CN111057288A - Composition for preventing polyolefin copolymer from photo-aging and polyolefin red-change - Google Patents
Composition for preventing polyolefin copolymer from photo-aging and polyolefin red-change Download PDFInfo
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0038—Use of organic additives containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/106—Radiation shielding agents, e.g. absorbing, reflecting agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/527—Cyclic esters
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Abstract
The invention relates to a composition for preventing polyolefin copolymer from photo-aging and polyolefin from reddening, such as stabilizing melt-blown and spun-bonded non-woven fabrics, preventing the melt-blown and spun-bonded non-woven fabrics from decomposing due to exposure to sunlight and preventing the melt-blown and spun-bonded non-woven fabrics from reddening under natural conditions; the composition is prepared from the following raw materials in percentage by mass: 40-80% of triazine hindered amine light stabilizer, 1-20% of inorganic salt and 10-40% of phosphite antioxidant; the invention also relates to a method for stabilizing polyolefin materials by using said additive composition, which is particularly suitable for articles with a large specific surface area, such as fibers, flat yarns and films, and which does not cause redness of the article surface while extending the useful life of the article.
Description
Technical Field
The invention relates to the field of polyolefin materials, in particular to a composition for preventing polyolefin copolymer from photo-aging and polyolefin red-turning, which can be applied to master batches and products, and is particularly suitable for film, flat filament and fiber polyolefin products with large specific surface area.
Background
Polyolefin materials are often degraded due to light, heat, oxygen and the like during processing, storage and use, and have aging problems such as reduced mechanical properties, surface color change and the like. Among them, light irradiation is a main cause of aging of polyolefin materials. Polyolefin thin films and fiber products are smaller in thickness and more prone to aging, and currently, hindered light stabilizers and hindered phenol antioxidants are widely used in the field. A single auxiliary agent cannot meet the processing, storage and use requirements of polyolefin products, so that a compound system with a synergistic effect is widely concerned, such as the early CN 1080283C, CN1178978C and CN 1311020C.
In the actual processing and storage processes of the polyolefin material, the use of the hindered amine light stabilizer and the hindered phenol antioxidant can prolong the service life of the product, the hindered amine light stabilizer mainly plays a role in resisting light aging, and the hindered phenol antioxidant mainly plays a role in preventing the product from being oxidized in the heat processing process. The triazine hindered amine light stabilizer has higher viscosity, has better compatibility with polyolefin compared with other additives, resists precipitation and is not easy to decompose in high-temperature processing, thus being a better choice for preventing aging of polyolefin products. However, introduction of hindered amine groups and hindered phenol groups often results in yellowing or reddening of the surface of polyolefin films and fibrous articles. In the reported formula system, most of injection-molded and extrusion-molded thick products are mainly age-resistant, and the cases of aging resistance and product reddening or yellowing are not solved for film and fiber products with larger specific surface area.
Fiber products and film products are often smaller in thickness, have larger air contact area in unit weight than injection molding and extrusion products, are easier to contact with air, and are easier to contact with oxygen, ozone and nitrogen oxides in the air. Polyolefin products, especially film, tape and fiber products with similar surface areas, are often reddened or yellowed after an anti-aging auxiliary agent is introduced, mainly because hindered amine light stabilizers generate nitroxide radicals (the nitroxide radicals are red), and hindered phenol antioxidants form quinone structures (the quinone structures are often red or yellow). The zinc salt or the calcium salt in the hindered amine system can effectively reduce the amount of red substances; the hindered phenol antioxidant is removed in an anti-aging system, and the phosphite antioxidant is used to effectively prevent the product from turning red or yellow.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a composition for preventing polyolefin copolymer from photo-aging and polyolefin from reddening, and simultaneously solves the problems of the aging of polyolefin materials and the reddening or yellowing of products after an anti-aging auxiliary agent is introduced, so that polyolefin films, flat yarns and fiber products have good anti-aging property and are not easy to redden or yellow.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the composition for preventing polyolefin copolymer from photo-aging and polyolefin from red-changing is prepared from the following raw materials in percentage by mass: 40-80% of triazine hindered amine light stabilizer, 1-20% of inorganic salt and 10-40% of phosphite antioxidant.
Preferably, the triazine hindered amine light stabilizer has a structure shown in formula (1):
wherein, in the formula (1), R1Is hydrogen, C1-8Alkyl radical, C1-8Alkoxy or hydroxy; r2Is hydrogen, C1-8An alkyl group; r3、R3Each independently selected from C1-8Alkyl radical, C1-8Amino-substituted alkyl, C1-8Diamino-substituted alkyl, pyrrolidinyl, amino-substituted cyclohexyl, amino-substituted cyclohexyloxy, morpholinyl, C1-8Amino-substituted alkyl piperidyl or has a structure shown in a formula (1-2),
wherein, in the formula (1-2), R5Is hydrogen, C1-8Alkyl radical, C1-8Alkoxy or hydroxy; r6Is hydrogen, C1-8An alkyl group.
