CN116745353A - Compositions and methods for protecting organic polymeric materials from the deleterious effects of UV-C light exposure - Google Patents

Compositions and methods for protecting organic polymeric materials from the deleterious effects of UV-C light exposure Download PDF

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CN116745353A
CN116745353A CN202180091292.2A CN202180091292A CN116745353A CN 116745353 A CN116745353 A CN 116745353A CN 202180091292 A CN202180091292 A CN 202180091292A CN 116745353 A CN116745353 A CN 116745353A
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hydroxy
tert
butyl
bis
triazine
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J·M-H·恩格
R·B·古普塔
李欣
卓兼仰
K·奥康诺
T·桑塔玛丽亚
王敏
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Cytec Industries Inc
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Cytec Industries Inc
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Priority claimed from PCT/US2021/060781 external-priority patent/WO2022115578A1/en
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Abstract

Provided herein are polymer compositions for use in the manufacture of stable polymer articles that are resistant to at least one of discoloration, cracking or crazing upon exposure to UV-C (190-280 nm) light, wherein the polymer compositions comprise: (i) an organic polymeric material; and (ii) a stabilizer composition comprising: an antioxidant selected from the group consisting of hindered phenols, phosphites and phosphonites and mixtures thereof; and is selected from the group consisting of Hindered Amine Light Stabilizers (HALS), UV absorbers (UVA), hindered benzoates, and mixtures thereofA group of light stabilizers, even in the absence of a barium compound (such as a barium salt) in the stabilizer composition, and provided that the HALS is not bis (2, 6, -tetramethyl-4-piperidinyl) sebacate alone (TINUVIN TM 770). At least one of reduced discoloration, cracking or crazing after exposure to UV-C light is associated with the use of the light stabilizer in combination with the antioxidant, as compared to the antioxidant in the absence of the light stabilizer. Methods of stabilizing organic polymeric materials against the deleterious effects of UV-C light by adding antioxidants and light stabilizers to the organic polymeric materials are also provided.

Description

Compositions and methods for protecting organic polymeric materials from the deleterious effects of UV-C light exposure
RELATED APPLICATIONS
The application claims priority from U.S. provisional application number 63/118,809 (docket number CYT 2020-006-US-PSP) filed on 11/27 and U.S. provisional application number 63/190,443 (docket number 2020-006-US-PSP 2) filed on 19/2021, each of which is incorporated herein by reference in its entirety. The application also relates to the subject matter and ownership of U.S. provisional application No. 63/118,807 (docket No. CYT 2020-005-US-PSP) filed on month 11 and 27 of 2020 and 63/190,431 (docket No. CYT 2020-005-US-PSP 2) filed on month 5 and 19 of 2021.
Background of the applicationand related art
Technical Field
The present disclosure relates generally to protecting organic polymeric materials and stabilized polymeric articles made therefrom from the deleterious effects of UV-C (190-280 nm) light exposure. Detrimental effects include discoloration, cracking, and/or crazing. More particularly, the present disclosure relates to stabilizer compositions having antioxidants and light stabilizers, wherein the stabilizer compositions are effective to reduce discoloration, cracking or crazing of organic polymeric materials upon repeated or prolonged exposure to germicidal UV-C light.
Description of related Art
Most polymeric organic materials undergo photodegradation upon exposure to UV radiation, resulting in irreversible chemical changes. These variations adversely affect the physical properties of the polymeric organic material. Exposure to UV radiation is also harmful to human skin and results in sunburn and skin cancer. Ultraviolet radiation ranges from 100 to 400nm and is divided into three sub-regions, namely 100 to 280nm (UV-C), 280 to 320nm (UV-B) and 320 to 400nm (UV-A). The primary source of UV radiation is sunlight. Solar radiation in the UV-C range does not reach the earth's surface because it is absorbed by the ozone layer of the stratosphere and the oxygen of the upper layers. Thus, over the last 60 years, great efforts have been made to develop stabilizers to protect organic polymer materials and human skin from the deleterious effects of UV-B and UV-Sup>A radiation. Not surprisingly, although stabilization against UV-C light has been largely neglected, as this is never a problem. However, as the new coronavirus covd-19 spreads around the world, scientists have been striving to reduce spread in a variety of ways, including disinfecting various objects or items with germicidal UV-C radiation. The use of UV-C light radiation as a disinfection tool has grown exponentially in a short period of time, mainly for indoor applications. Various UV-C devices are manufactured and used for indoor applications, such as for disinfection of: medical architecture/hospital; various modes of transportation, such as aircraft, trains, automobiles, buses (including stations and airports); commercial and residential interiors, including retail stores, restaurants, bars; indoor equipment including furniture, paint, personal Protection Equipment (PPE), carpeting and textiles, electrical and electronic devices, and the like.
