CN105885339B - Antioxidant composition and modified polyformaldehyde resin composition and modified polyformaldehyde resin and preparation method thereof - Google Patents
Antioxidant composition and modified polyformaldehyde resin composition and modified polyformaldehyde resin and preparation method thereof Download PDFInfo
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Abstract
本发明提供了一种抗氧剂组合物和改性聚甲醛树脂组合物以及改性聚甲醛树脂及其制备方法。所述抗氧剂组合物含有异氰酸酯类化合物、自由基捕捉剂和吸醛剂，其重量份分别为(0.5‑2)、(0.5‑1)、(0.5‑1.3)。所述自由基捕捉剂选自2,2,6,6‑四甲基哌啶‑氮‑氧化物、2,2‑二苯基‑1‑三硝基苯肼、对苯醌、四甲基苯醌、N‑叔丁基‑α‑苯基硝酮和3‑2‑(2‑溴乙酰氨基)乙酰胺]‑2,2,5,5‑四甲基‑1‑吡咯烷基氧化物中的至少一种，所述吸醛剂可以为聚酰胺。当将聚甲醛树脂采用上述抗氧剂组合物进行改性时，能够非常显著地提高聚甲醛树脂的热稳定性。The invention provides an antioxidant composition, a modified polyoxymethylene resin composition, a modified polyoxymethylene resin and a preparation method thereof. The antioxidant composition contains an isocyanate compound, a free radical scavenger and an aldehyde absorbing agent, and the parts by weight are (0.5-2), (0.5-1), and (0.5-1.3) respectively. The free radical scavenger is selected from 2,2,6,6-tetramethylpiperidine-nitrogen-oxide, 2,2-diphenyl-1-trinitrophenylhydrazine, p-benzoquinone, tetramethyl Benzoquinone, N-tert-butyl-α-phenylnitrone and 3-2-(2-bromoacetamido)acetamide]-2,2,5,5-tetramethyl-1-pyrrolidinyl oxide At least one of the aldehyde absorbing agent can be polyamide. When the polyoxymethylene resin is modified with the above antioxidant composition, the thermal stability of the polyoxymethylene resin can be significantly improved.
Description
Technical field
The present invention relates to a kind of antioxidant compositions, a kind of modified polyformaldehyde resin group containing the antioxidant composition
Close object, a kind of preparation method of modified polyformaldehyde resin and the modified polyformaldehyde resin that is prepared by this method.
Background technique
Polyformaldehyde (POM) is due to special molecular structure, and thermal stability is poor, thus the thermostabilization of POM is at it
Most important, most basic key technology during synthesis and processed and applied.POM is easy to happen heat effect during melt-processed
It is acted on oxygen, molecule, which once generates free radicals, will occur chain rupture, and continuous piptonychia aldehyde reaction then occurs.And formaldehyde and
Thermal decomposition process will be promoted by the micro formic acid that oxidation of formaldehyde generates again, greatly accelerate piptonychia aldehyde reaction, until big point of POM
Subchain is decomposed totally.Antioxidant is the thermal oxidation stability auxiliary agent that polymer material is most important, most basic.Antioxidant is poly- by capturing
It closes the free radical that objects system generates under heat effect, oxygen effect and reaches stable to interrupt whole system autoxidation cyclic process
Purpose.Frequently with the phenolic antioxidant of Irganox259 and Irganox245 as antioxidant in domestic and international POM production application,
Studies have shown that the kind antioxidant has significant thermostable effect to POM, the thermal stability of POM can be increased substantially, is suitable
Improve the excellent antioxidant of the thermal oxidation stability performance of POM.But it in order to achieve the effect that preferable heat resistanceheat resistant oxygen effect, usually needs
The antioxidant of larger dosage is wanted, and the price of this kind antioxidant is typically more expensive, therefore has become influence POM production cost
One of principal element.
