CN114381034A - High-performance weather-resistant compound for agricultural polyolefin thin products and preparation method thereof - Google Patents
High-performance weather-resistant compound for agricultural polyolefin thin products and preparation method thereof Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 44
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000004611 light stabiliser Substances 0.000 claims abstract description 39
- 150000001412 amines Chemical class 0.000 claims abstract description 30
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims abstract description 15
- 230000002745 absorbent Effects 0.000 claims abstract description 11
- 239000002250 absorbent Substances 0.000 claims abstract description 11
- 239000000516 sunscreening agent Substances 0.000 claims abstract description 10
- 239000006096 absorbing agent Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 238000005520 cutting process Methods 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 10
- -1 2- (2' -hydroxyphenyl) -1,3, 5-triazine compound Chemical class 0.000 claims description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000292 calcium oxide Substances 0.000 claims description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 7
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 7
- 235000013539 calcium stearate Nutrition 0.000 claims description 7
- 239000008116 calcium stearate Substances 0.000 claims description 7
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 6
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 238000009472 formulation Methods 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910001038 basic metal oxide Inorganic materials 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 2
- 229960001545 hydrotalcite Drugs 0.000 claims description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- SWZDQOUHBYYPJD-UHFFFAOYSA-N tridodecylamine Chemical compound CCCCCCCCCCCCN(CCCCCCCCCCCC)CCCCCCCCCCCC SWZDQOUHBYYPJD-UHFFFAOYSA-N 0.000 claims description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 230000002378 acidificating effect Effects 0.000 abstract description 3
- 239000012752 auxiliary agent Substances 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 18
- 229920005989 resin Polymers 0.000 description 18
- 239000011347 resin Substances 0.000 description 18
- 239000004594 Masterbatch (MB) Substances 0.000 description 13
- 239000003963 antioxidant agent Substances 0.000 description 13
- 230000003078 antioxidant effect Effects 0.000 description 13
- 239000008187 granular material Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000004698 Polyethylene Substances 0.000 description 7
- 229920000573 polyethylene Polymers 0.000 description 7
- 229920000092 linear low density polyethylene Polymers 0.000 description 6
- 239000004707 linear low-density polyethylene Substances 0.000 description 6
- 229920005672 polyolefin resin Polymers 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 3
- 230000001133 acceleration Effects 0.000 description 3
- 238000010096 film blowing Methods 0.000 description 3
- 238000003958 fumigation Methods 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000004746 geotextile Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 230000003211 malignant effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 229940124543 ultraviolet light absorber Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
Classifications
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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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34926—Triazines also containing heterocyclic groups other than triazine groups
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- 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
- 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
- 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
- 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
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
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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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- 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
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—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
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—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
- C08J2423/10—Homopolymers or copolymers of propene
- C08J2423/12—Polypropene
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- C08K3/20—Oxides; Hydroxides
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- C08K3/22—Oxides; Hydroxides of metals
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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Abstract
The invention discloses a high-performance weather-resistant compound for agricultural polyolefin thin products, which comprises the following components in percentage by mass: 50-80% of hindered amine light stabilizer; 5-20% of triazine ultraviolet absorbent; 5-20% of an inorganic sunscreen agent and 5-10% of an acid-absorbing agent; after the compound provided by the invention is added into an agricultural polyolefin thin product, the synergistic weather-resistant effect of the hindered amine light stabilizer and the ultraviolet absorber can be greatly enhanced, and the impact of an acidic substance on a weather-resistant auxiliary agent is reduced, so that the service life of the agricultural polyolefin thin product in a severe environment can be greatly prolonged; the invention also discloses a specific preparation method of the compound.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a high-performance weather-resistant compound for an agricultural polyolefin thin product and a preparation method thereof.
