CN102532795A - End-capped modified polyformaldehyde resin and preparation method thereof - Google Patents
End-capped modified polyformaldehyde resin and preparation method thereof Download PDFInfo
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- CN102532795A CN102532795A CN2011104390084A CN201110439008A CN102532795A CN 102532795 A CN102532795 A CN 102532795A CN 2011104390084 A CN2011104390084 A CN 2011104390084A CN 201110439008 A CN201110439008 A CN 201110439008A CN 102532795 A CN102532795 A CN 102532795A
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Abstract
The invention discloses end-capped modified polyformaldehyde resin and a preparation method of the resin. The resin mainly comprises polyformaldehyde, polyfunctional group isocyanate end capping agent, antioxidant, formic acid absorbent, formaldehyde absorbent, lubricating agent and the like. The end-capped modified polyformaldehyde resin is characterized in that isocyanate compounds are used as the end capping agent, polyformaldehyde can directly react with isocyanate group in extrusion process by using the reaction of the isocyanate compounds with the compounds containing active hydrogen and adopting a melt extrusion manner of an exhaust double-screw extruder, so as to form stable carbamic acid ester bonds to carry out end capping on original unstable group ends and newly-generated unstable group ends in the resin, thus reaching a better stabilization effect of end groups, improving heat stability of the resin, being capable of effectively preventing breakage of molecular chains in the end group stabilization process, and being beneficial to keeping resin molecular weight.
Description
Technical field
The present invention relates to the polyoxymethylene resin modification technology, more specifically, relate to polyoxymethylene resin of a kind of blocking modification and preparation method thereof.
Background technology
Polyoxymethylene (POM) is that a kind of molecular backbone chain is by oxidation methylene radical [CH
2O-] thermoplastic engineering plastic of the line style formed of repeating unit, HMP, high-density, high crystalline.It has hardness, intensity and the rigidity of metalloid, in very wide temperature and humidity scope, all has good self lubricity, good resistance to fatigue, and springiness, and it also has chemical-resistant preferably in addition.Polyoxymethylene is to be lower than the cost of other many engineering plastics; Substituting some traditionally by market that metal captured; Like metals such as instead of zinc, brass, aluminium and steel as structural timber; Make the engineering equipment parts, be widely used in fields such as electric, mechanical, instrument, daily light industry, automobile, building materials, agricultural.Especially as the various component (gear, bent axle, bearing etc.) that bear the power conduction, has irreplaceable critical role.Application in a lot of frontiers like aspects such as medical skill, exerciser, also shows staggering growth situation.
According to the difference of production technique, polyoxymethylene is divided into two kinds of homopolymer and multipolymers.The molecular backbone chain of acefal homopolymer is made up of carbon-oxygen bond fully, contains the CH of random distribution in the molecular backbone chain of copolymerized methanal
2-CH
2Structure.No matter be acefal homopolymer or copolymerized methanal, after they are just synthetic, all contain a large amount of unstable terminal hydroxy group [(OCH
2)
n-OH], under the effect of heat and oxygen, unstable end group very easily decomposes in the melt-processed process, thereby successive piptonychia aldehyde reaction takes place, and the formic acid that is generated by oxidation of formaldehyde simultaneously will cause copolymerized methanal generation chain rupture again, and decomposition reaction is quickened greatly.Therefore, the polyoxymethylene powder poor heat stability that polymerization obtains after accomplishing can not directly be used, and must carry out the end group stabilization processing, with the thermostability of raising polyoxymethylene, thereby reaches request for utilization.The end group stabilization processing is a most key step in the whole stabilization last handling process mainly based on the polyoxymethylene molecular structure is carried out modification.The end group stabilization effect is bad, and unstable endgroup content will be higher in the copolymerized methanal, causes the resin thermostability to descend.Discharge a large amount of formaldehyde simultaneously, also can influence the stability of the course of processing, cause goods inner formation pore and defective easily, and very easily produce mold deposit, influence the product appearance property.At present, polyoxymethylene end group stabilization practical implementation method comprises esterification or etherified sealed end method, heterogeneous soda solution grouting, solution method, fusion post treatment method etc.
