane.In general polyacetal homopolymer is better than multipolymer, because homopolymer has bigger rigidity and intensity.Preferred polyacetal homopolymer comprises ester or the ether group end-blocking that terminal hydroxy groups has been formed by chemical reaction, forms acetic ester especially respectively or methoxy group is advisable.
Crystallite or fibrous cellulose stablizer
Microcrystalline Cellulose and fibrous cellulose stablizer all contain formaldehyde activity hydroxy group all by naturally occurring cellulose-derived, and all are not fusible at the polyacetal melt processing temperature.Find that the both is effective stablizer of polyacetal.Wherein Microcrystalline Cellulose is preferably.
Microcrystalline Cellulose is known in the prior art, and available on market.At United States Patent (USP) 3,023, be described in detail (being incorporated herein by reference) herein in 104.Wherein be about arriving " cellulose crystallite condensation product ".Microcrystalline Cellulose is also at Hydrolysis and crystallization of collulose " (Industrial and Engineering chemistry; Vol.42 502-507(1950) narrated in.
With United States Patent (USP) 3,023,104 the report consistent, the Microcrystalline Cellulose that is used for the present composition can obtain maybe preparing from the standard technique of naturally occurring Mierocrystalline cellulose acidolysis from industrial source.Arbitrary situation in these two kinds, Microcrystalline Cellulose all can run into the purifying requirement of narrating below.In cellulosic acidolysis, any amorphous portion of the plain chain of acid dissolving protofibril, remaining not dissolve part be to be in granular non-fibrous or crystallized form in acidolysis, and this form is the result of constantly breaking of fine structure between plain crystallization of protofibril and the amorphous domain.Known that the insoluble part that is in crystallized form is not fusible at the polyacetal melt processing temperature.The melt processing temperature of polyacetal generally is no more than 280 ℃.Carrying out the method that acidolysis prepares Microcrystalline Cellulose by Mierocrystalline cellulose is known in the prior art, as at United States Patent (USP) 3,023, narrates among the 2nd hurdle in 104 and the embodiment.
The Microcrystalline Cellulose that is used for the present composition has certain stable polymerization degree.At United States Patent (USP) 3,023, the stable polymerization degree has been described in 104.Especially narrating Mierocrystalline cellulose stands acidolysis and reaches basically weighing apparatus after sometime and decide molecular weight.In other words, it is meant repeating unit or the monomer number (being designed to anhydroglucose unit sometimes) that constitutes cellulose materials, and it is fixed to become suitable weighing apparatus.Obviously the polymerization degree of material is stable, therefore claims the stable polymerization degree.
With United States Patent (USP) 3,023,104 is disclosed consistent, and the average stable polymerization degree that is used for the Microcrystalline Cellulose of the present composition is advisable with 125 to 375 anhydroglucose unit.At ideal situation, all material in this scope should have the identical polymerization degree, but this is difficult, if can not reach, the actual polymerization degree of at least 85% material is not more than 550 and is advisable to be not less than 50 orders.Average stable polymerization degree preferably is 125～375, the actual polymerization degree of at least 90% material should be in 75 to 500 scopes, the actual polymerization degree of at least 95% the material that is more preferably is in 75 to 450 scopes, the average stable polymerization degree of used Microcrystalline Cellulose is preferred in 200 to 300 scopes among the present invention, the actual polymerization degree of at least 90% material is in 75 to 550 scopes, and the most preferred scope of average stable polymerization degree that is used for Microcrystalline Cellulose of the present invention is 175 to 225.
As United States Patent (USP) 3,023, reported that the average particle size particle size that Microcrystalline Cellulose has usually is not more than 300 microns in 104.For finishing purpose of the present invention, average particle size particle size is that 50% particle is greater than mean value, and 50% particle is less than mean value.Average particle size particle size can be by standard technique such as microscopy, gravity settling, and screen analysis and electron microscope are measured.The preferred method of measuring particle size is a gravity settling.
The stability that has been found that composition of the present invention increases along with the reduction of the average particle size particle size of Microcrystalline Cellulose.Therefore, although the average particle size particle size of Microcrystalline Cellulose, is used for preferably 100 microns or littler of the average particle size particle size of Microcrystalline Cellulose of the present invention, more preferably 50 microns or littler up to about 300 microns, even more preferably 25 microns or littler, most preferred is 10 microns or littler.