The preferred UV-C wavelength range for disinfection is considered to be between 200 and 280nm, and the particularly preferred range is 222 to 254nm. UV-C exposure has been demonstrated to effectively and efficiently inactivate microorganisms, including covd-19 virus. However, it appears that there is no further insight into what adverse effects UV-C exposure has on organic polymeric materials or articles made with these materials. Polymeric organic materials for indoor applications and articles of manufacture generally do not require stabilizers to protect against UV-Sup>A and UV-B radiation because of limited exposure to UV-Sup>A and UV-B from sunlight in the room. In contrast, polymeric organic materials for indoor articles conventionally use processing additives, particularly antioxidants, such as organic phosphites and hindered phenols, to prevent degradation and color generation during exposure to the high temperatures required to process and form the manufactured polymeric articles. However, for indoor use of UV-C germicidal light, it is important to address whether a polymer article made from the organic polymer material used for processing and the antioxidant will have any detrimental effect due to UV-C exposure. Of particular concern is the fact that: UV-C radiation has Sup>A higher energy than UV-Sup>A and UV-B and may be more harmful to organic polymeric materials. Stability to UV-C exposure and what effect UV-C exposure has on antioxidants used to protect the polymeric organic material itself from UV-Sup>A and UV-B light is also lacking in understanding.
Although CN 111 286 116 discloses a UV-C radiation resistant polypropylene/polyethylene weatherable composite, it is composed of many raw materials, which unnecessarily increases the cost of the solution and thus does not make it practically useful in a wide range of industries in various applications.
CN 112 778 730 relates to a UV-C radiation resistant polycarbonate composition comprising polycarbonate, SAN, ASA rubber powder, triazine UV absorber, benzotriazole, hindered Amine Light Stabilizer (HALS), phosphite and thiodipropionate, and metal deactivator and other processing aids.
Thus, there is an urgent need for stabilizer compositions to protect polymeric organic materials and articles made therefrom from exposure to UV-C radiation. In particular, there is a need for stabilizer compositions that reduce discoloration, cracking and/or crazing of organic polymeric materials upon exposure to UV-C light. Such stabilizer compositions would be a useful advancement in the art and would be rapidly accepted by the industry.
Disclosure of Invention
The present disclosure provides polymer compositions for making stable polymer articles that are resistant to at least one of discoloration, cracking, and/or crazing upon repeated or prolonged exposure to UV-C (190-280 nm) light, wherein the polymer compositions include, but are not limited to: (i) an organic polymeric material; and (ii) a stabilizer composition having: an antioxidant selected from the group consisting of hindered phenols, phosphites and phosphonites and mixtures thereof; and a light stabilizer selected from the group consisting of Hindered Amine Light Stabilizers (HALS), UV absorbers (UVA), hindered benzoates, and mixtures thereof, even in the absence of a barium compound (such as a barium salt) in the stabilizer composition, and provided that the HALS is not bis (2, 6, -tetramethyl-4-piperidinyl) sebacate alone (TINUVIN TM 770). At least one of reduced discoloration, cracking and/or crazing after exposure to UV-C light is associated with the use of the light stabilizer in combination with the antioxidant, as compared to the antioxidant in the absence of the light stabilizer.
The present disclosure also provides stable polymeric articles that are resistant to discoloration, cracking or crazing upon exposure to UV-C (190-280 nm) light, wherein the polymeric articles comprise a polymeric composition as described herein. Reduced discoloration, cracking and/or crazing after repeated or prolonged exposure to UV-C light is associated with the use of the light stabilizer in combination with the antioxidant, even in the absence of a barium compound (such as a barium salt) in the stabilizer composition, as compared to the antioxidant in the absence of the light stabilizer.