Background
Polyolefin resins include Polyethylene (PE), polypropylene (PP), and the like, and are widely used in outdoor products such as greenhouse films, mulching films, grass protection cloths, flexible freight bags, geotextiles, and the like. The weak bond (such as tertiary carbon atom on the main chain) of the polyolefin resin is easily oxidized to generate more active free radicals under the irradiation of high-energy ultraviolet rays and the action of oxygen, and the active free radicals enter the cycle process of malignant autocatalytic oxidation, so that the molecular chain is broken, the mechanical property of the product is lost, and the service life is greatly reduced.
The most effective way to improve the weather resistance of the resin is to add a light stabilizer, and the mainstream light stabilizers include hindered amine light stabilizers and ultraviolet absorbers. Both were invented in the sixty-seven years of the 20 th century, in which the hindered amine light stabilizer was able to capture the free radicals in the resin system and to be recycled, and its high efficiency and long lasting weathering effect became the main weathering aid for polyolefin articles.
In order to prolong the service life of polyolefin products in the open air to the maximum extent, scientific workers carry out a plurality of researches and find that different light stabilizers have good synergistic effect. Kurumada T studied the optimum synergistic ratio of hindered amine light stabilizers to UV absorbers in the conventional outdoor conditions, wherein the optimum ratio of the two in the polyolefin resin is 3: 1-4: 1. EP1500675A1 mentions that the use of hindered amine light stabilizers having a number average molecular weight of more than 500 in combination with triazine UV absorbers provides good weathering resistance in extruded or molded articles.
The synergistic effect of the hindered amine light stabilizer and the ultraviolet absorber is closely related to the thickness of the product and the use environment. On the one hand, the polar weather-resistant auxiliary agent has insufficient compatibility with non-polar polyolefin resin, and particularly, the ultraviolet absorbent with low molecular weight is easy to be separated out to the surface in a thin product; on the other hand, the efficacy of the UV absorber is proportional to the thickness of the article (Lambert-beer's law), and when the thickness of the article is less than 100um, the UV absorber has relatively poor weather protection. In addition, the harsh use environment can also affect the exertion of the synergistic effect of the two, for example, agricultural greenhouse film which is subjected to sulfur fumigation for a long time, and in the spraying environment of a large amount of insecticide, the acidic compounds can gradually permeate into the PE greenhouse film to generate salt forming reaction with the alkaline hindered amine light stabilizer, so that the hindered amine light stabilizer can lose efficacy before the weather-resistant effect is exerted.
Therefore, there is a need to develop a novel light stabilizer compound system for agricultural polyolefin thin products, which satisfies the applicability and durability of the relevant products in the agricultural field.
Disclosure of Invention
In order to solve the problem of insufficient weather-resistant system in the prior art, the invention provides a high-performance weather-resistant compound for agricultural polyolefin thin products and a preparation method thereof, so that the agricultural polyolefin thin products in an acidic environment have excellent weather resistance.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention provides a high-performance weather-resistant compound for an agricultural polyolefin thin product, which comprises 50-80% of hindered amine light stabilizer, 5-20% of triazine ultraviolet absorbent, 5-20% of inorganic sun-screening agent and 5-10% of acid-absorbing agent by mass percent.
Further, the hindered amine light stabilizer has a number average molecular weight greater than 2000.
Further, the hindered amine light stabilizer is one or two of HALS 944, HALS 3346, HALS 3529, HALS 119, HALS 2020 and HALS 622.
Further, the triazine ultraviolet absorber is a 2- (2' -hydroxyphenyl) -1,3, 5-triazine compound.
Further, the triazine ultraviolet absorber is one of UV 1577, UV 1164, UV 1600 and UV 400.
Further, the particle size of the inorganic sun-screening agent is 10-200 nm; preferably 30 to 80 nm.
Further, the inorganic sun-screening agent is one of cerium oxide, titanium oxide, zinc oxide, montmorillonite and rectorite.
Further, the acid acceptor is one of basic metal oxide, tertiary amine organic matter and stearate compound.
Further, the acid-absorbing agent is one of calcium oxide, magnesium oxide, hydrotalcite, calcium stearate, zinc stearate and tri-n-dodecylamine.