Esterification or etherified sealed end method are to handle through unstable end group being carried out esterification or etherified sealed end, reach the purpose of end group stabilizationization.This method generally is in the homogeneous phase solution of polyoxymethylene, to carry out, and unstable end group elimination factor is near 100%, and the end group stabilization effect is better, like USP U.S.Pat.4105638.But because this method technological process is comparatively complicated, need use a large amount of organic solvents simultaneously, so this method application is less, only is applied to the processing of acefal homopolymer end group stabilization.
It is that the copolymerized methanal powder is suspended in heating and pressurizing in the alkaline aqueous medium that heterogeneous alkali lye is handled; Alkaline medium infiltrates in the polymer particle; Impel the unstable end group of macromole to issue estranged separating, thereby remove end of the chain l fraction, reach the stabilization purpose at alkaline condition.This method advantage equipment is simple, with low cost.But insoluble in alkaline water liquid owing to polymer suspension, molten, it is difficult that treating processes will reach complete hydrolysis, and unstable end group is eliminated not thorough, and the treatment time is long, and treating processes causes vitreous clinker easily.This method is seldom used at present.
The homogeneous phase soda solution grouting is that copolymerized methanal is added water-miscible organic solvent when the hydrolysis treatment, like Virahol, selects suitable temperature and prescription, can make multipolymer be dissolved into solution fully.Under the effect of compounds such as alkaline matter such as ammonia or amine, l fraction is decomposed, and reaches the purpose of end group stabilizationization.This method is handled the unstable end group in back and is eliminated more thoroughly, but the solvent usage quantity is big, and cost is high, and required equipment is complicated, and the wash ratio that stabilization treatment is accomplished the back material is difficult.This method is also seldom used.
The fusion post treatment method is mainly used in the end group stabilization processing of copolymerized methanal, is copolymerized methanal is heated between the fusing point to 240 ℃, and adds an amount of alkaline matter, impels unstable end group thermolysis, up to CH
2-CH
2-OH structure forms stable end groups, reaches the stabilization purpose.This method equipment is simple, can adopt the twin screw extruder serialization to produce, and need not other solvent, implements easily, and treatment effect is better.Many advantages of fusion post-treating method meet the required technical requirements of industriallization continuous production, are suitable for commercial applications, and therefore nearly all copolymerized methanal manufacturing concern all adopts this method that copolymerized methanal is carried out the end group stabilization aftertreatment.But when utilizing this method to carry out end group stabilization, can't avoid fully on the one hand causing molecular weight to reduce because residual catalyst and thermal-oxidative degradation cause the chain rupture of copolymerized methanal main chain.The molecule of chain rupture can form new unstable end group equally on the other hand, and this just causes unstable endgroup content to be difficult to further reduce.
By on can know that the quality of end group stabilization effect is directly connected to the quality of commodity polyoxymethylene thermostability.Therefore through updating polyoxymethylene end group stabilization method, become the direction that each polyoxymethylene manufacturing concern constantly makes great efforts, had important realistic meaning to improve the polyoxymethylene thermostability.
Summary of the invention
To the deficiency of polyoxymethylene resin modification prior art, first purpose of the present invention provides the blocking modification polyoxymethylene resin that a kind of thermostability is significantly improved; Second purpose of the present invention provides a kind of in polyoxymethylene end group stabilization treating processes, the method for preparing the blocking modification polyoxymethylene resin that need not other solvent, implement easily, the resin melt index keeps, the molecular chain chain rupture is controlled at all.
To first goal of the invention of the present invention, the blocking modification polyoxymethylene resin that thermostability is significantly improved, it is formed component and mainly comprises in weight part:
In order to realize the object of the invention better, said blocking modification polyoxymethylene resin also can contain other auxiliary agent of 0～1 weight part on the such scheme basis.Other auxiliary agent can be one or more in the auxiliary agents such as photostabilizer, whitening agent, staining agent.
In technique scheme, said many functional group isocyanates's end-capping reagent can be and is selected from 2,4-toluene-2,4-diisocyanate (TDI), 4, any in 4 '-diphenylmethanediisocyanate (MDI) and the hexamethylene diisocyanate (HDI).