Further provided is a method of stabilizing an organic polymeric material against the deleterious effects of UV-C (190-280 nm) light, the method comprising adding to the organic polymeric material a stabilizer composition as described herein. At least one of reduced discoloration, cracking and/or crazing upon exposure to UV-C light is associated with the use of the light stabilizer in combination with the antioxidant, even in the absence of a barium compound (such as a barium salt) in the stabilizer composition, as compared to the antioxidant in the absence of the light stabilizer.
Also provided are methods of making stable polymeric articles, wherein such methods comprise: adding a stabilizer composition having an antioxidant and a light stabilizer to an organic polymer material, even in the absence of a barium compound (such as a barium salt) in the stabilizer composition, and shaping the organic polymer material containing the stabilizer composition into the stabilized polymer article.
This summary may not list all features or elements and sub-combinations of elements may also constitute the invention. These and other objects, features and advantages of the present invention will become apparent from the following detailed description taken in conjunction with the accompanying examples and drawings.
Drawings
FIG. 1A is a photomicrograph of the unstabilized polypropylene sheet of example 5, sample 6-1, after 250 hours of exposure to UV-C radiation, showing significant surface cracking and/or crazing.
FIG. 1B is a composition containing 0.08% CYANOX TM Example 5 of 2777 photomicrographs of the polypropylene plate of sample 6-2 after 250 hours of exposure to UV-C radiation. It showed some surface cracking and/or crazing, but less than sample 6-1.
FIG. 1C is a graph containing 0.08% IRGANOX TM 1076 example 5 a photomicrograph of the polypropylene plate of sample 6-4 after 250 hours of exposure to UV-C radiation. It shows very little surface and/or crazing.
Detailed Description
The present inventors have found that stabilizer compositions including, but not limited to, both antioxidants and light stabilizers are particularly useful for making polymeric articles that are resistant to the deleterious effects of repeated or prolonged exposure to UV-C light. The antioxidant is selected from the group consisting of hindered phenols, phosphites and phosphonites and mixtures thereof; and the light stabilizer is selected from the group consisting of Hindered Amine Light Stabilizers (HALS), UV absorbers (UVA), hindered benzoates, and mixtures thereof, even in the absence of a barium compound such as a barium salt in the stabilizer composition, and provided that the HALS is not bis (2, 6, -tetramethyl-4-piperidinyl) sebacate alone (TINUVIN TM 770). Advantageously, at least one of reduced discoloration, cracking and/or crazing after exposure to UV-C light is associated with the use of a light stabilizer in combination with an antioxidant, as compared to an antioxidant in the absence of the light stabilizer.
Definition of the definition
As used herein, the following terms are provided to assist the reader. Unless otherwise defined, all technical terms, notations and other scientific terms used herein are intended to have the meanings commonly understood by those of ordinary skill in the chemical arts.
Throughout this specification, terms and substituents retain their definition. A comprehensive list of abbreviations used by organic chemists (i.e., those of ordinary skill in the art) appears in the first phase of each volume of Journal of Organic Chemistry [ journal of organic chemistry ]. This list, which is typically presented in a table titled "abbreviated criteria list (Standard List of Abbreviations)", is incorporated by reference herein.
The term "hydrocarbyl" is a generic term including aliphatic, cycloaliphatic, and aromatic groups having an all-carbon backbone and consisting of carbon and hydrogen atoms, unless otherwise specified. In some cases, one or more of the carbon atoms that make up the carbon backbone may be replaced by a particular atom or group of atoms, as defined herein. Examples of hydrocarbyl groups include alkyl, cycloalkyl, cycloalkenyl, carbocycle aryl, alkenyl, alkynyl, alkylcycloalkyl, cycloalkylalkyl, cycloalkenyl alkyl, and carbocycle aralkyl, alkylaryl, arylalkenyl, and arylalkynyl groups. Such groups may be optionally substituted with one or more substituents as defined herein. Accordingly, a chemical group or moiety discussed in the specification and claims should be understood to include substituted or unsubstituted forms. The examples and preferences indicated below apply to each of the hydrocarbyl substituents or hydrocarbyl-containing substituents referred to in the various definitions of substituents for compounds having the formulae described herein, unless the context indicates otherwise.