Fibrous cellulose is known in the prior art, and commercially available.It can usually be prepared by naturally occurring fiber by the technology that is easy to obtain for the those of skill in the art in present technique field.For example, then purify then, make fibrous cellulose thus to satisfy following required purity by the atomizing wood pulp.Fibrous cellulose also is naturally occurring material, and its example is a linters, and fibrous cellulose generally exists with the flat belt-like form.The width of the fibrous cellulose of these flat belt-likes and thickness are not quite strict (reaching embodiment result).But in general, the width of these flat belt-likes is by on average about 25 microns, and its thickness is by on average being about 6 microns.The length of the flat belt-like of fibrous cellulose is (the reaching embodiment result) of strictness quite, and the fibrous cellulose of the average fiber length in city's field energy has been bought this scope comprises from 300 microns dropping to less than 22 microns.Although the length of average fiber is not quite strict, the stability that hope produces is increased because the following general who has surrendered of average fiber length causes the surface-area of fibrous cellulose stablizer along with the decline of average fiber length improves.
The purification of stablizer
Because the Microcrystalline Cellulose stablizer and the essentially no Derlin unstable compounds that makes of fibrous cellulose stablizer of composition of the present invention, so this is very important.
In stabilization ester end-blocking or the end capped polyacetal homopolymer of part ester, Microcrystalline Cellulose stablizer and fibrous cellulose stablizer are substantially free of and make the unsettled alkaline matter of polyacetal.Preferably remove the alkaline impurities in the not fusible polymer stabilizer, make its content be not more than 50ppm, most preferably be not more than 10ppm.For crystallite and fibrous cellulose stablizer, have found that to allow higher alkaline impurities content, but this content preferably is not more than 200ppm, more preferably is not more than 10ppm.Stable basically all by ether capped Copolyacetal or homopolymer in, can allow to contain the alkaline matter of higher concentration.In addition, think, can allow to contain high relatively amount if impurity is weakly alkaline.
In stable homopolymer and multipolymer polyacetal, should make the acidic impurities in Microcrystalline Cellulose stablizer and the fibrous cellulose stablizer reduce to minimum value.For crystallite and fibrous cellulose stablizer, have found that the acidic impurities that can allow high level, but this content preferably is not more than 250ppm, more preferably no more than 10ppm.As the same with the situation of alkaline impurities, think if impurity is slightly acidic, can allow to contain high relatively amount.
When the acidity in Microcrystalline Cellulose stablizer or fibrous cellulose stablizer and/or the amount of alkaline impurities are stablized even as big as polyacetal composition is lost, before being incorporated into the present composition, stablizer should carry out purifying.The stablizer that is used in the present composition can be by carrying out purifying with suitable liquid such as methyl alcohol and/or water washing.Easy volatile impurity in crystallite or fibrous cellulose stablizer can be removed with vacuum drying oven.
Except top said, may be present in going in the market gained crystallite that is used in the present composition or the fibrous cellulose stablizer stablize impurity can be via (1) 1～10%(weight) the pH value of Microcrystalline Cellulose or fibrous cellulose aqeous suspension, (2) non-volatile ash oontent, and/or (3) heavy metal content detects.
More especially, in order to obtain optimum, suggestion is used in 1～10%(weight in the present composition) the pH value of Microcrystalline Cellulose or the fibrous cellulose aqeous suspension scope that is suitable for the homopolymer polyacetal is 5～7, the scope that is suitable for the multipolymer polyacetal is 5～8, and the scope that the pH value of preferred suspension is suitable for homopolymer or multipolymer polyacetal is 5～7.Non-volatile ash content (carrying out ashing more than or equal to the 800 ℃) amount in Microcrystalline Cellulose or the fibrous cellulose of also advising is lower than 0.25%, more preferably less than 0.1%, most preferably is lower than 0.02%.Advise that also the heavy metal content in Microcrystalline Cellulose and the fibrous cellulose is lower than 10ppm.As mentioned above, for obtaining high thermal stability, Mierocrystalline cellulose used in this invention should remain in 5～8 the scope.