The invention also provides a preparation method of the high-performance weather-resistant compound for the agricultural polyolefin thin product, which comprises the following steps:
s1: mixing a hindered amine light stabilizer, a triazine ultraviolet absorbent, an inorganic sun-screening agent and an acid absorbent in a high-speed mixer at the rotation speed of 800-1000rpm for 2-5 min;
s2: and (3) feeding the mixture obtained in the step S1 into a premixing granulator, setting the process temperature to be 80-130 ℃, setting the length-diameter ratio of a screw to be 25-40, and preparing the high-performance weather-resistant compound of the agricultural polyolefin thin product by adopting a hot ring-cutting and air-cooling process.
The invention has the beneficial effects that:
the high-performance weather-resistant compound for the agricultural polyolefin thin product utilizes the synergistic effect of different light stabilizers, so that the compound has good weather-resistant protection effect on polyolefin resin. The compound can still exert good weather-resistant effect under the conditions that the thickness of the product is less than 100um, the high-acidity environment and the like, does not influence the light transmittance of a transparent product, and breaks through the application limitation of the compound between the traditional hindered amine light stabilizer and the ultraviolet absorber. Secondly, the high-performance weather-resistant compound has low material cost and relatively simple production process, can be widely popularized and used in agricultural polyolefin thin products, and has good market application value.
Detailed Description
The present invention will be further illustrated below with reference to specific embodiments, which are to be understood as merely illustrative and not limitative of the scope of the present invention.
Example 1
1kg of hindered amine light stabilizer HALS 119, 0.4kg of triazine ultraviolet light absorber UV 1577, 0.4kg of nano zinc oxide with the particle size of 30-50nm and 0.2kg of calcium stearate are weighed and added into a high-speed mixer to be mixed for 5min at 800 rpm. Adding the uniformly mixed materials into a premixing granulator, setting the temperature control of an extruder to be 120 ℃, setting the length-diameter ratio of a screw to be 30:1, and adopting a hot ring cutting and air cooling process to obtain the high-performance weather-resistant compound with the formula.
100g of high-performance weather-resistant compound, 20g of antioxidant B215 and 880g of LLDPE resin are uniformly mixed, and then the mixture is processed by a double-screw extruder and cooled and formed to obtain weather-resistant master batch (A-1).
Example 2
1.4kg of hindered amine light stabilizer HALS 119, 0.2kg of triazine ultraviolet absorber UV 1577, 0.3kg of nano zinc oxide with the particle size of 30-50nm and 0.1kg of calcium stearate are weighed and added into a high-speed mixer to be mixed for 5min at 800 rpm. Adding the uniformly mixed materials into a premixing granulator, setting the temperature control of an extruder to be 120 ℃, and setting the length-diameter ratio of a screw to be 30:1, adopting a hot ring cutting and air cooling process to obtain the high-performance weather-resistant compound with the formula.
100g of the high-performance weather-resistant compound, 20g of the antioxidant B215 and 880g of LLDPE resin are uniformly mixed, and then the mixture is extruded by a double-screw extruder and cooled and cut into granules to obtain weather-resistant master batch (A-2).
Example 3
1.6kg of hindered amine light stabilizer HALS 119, 0.12kg of triazine ultraviolet absorber UV 1577, 0.16kg of nano zinc oxide with the particle size of 30-50nm and 0.12kg of calcium stearate are weighed and added into a high-speed mixer to be mixed for 5min at 800 rpm. Adding the uniformly mixed materials into a premixing granulator, setting the temperature control of an extruder to be 120 ℃, setting the length-diameter ratio of a screw to be 30:1, and adopting a hot ring cutting and air cooling process to obtain the high-performance weather-resistant compound with the formula.
100g of the high-performance weather-resistant compound, 20g of the antioxidant B215 and 880g of LLDPE resin are uniformly mixed, and then the mixture is extruded by a double-screw extruder and cooled and cut into granules to obtain weather-resistant master batch (A-3).
