CN103881276B - A kind of low aldehyde discharges polyoxymethylene resin and material modified - Google Patents
A kind of low aldehyde discharges polyoxymethylene resin and material modified Download PDFInfo
- Publication number
- CN103881276B CN103881276B CN201210558574.1A CN201210558574A CN103881276B CN 103881276 B CN103881276 B CN 103881276B CN 201210558574 A CN201210558574 A CN 201210558574A CN 103881276 B CN103881276 B CN 103881276B
- Authority
- CN
- China
- Prior art keywords
- polyoxymethylene resin
- formaldehyde
- compatilizer
- ethylene
- polyoxymethylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention provides a kind of the material modified of polyoxymethylene resin-formaldehyde burst size that reduce, it comprises the raw material of following weight proportion: ethylene-vinyl alcohol copolymer 0.05-5 part, formaldehyde absorption catalyst 0.01-3 part, compatilizer 0.01-0.5 part; Wherein, described compatilizer is reactive compatibilizers, and described formaldehyde absorption catalyst is boric acid compound. The present invention also provides a kind of low aldehyde to discharge polyoxymethylene resin. What in the present invention, provide is material modified, after ethylene-vinyl alcohol copolymer and specific compatilizer and formaldehyde absorption catalyst mix are used, the burst size of methanal in polyoxymethylene resin can be effectively reduced, polyoxymethylene resin modified can be widely used in. Simultaneously, provided by the inventionly use above-mentioned material modified polyoxymethylene resin, its burst size of methanal is extremely low, is obviously better than the polyoxymethylene resin with traditional formaldehyde absorbent modification, can use in PARA FORMALDEHYDE PRILLS(91,95) burst size and require extremely harsh application scenario.
Description
Technical field
The present invention relates to a kind of low aldehyde and discharge polyoxymethylene resin and material modified, belong to poly-Compound modification and processing technique field.
Background technology
Polyoxymethylene (polyoxymethylene), has another name called polyformaldehyde, and it is that main chain contains(–CH2– O –) the linear macromolecule polymer of chain link. Polyoxymethylene is high comprehensive performanceThermoplastic engineering plastic, first realizes industrialization by the U.S., then DuPont company nineteen fifty-nineConvenient with its machine-shaping, raw material is cheap and easy to get, especially its unique mechanical property, oil resistivity,Chemical-resistant, low water absorbable and good heat, electrical property, be used to replace non-ferrous metal and closeGold, is widely used in automobile, electronic apparatus industry, various precision optical machinery and five metals building materials etc. manyField.
Polyoxymethylene is milky crystalline solid, smooth surface, glossy, hard and fine and close,Density is at 1.41-1.42g/cm3. Polyoxymethylene is generally light tight, and thin wall parts is translucent.Press the difference of molecular structure and synthesis technique, polyoxymethylene can be divided into two large classes, and a class is threeThe copolymer of polyformaldehyde and a small amount of dioxolane or oxirane, is called common polyoxymethylene; SeparatelyOne class is the homopolymers of metaformaldehyde or pure formaldehyde, is called equal polyoxymethylene. Homopolymers togetherPolymers is compared, and all polyoxymethylene mechanical performance is slightly excellent, and polyoxymethylene is with heat endurance altogetherBe good at. On market, world today polyoxymethylene dominate altogether, only has Du PontWith Asahi Chemical IndustryFor equal polyoxymethylene. At present, at whole engineering plasticsIn industry, the annual production of polyoxymethylene is only second to nylon and Merlon, becomes current five largeOne of engineering plastics.
No matter be equal polyoxymethylene, or be total to polyoxymethylene, its macromolecular chain end is totalCan there is a certain amount of hemiacetal structure. These hemiacetal structures are contacting or hot procedure with airMiddle meeting is resolved into formaldehyde and is discharged. Therefore, in polyoxymethylene resin, formaldehyde absorptionMeasure is a link must considering. At present conventional absorption formaldehyde mode is for being used formaldehyde absorptionAgent. A large amount of Chinese invention patents such as CN101142249A, CN1158350C, CN1300245CIn disclosed formaldehyde absorbent, be mostly melamine, dicyandiamide, melamine derivative (melamine),Polyethylene polyamine, hydrazides, low molecule acid amides etc. The universals of these formaldehyde absorbents divide exactlyIn minor structure, contain active hydrogen, can be quantitative react with formaldehyde and be fixed, thereby riseTo the object that absorbs formaldehyde. But the formaldehyde absorbent generally adopting at present in use existsVariety of issue, as limited in formaldehyde absorption efficiency etc.