Summary of the invention
The purpose of the invention is to overcome the existing method of use to carry out the upper of thermal stability modification to acetal resin
Defect is stated, and provides a kind of do not contain or only containing the antioxidant composition of conventional antioxidant, one kind on a small quantity containing described
The modified polyformaldehyde resin composition of antioxidant composition, a kind of preparation method of modified polyformaldehyde resin and by party's legal system
Standby obtained modified polyformaldehyde resin.
Specifically, antioxidant composition provided by the invention contains isocyanate ester compound, free radical scavenger and suction
Aldehyde agent, parts by weight are respectively (0.5-2), (0.5-1), (0.5-1.3).
Modified polyformaldehyde resin composition provided by the invention contains polyformaldehyde and above-mentioned antioxidant composition, specifically,
The composition contains polyformaldehyde, isocyanate ester compound, free radical scavenger and inhales aldehyde agent, parts by weight are respectively 100,
(0.5-2)、(0.5-1)、(0.5-1.3)。
The preparation method of modified polyformaldehyde resin provided by the invention include by above-mentioned modified polyformaldehyde resin composition in
Melting extrusion is granulated at 180-225 DEG C, is then carried out and dry.
The present invention also provides modified polyformaldehyde resins prepared by the above method.
The present inventor by further investigation after find, when polyformaldehyde simultaneously use isocyanate ester compound and
When free radical scavenger and suction aldehyde agent are modified, the thermal stability of polyformaldehyde can be improved very significantly.Speculate its reason,
May be due to: on the one hand, the isocyanate ester compound in the antioxidant composition can not only remove acetal resin
In remaining lewis acid (lewis acidic residual is easy to cause polyformaldehyde to degrade), but also can be with the terminal hydroxy group of polyformaldehyde
Directly react during melt extrusion, generate relatively stable amino methyl ester bond, in acetal resin it is original with
And newly-generated unstable end-group is closed, to reduce the content of unstable end-group in acetal resin, is made it have
Lower burst size of methanal and superior thermal stability；On the other hand, the free radical scavenger and inhale aldehyde agent addition not
The conversion of terminal hydroxy group in lewis acidic removing and acetal resin can only be promoted, but also can be improved the antioxygen of system
Change effect, to be very beneficial for the raising of acetal resin thermal stability.
A preferred embodiment of the invention, when the polyamide contained in the antioxidant composition is copolymerization acyl
When amine, it is more advantageous to the raising of acetal resin thermal stability.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
Antioxidant composition provided by the invention contains isocyanate ester compound, free radical scavenger and inhales aldehyde agent,
Parts by weight are respectively (0.5-2), (0.5-1), (0.5-1.3).
The present invention is not particularly limited the type of the isocyanate ester compound, such as can be selected from diphenylmethyl
Alkane -4,4 '-diisocyanate (MDI), 2,4 tolylene diisocyanate (TDI), paraphenylene diisocyanate (PPDI), oneself two isocyanides
At least one of acid esters (HDI), isophorone diisocyanate (IPDI) and triphenylmethane triisocyanate.It is easy to get from raw material
The angle of property is set out, and the isocyanate ester compound is particularly preferably 4,4 '-diisocyanate of diphenyl methane-and/or 2,
4- toluene di-isocyanate(TDI).
The antioxidant composition provided according to the present invention, the free radical scavenger are particularly preferably 2,2,6,6- tetramethyls
Piperidines-nitrogen-oxide, 2,2- diphenyl -1- trinitrophenyl-hydrazine, 1,4-benzoquinone, tetramethyl-benzoquinone, N- tert-butyl-α-phenyinitrone
At least one of with 3-2- (2- bromacetamido) acetamide] -2,2,5,5- tetramethyl -1- pyrrolidinyl oxide.From original
Expect it is ready availability from the point of view of, the free radical scavenger is particularly preferably 2,2,6,6- tetramethyl piperidines-nitrogen-oxide
(TEMPO)。
The antioxidant composition provided according to the present invention, the suction aldehyde agent are preferably selected from melamine and polyamide extremely
Few one kind.