In technique scheme; Said oxidation inhibitor can be and is selected from four [β-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid] in pentaerythritol ester, β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester and Tri Ethyleneglycol-β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester etc. one or more.
In technique scheme, the formic acid absorption agent can be the inorganic or organic salt of weak acid of basic metal or earth alkali metal, like StNa, calcium stearate, Magnesium Stearate etc., and in the oxyhydroxide of earth alkali metal such as calcium hydroxide, the Marinco H any.Further, said formic acid absorption agent can be and is selected from StNa, calcium stearate, Magnesium Stearate, calcium hydroxide and the Marinco H etc. one or more.
In technique scheme, said formaldehyde absorption agent can be and is selected among trimeric cyanamide, polymeric amide PA6 and the polymeric amide PA66 one or more.
In technique scheme, said lubricant can be and is selected from glyceryl monostearate and the bis-stearamides one or more.
In technique scheme, said copolymerized methanal is the copolymerized methanal of melt index in 9～27g/10min scope.
Above-mentioned blocking modification polyoxymethylene resin can prepare through following method; After copolymerized methanal, many functional group isocyanates's end-capping reagent, oxidation inhibitor, formic acid absorption agent, formaldehyde absorption agent, lubricant and other auxiliary agent of formula ratio mixed; Through forcing machine in 180 ℃～220 ℃ melt extrude, granulation, drying, promptly obtain the copolymerized methanal resin of blocking modification.Said forcing machine is preferentially selected the exhaust twin screw extruder of rotating speed 50～150rpm for use, and pellet carries out drying in being not more than under 98 ℃ the condition, preferably at 80 ℃～90 ℃ following bake dryings.
Blocking modification copolymerized methanal resin of the present invention, its respectively form component all have commercially available, all can directly acquisition from the market.
The present invention is directed to the problem that exists in the existing polyoxymethylene end group stabilization technology, provide a kind of simple, efficient and can be used for the method that the thermally stable polyoxymethylene resin is produced in serialization.The present invention melt extrudes on the end group stabilization basis in tradition; Adopt isocyanate ester compound as end-capping reagent; Utilize it and contain the active hydrogen group reaction, adopt the mode that melt extrudes, make terminal hydroxy group and isocyanic ester direct reaction in extrusion in the polyoxymethylene; Form metastable amino-formate bond unstable end group original and newly-generated in the resin is sealed, thereby reach better end group stabilization effect.The unstable endgroup content of polyoxymethylene that obtains through the end group stabilization aftertreatment reduces, and burst size of methanal reduces, and thermostability improves.Through adding an amount of oxidation inhibitor, the molecular weight reduction has been avoided in the not chain rupture in melt extruding the chain extension process of protection polyoxymethylene main chain.
The present invention is the contriver through deep theoretical analysis and experimental study repeatedly, has chosen at last with many functional group isocyanates's compound as polyoxymethylene modified end-capping reagent, and polyoxymethylene resin is carried out modification, has accomplished the present invention, has obtained extraordinary effect.The blocking modification copolymerized methanal resin that the present invention obtains; Compare with the blocking modification copolymerized methanal resin that traditional fusion end group stabilization treatment method obtains; Its heat decomposition temperature all significantly improves with aging back mechanical property conservation rate; Significantly improved the thermostability of polyoxymethylene, shown in table 1 result.Simultaneously, cross in the treating processes in stabilization, the resin melt index keeps better, and the situation of molecular chain chain rupture has also obtained effective control in the extrusion.
The practical implementation method
Combine embodiment that the present invention is explained as follows at present.Here need to prove that embodiment just is used for the present invention is further described, and can not be interpreted as the qualification to protection domain of the present invention, all contents according to the present invention are made the improvement of unsubstantiality and the row that adjustment all belongs to the present invention's protection to it.
The twin screw extruder model of using among the present invention: KEYA-50.Manufacturer: times Long Keya machinery ltd of Nanjing section.Specifeca tion speeification: screw diameter 50mm, length-to-diameter ratio L/D 40: 1, screw rod maximum speed of revolution 600rpm, main motor current 55kW.