Preferably, the structure of the phosphite antioxidant is shown as formula (2):
wherein, in the formula (2), R7、R8Each independently selected from hydrogen and C1-8Alkyl radical, C1-8An alkoxy group; r9、R10Each independently selected from phenyl, C1-8Alkyl-substituted phenyl, C1-3Carboxy-substituted phenyl, C1-3Phosphorous acid substituted phenyl or a structure shown as a formula (2-2);
wherein, in the formula (2-2), R11、R12Each independently selected from hydrogen and C1-8Alkyl radical, C1-8An alkoxy group.
Preferably, the inorganic salt is a zinc salt or a calcium salt.
Preferably, the zinc salt is any one of zinc oxide, zinc stearate, zinc phosphate, zinc carbonate and zinc sulfate.
Preferably, the calcium salt is any one of calcium hydroxide, calcium stearate and calcium carbonate.
Preferably, the triazine-based hindered amine light stabilizer may be selected from any one of formula (3), formula (4), formula (5), formula (6), formula (7), formula (8), formula (9), formula (10), formula (11), formula (12), formula (13), and formula (14). .
Preferably, the phosphite antioxidant may be any one selected from the group consisting of formula (15), formula (16), formula (17), formula (18), formula (19), and formula (20).
The composition can be used for preparing anti-aging/anti-reddening weather-resistant master batches, and can also be directly added into products to prolong the service life of the products.
The composition group for preventing the polyolefin copolymer from photo-aging and preventing the polyolefin from red-changing is applied to products with larger specific surface area, such as fibers, flat wires and film products.
Compared with the prior art, the invention has the following beneficial effects because the technology is adopted:
1. compared with a product without the anti-aging auxiliary agent, the anti-aging agent can prevent the product from aging in the processing process after the formula is added.
2. Compared with a product without the anti-aging auxiliary agent, the service life of the product can be prolonged by more than 50% after the formula is added.
3. Compared with a direct single-type anti-aging auxiliary agent, the product with a large specific surface area is not easy to turn red after the formula is added, and the appearance quality of the product can be effectively ensured.
Detailed Description
The present invention will be further illustrated with reference to the following specific embodiments.
Example 1:
100g of hindered amine light stabilizer HALS 944, 20g of phosphite antioxidant AO 168 and 10.2g of zinc stearate were mixed and stirred to obtain 130g of the composition. 130g of the composition and 870g of polypropylene resin are mixed and extruded and granulated at the temperature of 150 ℃ and 200 ℃ to prepare the anti-aging master batch (A).
Comparative example 100g of hindered amine light stabilizer HALS 944, 10g of hindered phenol antioxidant AO 1010, 10g of phosphite antioxidant AO 168 and 10.2g of zinc stearate were mixed and stirred to give 130g of a composition. 130g of the composition and 870g of polypropylene resin are mixed, extruded and granulated at 150 to 200 ℃ to prepare the anti-aging master batch (B).
The anti-aging master batch (A) and the anti-aging master batch (B) prepared in example 1 are respectively added into PP resin in a proportion of 2%, and the anti-aging non-woven fabric 1 and the anti-aging non-woven fabric 2 are respectively made by high-temperature melting (280 ℃)/spinning/laying line/hot-pressing curling in the same process. The nonwoven fabric layers were dropped together, and it was found that the aging-resistant nonwoven fabric 2 was slightly reddish in light microscopy as compared with the aging-resistant nonwoven fabric 1.
Placing the single layers of the aging-resistant non-woven fabric 1 and the aging-resistant non-woven fabric 2 in a Q-LAB fluorescent ultraviolet aging test box, wherein the test conditions are as follows: UVA-340; irradiance of 0.89W/square meter/nm (340 nm); black mark temperature is 60 plus or minus 3 ℃/50 plus or minus 3 ℃; the illumination/condensation cycle was 480min/240 min. The aging resistance of the alloy is tested. As in the table below.
Example 3:
the Exxon Mobil MLLDPE 3518CB Polyethylene (PE) resin, the hindered amine light stabilizer HALS 2020, the phosphite antioxidant AO 168 and the zinc oxide are respectively mixed according to the formula shown in the following table and stirred to obtain the composition. The formulation C, D, E was then cast into white 60 μm thick PE anti-aging films at 190 ℃.
| PE | HALS 2020 | AO 168 | TiO2 | ZnO | |
| Formulation C | 100kg | 0.3kg | 0.15kg | 0.1kg | / |
| Formulation D | 100kg | 0.3kg | 0.15kg | 0.1kg | 0.1kg |
| Formulation E | 100kg | 0.3kg | 0.15kg | 0.1kg | 0.01kg |
The prepared film is coiled, bundled and placed in a warehouse, and is placed for 3 months without covering and sunshine, and the film still presents white in appearance, but the outer side of part of the whole coiled film appears red. Wherein, formula C reddened more severely, and the redness was clearly observed with the naked eye.