Preferred non-aromatic hydrocarbon groups are saturated groups such as alkyl and cycloalkyl groups. Generally, and by way of example, the hydrocarbyl group may have the highestUp to fifty carbon atoms unless the context requires otherwise. Hydrocarbyl groups having from 1 to 30 carbon atoms are preferred. Within a subset of hydrocarbon groups having 1 to 30 carbon atoms, a specific example is C 1-20 Hydrocarbyl radicals, e.g. C 1-12 Hydrocarbyl (e.g. C 1-6 Hydrocarbon or C 1-4 Hydrocarbyl), specific examples are from C 1 To any individual value or combination of values selected for the C30 hydrocarbyl group.
Alkyl is intended to include straight chain, branched, or cyclic hydrocarbon structures and combinations thereof. Lower alkyl refers to an alkyl group having from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms. Examples of lower alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclohexyl, and the like. Preferred alkyl groups are C 30 Or lower ones.
Alkoxy or alkoxyalkyl refers to a group of from 1 to 20 carbon atoms attached to the parent structure through oxygen in a straight chain, branched, cyclic configuration, and combinations thereof. Examples include methoxy, ethoxy, propoxy, isopropoxy, cyclopropoxy, cyclohexyloxy and the like.
Acyl refers to acyl and refers to groups of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, and 12 carbon atoms in linear, branched, cyclic configurations, saturated, unsaturated, and aromatic, and combinations thereof, attached to a parent structure through carbonyl functionality. Examples include acetyl, benzoyl, propionyl, isobutyryl, t-butoxycarbonyl, benzyloxycarbonyl, and the like. Lower acyl refers to acyl groups containing one to six carbons.
References to "carbocycle" or "cycloalkyl" as used herein shall include both aromatic and non-aromatic ring systems unless the context indicates otherwise. Thus, for example, the term includes within its scope aromatic, non-aromatic, unsaturated, partially saturated and fully saturated carbocyclic ring systems. Generally, such groups may be monocyclic or bicyclic and may contain, for example, 3 to 12 ring members, more typically 5 to 10 ring members. Examples of monocyclic groups are those containing 3, 4, 5, 6, 7 and 8 ring members, more typically 3 to 7, and preferably 5 or 6 ring membersIs a group of (2). Examples of bicyclic groups are those containing 8, 9, 10, 11 and 12 ring members, and more typically 9 or 10 ring members. Examples of non-aromatic carbocycles/cycloalkyl groups include c-propyl, c-butyl, c-pentyl, c-hexyl, and the like. C (C) 7 To C 10 Examples of polycyclic hydrocarbons include ring systems such as norbornyl and adamantyl.
Aryl (carbocycle aryl) refers to a 5-or 6-membered aromatic carbocycle containing: a bicyclic 9-or 10-membered aromatic ring system; or a tricyclic 13-or 14-membered aromatic ring system. Aromatic 6-to 14-membered carbocycles include, for example, substituted or unsubstituted phenyl, benzene, naphthalene, indane, tetralin, and fluorene.
Substituted hydrocarbyl, alkyl, aryl, cycloalkyl, alkoxy, and the like refer to a specific substituent wherein up to three H atoms in each residue are replaced by alkyl, halogen, haloalkyl, hydroxy, alkoxy, carboxy, alkyloxycarbonyl (also known as alkoxycarbonyl), carboxamido (also known as alkylaminocarbonyl), cyano, carbonyl, nitro, amino, alkylamino, dialkylamino, mercapto, alkylthio, sulfoxide, sulfone, amido, amidino, phenyl, benzyl, halobenzyl, heteroaryl, phenoxy, benzyloxy, heteroaryloxy, benzoyl, halobenzoyl, or lower alkyl hydroxy.
The term "halogen" means fluorine, chlorine, bromine or iodine.
The terms "polymer," "polymeric material," or "polymer composition" as used throughout the specification and claims of the present application refer to any combination of monomer units, but explicitly exclude polycarbonate and polychloroprene latex compositions.
All numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the present invention. Neither is it intended to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should be construed in light of the number of significant digits and by applying ordinary rounding techniques.