Ethylene-vinyl alcohol copolymer is a kind of half hitch crystal formation thermoplastic resin, has good machinery strongDegree, wearability, weatherability and higher case hardness. Ethylene-vinyl alcohol copolymer is normally by secondAlkene-vinyl acetate co-polymer is through saponification or alcoholysis product partly-hydrolysed and that make. At etheneIn-ethenol copolymer, the existence of vinyl makes ethylene-vinyl alcohol copolymer can pass through polyeneThe machine-shaping device of hydrocarbon carries out thermoplasticity processing, and the existence of ethene alcohol radical simultaneously makes ethylene-vinylAlcohol copolymer has iris action, and (chemical industry is published for CHEN Changjie, the printing of plastic sheeting and compoundSociety, 1998). Ethylene-vinyl alcohol copolymer molecular backbone is made up of ethene section and vinyl alcohol section, secondThe ratio of thiazolinyl segment is generally 20-45%, and vinyl alcohol segment is generally 55-80%, molecular side chainOn be rich in hydroxyl (OH). Ethylene-vinyl alcohol copolymer have good mechanical strength, case hardness,Weatherability, wearability and antistatic behaviour.
In order to overcome traditional formaldehyde absorbent various shortcomings in use, Duan Yifei (polyformaldehydeThermal degradation and stabilisation research, " Sichuan University's master thesis ", 2004,28-33) just reportRoad EVOH polyoxymethylene resin is had to certain heat stabilization, but this improvement is rightThe effect that reduces burst size of methanal is also not obvious. Therefore, low urea formaldehyde need further research.
Summary of the invention
The object of the invention is for the deficiencies in the prior art, overcome technology prejudice simultaneously, provideA kind ofly reduce the material modified of polyoxymethylene resin-formaldehyde burst size. The present invention also providesDischarge polyoxymethylene resin and preparation method taking this kind of material modified low aldehyde as basis.
The invention provides a kind of the material modified of polyoxymethylene resin-formaldehyde burst size that reduce,It comprises the raw material of following weight proportion:
Ethylene-vinyl alcohol copolymer 0.05-5 part, formaldehyde absorption catalyst 0.01-3 part, compatilizer0.01-0.5 part; Wherein, described compatilizer is reactive compatibilizers, described formaldehyde absorption catalystFor boric acid compound.
Further, the described material modified raw material by following weight proportion forms:
Ethylene-vinyl alcohol copolymer 0.05-5 part, formaldehyde absorption catalyst 0.01-3 part, compatilizer0.01-0.5 part.
Wherein, in described ethylene-vinyl alcohol copolymer, the molar content of ethene segment is30.0-40.0%; Described compatilizer is diisocyanate compound or diepoxides; DescribedFormaldehyde absorption catalyst is any one or several combination in boric acid, metaboric acid, tetraboric acid.
Wherein, described diisocyanate compound is methyl diphenylene diisocyanate or toluene twoIsocyanates.
Further, the model of described ethylene-vinyl alcohol copolymer be ET3803, DC3212,The combination of one or more in F104B; The particle diameter of ethylene-vinyl alcohol copolymer is less than 80Order.
The present invention also provides a kind of low aldehyde to discharge polyoxymethylene resin, and it is by following weightThe raw material of proportioning is prepared from:
Wherein, described compatilizer is reactive compatibilizers, and described formaldehyde absorption catalyst is boric acid classCompound.
Further, it is to be prepared from by the raw material of following weight proportion:
Wherein, in described ethylene-vinyl alcohol copolymer, the molar content of ethene segment is30.0-40.0%; Described compatilizer is diisocyanate compound or diepoxides; DescribedFormaldehyde absorption catalyst is any one or several combination in boric acid, metaboric acid, tetraboric acid.
Wherein, described diisocyanate compound is methyl diphenylene diisocyanate or toluene twoIsocyanates.
Further preferably, the model of described ethylene-vinyl alcohol copolymer be ET3803, DC3212,The combination of one or more in F104B; The particle diameter of ethylene-vinyl alcohol copolymer is less than 80Order.
