CN105482250B - A kind of composition being used in polyolefin - Google Patents
A kind of composition being used in polyolefin Download PDFInfo
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- CN105482250B CN105482250B CN201510980829.7A CN201510980829A CN105482250B CN 105482250 B CN105482250 B CN 105482250B CN 201510980829 A CN201510980829 A CN 201510980829A CN 105482250 B CN105482250 B CN 105482250B
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- polyolefin
- sodium borohydride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
A kind of composition being used in polyolefin, the composition is prepared from by raw material hindered phenol, phosphite ester, stearate and sodium borohydride, and the mass ratio of the raw material is as follows：mHindered phenol:mPhosphite ester:mStearate:mSodium borohydride=1:1‑4:0.5‑1.5:0.5‑3.The composition of the present invention is used in polyolefin, can improve the heat endurance of polyolefin, eliminates chromophoric group, prevents polyolefin products from changing colour, and improves the durabilities of polyolefin products and attractive in appearance.
Description
Technical field
The invention belongs to polymer arts, more particularly to a kind of composition being used in polyolefin.
Background technology
Polyolefin, including polyethylene, polypropylene and its copolymer, in hot-working and being used for a long time, by light and heat
Effect, can be lost, outward appearance becomes unsightly by the dioxygen oxidation in air, polyolefin mechanical property.Therefore need to add antioxygen
Agent, to improve the heat endurance of polyolefin.
Hindered phenol antioxygen is widely used in polymer, and for reducing the thermo-oxidative ageing in Polymer Processing, reduction is poly-
Performance reduction in compound use, extends the usage cycles of polymer.Conventional Hinered phenols antioxidant has：Four-[β-(3,5-
Di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythrite (trade name：Antioxidant 1010), 4- hydroxy-phenylpropionic acid octadecyls
(trade name：Antioxidant 1076), 1,3,5- trimethyl -2,4,6- tri- (3,5- di-tert-butyl-4-hydroxyl benzyl) benzene (trade name：
Antioxidant 1330).
But, hindered phenol antioxygen easily and radical reaction, generates the intermediate product of quinones, and quinones chemical combination
Thing carries chromophoric group, and can make the yellow colour index of polyolefin increases, and influences the outward appearance of polyolefin products.
The content of the invention
An object of the present invention is a kind of composition being used in polyolefin of offer, and said composition can improve polyene
The heat endurance of hydrocarbon, eliminates chromophoric group, prevents polyolefin products from changing colour, and improves the durabilities of polyolefin products and attractive in appearance.
The above-mentioned purpose of the present invention is achieved through the following technical solutions：
A kind of composition being used in polyolefin, the composition is by raw material hindered phenol, phosphite ester, stearate and boron
Sodium hydride is prepared from, and the mass ratio of the raw material is as follows：
mHindered phenol:mPhosphite ester:mStearate:mSodium borohydride=1:1-4:0.5-1.5:0.5-3.
Preferably, mHindered phenol:mPhosphite ester:mStearate:mSodium borohydride=1:2-3:1-1.5:1-2.
It is further preferred that mHindered phenol:mPhosphite ester:mStearate:mSodium borohydride=1:2:1.5:1.
Preferably, the sodium borohydride is powder.
It is further preferred that the volume average particle sizes of the sodium borohydride powder are 2-30 μm.
Preferably, the hindered phenol be selected from four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, β-
The positive octadecanol ester of (3,5- di-tert-butyl-hydroxy phenyls) propionic acid or (the tertiary fourths of 3,5- bis- of 1,3,5- trimethyls -2,4,6- three
Base -4- hydroxybenzyls) any of benzene or a variety of combinations.
Preferably, the hindered phenol is four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters.
Preferably, the phosphite ester is selected from three [2,4- di-tert-butyl-phenyl] phosphite esters or double (2,4- di-t-butyls
Phenol) any of pentaerythritol diphosphites or two kinds of combination.
Preferably, the phosphite ester is three [2,4- di-tert-butyl-phenyl] phosphite esters.
Preferably, the stearate is in calcium stearate, zinc stearate, zinc oxide, magnesium stearate or hydrotalcite
Any one or more combinations.
Preferably, the polyolefin is polyethylene or polyacrylic homopolymer or its copolymer.
Preferably, the polyolefin is polyacrylic homopolymer.
It is another object of the present invention to provide the preparation method of above-mentioned composition, the preparation method is first by boron
Sodium hydride is ground, and obtains the sodium borohydride powder that volume average particle sizes are 2-30 μm；Then by hindered phenol, phosphite ester, tristearin
Hydrochlorate and sodium borohydride powder, it is well mixed by the mass ratio, obtain composition.
It is preferred that sodium borohydride grinds 10-20h, further preferred 15h.
It is yet a further object of the present invention to provide a kind of preparation method of polyolefin, including addition combinations of the above thing,
Addition of the composition in polyolefin is 800-3000ppm.
Preferably, addition of the composition in polyolefin is 800-1800ppm.
The above-mentioned composition of the present invention can be obtained according to conventional preparation method.
Preferably, the composition is added in the form of a powder.