As used herein and in the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. For example, the terms "a/an" and "the" as used herein do not denote a limitation of quantity and are to be construed to include both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context.
For the purposes of describing the present invention, when an element, component, or feature is referred to as being included in and/or selected from a list of enumerated elements, components, or features, it will be understood by those skilled in the art that the element, component, or feature may also be any one of the individual enumerated elements, components, or features, or may also be selected from a group comprising any two or more of the enumerated elements, components, or features, in the related embodiments of the present invention described herein. Furthermore, any elements, components, or features listed in this list may be omitted from this list. Any optional component of the polymer composition, method of stabilizing the polymer article or reducing discoloration may be specifically excluded.
As used herein in connection with a manifest, "at least one" means that the manifest includes each element individually, as well as combinations of two or more elements in the manifest, as well as combinations of at least one element in the manifest with unnamed like elements.
It will be further understood by those within the art that any recitation of numerical ranges by endpoints herein includes all numbers subsumed within that range (including fractions), and endpoints and equivalents of that range, whether or not explicitly recited. Thus, the description (1 to 5 includes, for example, 1, 2, 3, 4 and 5 when referring to, for example, the number of elements, and may also include 1.5, 2, 2.75 and 3.8 when referring to, for example, the measured values). The disclosure of a narrower range or a more specific group is not intended to disclaim that broader range or larger group, except as indicated by the broader range or larger group.
This invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will satisfy applicable legal requirements.
Those skilled in the art will appreciate that while preferred embodiments are discussed in more detail below, various embodiments of polymer compositions, stabilized polymer articles, and methods of stabilizing polymers against the deleterious effects of UV-C light are contemplated within the scope of the present invention. Thus, it should be noted that any feature described in relation to one aspect or embodiment of the invention is interchangeable with another aspect or embodiment of the invention unless otherwise indicated. Those skilled in the art will appreciate that even any description of the invention described with respect to a particular embodiment or drawing may be applicable to and interchangeable with other embodiments of the invention.
Accordingly, in one aspect, the present invention provides polymer compositions for use in the manufacture of stable polymer articles that are resistant to discoloration, cracking and/or crazing upon repeated or prolonged exposure to UV-C (190-280 nm) light. In any or all embodiments, the polymer composition may comprise, but is not limited to: (i) an organic polymeric material; and (ii) a stabilizer composition having: an antioxidant selected from the group consisting of hindered phenols, phosphites and phosphonites and mixtures thereof; and a light stabilizer selected from the group consisting of Hindered Amine Light Stabilizers (HALS), UV absorbers (UVA), hindered benzoates, and mixtures thereof, even in the absence of a barium compound (such as a barium salt) in the stabilizer composition, and provided that the HALS is not bis (2, 6, -tetramethyl-4-piperidinyl) sebacate alone (TINUVIN TM 770). In any or all embodiments of the polymer composition, the reduced at least one of discoloration, cracking, and/or crazing upon exposure to UV-C light is associated with the use of a light stabilizer in combination with an antioxidant, even in the absence of a barium compound (such as a barium salt) in the stabilizer composition, as compared to an antioxidant in the absence of the light stabilizer.
As shown in the examples of the present invention, 1200. Mu.W/cm at 254nm exposure 2 After 24 hours of UV-C light of average irradiance, reduced discoloration is measured by comparing Δe and/or Δyellow index (YI). ΔE is measured according to ASTM D2244-16 and ΔYI is measured according to ASTM E313-20. To determine the reduced discoloration, the color change associated with the combination of light stabilizer and antioxidant was compared to the same amount of the same antioxidant in the absence of light stabilizer.
Crazing is the formation of a network of micro-cracks (crazes) on the surface of a polymeric organic material. Crazes differ from cracks in that they are not tactilely accessible on a surface and the cracked article can continue to support a load. To determine the reduced cracking or crazing, the cracking or crazing associated with the combination of light stabilizer and antioxidant is compared to the cracking or crazing associated with the same antioxidant in the same amount in the absence of light stabilizer. In particular, as shown in examples 5-10 of the present invention and FIGS. 1A-C, 1200 μW/cm at 254nm exposure 2 After 24 hours of UV-C light of average irradiance, the cracks or crazes were determined by visual inspection or by inspection at 20 x magnification using a digital stereo microscope.