Wherein the polyamide can be existing various polyamide, for example, can be homopolymerization polyamide, or altogether
Polyester-polyamide, preferably copolyamide.The present inventor has found after further investigation, when the polyamide is copolymerization
When polyamide, the thermal stability of polyformaldehyde can be improved extremely significantly.The example of the equal polyester-polyamide includes but is not limited to:
At least one of polyamide 6, polyamide 66, polyamide 610 etc..The example of the copolyamide includes but is not limited to: poly-
At least one of amide PA6/12, polyamide PA10/10, polyamide 6/66/1010, polyamide 548, polyamide 6/66 etc..
The antioxidant composition provided according to the present invention, in inhaling aldehyde agent, the parts by weight of the melamine and polyamide
Respectively (0.5), (0-1), particularly preferably, it is described to inhale the mixture that aldehyde agent is polyamide and melamine.When the antioxygen
When containing polyamide and melamine in agent composition simultaneously, acetal resin can be made to obtain superior thermal stability.It is special
Not preferably, the parts by weight of the melamine and polyamide are respectively (0.5), (0.8-1).
The antioxidant composition provided according to the present invention, it is preferable that the antioxidant composition also contain antioxidant and/or
Acid absorbent is more advantageous to further increasing for polyformaldehyde thermal stability in this way.
The present invention is not particularly limited the type and dosage of the antioxidant, for example, the antioxidant can be phenol
At least one of kind antioxidant, amine antioxidants and phosphite ester antioxidant.Wherein, the example packet of the phenolic antioxidant
It includes but is not limited to: 2- tert-butyl hydroquinone (antioxidant TBHQ), 1,3,5- trimethyl -2,4,6- (3,5- di-t-butyl -4- hydroxyl
Base benzyl) benzene (antioxidant 1330), triethylene-glycol be bis- [β-(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyl) propionic ester]
(antioxidant 245), four [3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters (antioxidant 1010), 2,2 '-Asias
At least one of methyl-bis- (4- methyl-6-tert-butylphenol) (antioxidant 2246s) etc..The example packet of the amine antioxidants
It includes but is not limited to: N- (1,3- dimethylbutyl)-N '-diphenyl-para-phenylene diamine (antioxidant 4020), N- cumenyl-N '-phenyl
At least one of p-phenylenediamine (antioxidant 4010NA), N- phenyl-2-naphthylamine (antioxidant D) etc..The phosphorous acid salt is anti-
The example of oxygen agent includes but is not limited to: three (2,4- di-tert-butyl-phenyl) phosphite esters (irgasfos 168).In addition, when described anti-
When oxygen agent composition contains antioxidant, the parts by weight of the antioxidant and isocyanate ester compound be preferably respectively (0.5),
(0.5-2)。
The present invention is not particularly limited the type of the acid absorbent, for example, the acid absorbent can be selected from hydroxide
At least one of magnesium, calcium hydroxide, calcium stearate, odium stearate and magnesium stearate.In addition, when the antioxidant composition contains
When having acid absorbent, the parts by weight of the acid absorbent and isocyanate ester compound are preferably respectively (0.5), (0.5-2).
Modified polyformaldehyde resin composition provided by the invention contains polyformaldehyde and above-mentioned antioxidant composition.Relative to
The polyformaldehyde of 100 parts by weight, resin combination of the invention contain each component of the antioxidant composition of aforementioned weight.
In the free radical scavenger, the type of isocyanate ester compound and polyamide and the antioxidant composition
The type and dosage of remaining component have been described herein above, and therefore not to repeat here.
The preparation method of modified polyformaldehyde resin provided by the invention include by above-mentioned modified polyformaldehyde resin composition in
Melting extrusion is granulated at 180-225 DEG C, is then dried.
The preparation method of the modified polyformaldehyde resin provided according to the present invention, this method are further preferably included in melting extrusion and make
Before grain, first each component in the modified resin composition is uniformly mixed, is more advantageous to the acetal resin heat in this way
The raising of stability.The step of melting extrusion is granulated usually can be in existing single screw extrusion machine or double screw extruder
Middle progress.In addition, the condition of the drying, which generally includes dry temperature, to be 50-100 DEG C, the dry time can be 1-
10 hours.