Preparation of compositions
The powerful mixing equipment that composition of the present invention can be generally used for preparing the thermoplastic polyacetal composite by use mixes stablizer and polyacetal polymer in the temperature that is higher than the polyacetal polymer fusing point and prepares, described mixing equipment is rubber mixing mill for example, Banbury mixer such as Banbury mixer and " Brabender mixing roll; single-blade or many oars stir Banbury mixer (have the indirect heating chamber or with rubbing); " KO formula continuous kneading machine "; multiple roll cartridge type mixing machine is as " Farrel-continuous mixer "; injection moulding machine; forcing machine, single screw rod and twin screw extruder, with rotary extruding and reversion type forcing machine, mutual meshing or non-mutual meshing forcing machine, these equipment can use separately, also can with static mixer, mix torpedo shape device and/or various device and be used in combination, for example the valve that designs for this purpose to increase internal pressure and/or mixture strength, gate or screw rod.The preferred forcing machine that uses mixes certainly and is to carry out under the temperature that polyacetal obviously degrades being lower than.
Can use any some kinds of ordinary methods to make moulded products by the present composition, these methods comprise compression moulding, injection moulding, extrusion molding, blowing, rotoforming, melt-spinning and thermoforming.The preferred injection moulding process that uses, the example of moulded products comprises sheet material, section bar, the bar shaped stock, film, long filament, fiber, bandage, band pipe and tubing, this moulded products can carry out aftertreatment by orientation, stretching, coating, annealing, japanning, lamination and spraying plating.This moulded products and its waste product can be milled and molding again.
Be used to prepare the present composition and comprise that by the processing conditions of its moulded products of making melt temperature is about 170-260 ℃, be preferably 185-240 ℃, most preferably be 200-230 ℃.When the injection moulding present composition, molding temperature is generally 10-120 ℃, is preferably 10-100 ℃, most preferably is about 50-90 ℃.
Embodiment
In the following embodiments, some comparative example that provides specific embodiments of the invention and compare with the embodiment of limited range of the present invention control experiment outward.The present composition is characterised in that and has improved stability as can be seen.Unless otherwise prescribed, all temperature all are centigradetemperatures, do not carry out suitable conversion and change by original the measuring of International System of Units (SI units).Crystallite in the polyacetal or fibrous cellulose
In the following embodiments, crystallite or fibrous cellulose all obtain from naturally occurring Mierocrystalline cellulose, and they are used as the stablizer of polyacetal.
The polyacetal polymer that uses in the following example is one of following:
(1) polyacetal " E "-number-average molecular weight is about 40,000 the end capped homopolymer of acetic ester.
(2) polyacetal " F "-number-average molecular weight is about 33,000 the end capped homopolymer of acetic ester.
The Microcrystalline Cellulose stablizer that uses in the following example is one of following:
(1) " MC11 " is the Microcrystalline Cellulose that a kind of market can get, and it is that to become average particle size particle size by the air-flow abrasive blasting be about 11 microns.
(2) " MC20 " is that a kind of average particle size particle size is the Microcrystalline Cellulose that about 20 microns market can get.
(3) " MC50 " is that a kind of average particle size particle size is the Microcrystalline Cellulose that about 50 microns market can get.
(4) " MC100 " is that a kind of average particle size particle size is the Microcrystalline Cellulose that about 100 microns market can get.
The average stable polymerization degree of the every kind of Microcrystalline Cellulose that uses in the following example is 190 to 200, and the every kind of Microcrystalline Cellulose that uses in the following example contains less than the 10ppm heavy metal with less than 0.05% ash.The pH value of 10% aq suspension that is used for every kind of Microcrystalline Cellulose of following example is about 5.5 to 7.
Be used in fibrous cellulose in the following example and be a kind of in following:
(1) " FC1 " advances the fibrous cellulose that a kind of average fiber length can get less than the market of 22 microns and the about 0.20%-0.25% ash content of ash oontent.
(2) " FC2 " is the fibrous cellulose that a kind of market can get, and its average fiber length is less than 90 microns, and ash oontent is about 0.15%, pH value (measuring) with 5% and 10% Mierocrystalline cellulose aq suspension be 5.2 and
(3) " FC
3" be the fibrous cellulose that a kind of market can get, its average fiber length is about 300 microns, ash oontent be about 0.16% and pH value (measuring) with 5% Mierocrystalline cellulose aq suspension be 5.95.