Example 4:
100kg of polypropylene (PP) resin, 0.3kg of hindered amine light stabilizer HALS 3346, 0.15kg of phosphite antioxidant AO 626, 0.2kg of foaming agent and 0.1kg of calcium stearate are mixed and stirred to obtain the composition. The composition is extruded and granulated, is molded into a 0.5cm plate, and is cooled and placed for 24 hours. And then placing the prepared 0.5cm plate in a mold, foaming for 5 hours at 150 ℃, and cooling to prepare a white PP foaming plate with the thickness of 4 cm.
The prepared foamed sheet is placed in a warehouse and is placed for 1 week without covering and sun irradiation, and the part exposed in the air is reddened in appearance. After cutting, placing the foamed board in an accelerated aging lamp box, and carrying out accelerated aging experiments under the aging conditions: lamp tube type: UVA-340; irradiance (340 nm): 0.89W/square meter/nm; black mark temperature: 60 +/-3 ℃/50 +/-3 ℃; light/condensation cycle: 480min/240 min. The aging time was 2700 h. After the light aging, the red color of the plate is found to fade away, and the plate is still not pulverized after accelerated aging for 2700 h.
The above-mentioned embodiments are merely preferred embodiments of the present invention, and should not be construed as limiting the present invention, and the scope of the present invention should be defined by the claims, and equivalents including technical features of the claims, i.e., equivalent modifications within the scope of the present invention.
Claims (6)
1. The composition for preventing polyolefin copolymer from photo-aging and polyolefin from red-changing is characterized by being prepared from the following raw materials in percentage by mass: 40-80% of triazine hindered amine light stabilizer, 1-20% of inorganic salt and 10-40% of phosphite antioxidant.
2. The composition for preventing polyolefin copolymer from photo-aging and polyolefin from red-discoloration according to claim 1, wherein the triazine hindered amine light stabilizer has the structure shown in formula (1):
wherein, in the formula (1), R1Is hydrogen, C1-8Alkyl radical, C1-8Alkoxy or hydroxy; r2Is hydrogen, C1-8An alkyl group; r3、R3Each independently selected from C1-8Alkyl radical, C1-8Amino-substituted alkyl, C1-8Diamino-substituted alkyl, pyrrolidinyl, amino-substituted cyclohexyl, amino-substituted cyclohexyloxy, morpholinyl, C1-8Amino-substituted alkyl piperidyl or has a structure shown in a formula (1-2),
wherein, in the formula (1-2), R5Is hydrogen, C1-8Alkyl radical, C1-8Alkoxy or hydroxy; r6Is hydrogen, C1-8An alkyl group.
3. The composition for preventing polyolefin copolymer from photo-aging and polyolefin from red-discoloration according to claim 1, wherein the phosphite antioxidant has the structure shown in formula (2):
wherein, in the formula (2), R7、R8Each independently selected from hydrogen and C1-8Alkyl radical, C1-8An alkoxy group; r9、R10Each independently selected from phenyl, C1-8Alkyl-substituted phenyl, C1-3Carboxy-substituted phenyl, C1-3Phosphorous acid substituted phenyl or a structure shown as a formula (2-2);
wherein, in the formula (2-2), R11、R12Each independently selected from hydrogen and C1-8Alkyl radical, C1-8An alkoxy group.
4. The composition for preventing polyolefin copolymer from photo-aging and polyolefin red-discoloration according to claim 1, wherein: the inorganic salt is zinc salt or calcium salt.
5. The composition for preventing polyolefin copolymer from photo-aging and polyolefin red-discoloration according to claim 4, wherein: the zinc salt is any one of zinc oxide, zinc stearate, zinc phosphate, zinc carbonate and zinc sulfate.
6. The composition for preventing polyolefin copolymer from photo-aging and polyolefin red-discoloration according to claim 4, wherein: the calcium salt is any one of calcium hydroxide, calcium stearate and calcium carbonate.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994024344A1 (en) * | 1993-04-15 | 1994-10-27 | Ciba-Geigy Ag | Low color processing, heat and light stabilizer system for polypropylene fiber |
| CN101955609A (en) * | 2010-09-28 | 2011-01-26 | 威高集团有限公司 | Medical irradiation resistant polypropylene alloy material |
| CN103834099A (en) * | 2012-11-27 | 2014-06-04 | 中国石油天然气股份有限公司 | Special radiation-resistant medical polypropylene material |
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2019
- 2019-12-12 CN CN201911275642.1A patent/CN111057288A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994024344A1 (en) * | 1993-04-15 | 1994-10-27 | Ciba-Geigy Ag | Low color processing, heat and light stabilizer system for polypropylene fiber |
| CN101955609A (en) * | 2010-09-28 | 2011-01-26 | 威高集团有限公司 | Medical irradiation resistant polypropylene alloy material |
| CN103834099A (en) * | 2012-11-27 | 2014-06-04 | 中国石油天然气股份有限公司 | Special radiation-resistant medical polypropylene material |
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