In the present examples, the total amount of antioxidants (e.g., hindered phenols and phosphites or phosphonites) is 0.08%, 0.10% or 0.15% by weight based on the total weight of the polymer composition. However, depending on the type of antioxidant, the polymeric organic material, and the degree of stabilization desired, the antioxidant may be present from 0.001 to 5.0wt.%, preferably from 0.005 to 3.0wt.%, and more preferably from 0.01 to 1.0% by weight, based on the total weight of the polymer composition.
In the examples of the invention, the total amount of light stabilizers (e.g., HALS, UVA, hindered benzoate) is 0.40%, 0.60%, 0.80%, or 1.6% by weight based on the total weight of the polymer composition. However, depending on the type of light stabilizer, the polymeric organic material and the desired degree of stabilization, the light stabilizer may be present from 0.005 to 5.0% by weight, preferably from 0.01 to 2.0% by weight, based on the total weight of the polymer composition.
In any or all embodiments, the amount of the stabilizer composition (e.g., the total amount of antioxidants and light stabilizers in certain embodiments) is from 0.001% to 10.0% by weight, preferably from 0.005% to 5.0% by weight, and more preferably from 0.01% to 3.0% by weight, based on the total weight of the polymer composition.
The organic polymeric material may be any polymeric organic material that undergoes a color change upon exposure to UV-C (190-280 nm) light. For example, the polymeric organic polymeric material may be at least one of: polyolefins, thermoplastic olefins (TPO), poly (ethylene-vinyl acetate) (EVA), polyesters, polyethers, polyketones, polyamides, natural and synthetic rubbers, polyurethanes, polystyrenes, polyacrylates, polymethacrylates, polybutyl acrylates, polyacetals, polyacrylonitriles, polybutadiene, acrylonitrile-butadiene-styrene (ABS), styrene-acrylonitrile (SAN), acrylonitrile-styrene-acrylate (ASA), cellulose acetate butyrate, cellulosic polymers, polyimides, polyamideimides, polyetherimides, polyphenylene sulfides, polyphenylene oxides, polysulfones, polyethersulfones, polyvinylchlorides, amino resin crosslinked polyacrylates and polyesters, polyisocyanate crosslinked polyesters and polyacrylates, phenol/formaldehyde, urea/formaldehyde and melamine/formaldehyde resins alkyd resins, polyester resins, acrylate resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, urethanes or epoxy resins, crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic and aromatic glycidyl ethers crosslinked with anhydrides or amines, polysiloxanes, michael addition polymers, addition polymers of amines or blocked amines with activated unsaturated and activated methylene compounds, addition polymers of ketimines with activated unsaturated and activated methylene compounds, combinations of polyketimines with unsaturated acrylic polyacetoacetate resins, coating compositions, radiation curable compositions, epoxy melamine resins, organic dyes, cosmetics, cellulose-based papers, photographic film papers, fibers, and the like, wax or ink.
In any or all embodiments, the organic polymeric material is a polyolefin. The polyolefin may be at least one of the following: (i) Polyethylene, polypropylene, polyisobutylene, polybut-1-ene or poly-4-methylpent-1-ene; (ii) polyisoprene or polybutadiene; (iii) cyclopentene or norbornene; (iv) Optionally crosslinked polyethylene, high Density Polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultra high molecular weight polyethylene (HDPE-UHMW), medium Density Polyethylene (MDPE), low Density Polyethylene (LDPE), linear Low Density Polyethylene (LLDPE), very Low Density Polyethylene (VLDPE), or Ultra Low Density Polyethylene (ULDPE); (v) thermoplastic olefins (TPOs); or (vi) copolymers of at least one of a mono-, di-or cyclic olefin.
The antioxidant is selected from the group consisting of hindered phenols, phosphites and phosphonites and mixtures thereof. In any or all embodiments, the antioxidant comprises a hindered phenol. The hindered phenol may have at least one group according to formula (IVa), (IVb) or (IVc):
wherein:indicating the attachment point of the molecular fragment to the parent compound (via a carbon-carbon single bond); r in each of the formulae (IVa), (IVb) or (IVc) 18 Is hydrogen or C 1-12 A hydrocarbon group; r in formula (IVa), (IVb) or (IVc) 19 And R is 20 Each of which is independently hydrogen or C 1 -C 20 A hydrocarbon group; and R in each of the formulae (IVa), (IVb) or (IVc) 37 Is C 1 -C 12 A hydrocarbon group. In any or all embodiments, R in formula (IVa), (IVb) or (IVc) 18 And R is 37 Independently selected from methyl or t-butyl.