Except that above-mentioned cellulose stabiliser, the stablizer that is used in the example is as follows in addition:
(1) " nylon B " be nylon 66, nylon 6/10 and nylon 6 respectively by the terpolymer of 33/23/43 ratio and
(2) " EVOH " contains 29%(weight) ethene and 71%(weight) the ethylene/vinyl alcohol copolymer of vinyl alcohol, be 9500 pools at 210 ℃ of its apparent melt viscosities, be purified to ash oontent and be lower than 10ppm.
The oxidation inhibitor that uses in example is a kind of in following:
(1) " oxidation inhibitor B " be triethylene glycol two (3-(3 '-tertiary butyl-4 '-hydroxyl-5 '-methyl amyl) propionic ester and
(2) " oxidation inhibitor C " is N, N '-hexa-methylene two (3,5-di-t-butyl-4-hydroxyl hydrocinnamamide).
In following example, the thermostability of composition is to use above-mentioned heat segregation formaldehyde (TEF) testing sequence to measure, and except some examples, test is carried out at 259 ℃.Heat segregation formaldehyde the results are shown in the following data sheet with " wt%CH
2O(is at X ℃) expression the hurdle head under, sample is also illustrated in the data sheet heat-up time.Long period heating gained result demonstrates the improvement of present composition permanent stability especially.
Embodiment 1-13 crystallite or fibrous cellulose are to the influence of the thermostability of polyacetal fine hair (FLUFF)
Embodiment 1-13 and reference examples C
1-C
2Component list in below the table I in.In each example, powdery Microcrystalline Cellulose or flour shape Mierocrystalline cellulose are added in the polyacetal fine hair, shake mixedly, and carry out above-mentioned heat segregation formaldehyde (CH
2O) test.Test-results is listed in the table below in the I.Find out obviously that from the result Microcrystalline Cellulose and fibrous cellulose are all to improving the thermostability role of polyacetal.
The influence of crystallite or fibrous cellulose in the table I polyacetal fine hair
Embodiment sequence number PAC stablizer CH
2@250 ℃ of O%(weight)
%(weight) %(weight) 15 minutes 30 minutes 60 minutes
C1 100E - 0.26 1.08 2.16
1 99.8E 0.2MC20 0.29 0.69 1.12
2 99.5E 0.5MC20 0.15 0.42 0.77
3 99.0E 1.0MC20 0.11 0.36 0.69
4 98.0E 2.0MC20 0.09 0.38 0.85
5 95.0E 5.0MC20 0.09 0.64 1.17
C2 100F - 0.72 1.02 2.08
6 99.75F 0.25MC20 0.38 0.28 0.68
7 99.5F 0.5MC20 0.24 0.32 0.52
8 99.0F 1.0MC20 0.24 0.26 0.54
9 98.0F 2.0MC20 0.20 0.43 0.54
10 99.75F 0.25FCl 0.38 0.64 0.92
11 99.5F 0.50FCl 0.34 0.63 0.96
12 99.0F 1.0FCl 0.35 2.22 1.34
13 98.0F 2.0FCl 0.30 1.24 1.70
The PAC=polyacetal
Embodiment 14-19 Microcrystalline Cellulose is to the influence of polyacetal thermostability (melt-processed)
Embodiment 14-19 and reference examples C
3-C
6Each component be listed in the table below among II A and the II B.To each example, each component is 150 ℃-180 ℃ at the machine barrel extrusion temperature, and the die head extrusion temperature is that 200 ℃ and spiro rod rate are to be mixed together with fusion in 150 rev/mins 28 millimeters Werner and the pfieiderer twin screw extruder to cooperate.The temperature of the melt of extrusion die is 221-224 ℃ in these examples, cooperates the melt of sample with above-mentioned TEF experimental test.The results are shown among following table II A and the II B, the result shows that in the long period test, the thermostability of Microcrystalline Cellulose polyacetal that stablizer gives (by on average) is than the Heat stability is good that adopts common stablizer.