The mensuration of melt index (MI):, under 190 ℃, 2.16kg condition, test according to GB/T3682-2000.
Initial heat decomposition temperature: adopt Q500 type thermal analyzer (TA company) to measure sample quality 8-10mg.All samples carry out heat analyze before equal 80 ℃ of dryings 2 hours in baking oven.10 ℃/min of temperature rise rate, the flow of air and nitrogen are 50ml/min.
222 ℃ of vacuum thermal weight losses of polyoxymethylene rate: take by weighing a certain amount of copolymerized methanal sample as in the test tube, vacuumize, be heated to 222 ℃, keep 60min, weigh after being cooled to room temperature, be calculated as follows 222 ℃ of vacuum thermal weight losses of copolymerized methanal rate (W
222): m wherein
0Be copolymerized methanal sample initial mass, m
1Be the quality sample heats 60min in 222 ℃ of following vacuum after, can estimate the unstable endgroup content of polyoxymethylene through this test, vacuum thermal weight loss rate is high more, and unstable endgroup content is high more.
The mensuration of burst size of methanal: take by weighing 2g copolymerized methanal sample; In nitrogen atmosphere (flow 200ml/min), be heated to 230 ℃; Impel unstable end group to decompose, decompose the formaldehyde that discharges and taken out of, and use concentration is that 4% sodium sulfite aqueous solution absorbs the formaldehyde that discharges by nitrogen; Utilize the accurate titration absorption liquid of standard salt acid solution of 0.01mol/L, consume hydrochloric acid V
1Ml measures blank simultaneously, consumes hydrochloric acid V
2Ml.Then polyoxymethylene sample burst size of methanal (C.F.G) is:
140 ℃ of accelerated weathering tests: after the copolymerized methanal sample is produced tension specimen by GB 1039-1992, the polyoxymethylene tension specimen as in the baking oven, in 140 ℃ of aging 3 weeks, is measured the variation of aging front and back tensile strength.Tensile strength is tested by GB/T 1040-1992.
Embodiment 1
With polyoxymethylene powder 10Kg, 4; 4 '-diphenylmethanediisocyanate (MDI) 50g, four [β-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid] adopt the exhaust twin screw extruder to melt extrude behind the pentaerythritol ester 10g, calcium stearate 10g, trimeric cyanamide 10g, glyceryl monostearate 10g uniform mixing; Extrusion temperature is 180 ℃～220 ℃, 100 rev/mins of screw speeds, after the granulation in 80 ℃ of dryings 3 hours.
Embodiment 2
With polyoxymethylene powder 10Kg, 4; 4 '-diphenylmethanediisocyanate (MDI) 100g, β-(3; The 5-di-tert-butyl-hydroxy phenyl) adopt the exhaust twin screw extruder to melt extrude behind propionic acid octadecanol ester 30g, calcium hydroxide 20g, trimeric cyanamide 30g, polymeric amide PA610g, the glyceryl monostearate 50g uniform mixing; Extrusion temperature is 180 ℃～220 ℃, 100 rev/mins of screw speeds, after the granulation in 80 ℃ of dryings 3 hours.
Embodiment 3
With polyoxymethylene powder 10Kg, 4; 4 '-diphenylmethanediisocyanate (MDI) 200g, four [β-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid] adopt the exhaust twin screw extruder to melt extrude behind the pentaerythritol ester 50g, β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester 5g, Marinco H 50g, trimeric cyanamide 50g, bis-stearamides 30g uniform mixing, extrusion temperature is 180 ℃～220 ℃; 100 rev/mins of screw speeds, after the granulation in 80 ℃ of dryings 3 hours.
Embodiment 4
With polyoxymethylene powder 10Kg, 2; 4-toluene-2,4-diisocyanate (TDI) 50g, four [β-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid] adopt the exhaust twin screw extruder to melt extrude behind the pentaerythritol ester 10g, calcium stearate 10g, calcium hydroxide 10g, trimeric cyanamide 20g, glyceryl monostearate 10g uniform mixing; Extrusion temperature is 180 ℃～220 ℃, 120 rev/mins of screw speeds, after the granulation in 80 ℃ of dryings 3 hours.