Wherein, described fomic acid absorber is in calcium stearate, zinc stearate, calcium oxide, zinc oxideAny one or more combinations;
Described lubricant is N, N-ethylene bis stearamide, bi-tristearin, pentaerythriteAny one or more combination in tetrastearate;
Described antioxidant be two β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic esters of triethylene glycol,N, N-pair-(3-(3,5-di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine or β-(3,5-di-t-butyl-4-hydroxy phenyl) one or more combination in the positive octadecanol ester of propionic acid;
Described nucleator is nano-calcium carbonate and precipitated calcium carbonate, and the mass ratio of the two is 1:1.
Further, in described nucleator, the particle diameter of nano-calcium carbonate is no more than 35nm, lightweightThe particle diameter of calcium carbonate is 2000-5000 order.
Wherein, the molten finger of described polyoxymethylene is at 2.0-500.0g/10min, its unstable fixed endBase section content is no more than 7000mg/kg.
The present invention also provides above-mentioned low aldehyde to discharge the preparation method of polyoxymethylene resin, its bagDraw together following operating procedure:
(1) take by weight ratio raw material;
(2) first by other raw material premixeds except compatilizer, and then add compatilizer to continue to mix,Finally adopt double screw extruder to carry out melting mixing and extruding pelletization, major diameter in double screw extruderThan being 20-55:1, screw speed is 20-600r/min, and processing temperature is 150-240 DEG C; Wherein,Each exhaust section vacuum≤-0.07MPa when described double screw extruder operation.
Except preparation method provided by the invention, resin of the present invention can also be by existing polyoxygenated AsiaThe conventional method preparation of methyl resin.
What in the present invention, provide is material modified, by ethylene-vinyl alcohol copolymer and specific compatilizer andFormaldehyde absorption catalyst mix can effectively reduce the formaldehyde in polyoxymethylene resin after usingBurst size, can be widely used in polyoxymethylene resin modified. Meanwhile, fortune provided by the inventionWith above-mentioned material modified polyoxymethylene resin, its burst size of methanal is extremely low, is obviously better thanWith the polyoxymethylene resin of traditional formaldehyde absorbent modification, can use in PARA FORMALDEHYDE PRILLS(91,95) burst sizeRequire extremely harsh application scenario.
Obviously, according to foregoing of the present invention, according to the ordinary skill knowledge of this area and usualMeans, are not departing under the above-mentioned basic fundamental thought of the present invention prerequisite, can also make that other is multipleAmendment, replacement or the change of form.
The detailed description of the invention of form by the following examples, to foregoing of the present invention remake intoThe detailed description of one step. But this should be interpreted as to the scope of the above-mentioned theme of the present invention only limits to followingExample. All technology realizing based on foregoing of the present invention all belong to scope of the present invention.
Specific implementation method
In embodiment and comparative example, polyoxymethylene resin-formaldehyde burst size is surveyed by the following methodFixed:
Utilize the high pure nitrogen that flow is 10L/h in closed container, to purge 200g polyoxymethyleneResin sample, sweep gas bubbling is through being equipped with in the Drexel bottle of 1500mL deionized water. TestedIn journey, polyoxymethylene sample temperature is 150 DEG C, testing time 60min. Test finishes rear profitConcentration of formaldehyde in Drexel bottle deionized water is entered by known acetylacetone,2,4-pentanedione ultraviolet spectrophotometryRow Accurate Measurement, is then scaled burst size of methanal. Acetylacetone method principle is to utilize formaldehyde and secondAcyl acetone and ammonia generate yellow compound 3,5-diacetyl Isosorbide-5-Nitrae-dihydro lutidine, andUnder 412nm wavelength, carry out spectrophotometry.
In embodiment and comparative example, other performance is measured by the following method:
Molten establishing criteria ISO1133,190 DEG C, the 2.16kg of referring to;
Hot strength establishing criteria ISO527-1,2;
Bending strength establishing criteria ISO178;
Simply supported beam notched Izod impact strength establishing criteria ISO179-1eA.
Embodiment 1 the present invention is material modified
Material prescription is as follows:
Ethylene-vinyl alcohol copolymer 0.2g, formaldehyde absorption catalyst 0.05g, compatilizer 0.2g; ItsIn, described compatilizer is reactive compatibilizers, can be selected from diisocyanate compound, as twoMethylenebis phenyl isocyanate, toluene di-isocyanate(TDI). Described formaldehyde absorption catalyst is boric acid classCompound, as boric acid, metaboric acid, tetraboric acid.
