CN102942725B - A kind ofly provide the composition of thermostability for polyolefine - Google Patents
A kind ofly provide the composition of thermostability for polyolefine Download PDFInfo
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- CN102942725B CN102942725B CN201210423891.2A CN201210423891A CN102942725B CN 102942725 B CN102942725 B CN 102942725B CN 201210423891 A CN201210423891 A CN 201210423891A CN 102942725 B CN102942725 B CN 102942725B
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- tallow group
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Abstract
The present invention relates to a kind ofly provides the composition of thermostability for polyolefine.The technical scheme adopted is: composition is made up of the mixture of N, N-dialkylhydroxylamine and N, N-dialkylamine, hindered phenol, phosphorous acid ester and Metallic stearates; The mass ratio of each raw material is as follows, the mixture of N, N-dialkylhydroxylamine and N, N-dialkylamine: hindered phenol: phosphorous acid ester: Metallic stearates=0.05-2:1:2-3:0.5-1.The structural formula of described N, N-dialkylamine is R
1r
2the structural formula of NH, N, N-dialkylhydroxylamine is R
1r
2nOH, wherein, R
1and R
2identical or different, be the alkyl of 12 to 30 carbon.
Description
Technical field
The present invention relates to a kind of composition, relating to particularly a kind ofly provides the composition of thermostability for polyolefine.
Background technology
Polyolefine, comprises polyethylene, polypropylene and multipolymer thereof, in hot-work and life-time service, is subject to the effect of light and heat, can by the dioxygen oxidation in air, and mechanical properties of polymer is lost, and outward appearance becomes unsightly.Therefore need to add oxidation inhibitor, to improve polyolefinic thermostability.
Long-chain N, N-dialkylhydroxylamine is known is a kind of effective oxidation inhibitor, but when it is used alone in polyolefine, to polyolefinic resisting ageing for long time performance and anti-yellowing property solve bad.
Summary of the invention
In order to solve the problem, the object of the present invention is to provide a kind of composition that the thermostability of excellence can be provided for polyolefine.
The technical solution used in the present invention is: a kind ofly provide the composition of thermostability for polyolefine, is made up of the mixture of N, N-dialkylhydroxylamine and N, N-dialkylamine, hindered phenol, phosphorous acid ester and stearate; The mass ratio of each raw material is as follows,
The mixture of N, N-dialkylhydroxylamine and N, N-dialkylamine: hindered phenol: phosphorous acid ester: stearate=0.05-0.2:1:2-3:0.5-1.
The structural formula of described N, N-dialkylamine is R
1r
2the structural formula of NH, N, N-dialkylhydroxylamine is R
1r
2nOH, wherein, R
1and R
2identical or different, be the alkyl of 12 to 30 carbon.
The preparation method of the mixture of N, N-dialkylhydroxylamine and N, N-dialkylamine has the following two kinds: (1) is by N, N-dialkylamine (R
1r
2nH) be dissolved in lower alcohol, add aqueous hydrogen peroxide solution, at 40-80 DEG C, react after 2-6 hour, underpressure distillation goes out lower alcohol, and gained solid is N, N-dialkylhydroxylamine (R
1r
2and N, N-dialkylamine (R NOH)
1r
2nH) mixture, R
1r
2nH and R
1r
2r in NOH mixture
1r
2nH quality is less than 10%.(2) by N, N-dialkylamine (R
1r
2nH) be dissolved in lower alcohol, add aqueous hydrogen peroxide solution, at 40-80 DEG C, react after 2-6 hour, filter at this temperature, and wash solid with the lower alcohol at this temperature, filter cake is N, N-dialkylhydroxylamine (R
1r
2nOH); Underpressure distillation after filtrate being merged, the product after underpressure distillation is the mixture of N, N-dialkylhydroxylamine and N, N-dialkylamine, R
1r
2nH and R
1r
2r in NOH mixture
1r
2nH quality is less than 20%.Described lower alcohol is the alkyl alcohol being less than six carbon, comprises one or more mixing of methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, Pentyl alcohol, primary isoamyl alcohol, n-hexyl alcohol or hexalin.Preferably, lower alcohol is one or more mixing of ethanol, propyl alcohol, Virahol or propyl carbinol.