The present invention also provides modified polyformaldehyde resins prepared by the above method.
The present invention will be described in detail by way of examples below.
Embodiment 1
The embodiment is for illustrating antioxidant composition and modified polyformaldehyde resin composition provided by the invention and changing
Property acetal resin and preparation method thereof.
By 100 parts by weight of polyoxymethylene resins (being purchased from coal chemical industry branch company, Shenhua Ning Mei group, trade mark MC90G, similarly hereinafter),
0.5 parts by weight diphenyl methane -4,4 '-diisocyanate (MDI) (Alfa Aesar company, similarly hereinafter), 1 parts by weight 2,2,6,6-
Tetramethyl piperidine-nitrogen-oxide (TEMPO), bis- [β-(the 3- tertiary butyl-4-hydroxies-of 0.5 parts by weight antioxidant triethylene-glycol
5- aminomethyl phenyl) propionic ester] (antioxidant 245), 0.5 parts by weight melamine, 0.5 parts by weight magnesium hydroxide adopt after evenly mixing
It is granulated with vented twin-screw extruder melting extrusion, extrusion temperature is 180 DEG C -225 DEG C, and screw speed is 100 revs/min, is made
It is 2 hours dry at 80 DEG C after grain, obtain modified polyformaldehyde resin G1.
Embodiment 2
The embodiment is for illustrating antioxidant composition and modified polyformaldehyde resin composition provided by the invention and changing
Property acetal resin and preparation method thereof.
By 100 parts by weight of polyoxymethylene resins, 2 parts by weight diphenyl methanes -4,4 '-diisocyanate (MDI), 1 parts by weight
2,2,6,6- tetramethyl piperidine-nitrogen-oxide (TEMPO), 1 weight parts of polyamide PA6/12 are (purchased from the limited public affairs of EMS Switzerland chemistry
Department, trade mark Grilamid, similarly hereinafter), four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] season of 0.5 parts by weight antioxidant
Doutrate (antioxidant 1010), 0.5 parts by weight melamine, 0.5 parts by weight magnesium hydroxide use exhaust after evenly mixing
Double screw extruder melting extrusion be granulated, extrusion temperature be 180 DEG C -225 DEG C, screw speed be 100 revs/min, after granulation then at
It is 2 hours dry at 80 DEG C, obtain modified polyformaldehyde resin G2.
Embodiment 3
The embodiment is for illustrating antioxidant composition and modified polyformaldehyde resin composition provided by the invention and changing
Property acetal resin and preparation method thereof.
By 100 parts by weight of polyoxymethylene resins, 2 parts by weight 2,4 tolylene diisocyanates (TDI), 0.5 parts by weight 2,2,6,
6- tetramethyl piperidine-nitrogen-oxide (TEMPO), 0.8 weight parts of polyamide PA6/12,0.5 parts by weight antioxidant two, three second two of contracting
Alcohol bis- [β-(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyl) propionic ester] (antioxidant 245), 0.5 parts by weight melamines, 0.5 weight
Amount part magnesium hydroxide, 0.5 parts by weight of calcium stearate use vented twin-screw extruder melting extrusion to be granulated after evenly mixing, squeeze
Temperature is 180 DEG C -225 DEG C out, and screw speed is 100 revs/min, 2 hours dry at 80 DEG C after granulation, obtains being modified poly- first
Urea formaldehyde G3.
Comparative example 1
The comparative example is used to illustrate the antioxidant composition and modified polyformaldehyde resin composition and modified poly- first of reference
Urea formaldehyde and preparation method thereof.