Embodiment 5
With polyoxymethylene powder 10Kg, 2; 4-toluene-2,4-diisocyanate (TDI) 100g, four [β-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 50g, β-(3; The 5-di-tert-butyl-hydroxy phenyl) adopt the exhaust twin screw extruder to melt extrude behind propionic acid octadecanol ester 10g, calcium stearate 20g, trimeric cyanamide 15g, polymeric amide PA6610g, the glyceryl monostearate 10g uniform mixing; Extrusion temperature is 180 ℃～220 ℃, 120 rev/mins of screw speeds, after the granulation in 80 ℃ of dryings 3 hours.
Embodiment 6
With polyoxymethylene powder 10Kg, hexamethylene diisocyanate (HDI) 50g, four [β-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid] adopt the exhaust twin screw extruder to melt extrude behind the pentaerythritol ester 30g, calcium stearate 20g, trimeric cyanamide 20g, bis-stearamides 10g uniform mixing; Extrusion temperature is 180 ℃～220 ℃; 150 rev/mins of screw speeds, after the granulation in 80 ℃ of dryings 3 hours.
Embodiment 7
With polyoxymethylene powder 10Kg, hexamethylene diisocyanate (HDI) 200g, β-(3; The 5-di-tert-butyl-hydroxy phenyl) adopt the exhaust twin screw extruder to melt extrude behind propionic acid octadecanol ester 30g, Marinco H 20g, trimeric cyanamide 20g, the glyceryl monostearate 10g uniform mixing; Extrusion temperature is 180 ℃～220 ℃; 150 rev/mins of screw speeds, after the granulation in 80 ℃ of dryings 3 hours.
Comparison example
With polyoxymethylene powder 10Kg, four [β-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid] adopt the exhaust twin screw extruder to melt extrude behind the pentaerythritol ester 30g, calcium stearate 20g, trimeric cyanamide 20g, glyceryl monostearate 10g uniform mixing; Extrusion temperature is 180 ℃～220 ℃; 100 rev/mins of screw speeds, after the granulation in 80 ℃ of dryings 3 hours.
Table 1. polyoxymethylene performance
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 | 7 | Comparison example | Appearance is untreated |
| Melt index | 8.6 | 8.4 | 4.4 | 8.7 | 7.6 | 8.8 | 7.2 | 9.4 | 8.5 |
| Initial heat decomposition temperature ℃ (nitrogen) | 338 | 348 | 356 | 334 | 345 | 329 | 341 | 323 | 261 |
| Initial heat decomposition temperature ℃ (air) | 281 | 286 | 293 | 282 | 290 | 278 | 284 | 276 | 211 |
| Vacuum thermal weight loss rate % | 0.34 | 0.29 | 0.21 | 0.25 | 0.21 | 0.38 | 0.32 | 0.57 | 2.15 |
| Burst size of methanal ppm | 1785 | 1560 | 1350 | 1470 | 1093 | 2027 | 1695 | 2550 | 15390 |
| Tensile strength MPa before aging | 59.1 | 59.5 | 59.6 | 58.3 | 58.6 | 57.4 | 58.5 | 58.4 | 58.4 |
| Aging back draft intensity MPa | 49.8 | 54.2 | 54.7 | 51.8 | 52.5 | 50.3 | 51.6 | 46.3 | Efflorescence |
| Stretching strength retentivity % | 84.2 | 91.0 | 91.8 | 88.9 | 89.7 | 87.6 | 88.2 | 79.3 | -- |
Claims (10)
1. blocking modification polyoxymethylene resin is characterized in that forming component and mainly comprises in weight part:
2. blocking modification polyoxymethylene resin as claimed in claim 1 is characterized in that also containing other auxiliary agent in photostabilizer, whitening agent and the staining agent that is selected from of 0～1 weight part.
3. according to claim 1 or claim 2 blocking modification polyoxymethylene resin is characterized in that said many functional group isocyanates's end-capping reagent is selected from 2,4-toluene-2,4-diisocyanate, 4, a kind of in 4 '-diphenylmethanediisocyanate, the hexamethylene diisocyanate.