Above-mentioned a kind ofly provide the composition of thermostability for polyolefine, described hindered phenol is selected from four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, β-(3,5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid or 1,3,5-trimethylammonium-2,4, one or more combination of 6-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) benzene.Preferably, hindered phenol is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester.
Above-mentioned a kind ofly provide the composition of thermostability for polyolefine, described phosphorous acid ester is selected from one or both the mixing of three ［ 2.4-di-tert-butyl-phenyl ］ phosphorous acid esters or two (2,4-DTBP) pentaerythritol diphosphites.Preferably, phosphorous acid ester is three ［ 2.4-di-tert-butyl-phenyl ］ phosphorous acid ester.
Above-mentioned a kind ofly provide the composition of thermostability for polyolefine, described stearate is selected from one or more mixing of calcium stearate, Zinic stearas or Magnesium Stearate.Preferably, stearate is calcium stearate.
Above-mentioned a kind ofly the composition of thermostability, described polyolefine is provided to refer to polyethylene or polyacrylic homopolymer or its multipolymer for polyolefine.Preferably, polyolefine is homopolymer polypropylene.
Composition of the present invention is as oxidation inhibitor, and the add-on in polyolefine processing is 800-3000ppm.Especially, the add-on of composition in polyolefine is 800-1800ppm.Composition of the present invention can join in polyolefine in powder form.Also can form particle after granulation to join in polyolefine.
The preparation method of the mixture of N, N-dialkylhydroxylamine of the present invention and N, N-dialkylamine, first method is simple, and do not have still residual, all raw materials all utilize, and the cost of product is very low.In product, the content of N, N-dialkylamine is not more than 10%.Second method can obtain pure N, the mixture of N-dialkylhydroxylamine and N, N-dialkylhydroxylamine and N, N-dialkylamine, and in mixture, the content of N, N-dialkylamine is not more than 20%.In the second preparation method, the filter cake obtained is highly purified N, N-dialkylhydroxylamine, can use as oxidation inhibitor separately.
N, N-dialkylhydroxylamine Wheat Protein in composition of the present invention, N, N-dialkylamine has the effect of acid scavenger.N, N-dialkylamine is typical alkaline compound, can with residual Cl in pp material
-ionic reaction, can play the effect of deacidification.The mixture of N, N-dialkylhydroxylamine and N, N-dialkylamine can as antioxygen acid scavenger.
But, N, N-dialkylhydroxylamine and N, when N-dialkylamine mixture is used alone, its antioxidant effect can't meet polyolefinic service requirements completely, when jointly using with hindered phenol antioxygen, phosphorous acid ester auxiliary anti-oxidant and a certain amount of acid scavenger, excellent thermal oxidation stability habit can be provided for polyolefine.
The invention has the beneficial effects as follows: N, N-dialkylhydroxylamine and N, the mixture cost of N-dialkylamine is low, there is antioxygen deacidification effect simultaneously, when jointly using with hindered phenol antioxygen, phosphorous acid ester auxiliary anti-oxidant and a certain amount of acid scavenger, excellent thermo-oxidative stability can be provided for polyolefine.
Embodiment
Twin-screw extrusion is tested: extrude in twin screw extruder, screw temperature set is TS1:180 DEG C, TS2-TS10:200 DEG C.
Homopolymer polypropylene: melting index is 7.3g/10min.
Natene: melting index is 10g/10min.
Test total amine value by the following method:
1,50mL Glacial acetic acid adds about 0.5g sample;
2, Viola crystallina indicator is added, with the HClO of 0.1N
4be titrated to purple to disappear, in blue.
Calculate: total amine value=(N × V × 56.11)/M
N---HClO
4equivalent concentration
V---consumption HClO
4number
M---sample grams
In N, N-dialkylhydroxylamine and N, N-dialkylamine mixture, the content of N, N-dialkylamine is by the change calculations of amine value total before and after reaction.
the mixture of embodiment 1 pair of hydrogenated-tallow group oxyamine and two hydrogenated-tallow group amine
Two for 10g hydrogenated-tallow group amine (diamines is greater than 90%) is dissolved in the 50mL propyl carbinol of 60 DEG C, drip the hydrogen peroxide of 2mL 70% wherein, be added dropwise to complete in 30min, react after two hours, underpressure distillation goes out propyl carbinol, and solid is carried out vacuum-drying, obtains the mixture of the two hydrogenated-tallow group oxyamine of 10g and two hydrogenated-tallow group amine, wherein, the content of two hydrogenated-tallow group amine is 3%.
