阅读说明：本技术 一种低甲醛释放量的pom组合物及其制备方法、应用 (A kind of POM composition of low burst size of methanal and preparation method thereof, application ) 是由 陈锋 黄险波 叶南彪 曹绍强 付学俊 丁超 王中林 陶四平 于 2019-09-11 设计创作，主要内容包括：本发明提供了一种低甲醛释放量的POM组合物及其制备方法、应用,其中,低甲醛释放量的POM组合物,包括以下重量份的各组分：POM树脂90-110份,聚酰胺0.5-1.5份,主抗氧剂0.1-0.5份,辅助抗氧剂0.05-0.3份,亚硫酸氢钠0.05-0.3份。本发明所述的低甲醛释放量的POM组合物,甲醛释放量低,且可减少组合物注塑过程中产生的模垢。(The present invention provides POM compositions of a kind of low burst size of methanal and preparation method thereof, application, wherein, the POM composition of low burst size of methanal, each component including following parts by weight: 90-110 parts of POM resin, 0.5-1.5 parts of polyamide, 0.1-0.5 parts of primary antioxidant, 0.05-0.3 parts of auxiliary antioxidant, 0.05-0.3 parts of sodium hydrogensulfite.The POM composition of low burst size of methanal of the present invention, burst size of methanal is low, and can reduce the mold deposit generated in composition injection moulding process.)

1. a kind of POM composition of low burst size of methanal, it is characterised in that: each component including following parts by weight: POM resin 90-110 parts, 0.5-1.5 parts of polyamide, 0.1-0.5 parts of primary antioxidant, 0.05-0.3 parts of auxiliary antioxidant, sodium hydrogensulfite 0.05-0.3 parts.

2. the POM composition of low burst size of methanal according to claim 1, it is characterised in that: the content of the POM resin For 100 parts by weight；The sodium hydrogensulfite purity is greater than 99.5wt%.

3. the POM composition of low burst size of methanal according to claim 1 or 2, it is characterised in that: the melting of POM resin Index is 190 DEG C, 2.16kg, 1~50g/10min；The relative density of POM resin is 1.38~1.44g/cm³。

4. the POM composition of low burst size of methanal according to claim 1, it is characterised in that: the polyamide is half hitch Brilliant or amorphous resin, fusing point are 80-230 DEG C；Preferably, the polyamide is that fusing point is poly- between 120-220 DEG C Amide resin；It is furthermore preferred that the polyamide is polyamide of the fusing point between 145-210 DEG C.

5. the POM composition of low burst size of methanal according to claim 1, it is characterised in that: the primary antioxidant is phenol Kind antioxidant；Preferably, primary antioxidant is four (β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol esters, 2,2'- Bis- [the β-(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyl) of methylene-bis- (4- methyl-6-tert-butylphenols), triethylene-glycol Propionic ester], triethylene glycol double β-(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyl) propionic esters, bis- [3- (the tertiary fourths of 3,5- bis- of hexylene glycol Base -4- hydroxy phenyl) propionic ester], N, N'- is bis--(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine, β-(3, One of 5- di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester；It is furthermore preferred that primary antioxidant is triethylene-glycol The double β-(3- tertiary butyl-4-hydroxy -5- methylbenzenes of bis- [β-(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyl) propionic esters] or triethylene glycol Base) propionic ester.

6. the POM composition of low burst size of methanal according to claim 1, it is characterised in that: the auxiliary anti-oxidant is Three (2,4- di-tert-butyl-phenyl) phosphite esters, bis- (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphates, four (2,4- di-tert-butylphenol) -4,4'- xenyl diphosphites (antioxidant P-EPQ), bis- (2,4- di-tert-butyl-phenyl) seasons penta One or both of tetrol diphosphites.

7. according to claim 1,2, the POM composition of low burst size of methanal described in 4-6 any one, it is characterised in that: also Auxiliary agent including 0.01-2 parts by weight；The auxiliary agent is selected from one or more of light stabilizer, lubricant.

8. the POM composition of low burst size of methanal according to claim 7, it is characterised in that: the light stabilizer be by One or more of hindered amine, benzotriazole, benzoxazine ketone compound compounding；The lubricant is low molecule One or more of esters stearic acid, metallic soap, stearic acid complex ester, amides compounding.

9. a kind of method for the POM composition for preparing the low burst size of methanal as described in claim 1 to 8 any one, special Sign is: the double screw extruder is respectively by each barrel temperature of feed opening to head: 150-180 DEG C, 170-220 DEG C, 170-220℃、170-210℃、170-210℃、170-200℃、170-200℃、170-200℃、170-200℃、170-210 ℃；Screw speed is 250-350 revs/min, feeding capacity 50-200kg/h, and vacuum degree is (- 0.1) -0MPa.

10. the POM composition of the low burst size of methanal as described in claim 1 to 8 any one is in automobile, household electrical appliances, electronics electricity Application in gas, office equipment and toy art.

Technical field

The invention belongs to polymeric material field, be related to POM composition of a kind of low burst size of methanal and preparation method thereof, Using in particular to a kind of polyformaldehyde composition and preparation and application with low burst size of methanal and low mold deposit.

Background technique

Acetal resin (POM) has excellent self-lubricating property, fatigue-resistance characteristics and the mechanical property of equilibrium, in vapour The fields such as vehicle, household electrical appliances, electric have a wide range of applications.But common POM material thermal stability itself is poor, in process It is easy to decompose and generates formaldehyde gas, and mold deposit easy to form is attached to product surface in injection moulding process.This of POM material lacks Fall into the use scope for greatly limiting material.

The decomposition mechanism of POM material is POM in process because generation is decomposed in external hot and shearing influence Formaldehyde can be oxidized to formic acid, and formic acid can further promote the backbone breaking of POM material, thus generate a large amount of formaldehyde gas with And mold deposit.

Have issued for many methods at present to improve the thermal stability of POM material and then reduce burst size of methanal and mould Dirt, such as aldehyde agent and alkali metal, alkaline earth metal compound such as magnesia etc. are inhaled using aminated compounds such as dicyandiamide, melamine Aldehyde agent is inhaled, the generation of the effective less formaldehyde gas of the acid absorbents such as alkali metal, alkaline earth metal compound such as magnesia energy is used.

Summary of the invention

In view of this, the present invention is directed to propose a kind of POM composition of low burst size of methanal, to overcome lacking for the prior art It falls into, burst size of methanal is low, and can reduce the mold deposit generated in composition injection moulding process.

In order to achieve the above objectives, the technical scheme of the present invention is realized as follows:

The each component including following parts by weight: a kind of POM composition of low burst size of methanal 90-110 parts of POM resin, gathers 0.5-1.5 parts of amide, 0.1-0.5 parts of primary antioxidant, 0.05-0.3 parts of auxiliary antioxidant, 0.05-0.3 parts of sodium hydrogensulfite.

Preferably, the content of the POM resin is 100 parts by weight.

Preferably, the melt index of POM resin is 190 DEG C, 2.16kg, 1~50g/10min；The relative density of POM resin For 1.38~1.44g/cm³。

Preferably, the polyamide is hypocrystalline or amorphous resin, and fusing point is 80-230 DEG C；Preferably, described Polyamide is polyamide of the fusing point between 120-220 DEG C；It is furthermore preferred that the polyamide is fusing point at 145-210 DEG C Between polyamide.

Preferably, the primary antioxidant is phenolic antioxidant, preferably four (β-(3,5- di-tert-butyl-hydroxy phenyl) Propionic acid) pentaerythritol ester (namely antioxidant 1010), 2,2'- methylene-bis- (4- methyl-6-tert-butylphenol) (namely antioxygen Agent 2246), triethylene-glycol bis- [β-(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyl) propionic esters], double β-(uncles 3- of triethylene glycol Butyl -4- hydroxy-5-methyl base phenyl) propionic ester (namely antioxidant 245), the bis- [3- (3,5- di-t-butyl -4- hydroxyls of hexylene glycol Phenyl) propionic ester] (namely antioxidant 259), N, N'- is bis--(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine In (namely antioxidant 1098), β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester (namely antioxidant 1076) One kind；More preferably triethylene-glycol bis- [β-(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyl) propionic esters] or triethylene glycol are double β-(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyl) propionic ester (namely antioxidant 245).

Preferably, the auxiliary anti-oxidant is three (2,4- di-tert-butyl-phenyl) phosphite esters, bis- (2,6- di-t-butyls- 4- aminomethyl phenyl) pentaerythritol diphosphate, four (2,4- di-tert-butylphenol) -4,4'- xenyl diphosphites (antioxidant P- EPQ), one or both of bis- (2,4- di-tert-butyl-phenyl) pentaerythritol diphosphites.

Preferably, the sodium hydrogensulfite purity is greater than 99.5wt%.

Preferably, the POM composition of the low burst size of methanal, it is characterised in that: further include 0.01-2 parts by weight Auxiliary agent；The auxiliary agent is selected from one or more of light stabilizer, lubricant.Material can be improved in suitable light stabilizer Light aging resisting property in use.

Preferably, the light stabilizer be one of hindered amines, benzotriazole, benzoxazine ketone compound or Two or more compoundings；The lubricant is one of low molecule esters stearic acid, metallic soap, stearic acid complex ester, amides Or two or more compoundings.

Another object of the present invention is to propose a kind of preparation method of the POM composition of low burst size of methanal, with preparation The POM composition of above-mentioned low burst size of methanal.

A kind of preparation method of the POM composition of low burst size of methanal, the double screw extruder is by feed opening to head Each barrel temperature be respectively: 150-180 DEG C, 170-220 DEG C, 170-220 DEG C, 170-210 DEG C, 170-210 DEG C, 170-200 ℃,170-200℃,170-200℃,170-200℃,170-210℃；Screw speed is 250-350 revs/min, and feeding capacity is 50-200kg/h, vacuum degree are (- 0.1) -0MPa.

The invention further relates to the POM compositions of low burst size of methanal in automobile, household electrical appliances, electric, office equipment and object for appreciation Application in the fields such as tool.

Compared with the existing technology, a kind of POM composition of low burst size of methanal of the present invention has the advantage that

The POM composition of a kind of low burst size of methanal of the present invention, by selecting nylon resin, primary antioxidant, auxiliary The processing stabilising system of antioxidant and sodium hydrogensulfite as POM, can greatly reduce the burst size of methanal of POM composition, The mold deposit generated in composition injection moulding process can be also reduced simultaneously.

Wherein, the principle that burst size of methanal can substantially reduce is: POM is in process because of external warm and shearing The formaldehyde for influencing to decompose generation can be oxidized to formic acid, and formic acid can further promote the backbone breaking of POM material, to generate big The formaldehyde gas of amount, and aldehyde can be absorbed in polyamide (nylon resin), sodium hydrogensulfite can easily absorb formic acid.In this manner it is possible to Reduce the content of formaldehyde.

A kind of preparation method of the POM composition of low burst size of methanal is combined with the POM of above-mentioned low burst size of methanal Possessed advantage is identical compared with the existing technology for object, and details are not described herein.

Specific embodiment

In addition to being defined, technical term used in following embodiment has universal with those skilled in the art of the invention The identical meanings of understanding.Test reagent used in following embodiment is unless otherwise specified conventional biochemical reagent；It is described Experimental method is unless otherwise specified conventional method.

Below with reference to embodiment, the present invention will be described in detail.

One, raw material sources

POM resin: JinFa Science Co., Ltd, trade mark POM M25-44, melting means 2.5, density 1.4g/cm³； POM M90-44, melting means 9, density 1.4g/cm³；POM M270-44, melting means 27, density 1.4g/cm³；POM M450-44, Melting means is 45, density 1.4g/cm³。

Polyamide: ARKEMA, trade mark TMFO F, 202 DEG C of fusing point；

DUPONT, trade mark ELVAMIDE 8061,156 DEG C of fusing point.

Primary antioxidant: IRGANOX 245, IRGANOX 1076, IRGANOX 1098, BASF.

Auxiliary antioxidant: IRGANOX 168, IGANOX 1010, BASF；

PEP-36, AKD；

SONOX 626, Linyi San Feng chemical industry.

Sodium hydrogensulfite, commercially available, purity 99.8wt%.

Lubricant: EBS, it is commercially available.

Two, embodiment 1-7 and comparative example 1-7

The preparation of the POM composition of low burst size of methanal:

By POM resin, polyamide, primary antioxidant, auxiliary anti-oxidant, sodium hydrogensulfite and auxiliary agent (the not situation of auxiliary agent Under, only POM resin, polyamide, primary antioxidant, auxiliary anti-oxidant, sodium hydrogensulfite) it mixes 1-2 minutes in a high speed mixer Premix is obtained, melting extrusion, cooling, granulation at 150-220 DEG C obtain POM composition through double screw extruder for premix. Wherein, the double screw extruder is respectively by each barrel temperature of feed opening to head: 150-180 DEG C, 170-220 DEG C, 170-220℃、170-210℃、170-210℃、170-200℃、170-200℃、170-200℃、170-200℃、170-210 DEG C, screw speed is 250-350 revs/min, feeding capacity 50-200kg/h, and vacuum degree is (- 0.1) -0MPa.