4. according to claim 1 or claim 2 blocking modification polyoxymethylene resin; It is characterized in that said oxidation inhibitor is selected from four [β-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester and Tri Ethyleneglycol-β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester.
5. according to claim 1 or claim 2 blocking modification polyoxymethylene resin is characterized in that said formic acid absorption agent is selected from StNa, calcium stearate, Magnesium Stearate, calcium hydroxide and Marinco H.
6. according to claim 1 or claim 2 blocking modification polyoxymethylene resin is characterized in that said formaldehyde absorption agent is selected from trimeric cyanamide, polymeric amide PA6 and polymeric amide PA66.
7. according to claim 1 or claim 2 blocking modification polyoxymethylene resin is characterized in that said lubricant is selected from glyceryl monostearate and bis-stearamides.
8. the method for preparing the said blocking modification polyoxymethylene resin of one of claim 1 to 7; After polyoxymethylene, many functional group isocyanates's end-capping reagent, oxidation inhibitor, formic acid absorption agent, formaldehyde absorption agent, lubricant and other auxiliary agent that it is characterized in that formula ratio mixes; Through forcing machine in 180 ℃～220 ℃ melt extrude, granulation, drying, promptly obtain the copolymerized methanal resin of blocking modification.
9. the method for preparing the blocking modification polyoxymethylene resin as claimed in claim 8 is characterized in that said forcing machine is the exhaust twin screw extruder of rotating speed 50～150rpm.
10. like claim 8 or the 9 described methods that prepare the blocking modification polyoxymethylene resin, it is characterized in that the pellet behind the extruding pelletization carries out drying in being not more than under 98 ℃ the condition.
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| CN106893446A (en) * | 2015-12-17 | 2017-06-27 | 中国科学院金属研究所 | A kind of epoxy radicals wear resistant and impact resistant anticorrosive paint and preparation method without inorganic matter |
| CN108914625A (en) * | 2018-05-29 | 2018-11-30 | 东华大学 | A kind of polyformaldehyde fibre colouring method |
| CN109061042A (en) * | 2018-08-16 | 2018-12-21 | 国家能源投资集团有限责任公司 | A kind of method of unstable hydroxy radical content in measurement polyformaldehyde |
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| CN113166354A (en) * | 2018-11-16 | 2021-07-23 | 科思创知识产权两合公司 | Method for producing prepolymers comprising polyoxymethylene blocks |
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| CN105885340A (en) * | 2014-12-26 | 2016-08-24 | 神华集团有限责任公司 | Antioxidant composition, modified polyformaldehyde resin composition and modified polyformaldehyde resin and preparation method thereof |
| CN105885339A (en) * | 2014-12-26 | 2016-08-24 | 神华集团有限责任公司 | Antioxidant composition, modified polyformaldehyde resin composition and modified polyformaldehyde resin and preparation method thereof |
| CN105885339B (en) * | 2014-12-26 | 2019-03-29 | 神华集团有限责任公司 | Antioxidant composition and modified polyformaldehyde resin composition and modified polyformaldehyde resin and preparation method thereof |
| CN105237943A (en) * | 2015-10-12 | 2016-01-13 | 神华集团有限责任公司 | Rigidity-reinforced polyformaldehyde composite material and preparation method thereof |
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| CN108914625B (en) * | 2018-05-29 | 2021-01-01 | 东华大学 | Polyformaldehyde fiber dyeing method |
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| CN110527240A (en) * | 2019-09-11 | 2019-12-03 | 天津金发新材料有限公司 | A kind of POM composition of low burst size of methanal and preparation method thereof, application |
| CN110885415A (en) * | 2019-11-29 | 2020-03-17 | 万华化学集团股份有限公司 | Antistatic and antibacterial polyacetal resin and preparation method thereof |
| CN110885415B (en) * | 2019-11-29 | 2023-01-13 | 万华化学集团股份有限公司 | Antistatic and antibacterial polyacetal resin and preparation method thereof |
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Application publication date: 20120704 |