the mixture of embodiment 2 pairs of hydrogenated-tallow group oxyamines and two hydrogenated-tallow group amine
two for 10g hydrogenated-tallow group amine (diamines is greater than 90%) is dissolved in the 50mL propyl carbinol of 60 DEG C, drip the hydrogen peroxide of 2mL 70% wherein, be added dropwise to complete in 30min, react after two hours, filter out propyl carbinol, wash twice at 60 DEG C with 50mL propyl carbinol, filter cake by analysis, for the two hydrogenated-tallow group oxyamine of high purity, wherein, two hydrogenated-tallow group amine content is 0.2%.Filtrate is merged, underpressure distillation goes out propyl carbinol, product after underpressure distillation is the mixture of two hydrogenated-tallow group oxyamine and two hydrogenated-tallow group amine, mixture is carried out vacuum-drying, obtain the mixture of the two hydrogenated-tallow group oxyamine of 5.0g and two hydrogenated-tallow group amine, the content of two hydrogenated-tallow group amine is 16%.
embodiment 3 one kinds provides the composition of thermostability for polyolefine
The mixture of two hydrogenated-tallow group oxyamine prepared by embodiment 1 and two hydrogenated-tallow group amine, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, three ［ 2.4-di-tert-butyl-phenyl ］ phosphorous acid ester and calcium stearates, 0.11:1:2.22:0.83 mixes and makes in mass ratio.
It mixed with powder, join in polypropylene, add-on is 1500ppm, and extrude three times in screw rod after, polypropylene melt index is 9.3 g/10min, and yellowness index is 3.5.
embodiment 4
a kind ofly provide the composition of thermostability for polyolefine
The mixture of two hydrogenated-tallow group oxyamine prepared by embodiment 1 and two hydrogenated-tallow group amine, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, three ［ 2.4-di-tert-butyl-phenyl ］ phosphorous acid ester and calcium stearates, 0.18:1:2.35:0.88 mixes and makes in mass ratio.
It mixed with powder, join in polypropylene, add-on is 1500ppm, and extrude three times in screw rod after, polypropylene melt index is 10.2 g/10min, and yellowness index is 2.5.
embodiment 5
a kind ofly provide the composition of thermostability for polyolefine
The mixture of two hydrogenated-tallow group oxyamine prepared by embodiment 1 and two hydrogenated-tallow group amine, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, three ［ 2.4-di-tert-butyl-phenyl ］ phosphorous acid ester and calcium stearates, 0.05:1:2.1:0.79 mixes and makes in mass ratio.
It mixed with powder, join in polypropylene, add-on is 1500ppm, and extrude three times in screw rod after, polypropylene melt index is 8.7 g/10min, and yellowness index is 3.4.
embodiment 6
a kind ofly provide the composition of thermostability for polyolefine
The mixture of two hydrogenated-tallow group oxyamine prepared by embodiment 2 and two hydrogenated-tallow group amine, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, three ［ 2.4-di-tert-butyl-phenyl ］ phosphorous acid ester and calcium stearates, 0.05:1:2.1:0.79 mixes and makes in mass ratio.
It mixed with powder, join in polypropylene, add-on is 1200ppm, and extrude three times in screw rod after, polypropylene melt index is 9.3 g/10min, and yellowness index is 3.7.
embodiment 7
a kind ofly provide the composition of thermostability for polyolefine
The mixture of two hydrogenated-tallow group oxyamine prepared by embodiment 2 and two hydrogenated-tallow group amine, 1,3,5-trimethylammonium-2,4,6-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) benzene, two (2,4-DTBP) pentaerythritol diphosphites and Magnesium Stearate composition, make for 0.05:1:2.1:0.79 mixes in mass ratio.
It mixed with powder, join in polypropylene, add-on is 1500ppm, and extrude three times in screw rod after, polypropylene melt index is 8.2 g/10min, and yellowness index is 1.6.
embodiment 8
a kind ofly provide the composition of thermostability for polyolefine
The mixture of two hydrogenated-tallow group oxyamine prepared by embodiment 2 and two hydrogenated-tallow group amine, β-(3,5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid, three ［ 2.4-di-tert-butyl-phenyl ］ phosphorous acid ester and Zinic stearass, make for 0.05:1:2.1:0.79 mixes in mass ratio.