Embodiment 2 the present invention are material modified
Material prescription is as follows:
0.8 part of ethylene-vinyl alcohol copolymer, 0.5 part of formaldehyde absorption catalyst, compatilizer 0.35Part;
Wherein, described compatilizer is reactive compatibilizers, can be selected from diepoxides, as twoPhenol A type epoxy resin; Described formaldehyde absorption catalyst is boric acid compound, as boric acid, inclined to one side boronAcid, tetraboric acid.
The low aldehyde of embodiment 3 the present invention discharges the preparation of polyoxymethylene resin
First by polyoxymethylene matrix resin 100 weight portions, large molecule formaldehyde absorbent 0.2 weightAmount part, formaldehyde absorption catalyst 0.05 weight portion, fomic acid absorber 0.4 weight portion, antioxidant 0.5Weight portion, lubricant 0.15 weight portion and nucleator 0.2 weight portion add in high-speed mixer and carry outPremixed, and then in high-speed mixer, add the compatilizer of 0.2 weight portion to continue to mix,Rear employing double screw extruder carries out melting mixing and extruding pelletization, and screw speed is 200r/min,Processing temperature is 170-220 DEG C. The molten finger of polyoxymethylene matrix resin is at 9.0g/10min,Unstable terminal portion content is 6800mg/kg; Large molecule formaldehyde absorbent be Powdered ethene-Ethenol copolymer (adopting SoarnolET3803EVOH, then freezing pulverizing), its ethylene chainThe molar content of section is 38.0%, and the particle diameter of powder ethylene-vinyl alcohol copolymer is 200 orders; FormaldehydeAbsorbing catalyst is boric acid; Compatilizer is methyl diphenylene diisocyanate; Fomic acid absorber is hardResin acid calcium; Antioxidant is two β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic esters of triethylene glycol;Lubricant is N, N-ethylene bis stearamide; Nucleator is nano-calcium carbonate and precipitated calcium carbonate,Mass ratio is 1:1, and wherein the particle diameter of nano-calcium carbonate is 35nm, and the particle diameter of precipitated calcium carbonate exists2500 orders. Double screw extruder belongs to large capacity evaporation (multistage exhaust) devolatilization double screw extruder group, longFootpath ratio is 40, and when operation, each exhaust section vacuum is-0.07MPa.
The present invention, in the situation that not changing embodiment 1 preparation method, adjusts resin additive(seeing comparative example 1,2,3,4,5), to investigate beneficial effect of the present invention.
Table 1
The low aldehyde of embodiment 4 the present invention discharges the preparation of polyoxymethylene resin
First by polyoxymethylene matrix resin 100 weight portions, large molecule formaldehyde absorbent 0.8 weightAmount part, formaldehyde absorption catalyst 0.5 weight portion, fomic acid absorber 0.3 weight portion, antioxidant 0.8Weight portion, lubricant 0.5 weight portion and nucleator 0.3 weight portion add in high-speed mixer and carry outPremixed, and then in high-speed mixer, add the compatilizer of 0.35 weight portion to continue to mix,Rear employing double screw extruder carries out melting mixing and extruding pelletization, and screw speed is 100r/min,Processing temperature is 170-230 DEG C. The molten finger of polyoxymethylene matrix resin is at 2.5g/10min,Unstable terminal portion content is 6200mg/kg; Large molecule formaldehyde absorbent be Powdered ethene-Ethenol copolymer (adopting SoarnolDC3212EVOH, then freezing pulverizing), its ethylene chainThe molar content of section is 32.0%, and the particle diameter of powder ethylene-vinyl alcohol copolymer is 250 orders; FormaldehydeAbsorbing catalyst is metaboric acid; Compatilizer is toluene di-isocyanate(TDI); Fomic acid absorber is stearic acidZinc; Antioxidant is two β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic esters of triethylene glycol; LubricatedAgent is pentaerythritol tetrastearate; Nucleator is nano-calcium carbonate and precipitated calcium carbonate, mass ratioFor 1:1, wherein the particle diameter of nano-calcium carbonate is 30nm, and the particle diameter of precipitated calcium carbonate is 2000Order. Double screw extruder belongs to large capacity evaporation (multistage exhaust) devolatilization double screw extruder group, draw ratioBe 55, when operation, each exhaust section vacuum is-0.08MPa.
The present invention, in the situation that not changing embodiment 2 preparation method, adjusts resin additive(seeing comparative example 6), to investigate beneficial effect of the present invention.