Modified polyformaldehyde resin is prepared according to the method for embodiment 1, unlike, it is added without diphenyl methane -4,4 '-two
Isocyanates (MDI) and 2,2,6,6- tetramethyl piperidines-nitrogen-oxide (TEMPO), specifically, by 100 parts by weight of polyoxymethylene trees
Bis- [β-(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyl) the propionic ester] (antioxidant of rouge, 0.5 parts by weight antioxidant triethylene-glycol
245), 0.5 parts by weight melamine, 0.5 parts by weight magnesium hydroxide use vented twin-screw extruder to melt after evenly mixing
Extruding pelletization, extrusion temperature are 180 DEG C -225 DEG C, and screw speed is 100 revs/min, 2 hours dry at 80 DEG C after granulation,
Obtain reference modified polyformaldehyde resin DG1.
Comparative example 2
The comparative example is used to illustrate the antioxidant composition and modified polyformaldehyde resin composition and modified poly- first of reference
Urea formaldehyde and preparation method thereof.
Modified polyformaldehyde resin is prepared according to the method for embodiment 2, unlike, it is added without 2,2,6,6- tetramethyl piperazines
Pyridine-nitrogen-oxide (TEMPO) and polyamide PA6/12, specifically, by 100 parts by weight of polyoxymethylene resins, 2 parts by weight diphenyl
Methane -4,4 '-diisocyanate (MDI), 0.5 parts by weight antioxidant four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid]
Pentaerythritol ester (antioxidant 1010), 0.5 parts by weight melamine, 0.5 parts by weight magnesium hydroxide are after evenly mixing using exhaust
Formula double screw extruder melting extrusion is granulated, and extrusion temperature is 180 DEG C -225 DEG C, and screw speed is 100 revs/min, after granulation again
It is 2 hours dry at 80 DEG C, obtain reference modified polyformaldehyde resin DG2.
Test case
Test case is used to illustrate the test of modified polyformaldehyde resin performance.
(1) melt index:
By untreated acetal resin, the modified polyformaldehyde resin G1-G3 being prepared by embodiment 1-3 and by right
The reference modified polyformaldehyde resin DG1-DG2 that ratio 1 and 2 is prepared is respectively according to method specified in GB/T 3682-2000
It is measured melt index, wherein test condition includes: that test temperature is 190 DEG C, load 2.16kg.Acquired results such as table 1
It is shown.
Respectively by untreated acetal resin, by the embodiment 1-3 modified polyformaldehyde resin G1-G3 being prepared and
The reference modified polyformaldehyde resin DG1-DG2 being prepared by comparative example 1 and 2 melting extrusion three under 210 DEG C of extrusion temperature
It is secondary, melt index then is measured according to method specified in GB/T 3682-2000 respectively, wherein test condition includes: test
Temperature is 190 DEG C, load 2.16kg.Acquired results are as shown in table 1.
(2) thermal decomposition temperature:
Untreated acetal resin is measured, by embodiment using the thermal gravimetric analyzer (TGA) of German NETZSCH company
The modified polyformaldehyde resin G1-G3 that 1-3 the is prepared and reference modified polyacetal DG1- being prepared by comparative example 1 and 2
Starting thermal decomposition temperature of the DG2 in nitrogen and air, temperature when decomposing 10% and thermal decomposition terminate temperature.Acquired results
As shown in table 1.
(3) burst size of methanal:
Untreated acetal resin is detected using the TGA-MS instrument of German NETZSCH company, is prepared by embodiment 1-3
Obtained modified polyformaldehyde resin G1-G3 and the reference modified polyacetal DG1-DG2 being prepared by comparative example 1 and 2 are in nitrogen
Burst size of methanal when being thermally decomposed in gas and air, wherein ion stream current signal peak when burst size of methanal=Form aldehyde release
Area (A*s)/sample quality (mg).Acquired results are as shown in table 1.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, it can be combined in any appropriate way.In order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (12)
1. a kind of modified polyformaldehyde resin composition, which is characterized in that the composition contains polyformaldehyde, isocyanates chemical combination
Object, free radical scavenger and suction aldehyde agent, parts by weight are respectively 100, (0.5-2), (0.5-1), (0.5-1.3)；
The free radical scavenger be selected from 2,2,6,6- tetramethyl piperidine-nitrogen-oxide, 2,2- diphenyl -1- trinitrophenyl-hydrazine,
1,4-benzoquinone, tetramethyl-benzoquinone, N- tert-butyl-α-phenyinitrone and 3-2- (2- bromacetamido) acetamide] -2,2,5,5- tetramethyl
At least one of base -1- pyrrolidinyl oxide；
The suction aldehyde agent is selected from least one of melamine and polyamide.