The influence of table II B Microcrystalline Cellulose in the polyacetal melt-processed
Embodiment sequence number PAC stablizer Wt% wt%CH
2O @259 ℃
%(weight) %(weight) AO is 15 minutes 30 minutes
16 98.9E 1.0MC11 0.1B 0.15 0.63
17 99.65E 0.25MC11 0.1B 0.21 0.74
18 99.4E 0.5MC11 0.1B 0.27 0.87
19 99.4E 0.5MC20 0.1B 0.20 0.66
C5 99.7E 0.2EVOH 0.1B 0.18 0.99
C6 98.9E 1.0EVOH 0.1B 0.07 0.52
The PAC=polyacetal
Embodiment 20 and C
8Fibrous cellulose is to the influence of the thermostability (melt-processed) of polyacetal
Embodiment 20 and reference examples C
7-C
8Each component be listed in the table below in the III, to each embodiment, be same as under the condition of routine 14-19, each component is mixed together, fusion cooperates also extrudes, each sample carries out above-mentioned TEF test.
The results are shown in the following table III, reference examples 8 has shown the result who impure fibrous cellulose (the pH value is lower than 5.5) is added to gained in the polyacetal.
The influence of table III fibrous cellulose in the melt-processed polyacetal
Embodiment sequence number PAC stablizer Wt% wt% CH
2O @259 ℃
%(weight) %(weight) AO is 15 minutes 30 minutes
20 94.90F 5.0FC3 0.095C 0.03 0.27
C7 99.1F 0.8EVOH 0.1C 0.06 0.47
C8 94.90F 5.0FC2 0.095C 0.68 3.49
The PAC=polyacetal
Embodiment 21-26 contains the polyacetal of the Microcrystalline Cellulose of various particle sizes
Embodiment 21-26 and reference examples C
9Each the group respectively among following table IV A and the IV B.Each component is mixed together and the fusion cooperation by routine 14-19 is described, and each sample carries out above-mentioned TEF test.
Embodiment 21-23 the results are shown among the following table IV A.The result shows that the average particle size particle size along with Microcrystalline Cellulose reduces, and the stability of polyacetal composition improves.
Embodiment 24-26 the results are shown among the following table IV B, and in these examples, the test period of gained TEF value was longer than 30 fens.The result shows that once more the Microcrystalline Cellulose average particle size particle size is more little, and the polyacetal thermostability is good more.
Claims (5)
1, a kind of thermoplastic polyacetal composite, it basic composition is
(a) 0.05-5% (weight) be selected from Microcrystalline Cellulose and fibrous cellulose stablizer and
(b) polyacetal polymer of 95-99.95% (weight), it is defined as above-mentioned percentage ratio is to be benchmark with component (a) and total amount (b), wherein the average particle size particle size of Microcrystalline Cellulose is 100 microns or littler.
2, according to the composition of claim 1, wherein polyacetal is a homopolymer, and the polymkeric substance of component (a) is gone up no acidic material or alkaline matter substantially.
3, according to the composition of claim 1 or 2, wherein polyacetal polymer is a multipolymer.
4, according to the composition of claim 1 or 2, also comprise at least a co-stabilizer, oxidation inhibitor, pigment, dyestuff, toughener, ultra-violet stabilizer, hindered amine stabilizer, glass fibre, lubricant, nucleator, toughner and filler.
5, claim 1 or 2 the composition application that is used to make moulded products.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/327,664 US5011890A (en) | 1989-03-17 | 1989-03-17 | Polyacetal resins containing non-meltable polymer stabilizers |
| US327,664 | 1989-03-17 | ||
| US48360390A | 1990-02-22 | 1990-02-22 | |
| US483,603 | 1990-02-22 | ||
| CN90102472A CN1017711B (en) | 1989-03-17 | 1990-03-17 | Polyacetal resins containing non-meltable polymer stabilizers |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN90102472A Division CN1017711B (en) | 1989-03-17 | 1990-03-17 | Polyacetal resins containing non-meltable polymer stabilizers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1066280A true CN1066280A (en) | 1992-11-18 |
| CN1024804C CN1024804C (en) | 1994-06-01 |
Family
ID=27178972
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92102673 Expired - Lifetime CN1024804C (en) | 1989-03-17 | 1992-04-10 | Polyacetal resins containing cellulose stabilizers |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1024804C (en) |
-
1992
- 1992-04-10 CN CN 92102673 patent/CN1024804C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1024804C (en) | 1994-06-01 |
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