Preferably, the composition is added in the form of granules, and the particle is obtained by the composition through granulation.
A further object of the present invention is to provide application of the above-mentioned composition in polyolefin is prepared.
The beneficial effects of the present invention are：The composition of the present invention, by three kinds of raw materials of sodium borohydride and other with certain
Ratio is mixed to get, with stronger reproducibility, in the preparation for using it for polyolefin, can improve the heat endurance of polyolefin,
Chromophoric group is eliminated, prevents polyolefin products from changing colour, the durabilities of polyolefin products is improved and attractive in appearance.
Embodiment
Technical solution of the present invention and its effect are described further below by way of specific embodiment.Following examples are only used
In explanation present disclosure, the protection domain being not intended to limit the invention.The present invention is carried out using the design of the present invention
Simple change all in the scope of protection of present invention.
The raw material specification and source used in following examples of the present invention are as follows：
Sodium borohydride：Analyze pure, Chinese medicines group chemical reagent Beijing Co., Ltd；
Calcium stearate：Chemical pure, Chinese medicines group chemical reagent Beijing Co., Ltd；
Zinc stearate：Chemical pure, Chinese medicines group chemical reagent Beijing Co., Ltd；
Magnesium stearate：Chemical pure, Chinese medicines group chemical reagent Beijing Co., Ltd；
Zinc oxide：Analyze pure, Chinese medicines group chemical reagent Beijing Co., Ltd；
Hydrotalcite：99%, Beijing Yi Nuokai Science and Technology Ltd.s；
Antioxidant (hindered phenol and phosphorous acid esters)：Technical grade, YingKou Viewchem CO.,Ltd.
Embodiment 1-14 composition prepares part and carried out according to herein below：
Sodium borohydride is put into ball mill first and grinds 10-20h, the hydroboration that volume average particle sizes are 2-30 μm is obtained
Sodium powder end；Then by hindered phenol, phosphite ester, stearate and sodium borohydride powder, by certain mass than well mixed, obtain
Composition.
The composition of embodiment 15 prepares part and carried out according to herein below：
By hindered phenol, phosphite ester and stearate, by certain mass than well mixed, composition is obtained.
Embodiment 1-15 is carried out after preparing composition according to herein below：
Obtained composition is added in polyolefin and is well mixed, is tested according to twin-screw extrusion, by it in screw rod
Extrusion three times, determines the melt index and yellow colour index of polyolefin.
Twin-screw extrusion is tested：Extruded in double screw extruder, screw temperature set is TS1：195 DEG C, TS2:
205 DEG C, TS3-TS9：210 DEG C, TS10：200℃.
The measure of melt index：According to《GB/T3682-2000 thermoplastics melt mass flow rate and melt volume
The measure of flow rate》Method determine.
The mobility of melt index representation polymer, melt index is higher, and the mobility of polymer is better, and heat endurance is got over
Difference.
The measure of yellow colour index：According to《HB/T3862-2006 plastics yellow colour index test methods》Method determine.
The yellowing of yellow colour index representation polymer, yellow colour index is higher, and the oxidation of polymer is more serious.
Embodiment 1-15 experimental result is as shown in table 1.
The embodiment 1-15 of table 1 related content and experimental result
From the embodiment 1-7 in table 1, when the addition of sodium borohydride is in mHindered phenol:mPhosphite ester:mStearate:mSodium borohydride=1:
1-4:0.5-1.5:The composition obtained when in the range of 0.5-3, after being added into polymer, the melting of obtained polymer refers to
Number and yellow colour index are relatively low, and this obtained polymer thermostable is good, and the eradicating efficacy of chromophoric group is good, and polymer is not
Easy to change, yellowing is light, appearance looks elegant；And when the addition of sodium borohydride exceeds mHindered phenol:mPhosphite ester:mStearate:mSodium borohydride=1:
1-4:0.5-1.5:The composition obtained during 0.5-3 scope, after being added into polymer, the melt index of obtained polymer
Higher with yellow colour index, the polymer thermostable that this is obtained is poor, and the eradicating efficacy of chromophoric group is poor, and polymer is variable
Color, yellowing is high.
From the embodiment 5,8,9 in table 1, when the mass ratio of several raw materials of composition exceeds mHindered phenol:mPhosphite ester:
mStearate:mSodium borohydride=1:1-4:0.5-1.5:The composition obtained during 0.5-3 scope, after being added into polymer, is obtained
The melt index and yellow colour index of polymer are higher, and the polymer thermostable that this is obtained is poor, the elimination of chromophoric group
Effect is poor, and polymer is easy to change, and yellowing is high.
From the embodiment 5 and 15 in table 1, the combination obtained when not including sodium borohydride in the raw material of composition
Thing, after being added into polymer, the melt index and yellow colour index of obtained polymer are higher, this obtained polymer
Heat endurance is poor, and the eradicating efficacy of chromophoric group is poor, and polymer is easy to change, and yellowing is high, also further illustrates sodium borohydride
Property to composition has a major impact.