It mixed with powder, join in polypropylene, add-on is 1000ppm, and extrude three times in screw rod after, polypropylene melt index is 12.6 g/10min, and yellowness index is 0.9.
simultaneous test
simultaneous test 1
By four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, three ［ 2.4-di-tert-butyl-phenyl ］ phosphorous acid ester, calcium stearate forms, and 1:2.22:0.83 mixes and makes in mass ratio.
It mixed with powder, join in polypropylene, add-on is 1500ppm, and extrude three times in screw rod after, polypropylene melt index is 12.3 g/10min, and yellowness index is 4.1.
simultaneous test 2
Join in polypropylene powder by mixture prepared by embodiment 1, add-on is 400ppm, and extrude three times in screw rod after, polypropylene melt index is 23.9 g/10min, and yellowness index is 5.9.
From above-mentioned simultaneous test, composition of the present invention is excellent antioxidant system, can effectively improve polyolefinic thermostability.
Claims (1)
1. for polyolefine provides a composition for thermostability, it is characterized in that: the formula of composition is as follows:
In mass ratio, the mixture of two hydrogenated-tallow group oxyamine and two hydrogenated-tallow group amine: 1,3,5-trimethylammonium-2,4,6-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) benzene: two (2,4-DTBP) pentaerythritol diphosphites: Magnesium Stearate=0.05:1:2.1:0.79; Or
In mass ratio, the mixture of two hydrogenated-tallow group oxyamine and two hydrogenated-tallow group amine: β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid: three ［ 2.4-di-tert-butyl-phenyl ］ phosphorous acid ester: Zinic stearas=0.05:1:2.1:0.79;
The preparation method of the mixture of described two hydrogenated-tallow group oxyamine and two hydrogenated-tallow group amine is as follows:
10g diamine contents is greater than two hydrogenated-tallow group amine solvents of 90% in the 50mL propyl carbinol of 60 DEG C, drip the hydrogen peroxide of 2mL 70% wherein, be added dropwise to complete in 30min, react after two hours, filter out propyl carbinol, wash twice at 60 DEG C with 50mL propyl carbinol, filtrate is merged, underpressure distillation goes out propyl carbinol, product after underpressure distillation is the mixture of two hydrogenated-tallow group oxyamine and two hydrogenated-tallow group amine, mixture is carried out vacuum-drying, obtain the mixture of the two hydrogenated-tallow group oxyamine of 5.0g and two hydrogenated-tallow group amine, the content of two hydrogenated-tallow group amine is 16%.
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| CN104419015B (en) * | 2013-09-03 | 2017-06-09 | 中国科学院化学研究所 | A kind of composition and its application that heat endurance is provided for polymer |
| KR102389451B1 (en) * | 2017-05-25 | 2022-04-22 | 셰브론 필립스 케미컬 컴퍼니 엘피 | How to Improve Color Stability in Polyethylene Resins |
| CN107254085B (en) * | 2017-06-20 | 2020-09-25 | 北京吉海川科技发展有限公司 | Polyolefin auxiliary agent composition with high oxidation resistance |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0286596A2 (en) * | 1987-04-10 | 1988-10-12 | Ciba-Geigy Ag | Use of n,n-dialkylhydroxylamines and their preparation |
| US4876300A (en) * | 1987-12-30 | 1989-10-24 | Ciba-Geigy Corporation | Polyolefin compositions stabilized with long chain N,N-dialkylhydroxylamines |
| CN1272863A (en) * | 1998-06-12 | 2000-11-08 | 蒙岱尔北美股份有限公司 | Olefin polymer composition having low smoke generation and fiber, film and fabric prepared therefrom |
-
2012
- 2012-10-31 CN CN201210423891.2A patent/CN102942725B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0286596A2 (en) * | 1987-04-10 | 1988-10-12 | Ciba-Geigy Ag | Use of n,n-dialkylhydroxylamines and their preparation |
| US4876300A (en) * | 1987-12-30 | 1989-10-24 | Ciba-Geigy Corporation | Polyolefin compositions stabilized with long chain N,N-dialkylhydroxylamines |
| CN1272863A (en) * | 1998-06-12 | 2000-11-08 | 蒙岱尔北美股份有限公司 | Olefin polymer composition having low smoke generation and fiber, film and fabric prepared therefrom |
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