Table 2
The low aldehyde of embodiment 5 the present invention discharges the preparation of polyoxymethylene resin
First by polyoxymethylene matrix resin 100 weight portions, large molecule formaldehyde absorbent 2 weightPart, formaldehyde absorption catalyst 1 weight portion, fomic acid absorber 1 weight portion, antioxidant 1.5 weightPart, lubricant 0.3 weight portion and nucleator 1 weight portion add and in high-speed mixer, carry out premixed,And then in high-speed mixer, add the compatilizer of 0.5 weight portion to continue mixing, finally adopt twoScrew extruder carries out melting mixing and extruding pelletization, and screw speed is 400r/min, processing temperatureFor 170-240 DEG C. The molten finger of polyoxymethylene matrix resin is at 27.0g/10min, unstable fixed endBase section content is 5200mg/kg; Large molecule formaldehyde absorbent is that Powdered ethylene-vinyl alcohol is total toPolymers (adopt EVALF104BEVOH, then freezing pulverizing), mole the containing of its ethene segmentAmount is 32.0%, and the particle diameter of powder ethylene-vinyl alcohol copolymer is 100 orders; Formaldehyde absorption catalystFor tetraboric acid; Compatilizer is methyl diphenylene diisocyanate; Fomic acid absorber is zinc oxide; Anti-Oxygen agent is two β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic esters of triethylene glycol; Lubricant is twoTristerin; Nucleator is nano-calcium carbonate and precipitated calcium carbonate, and mass ratio is 1:1, itsThe particle diameter of middle nano-calcium carbonate is 20nm, and the particle diameter of precipitated calcium carbonate is at 5000 orders. Twin-screw squeezesGo out machine and belong to large capacity evaporation (multistage exhaust) devolatilization double screw extruder group, draw ratio is 20, when operationEach exhaust section vacuum is-0.095MPa.
The present invention, in the situation that not changing embodiment 3 preparation method, adjusts resin additive(seeing comparative example 7,8,9), to investigate beneficial effect of the present invention.
Table 3
Conclusion:
(1) inventor is in the middle discovery that studies for a long period of time, although EVOH is rich in hydroxyl, and these hydroxylsThe reaction speed of base and formaldehyde molecule is very slow, can not play the effect that absorbs formaldehyde; Secondly, EVOHBad with polyformaldehyde compatibility, phase-splitting is serious, and this has also caused emitting in polyoxymethylene resinFormaldehyde molecule can not fully contact with EVOH and react. Above shortcoming all makes should be excellentElegant EVOH cannot use as formaldehyde absorbent in polyoxymethylene resin.
In the present invention, creatively adopted acid formaldehyde absorption catalyst, compatilizer and ethene-Ethenol copolymer, also with (being that the present invention is material modified), has greatly increased EVOH in polyoxygenatedCompatibility in methylene resin has significantly improved reacting of hydroxyl and formaldehyde molecule in EVOH simultaneouslySpeed, significantly reduces the burst size of methanal of resin, is better than traditional formaldehyde absorbent.
Above-mentioned conclusion shows, what in the present invention, provide is material modified, can effectively reduce polyoxygenated AsiaBurst size of methanal in methyl resin, can be widely used in polyoxymethylene resin modified.
(2) known according to table 3, compared with independent use ethylene-vinyl alcohol copolymer, add simultaneouslyAdd ethylene-vinyl alcohol copolymer, compatilizer or/and after formaldehyde absorption catalyst, can be more remarkableGround reduces burst size of methanal, and this just shows, compatilizer is or/and adding of formaldehyde absorption catalyst canSignificantly promote the formaldehyde absorption effect of ethylene-vinyl alcohol copolymer.
Meanwhile, according to table 1, research is found, only has vulcabond and diepoxides (as bis-phenolA type epoxy resin) just there is the effect that promotes EVOH to absorb formaldehyde, wherein, more with two isocyanidesThe facilitation of acid esters is the most obvious, and its formaldehyde reduced releasing effect is obviously better than diepoxides,Therefore, the preferred diisocyanate compound of the present invention is compatilizer.
(3) simultaneously, inventor finds in trial test in early stage, and the molar content of ethene segment isEthylene-vinyl alcohol copolymer effect beyond 30.0-40.0% is poor compared with the present invention, may be due to contentHigher than 40% time, in ethylene-vinyl alcohol copolymer, available hydroxyl content reduces, and absorbing formaldehyde effect is fallenLow; Content lower than 30% time, available hydroxyl too high levels in ethylene-vinyl alcohol copolymer, moleculeBetween hydrogen bond action too strong to such an extent as to cannot melt-processed and reach the object of fine dispersion, absorbing formaldehyde effectFruit is same to reduce.