From the embodiment 1-15 in table 1, when the raw material of composition is hindered phenol, phosphite ester, stearate and boron
Sodium hydride, and several raw materials mass ratio in mHindered phenol:mPhosphite ester:mStearate:mSodium borohydride=1:1-4:0.5-1.5:0.5-3 scope
The composition obtained when interior, especially works as mHindered phenol:mPhosphite ester:mStearate:mSodium borohydride=1:2:1.5:The composition obtained when 1, addition
After entering in polymer, the melt index and yellow colour index of obtained polymer are very low, this obtained polymer thermostable
Property is good, and the eradicating efficacy of chromophoric group is good, and polymer is not easy to change, the low appearance looks elegant of yellowing；Also further illustrate terrible
To composition be used for polymer in, the heat endurance of polymer can not only be improved, while also improving the anti-oxidant of polymer
Property, effectively eliminate chromophoric group.
Claims (18)
1. a kind of composition being used in polyolefin, it is characterised in that the composition is by raw material hindered phenol, phosphite ester, hard
Resin acid salt and sodium borohydride are prepared from, and the mass ratio of the raw material is as follows：mHindered phenol:mPhosphite ester:mStearate:mSodium borohydride=1:1-4:
0.5-1.5:0.5-3。
2. composition according to claim 1, it is characterised in that
mHindered phenol:mPhosphite ester:mStearate:mSodium borohydride=1:2-3:1-1.5:1-2.
3. composition according to claim 2, it is characterised in that mHindered phenol:mPhosphite ester:mStearate:mSodium borohydride=1:2:1.5:1.
4. composition according to claim 1 or 2, it is characterised in that the sodium borohydride is powder.
5. composition according to claim 4, it is characterised in that the volume average particle sizes of the sodium borohydride powder are 2-
30μm。
6. composition according to claim 4, it is characterised in that the hindered phenol be selected from four [β-(3,5- di-t-butyls-
4- hydroxy phenyls) propionic acid] pentaerythritol ester, the β-positive octadecanol ester of (3,5- di-tert-butyl-hydroxy phenyls) propionic acid or 1,3,
Any of 5- trimethyls -2,4,6- three (3,5- di-tert-butyl-4-hydroxyl benzyls) benzene or a variety of combinations.
7. composition according to claim 6, it is characterised in that the hindered phenol is four [β-(3,5- di-t-butyl -4-
Hydroxy phenyl) propionic acid] pentaerythritol ester.
8. composition according to claim 4, it is characterised in that the phosphite ester is selected from three [2,4- di-tert-butyls
Base] any of phosphite ester or double (2,4- DI-tert-butylphenol compounds) pentaerythritol diphosphites or two kinds of combination.
9. composition according to claim 8, it is characterised in that the phosphite ester is three [2,4- di-tert-butyl-phenyls]
Phosphite ester.
10. composition according to claim 4, it is characterised in that the stearate is selected from calcium stearate, zinc stearate
Or any of magnesium stearate or a variety of combinations.
11. the composition according to claim any one of 6-10, it is characterised in that the polyolefin is polyethylene or poly- third
The homopolymer of alkene or its copolymer.
12. composition according to claim 11, it is characterised in that the polyolefin is polyacrylic homopolymer.
13. a kind of preparation method of composition as described in claim any one of 1-12, it is characterised in that the preparation method
It is first to grind sodium borohydride, obtains the sodium borohydride powder that volume average particle sizes are 2-30 μm；Then by hindered phenol, phosphorous
Acid esters, stearate and sodium borohydride powder, it is well mixed by the mass ratio, obtain composition.
14. a kind of preparation method of polyolefin, including the composition as described in claim any one of 1-12 is added, its feature exists
In addition of the composition in polyolefin is 800-3000ppm.
15. according to method according to claim 14, it is characterised in that addition of the composition in polyolefin be
800-1800ppm。
16. according to method according to claim 14, it is characterised in that the composition is added in the form of a powder.
17. according to method according to claim 14, it is characterised in that the composition is added in the form of granules, institute
Particle is stated to be obtained through granulation by the composition.
18. application of the composition as described in claim any one of 1-12 in polyolefin is prepared.
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| CN105482250B true CN105482250B (en) | 2017-09-15 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1944511A (en) * | 2006-10-26 | 2007-04-11 | 上海金海雅宝精细化工有限公司 | Premixed composite granular antioxidant for polyolifen and its preparing method |
| CN103146028A (en) * | 2013-03-08 | 2013-06-12 | 江西吉祥新材料有限公司 | Additive composition for polyolefin and application of additive composition as well as polyolefin combustion |
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2015
- 2015-12-23 CN CN201510980829.7A patent/CN105482250B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1944511A (en) * | 2006-10-26 | 2007-04-11 | 上海金海雅宝精细化工有限公司 | Premixed composite granular antioxidant for polyolifen and its preparing method |
| CN103146028A (en) * | 2013-03-08 | 2013-06-12 | 江西吉祥新材料有限公司 | Additive composition for polyolefin and application of additive composition as well as polyolefin combustion |
Non-Patent Citations (1)
| Title |
|---|
| 复合抗氧剂对聚丙烯抗氧化性能的研究;王芳等;《现代塑料加工应用》;20130831;第25卷(第4期);第37-39页 * |
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