2. modified polyformaldehyde resin composition according to claim 1, wherein
The isocyanate ester compound is selected from diphenyl methane -4,4 '-diisocyanate, 2,4 tolylene diisocyanate, right
At least one of phenylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and triphenylmethane triisocyanate.
3. modified polyformaldehyde resin composition according to claim 2, wherein the polyamide is copolyamide.
4. modified polyformaldehyde resin composition according to claim 3, wherein the polyamide be polyamide PA6/12,
At least one of polyamide 6/66/1010, polyamide 548 and polyamide 6/66.
5. -4 any modified polyformaldehyde resin composition according to claim 1, wherein the suction aldehyde agent is melamine
The mixture of amine and polyamide, and the polyformaldehyde relative to 100 parts by weight, parts by weight are respectively (0.5), (0-1).
6. modified polyformaldehyde resin composition according to claim 5, wherein relative to the polyformaldehyde of 100 parts by weight, institute
The parts by weight for stating melamine and polyamide are respectively (0.5), (0.8-1).
7. -4 any modified polyformaldehyde resin composition according to claim 1, wherein the modified polyformaldehyde resin
Composition also contains antioxidant and/or acid absorbent, and the polyformaldehyde relative to 100 parts by weight, parts by weight are respectively 0.5,
0.5；
The antioxidant is selected from least one of phenolic antioxidant, amine antioxidants and phosphite ester antioxidant.
8. modified polyformaldehyde resin composition according to claim 7, wherein when the modified polyformaldehyde resin composition
When containing antioxidant, relative to the polyformaldehyde of 100 parts by weight, the parts by weight of the antioxidant and isocyanate ester compound are distinguished
For (0.5), (0.5-2).
9. modified polyformaldehyde resin composition according to claim 7, wherein when the modified polyformaldehyde resin composition
When containing acid absorbent, relative to the polyformaldehyde of 100 parts by weight, the parts by weight of the acid absorbent and isocyanate ester compound are
(0.5)、(0.5-2)。
10. modified polyformaldehyde resin composition according to claim 9, wherein the acid absorbent is selected from magnesium hydroxide, hydrogen
At least one of calcium oxide, calcium stearate, odium stearate and magnesium stearate.
11. a kind of preparation method of modified polyformaldehyde resin, this method includes by any modification of claim 1-10
Polyoxymethylene resin composition melting extrusion at 180-225 DEG C is granulated, and is then dried.
12. the modified polyformaldehyde resin that the method as described in claim 11 is prepared.
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| CN115819961B (en) * | 2022-11-30 | 2024-05-07 | 江苏集萃先进高分子材料研究所有限公司 | Preparation method of nylon 6 flame-retardant composite material |
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| CN102532795A (en) * | 2011-12-23 | 2012-07-04 | 四川大学 | End-capped modified polyformaldehyde resin and preparation method thereof |
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| CN101935424B (en) * | 2010-08-06 | 2013-11-06 | 四川长虹电器股份有限公司 | ABS (Acrylonitrile Butadiene Styrene) thermoplastic resin and preparation method thereof |
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| CN101568595A (en) * | 2006-12-25 | 2009-10-28 | 宝理塑料株式会社 | Polyacetal resin composition and molded article thereof |
| CN102532795A (en) * | 2011-12-23 | 2012-07-04 | 四川大学 | End-capped modified polyformaldehyde resin and preparation method thereof |
| CN102558754A (en) * | 2011-12-23 | 2012-07-11 | 四川大学 | Chain-extended modified and copolymerized formaldehyde resin and preparation method thereof |
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