Comparative example 1
100g of light stabilizer HALS 119, 20g of antioxidant B215 and 880g of LLDPE resin are uniformly mixed, then the mixture is extruded by a double-screw extruder and cooled and cut into granules to obtain weather-resistant master batch (A-4), the temperature control of the extruder is set to be 120 ℃, and the length-diameter ratio of a screw is 30: 1.
Comparative example 2
1.4kg of hindered amine light stabilizer HALS 119, 0.5kg of triazine ultraviolet absorber UV 1577 and 0.1kg of calcium stearate are weighed and mixed in a high-speed mixer at 800rpm for 5 min. Adding the uniformly mixed materials into a premixing granulator, setting the temperature control of an extruder to be 120 ℃, and setting the length-diameter ratio of a screw to be 30:1, adopting a hot ring cutting and air cooling process to obtain the high-performance weather-resistant compound with the formula.
100g of the high-performance weather-resistant compound, 20g of the antioxidant B215 and 880g of LLDPE resin are uniformly mixed, and then the mixture is extruded by a double-screw extruder and cooled and cut into granules to obtain weather-resistant master batch (A-5).
Comparative example 3
1.4kg of hindered amine light stabilizer HALS 119, 0.4kg of nano zinc oxide with the particle size of 30-50nm and 0.2kg of calcium stearate are weighed and added into a high-speed mixer to be mixed for 5min at 800 rpm. Adding the uniformly mixed materials into a premixing granulator, setting the temperature control of an extruder to be 120 ℃, setting the length-diameter ratio of a screw to be 30:1, and adopting a hot ring cutting and air cooling process to obtain the high-performance weather-resistant compound with the formula.
100g of the high-performance weather-resistant compound, 20g of the antioxidant B215 and 880g of LLDPE resin are uniformly mixed, and then the mixture is extruded by a double-screw extruder and cooled and cut into granules to obtain weather-resistant master batch (A-6).
Film sample preparation
The weather-resistant master batches A-1-A-3 prepared in the examples 1-3 and the weather-resistant master batches A-4-A-6 prepared in the comparative examples 1-3 are added into a PE film blowing resin matrix according to the proportion of 8%, and a film sample with the thickness of 8 filaments (80 um) is prepared by film blowing through a film blowing machine.
And (3) performance testing:
carrying out a sulfur-resistant sulfur fumigation test on a film sample outdoors for 10 days (the amount of sulfur in a single time is 100g, 2 times a day), carrying out a weather-resistant acceleration test after the fumigation is finished, wherein the test standard adopts GB/T16644.2, and the specific conditions are as follows: UV-A lamp source, 0.76W/m2Illumination for 8h, and a lamp box is 60 ℃; condensing in dark for 4h, and aging at 50 deg.C in lamp box for 1000 h. And (3) testing the mechanical property of the film sample, and calculating the retention rate of the mechanical property after aging, wherein the test result is shown in table 1.
TABLE 1 film sample weather resistance accelerated test results
As can be seen from the data in Table 1, the PE film containing the ordinary hindered amine light stabilizer cannot effectively resist the weather resistance in an acidic environment, and the weather resistance of the PE film can not be effectively improved by simply compounding the hindered amine light stabilizer with an ultraviolet absorbent or an inorganic sunscreen agent, but the embodiment of the invention can greatly improve the weather resistance of the PE film.
Example 4
1.2kg of hindered amine light stabilizer HALS 611 (HALS 119: HALS 622=2: 1), 0.4kg of triazine ultraviolet absorber UV 1164, 0.2kg of nano cerium oxide with particle size of 60-80nm and 0.2kg of calcium oxide were weighed and added to a high-speed mixer to mix for 5min at 800 rpm. Adding the uniformly mixed materials into a premixing granulator, setting the temperature control of an extruder to be 100 ℃, setting the length-diameter ratio of a screw to be 35, and adopting a hot circular cutting and air cooling process to obtain the high-performance weather-resistant compound with the formula.