(4) compared with copolyamide/EVOH modification, the present invention fills a prescription and reduces burst size of methanalAct on more remarkable.
Claims (10)
1. one kind is reduced the material modified of polyoxymethylene resin-formaldehyde burst size, it is characterized in that: itComprise the raw material of following weight proportion:
Ethylene-vinyl alcohol copolymer 0.05-5 part, formaldehyde absorption catalyst 0.01-3 part, compatilizer 0.01-0.5Part;
Wherein, described compatilizer is reactive compatibilizers, and described formaldehyde absorption catalyst is boric acid class chemical combinationThing.
2. according to claim 1 material modified, it is characterized in that: described ethylene-vinyl alcohol is altogetherIn polymers, the molar content of ethene segment is 30.0-40.0%; Described compatilizer is diisocyanatesCompound or diepoxides; Described formaldehyde absorption catalyst is appointing in boric acid, metaboric acid, tetraboric acidThe combination of one or more.
3. according to claim 2 material modified, it is characterized in that: described diisocyanatesCompound is methyl diphenylene diisocyanate or toluene di-isocyanate(TDI).
4. according to claim 1 and 2 material modified, it is characterized in that: described ethylene-vinylThe model of alcohol copolymer is one or more the combination in ET3803, DC3212, F104B;The particle diameter of ethylene-vinyl alcohol copolymer is less than 80 orders.
5. low aldehyde discharges a polyoxymethylene resin, it is characterized in that: it is by following weight proportionRaw material be prepared from:
Wherein, described compatilizer is reactive compatibilizers, and described formaldehyde absorption catalyst is boric acid class chemical combinationThing.
6. low aldehyde according to claim 5 discharges polyoxymethylene resin, it is characterized in that: itTo be prepared from by the raw material of following weight proportion:
7. discharge polyoxymethylene resin according to the low aldehyde described in claim 5 or 6, it is characterized in that:Described fomic acid absorber is any one or two kinds of in calcium stearate, zinc stearate, calcium oxide, zinc oxideAbove combination;
Described lubricant is N, and N-ethylene bis stearamide, bi-tristearin, pentaerythrite four are hardAny one or more combination in resin acid ester;
Described antioxidant is two β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic esters of triethylene glycol, N, N-Two-(3-(3,5-di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine or β-(3,5-di-t-butyl-4-hydroxy benzenesBase) one or more combination in the positive octadecanol ester of propionic acid;
Described nucleator is nano-calcium carbonate and precipitated calcium carbonate, and the mass ratio of the two is 1:1.
8. low aldehyde according to claim 7 discharges polyoxymethylene resin, it is characterized in that: instituteState in nucleator, the particle diameter of nano-calcium carbonate is no more than 35nm, and the particle diameter of precipitated calcium carbonate is 2000-5000Order.
9. discharge polyoxymethylene resin according to the low aldehyde described in claim 5 or 6 any one, itsBe characterised in that: the molten finger of described polyoxymethylene is at 2.0-500.0g/10min its unstable terminal portionContent is no more than 7000mg/kg.