Examples of hindered phenols suitable for use in the invention disclosed herein are provided below, organized by genus:
a) Alkylated monophenols include, for example, 2, 6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4, 6-dimethylphenol, 2, 6-di-tert-butyl-4-ethylphenol, 2, 6-di-tert-butyl-4-n-butylphenol, 2, 6-di-tert-butyl-4-isobutylphenol, 2, 6-dicyclopentyl-4-methylphenol, 2- α -methylcyclohexyl) -4, 6-dimethylphenol, 2, 6-dioctadecyl-4-methylphenol, 2,4, 6-tricyclohexylphenol, 2, 6-di-tert-butyl-4-methoxymethylphenol or 2, 6-dinonyl-4-methylphenol.
b) Alkylthiomethylphenols, for example, include 2, 4-dioctylthiomethyl-6-tert-butylphenol, 2, 4-dioctylthiomethyl-6-methylphenol, 2, 4-dioctylthiomethyl-6-ethylphenol or 2, 6-didodecylthiomethyl-4-nonylphenol.
c) Hydroquinones and alkylated hydroquinones include, for example, 2, 6-di-tert-butyl-4-methoxyphenol, 2, 5-di-tert-butylhydroquinone, 2, 5-di-tert-amylhydroquinone, 2, 6-diphenyl-4-octadecyloxyphenol, 2, 6-di-tert-butylhydroquinone, 2, 5-di-tert-butyl-4-hydroxyanisole, 3, 5-di-tert-butyl-4-hydroxyphenyl stearate or bis (3, 5-di-tert-butyl-4-hydroxyphenyl) adipate.
d) Hydroxylated thiodiphenyl ethers include, for example, 2 '-thiobis (6-tert-butyl-4-methylphenol), 2' -thiobis (4-octylphenol), 4 '-thiobis (6-tert-butyl-3-methylphenol), 4' -thiobis (6-tert-butyl-2-methylphenol), 4 '-thiobis (3, 6-di-sec-amylphenol) or 4,4' -bis (2, 6-dimethyl-4-hydroxyphenyl) disulfide.
e) An alkylene bisphenol which is used as a starting material for the catalyst, including, for example, 2' -methylenebis (6-tert-butyl-4-methylphenol), 2' -methylenebis (6-tert-butyl-4-ethylphenol), 2' -methylenebis [ 4-methyl-6- (. Alpha. -methylcyclohexyl) phenol ], 2' -methylenebis (4-methyl-6-cyclohexylphenol), 2' -methylenebis (6-nonyl-4-methylphenol) 2,2' -methylenebis (4, 6-di-t-butylphenol), 2' -ethylenebis (6-t-butyl-4-isobutylphenol), 2' -methylenebis [6- (. Alpha. -methylbenzyl) -4-nonylphenol ], 2' -methylenebis [6- (. Alpha., alpha-dimethylbenzyl) -4-nonylphenol ], 4' -methylenebis (2, 6-di-t-butylphenol), 4' -methylenebis (6-t-butyl-2-methylphenol), 1-bis (5-t-butyl-4-hydroxy-2-methylphenyl) butane, 2, 6-bis (3-t-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1, 3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecylmercaptobutane, ethylene glycol bis [3, 3-bis (3 ' -tert-butyl-4 ' -hydroxyphenyl) butyrate ], bis (3-tert-butyl-4-hydroxy-5-methyl-phenyl) dicyclopentadiene bis [2- (3 ' -tert-butyl-2 ' -hydroxy-5 ' -methylbenzyl) -6-tert-butyl-4-methylphenyl ] terephthalate, 1-bis (3, 5-dimethyl-2-hydroxyphenyl) butane, 2-bis (3, 5-di-tert-butyl-4-hydroxyphenyl) propane, 2-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecylmercaptobutane or 1, 5-tetrakis- (5-tert-butyl-4-hydroxy-2-methylphenyl) pentane.