100g of high-performance weather-resistant compound, 20g of antioxidant B215 and 880giPP resin are uniformly mixed, and then the mixture is extruded by a double-screw extruder and cooled and cut into granules to obtain weather-resistant master batch (B-1).
Example 5
1.3kg of hindered amine light stabilizer HALS 611, 0.3kg of triazine ultraviolet absorber UV 1164, 0.3kg of nano cerium oxide with the particle size of 60-80nm and 0.1kg of calcium oxide are weighed and added into a high-speed mixer to be mixed for 5min at 800 rpm. Adding the uniformly mixed materials into a premixing granulator, setting the temperature control of an extruder to be 100 ℃, setting the length-diameter ratio of a screw to be 35, and adopting a hot circular cutting and air cooling process to obtain the high-performance weather-resistant compound with the formula.
100g of high-performance weather-resistant compound, 20g of antioxidant B215 and 880giPP resin are uniformly mixed, and then the mixture is extruded by a double-screw extruder and cooled and cut into granules to obtain weather-resistant master batch (B-2).
Example 6
1.5kg of hindered amine light stabilizer HALS 611, 0.2kg of triazine ultraviolet absorber UV 1164, 0.2kg of nano cerium oxide with the particle size of 60-80nm and 0.1kg of calcium oxide are weighed and added into a high-speed mixer to be mixed for 5min at 800 rpm. Adding the uniformly mixed materials into a premixing granulator, setting the temperature control of an extruder to be 100 ℃, setting the length-diameter ratio of a screw to be 35, and adopting a hot circular cutting and air cooling process to obtain the high-performance weather-resistant compound with the formula.
100g of high-performance weather-resistant compound, 20g of antioxidant B215 and 880giPP resin are uniformly mixed, and then the mixture is extruded by a double-screw extruder and cooled and cut into granules to obtain weather-resistant master batch (B-3).
Comparative example 4
100g of light stabilizer HALS 611, 20g of antioxidant B215 and 880giPP resin are uniformly mixed, and then the mixture is extruded by a double-screw extruder and cooled and cut into granules to obtain the weather-resistant master batch (B-4).
Comparative example 5
100g of light stabilizer UV 1164, 20g of antioxidant B215 and 880giPP resin are uniformly mixed, and then the mixture is extruded by a double-screw extruder and cooled and cut into granules, so as to obtain the weather-resistant master batch (B-5).
Comparative example 6
1.5kg of hindered amine light stabilizer HALS 611, 0.4kg of triazine ultraviolet absorber UV 1164 and 0.1kg of calcium oxide were weighed and mixed in a high-speed mixer at 800rpm for 5 min. Adding the uniformly mixed materials into a premixing granulator, setting the temperature control of an extruder to be 100 ℃, setting the length-diameter ratio of a screw to be 35, and adopting a hot circular cutting and air cooling process to obtain the high-performance weather-resistant compound with the formula.
100g of high-performance weather-resistant compound, 20g of antioxidant B215 and 880giPP resin are uniformly mixed, and then the mixture is extruded by a double-screw extruder and cooled and cut into granules to obtain weather-resistant master batch (B-6).
Comparative example 7
1.5kg of hindered amine light stabilizer HALS 611, 0.4kg of nano cerium oxide with the particle size of 60-80nm and 0.1kg of calcium oxide are weighed and added into a high-speed mixer to be mixed for 5min at 800 rpm. Adding the uniformly mixed materials into a premixing granulator, setting the temperature control of an extruder to be 100 ℃, setting the length-diameter ratio of a screw to be 35, and adopting a hot circular cutting and air cooling process to obtain the high-performance weather-resistant compound with the formula.
100g of high-performance weather-resistant compound, 20g of antioxidant B215 and 880giPP resin are uniformly mixed, and then the mixture is extruded by a double-screw extruder and cooled and cut into granules to obtain weather-resistant master batch (B-7) containing the light stabilizer.
Monofilament sample preparation
The weather-resistant master batches B-1 to B-3 prepared in the examples 4 to 6 and the weather-resistant master batches B-4 to B-7 prepared in the comparative examples 4 to 7 are added into a homo-polypropylene film-grade resin matrix according to the proportion of 5%, and a monofilament sample with the thickness of 5 filaments (50 um) is prepared by a wire drawing machine.
And (3) performance testing:
after soaking the monofilament samples in a sulfurous acid solution (sulfurous acid: water = 1: 4 volume ratio) for 15 days, a weather resistance acceleration test was performed, and the test standard adopted the specific conditions of GB/T16644.2: UV-B lamp source, 0.89W/m2Illumination for 8h, and a lamp box is 60 ℃; condensing in dark for 4h, and aging at 50 deg.C in lamp box for 300 h. The mechanical properties of the monofilament sample are tested, the retention rate of the mechanical properties after aging is calculated, and the test results are shown in Table 2.
TABLE 2 acceleration test results of weathering resistance of monofilament samples
As can be seen from the data in table 2, the examples of the present invention provide the best mechanical protection to polypropylene monofilament articles when compared to the comparative examples and formulation schemes well known in the art, without affecting the initial properties of the resin.
It should be noted that the above-mentioned contents only illustrate the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and it is obvious to those skilled in the art that several modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations fall within the protection scope of the claims of the present invention.
Claims (10)
1. The high-performance weather-resistant compound for the agricultural polyolefin thin product is characterized by comprising 50-80% of hindered amine light stabilizer, 5-20% of triazine ultraviolet absorbent, 5-20% of inorganic sun-screening agent and 5-10% of acid-absorbing agent by mass percent.
2. The high performance weathering formulation of claim 1 wherein the hindered amine light stabilizer has a number average molecular weight greater than 2000.
3. The high performance weathering formulation of claim 2 wherein the hindered amine light stabilizer is one or two of HALS 944, HALS 3346, HALS 3529, HALS 119, HALS 2020, and HALS 622.
4. The high-performance weather-resistant compound for the agricultural polyolefin thin product as claimed in claim 1, wherein the triazine ultraviolet absorber is a 2- (2' -hydroxyphenyl) -1,3, 5-triazine compound.
5. The high-performance weather-resistant compound for the agricultural polyolefin thin product as claimed in claim 4, wherein the triazine ultraviolet absorber is one of UV 1577, UV 1164, UV 1600 and UV 400.
6. The high-performance weather-resistant compound for the agricultural polyolefin thin product as claimed in claim 1, wherein the particle size of the inorganic sunscreen agent is 10-200 nm.
7. The high-performance weather-resistant compound for the agricultural polyolefin thin product as claimed in claim 6, wherein the inorganic sun-screening agent is one of cerium oxide, titanium oxide, zinc oxide, montmorillonite and rectorite.
8. The high-performance weather-resistant compound for the agricultural polyolefin thin product as claimed in claim 1, wherein the acid absorbent is one of basic metal oxide, tertiary amine organic compound and stearate compound.
9. The high-performance weather-resistant compound for the agricultural polyolefin thin product as claimed in claim 8, wherein the acid absorbent is one of calcium oxide, magnesium oxide, hydrotalcite, calcium stearate, zinc stearate and tri-n-dodecylamine.
10. A process for the preparation of a high performance weatherable formulation of an agricultural polyolefin film as claimed in any one of claims 1 to 9, comprising the steps of:
s1: mixing a hindered amine light stabilizer, a triazine ultraviolet absorbent, an inorganic sun-screening agent and an acid absorbent in a high-speed mixer at the rotation speed of 800-1000rpm for 2-5 min;
s2: feeding the mixture obtained in the step S1 into a premixing granulator, setting the process temperature to be 80-130 ℃, setting the length-diameter ratio of a screw to be 25-40: 1, preparing the high-performance weather-resistant compound for the agricultural polyolefin thin product by adopting a hot ring cutting and air cooling process.
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