10. the preparation method of low aldehyde release polyoxymethylene resin described in claim 5-9 any one,It is characterized in that: it comprises following operating procedure:
(1) take by weight ratio raw material;
(2) first by other raw material premixeds except compatilizer, and then add compatilizer to continue to mix,Rear employing double screw extruder carries out melting mixing and extruding pelletization, and in double screw extruder, draw ratio is20-55:1, screw speed is 20-600r/min, processing temperature is 150-240 DEG C; Wherein, described twoEach exhaust section vacuum≤-0.07MPa when screw extruder operation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210558574.1A CN103881276B (en) | 2012-12-20 | 2012-12-20 | A kind of low aldehyde discharges polyoxymethylene resin and material modified |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210558574.1A CN103881276B (en) | 2012-12-20 | 2012-12-20 | A kind of low aldehyde discharges polyoxymethylene resin and material modified |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103881276A CN103881276A (en) | 2014-06-25 |
| CN103881276B true CN103881276B (en) | 2016-05-04 |
Family
ID=50950425
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210558574.1A Active CN103881276B (en) | 2012-12-20 | 2012-12-20 | A kind of low aldehyde discharges polyoxymethylene resin and material modified |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103881276B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6864472B2 (en) * | 2016-12-27 | 2021-04-28 | オイレス工業株式会社 | Polyacetal resin composition and sliding members |
| CN114940802B (en) * | 2022-02-23 | 2024-03-22 | 金发科技股份有限公司 | Homopolymerized POM composition with good thermal stability and low mold deposit and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87102759A (en) * | 1986-04-15 | 1987-12-30 | 纳幕尔杜邦公司 | The polyformaldehyde composition of stabilization |
| CN101508819A (en) * | 2009-03-18 | 2009-08-19 | 四川大学 | Thermal stable polyoxymethylene containing high-efficiency anti-oxidant and method for producing the same |
| CN102131866A (en) * | 2008-08-29 | 2011-07-20 | 纳幕尔杜邦公司 | Polyoxymethylene compositions and articles made from these |
| CN102558754A (en) * | 2011-12-23 | 2012-07-11 | 四川大学 | Chain-extended modified and copolymerized formaldehyde resin and preparation method thereof |
-
2012
- 2012-12-20 CN CN201210558574.1A patent/CN103881276B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87102759A (en) * | 1986-04-15 | 1987-12-30 | 纳幕尔杜邦公司 | The polyformaldehyde composition of stabilization |
| CN102131866A (en) * | 2008-08-29 | 2011-07-20 | 纳幕尔杜邦公司 | Polyoxymethylene compositions and articles made from these |
| CN101508819A (en) * | 2009-03-18 | 2009-08-19 | 四川大学 | Thermal stable polyoxymethylene containing high-efficiency anti-oxidant and method for producing the same |
| CN102558754A (en) * | 2011-12-23 | 2012-07-11 | 四川大学 | Chain-extended modified and copolymerized formaldehyde resin and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 共聚甲醛颜色稳定性能的研究;汤思聪;《中国优秀硕士学位论文全文数据库》;20080531;第36页第10-13行，第49页表5.5 * |
| 聚甲醛的热降解和稳定化研究;段怡飞;《中国优秀硕士学位论文全文数据库》;20050131;第28页倒数第10行-第29页第4行 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103881276A (en) | 2014-06-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2226358B1 (en) | Polyacetal resin composition | |
| CN1749311B (en) | Polyacetal resin composition | |
| US7619020B2 (en) | Polyacetal resin composition | |
| CN104302683B (en) | Aoxidize the manufacture method of methylene base co-polymer | |
| CN109794601A (en) | A kind of metal powder injection molding uses feeding and preparation method thereof with high circulation | |
| KR101722266B1 (en) | Coated polyoxymethylenes | |
| CN102558754A (en) | Chain-extended modified and copolymerized formaldehyde resin and preparation method thereof | |
| CN102131865A (en) | Polyacetal resin composition | |
| CN103881276B (en) | A kind of low aldehyde discharges polyoxymethylene resin and material modified | |
| CN1331939C (en) | Polyacetal resin composition | |
| CN103450628A (en) | Polyacetal resin composition and preparation method thereof | |
| WO2007020931A1 (en) | Polyacetal resin composition and molded resin | |
| CN1122054C (en) | Process for producing branched or crosslined polyacetal resin | |
| CN104774422B (en) | Low mold deposit polyformaldehyde composition of high heat stability and preparation method and application | |
| CN103865229B (en) | High thermal stable polyoxymethylene resin and preparation method thereof | |
| CN100999602A (en) | Degradable carbon dioxide plastic base composite material and preparation process thereof | |
| CN105121488A (en) | Polyoxymethylene copolymers and thermoplastic POM composition | |
| CN103044852A (en) | Polyacetal resin composition | |
| CN104774423A (en) | Low-corrosion and low-formaldehyde-release polyformaldehyde composition and preparation method and application thereof | |
| CN1039024C (en) | Polyoxymethylene resin composition | |
| CN111560135B (en) | High-flow, high-impact and low-emission PP/PE composite material based on electrostatic self-assembly and preparation method thereof | |
| JP2016089069A (en) | Polyacetal resin pellet and molded body | |
| US11898033B2 (en) | Oxymethylene copolymer resin composition and method for producing same | |
| EP3545039B1 (en) | Polyoxymethylene compositions | |
| CN112852046A (en) | Preparation method of modified plastic |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |