CN102337001A - Polyformaldehyde with thermal stability and weather resistance and preparation method thereof - Google Patents
Polyformaldehyde with thermal stability and weather resistance and preparation method thereof Download PDFInfo
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- polyoxymethylene
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Abstract
The invention relates to polyformaldehyde with thermal stability and weather resistance, which is characterized by comprising the following components in percentage by weight: 97.8-99% of polyformaldehyde (melt index g/10mim), 0.4-0.8% of unsymmetric hindered phenol antioxidant, 0.4-0.8% of hindered amine light stabilizer, 0.1-0.3% of calcium stearate and 0.1-0.3% of melamine. The unsymmetric hindered phenol antioxidant is unsymmetric hindered phenol with one tert-butyl group or one methyl group in ortho-position of phenolic hydroxyl group.
Description
[technical field]
The present invention relates to polyformaldehyde composite material, relate in particular to a kind of polyoxymethylene and preparation method thereof with thermally-stabilised and weathering resistance.
[background technology]
Polyoxymethylene (POM) is a linear junction crystal formation polymkeric substance; Molecular chain structure is regular, cohesive energy density(CED) is big, percent crystallinity is high, mechanical property is excellent; Have higher modulus of elasticity, very high rigidity and hardness, tensile strength, flexural strength, creep resistant and superior fatigue resistance, specific tenacity and specific rigidity approach metal, be in the engineering plastics mechanical property near the material of metal; The title that metal plastic is arranged; Shortcoming is poor fire, easy firing, shock strength is low, notch sensitivity is big, poor heat stability, weathering resistance are undesirable, how to overcome the thermostability and the weathering resistance difference problem of polyoxymethylene, is that chemical industry exists a difficult problem always.
Thermal stability problems to polyoxymethylene; Hinered phenols antioxidant is to prevent the most important kind antioxidant of polymkeric substance oxidative degradation as the polyoxymethylene primary antioxidant; Phenolic antioxidant all has the hindered phenol structure, and promptly the hydroxyl ortho position has two (or one) sterically hindered bigger alkyl (X, R).General formula is following:
Tradition is employed in and adds hindered phenol antioxygen in the polyoxymethylene, promptly is the verivate of parent with the 2,6 di t butyl phenol; X and R are the tertiary butyl :-C (CH3) 3 is called complete hindered phenol or symmetric form hindered phenol antioxygen, and the symmetric form hindered phenol antioxygen is as 1010,1076 etc., and there is the tertiary butyl of two larger molecular weights at the ortho position of hydroxyl in the molecule; Because steric restriction is big; Reactive behavior is little, and speed of response is slow, is prone to make plastics painted; Thermal oxidation stability efficient is improved, but polyoxymethylene is repeatedly processed the back unstable properties.
Because polyoxymethylene is a linear polymer, highly crystalline, molecular backbone chain are the C-O key; Responsive to the UV-light of wavelength in 280～400nm scope; UV-irradiation is a POM aged principal element, and to the weathering resistance problem of polyoxymethylene, the method that improves the POM ultraviolet-resistant performance at present mainly is to add photostabilizer; Comprise photomask agent, UV light absorber, quencher and hindered amine light stabilizer etc., but effect not very good.
[summary of the invention]
It is low that first purpose of the present invention provides a kind of production cost, can improve antioxidant effect and weathering resistance, can satisfy the repeatedly polyoxymethylene of processing back stable performance.
It is low that second purpose of the present invention provides a kind of production cost, can improve antioxidant effect and weathering resistance, can satisfy the repeatedly preparation method of the polyoxymethylene of processing back stable performance.
In order to realize above-mentioned first purpose, adopt following technical scheme:
A kind of have thermally-stabilised and polyoxymethylene weathering resistance, and this is thermally-stabilised composed of the following components with polyoxymethylene weathering resistance, is by weight percentage:
Further technical scheme is, said asymmetric hindered phenol antioxygen has the asymmetric hindered phenol of a tertiary butyl and a methyl for adopting the phenolic hydroxyl group ortho position.
Further technical scheme is, said hindered amine as light stabilizer (HALS) is one type of organic amine compound with space steric effect, and with 2,2,6,6-tetramethyl--4-piperidyl is a parent, and its structural formula is:
Wherein: R=methyl-CH
3
R
1=OH, NH2 or various group;
R
2=H, O, alkyl, alkoxyl group-OR3.
Further technical scheme is said R
2In alkyl be-CH
3
In order to realize above-mentioned second purpose, adopt following technical scheme:
A kind of preparation method with polyoxymethylene of thermally-stabilised and weathering resistance comprises the steps:
(1) asymmetric hindered phenol antioxygen is synthetic:
A) alkylated reaction: react with ortho-cresol and iso-butylene, generate the nfrastructure of asymmetric hindered phenol antioxygen: 2-methyl-6-tert butyl phenol;
B) addition reaction: react synthetic intermediate β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) methyl propionate with 2-methyl-6-tert butyl phenol and methyl acrylate;
C) transesterify or substitution reaction: with glycol or the cyanuric chloride organic raw material reaction of contracting of midbody β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) methyl propionate and tetramethylolmethane, straight chain, synthetic asymmetric hindered phenol antioxygen.
(2) hindered amine as light stabilizer is synthetic
A) with 2,2,6,6-tetramethyl--4-piperidines alcohol is that raw material and acetaldehyde, butyral, ethylene chlorhydrin reaction obtain midbody 1-(beta-hydroxyethyl) 2,2,6,6-tetramethyl--4-piperidines alcohol (hereinafter to be referred as HTMP);
B) midbody 1-(beta-hydroxyethyl) 2,2,6,6-tetramethyl--4-piperidines alcohol generates hindered amine as light stabilizer with the one of which reaction of straight chain dibasic acid esters or acid anhydrides.
(3) polyoxymethylene of preparation thermostability and weathering resistance
C) at first, polyoxymethylene, asymmetric hindered phenol antioxygen, asymmetric hindered phenol antioxygen, hindered amine as light stabilizer, calcium stearate and trimeric cyanamide are mixed, add in the impeller and stir, obtain mixture;
D) then, mixture is added in the twin screw extruder, the working temperature that twin screw extruder is set is 180 ℃～220 ℃, and screw speed is 150r/min～300r/min, obtains having the polyoxymethylene of thermostability and weathering resistance.
Further technical scheme is that said straight chain dibasic acid esters is dimethyl adipate or dimethyl sebacate.
Further technical scheme is to it is characterized in that said acid anhydrides is a maleic anhydride.
Advantage of the present invention:
The present invention adopts the asymmetric Hinered phenols antioxidant of synthetic; Be that hindered phenol hydroxyl ortho position has a tertiary butyl (X is the tertiary butyl) and methyl (R is the asymmetric hindered phenol of methyl-CH3); With 2-methyl-6-tert butyl phenol is the characteristic that the asymmetric hindered phenol antioxygen of skeleton not only possesses general Hinered phenols antioxidant; Weakened the sterically hindered of hindered phenol hydroxyl to a certain extent, accelerated anti-oxidant speed of response, thereby made the oxidation inhibitor of new texture give play to the effect that is superior to traditional hindered phenol antioxygen; And with the collaborative stabilization and the coloring resistance effect of auxiliary antioxidant; Symmetric form hindered phenol than traditional is more outstanding, can effectively reduce the production cost of polyoxymethylene, improves antioxidant effect; Satisfy polyoxymethylene and repeatedly process the requirement of back stable performance, be applicable to easy thermooxidative degradation, require highly heat-resistant and stable polyformaldehyde material and the goods of high color and luster.
In addition, in the polyoxymethylene production process of this invention, with 2; 2,6,6-tetramethyl--4-piperidines alcohol (hereinafter to be referred as TMP) is raw material; Obtain midbody with reactions such as acetaldehyde, butyral, ethylene chlorhydrins, as: 1-(beta-hydroxyethyl) 2,2; 6,6-tetramethyl--4-piperidines alcohol (hereinafter to be referred as HTMP), midbody HTMP and straight chain dibasic acid esters or acid anhydrides (like dimethyl adipate, dimethyl sebacate and maleic anhydride etc.) reaction generates hindered amine as light stabilizer.This photostabilizer not only has the N alkyl group; And in the course of processing control hindered amine the polymerization degree; Make its molecular weight about 2500; Decompose the formaldehyde of generation and the influence of formic acid to eliminate polyoxymethylene, be used, reach the purpose of obvious raising Weatherability of Polyoxymethylene with ultraviolet absorbers and photomask agent.
[embodiment]
Below in conjunction with embodiment the present invention is done further description:
At first, synthesize asymmetric hindered phenol antioxygen and hindered amine as light stabilizer.
(1) asymmetric hindered phenol antioxygen is synthetic:
A) alkylated reaction: react with ortho-cresol and iso-butylene, generate the nfrastructure of asymmetric hindered phenol antioxygen: 2-methyl-6-tert butyl phenol;
B) addition reaction: react synthetic intermediate β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) methyl propionate with 2-methyl-6-tert butyl phenol and methyl acrylate;
C) transesterify or substitution reaction: with glycol or the cyanuric chloride organic raw material reaction of contracting of midbody β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) methyl propionate and tetramethylolmethane, straight chain, synthetic asymmetric hindered phenol antioxygen.
(2) hindered amine as light stabilizer is synthetic
A) with 2,2,6,6-tetramethyl--4-piperidines alcohol is that raw material and acetaldehyde, butyral, ethylene chlorhydrin reaction obtain midbody 1-(beta-hydroxyethyl) 2,2,6,6-tetramethyl--4-piperidines alcohol;
B) midbody 1-(beta-hydroxyethyl) 2,2,6,6-tetramethyl--4-piperidines alcohol generates hindered amine as light stabilizer with one of which (like dimethyl adipate, dimethyl sebacate, the maleic anhydride) reaction of straight chain dibasic acid esters or acid anhydrides.
Then, the polyoxymethylene of preparation thermostability and weathering resistance.
Embodiment one:
A) at first, mix, add in the impeller and stir, obtain mixture by proportioning 98.55% polyoxymethylene, 0.5% asymmetric hindered phenol antioxygen, 0.5% hindered amine as light stabilizer, 0.25% calcium stearate and 0.2% trimeric cyanamide;
B) then, mixture is added in the twin screw extruder, the working temperature that twin screw extruder is set is 200 ℃, and screw speed is 220r/min, obtains having the polyoxymethylene of thermostability and weathering resistance.
The polyoxymethylene performance that embodiment one generates sees the following form 1.
Embodiment two:
A) at first, mix, add in the impeller and stir, obtain mixture by proportioning 98.5% polyoxymethylene, 0.6% asymmetric hindered phenol antioxygen, 0.6% hindered amine as light stabilizer, 0.15% calcium stearate and 0.15% trimeric cyanamide;
B) then, mixture is added in the twin screw extruder, the working temperature that twin screw extruder is set is 220 ℃, and screw speed is 180r/min, obtains having the polyoxymethylene of thermostability and weathering resistance.
The polyoxymethylene performance that embodiment two generates also sees the following form 1.
Embodiment three:
A) at first, mix, add in the impeller and stir, obtain mixture by proportioning 98.35% polyoxymethylene, 0.7% asymmetric hindered phenol antioxygen, 0.65% hindered amine as light stabilizer, 0.2% calcium stearate and 0.1% trimeric cyanamide;
B) then, mixture is added in the twin screw extruder, the working temperature that twin screw extruder is set is 215 ℃, and screw speed is 190r/min, obtains having the polyoxymethylene of thermostability and weathering resistance.
The polyoxymethylene performance that embodiment three generates sees the following form 1.
Embodiment four:
A) at first, mix, add in the impeller and stir, obtain mixture by proportioning 98.55% polyoxymethylene, 0.45% asymmetric hindered phenol antioxygen, 0.5% hindered amine as light stabilizer, 0.2% calcium stearate and 0.3% trimeric cyanamide;
B) then, mixture is added in the twin screw extruder, the working temperature that twin screw extruder is set is 205, and screw speed is 280r/min, obtains having the polyoxymethylene of thermostability and weathering resistance.
The polyoxymethylene performance that embodiment four generates also sees the following form 1.
Embodiment five:
A) at first, mix, add in the impeller and stir, obtain mixture by proportioning 98.8% polyoxymethylene, 0.45% asymmetric hindered phenol antioxygen, 0.55% hindered amine as light stabilizer, 0.1% calcium stearate and 0.1% trimeric cyanamide;
B) then, mixture is added in the twin screw extruder, the working temperature that twin screw extruder is set is 220 ℃, and screw speed is 250r/min, obtains having the polyoxymethylene of thermostability and weathering resistance.
The polyoxymethylene performance that embodiment five generates also sees the following form 1.
Embodiment six:
A) at first, mix, add in the impeller and stir, obtain mixture by proportioning 97.95% polyoxymethylene, 0.7% asymmetric hindered phenol antioxygen, 0.8% hindered amine as light stabilizer, 0.3% calcium stearate and 0.25% trimeric cyanamide;
B) then, mixture is added in the twin screw extruder, the working temperature that twin screw extruder is set is 185 ℃, and screw speed is 250r/min, obtains having the polyoxymethylene of thermostability and weathering resistance.
The polyoxymethylene performance that embodiment six generates also sees the following form 1.
Embodiment seven:
A) at first, mix, add in the impeller and stir, obtain mixture by proportioning 98.1% polyoxymethylene, 0.8% asymmetric hindered phenol antioxygen, 0.75% hindered amine as light stabilizer, 0.15% calcium stearate and 0.2% trimeric cyanamide;
B) then, mixture is added in the twin screw extruder, the working temperature that twin screw extruder is set is 220 ℃, and screw speed is 245r/min, obtains having the polyoxymethylene of thermostability and weathering resistance.
The polyoxymethylene performance that embodiment seven generates also sees the following form 1.
Embodiment eight:
A) at first, mix, add in the impeller and stir, obtain mixture by proportioning 98.1% polyoxymethylene, 0.5% asymmetric hindered phenol antioxygen, 0.8% hindered amine as light stabilizer, 0.3% calcium stearate and 0.3% trimeric cyanamide;
B) then, mixture is added in the twin screw extruder, the working temperature that twin screw extruder is set is 190 ℃, and screw speed is 210r/min, obtains having the polyoxymethylene of thermostability and weathering resistance.
The polyoxymethylene performance that embodiment eight generates also sees the following form 1.
Table 1
Can know through embodiment performance comparison in the table 1; The present invention has weakened the sterically hindered of hindered phenol hydroxyl to a certain extent, has accelerated anti-oxidant speed of response, thereby makes the oxidation inhibitor of new texture give play to the effect that is superior to traditional hindered phenol antioxygen; And with the collaborative stabilization and the coloring resistance effect of auxiliary antioxidant; Symmetric form hindered phenol than traditional is more outstanding, can effectively reduce the production cost of polyoxymethylene, improves antioxidant effect; Satisfy polyoxymethylene and repeatedly process the requirement of back stable performance, be applicable to easy thermooxidative degradation, require highly heat-resistant and stable polyformaldehyde material and the goods of high color and luster.
Last embodiment is the unrestricted technical scheme of the present invention in order to explanation only, does not break away from any modification or the local replacement of spirit and scope of the invention, should be encompassed in the middle of the claim scope of the present invention.
Claims (7)
1. one kind has thermally-stabilised and polyoxymethylene weathering resistance, it is characterized in that, this is thermally-stabilised composed of the following components with polyoxymethylene weathering resistance, is by weight percentage:
2. according to claim 1 said a kind of have thermally-stabilised and polyoxymethylene weathering resistance, it is characterized in that said asymmetric hindered phenol antioxygen has the asymmetric hindered phenol of a tertiary butyl and a methyl for adopting the phenolic hydroxyl group ortho position.
3. according to claim 1 said a kind of have thermally-stabilised and polyoxymethylene weathering resistance, it is characterized in that said hindered amine as light stabilizer (HALS) is one type of organic amine compound with space steric effect; And with 2,2,6; 6-tetramethyl--4-piperidyl is a parent, and its structural formula is:
Wherein: R=methyl-CH
3
R
1=OH, NH2 or various group;
R
2=H, O, alkyl, alkoxyl group-OR3.
4. according to claim 1 said a kind of have thermally-stabilised and polyoxymethylene weathering resistance, it is characterized in that said R
2In alkyl be-CH
3
5. the preparation method with polyoxymethylene of thermally-stabilised and weathering resistance is characterized in that, comprises the steps:
(1) asymmetric hindered phenol antioxygen is synthetic:
A) alkylated reaction: react with ortho-cresol and iso-butylene, generate the nfrastructure of asymmetric hindered phenol antioxygen: 2-methyl-6-tert butyl phenol;
B) addition reaction: react synthetic intermediate β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) methyl propionate with 2-methyl-6-tert butyl phenol and methyl acrylate;
C) transesterify or substitution reaction: with glycol or the cyanuric chloride organic raw material reaction of contracting of midbody β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) methyl propionate and tetramethylolmethane, straight chain, synthetic asymmetric hindered phenol antioxygen.
(2) hindered amine as light stabilizer is synthetic
A) with 2,2,6,6-tetramethyl--4-piperidines alcohol is that raw material and acetaldehyde, butyral, ethylene chlorhydrin reaction obtain midbody 1-(beta-hydroxyethyl) 2,2,6,6-tetramethyl--4-piperidines alcohol (hereinafter to be referred as HTMP);
B) midbody 1-(beta-hydroxyethyl) 2,2,6,6-tetramethyl--4-piperidines alcohol generates hindered amine as light stabilizer with the one of which reaction of straight chain dibasic acid esters or acid anhydrides.
(3) polyoxymethylene of preparation thermostability and weathering resistance
A) at first, polyoxymethylene, asymmetric hindered phenol antioxygen, asymmetric hindered phenol antioxygen, hindered amine as light stabilizer, calcium stearate and trimeric cyanamide are mixed, add in the impeller and stir, obtain mixture;
B) then, mixture is added in the twin screw extruder, the working temperature that twin screw extruder is set is 180 ℃～220 ℃, and screw speed is 150r/min～300r/min, obtains having the polyoxymethylene of thermostability and weathering resistance.
6. according to the said a kind of preparation method of claim 5, it is characterized in that said straight chain dibasic acid esters is dimethyl adipate or dimethyl sebacate with polyoxymethylene of thermally-stabilised and weathering resistance.
7. according to the said a kind of preparation method of claim 5, it is characterized in that said acid anhydrides is a maleic anhydride with polyoxymethylene of thermally-stabilised and weathering resistance.
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| CN 201110309284 CN102337001A (en) | 2011-10-13 | 2011-10-13 | Polyformaldehyde with thermal stability and weather resistance and preparation method thereof |
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| CN 201110309284 CN102337001A (en) | 2011-10-13 | 2011-10-13 | Polyformaldehyde with thermal stability and weather resistance and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107531981A (en) * | 2015-06-30 | 2018-01-02 | 宝理塑料株式会社 | Polyacetal resin composite |
| CN108997610A (en) * | 2018-08-15 | 2018-12-14 | 湘潭大学 | A kind of steady antioxidant stabilizer of light |
| CN112795131A (en) * | 2020-12-30 | 2021-05-14 | 甘肃泰尔精细化工有限公司 | Anti-aging polyformaldehyde material and preparation method thereof |
| CN113264869A (en) * | 2021-05-20 | 2021-08-17 | 宿迁联盛科技股份有限公司 | Hindered phenol antioxidant and preparation method thereof |
| CN114514272A (en) * | 2019-10-17 | 2022-05-17 | 巴斯夫欧洲公司 | Melamine-formaldehyde foams having improved weatherability |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107531981A (en) * | 2015-06-30 | 2018-01-02 | 宝理塑料株式会社 | Polyacetal resin composite |
| CN107531981B (en) * | 2015-06-30 | 2020-11-20 | 宝理塑料株式会社 | Polyacetal resin composition |
| CN108997610A (en) * | 2018-08-15 | 2018-12-14 | 湘潭大学 | A kind of steady antioxidant stabilizer of light |
| CN114514272A (en) * | 2019-10-17 | 2022-05-17 | 巴斯夫欧洲公司 | Melamine-formaldehyde foams having improved weatherability |
| CN114514272B (en) * | 2019-10-17 | 2023-12-01 | 巴斯夫欧洲公司 | Melamine formaldehyde foam with improved weatherability |
| CN112795131A (en) * | 2020-12-30 | 2021-05-14 | 甘肃泰尔精细化工有限公司 | Anti-aging polyformaldehyde material and preparation method thereof |
| CN112795131B (en) * | 2020-12-30 | 2023-06-27 | 甘肃泰尔精细化工有限公司 | Ageing-resistant polyformaldehyde material and preparation method thereof |
| CN113264869A (en) * | 2021-05-20 | 2021-08-17 | 宿迁联盛科技股份有限公司 | Hindered phenol antioxidant and preparation method thereof |
| CN113264869B (en) * | 2021-05-20 | 2022-07-12 | 宿迁联盛科技股份有限公司 | Hindered phenol antioxidant and preparation method thereof |
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Application publication date: 20120201 |