f) O-, N-and S-benzyl compounds, including, for example, 3,5,3',5' -tetra-tert-butyl-4, 4' -dihydroxydibenzyl ether, octadecyl-4-hydroxy-3, 5-dimethylbenzyl mercaptoacetate, tridecyl-4-hydroxy-3, 5-di-tert-butylbenzylmercaptoacetate, tris (3, 5-di-tert-butyl-4-hydroxybenzyl) amine, bis (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) dithioterephthalate, bis (3, 5-di-tert-butyl-4-hydroxybenzyl) sulfide or isooctyl-3, 5-di-tert-butyl-4-hydroxybenzyl mercaptoacetate.
g) Hydroxybenzylated malonates including, for example, dioctadecyl-2, 2-bis (3, 5-di-tert-butyl-2-hydroxybenzyl) malonate, dioctadecyl-2- (3-tert-butyl-4-hydroxy-5-methylbenzyl) malonate, didodecylmercaptoethyl-2, 2-bis (3, 5-di-tert-butyl-4-hydroxybenzyl) malonate or bis [4- (1, 3-tetramethylbutyl) phenyl ] -2, 2-bis (3, 5-di-tert-butyl-4-hydroxybenzyl) malonate.
h) Aromatic hydroxybenzyl compounds include, for example, 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -2,4, 6-trimethylbenzene, 1, 4-bis (3, 5-di-tert-butyl-4-hydroxybenzyl) -2,3,5, 6-tetramethylbenzene or 2,4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) phenol.
i) Triazine compounds including, for example, 2, 4-bis (octylmercapto) -6- (3, 5-di-tert-butyl-4-hydroxyanilino) -1,3, 5-triazine, 2-octylmercapto-4, 6-bis (3, 5-di-tert-butyl-4-hydroxyphenoxy) -1,3, 5-triazine, 2,4, 6-tris (3, 5-di-tert-butyl-4-hydroxyphenoxy) -1,2, 3-triazine, 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) isocyanurate, 2,4, 6-tris (3, 5-di-tert-butyl-4-hydroxyphenylethyl) -1,3, 5-triazine, 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxyphenylpropionyl) -hexahydro-1, 3, 5-triazine or 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxyphenylpropionyl) isocyanurate.
j) Benzyl phosphonate including, for example, dimethyl-2, 5-di-tert-butyl-4-hydroxybenzyl phosphonate, diethyl-3, 5-di-tert-butyl-4-hydroxybenzyl phosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzyl phosphonate, 3, 5-di-tert-butyl-4-hydroxybenzyl phosphonic acid monoethyl ester calcium salt.
k) Acylaminophenols, for example, include 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N- (3, 5-di-tert-butyl-4-hydroxyphenyl) carbamate.
l) [ esters of 5- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid with monohydric or polyhydric alcohols, for example with methanol, ethanol, N-octanol, isooctanol, octadecanol, 1, 6-hexanediol, 1, 9-nonanediol, ethylene glycol, 1, 2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N' -bis (hydroxyethyl) ethylenediamine, 3-thiaundecanol, 3-thiapentadecanol, 2, 4-trimethyl-1, 6-hexanediol, trimethylolpropane or 4-hydroxymethyl-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane.
m) esters of β - (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with monohydric or polyhydric alcohols, for example with methanol, ethanol, N-octanol, isooctanol, octadecanol, 1, 6-hexanediol, 1, 9-nonanediol, ethylene glycol, 1, 2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N' -bis (hydroxyethyl) ethylenediamine, 3-thiaundecanol, 3-thiapentadecanol, 2, 4-trimethyl-1, 6-hexanediol, trimethylolpropane or 4-hydroxymethyl-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane; or 3, 9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy } -1, 1-dimethylethyl ] -2,4,8, 10-tetraoxaspiro [5.5] undecane.
N) esters of beta- (3, 5-dicyclohexyl-4-hydroxyphenyl) propionic acid with monohydric or polyhydric alcohols, for example with methanol, ethanol, octanol, octadecanol, 1, 6-hexanediol, 1, 9-nonanediol, ethylene glycol, 1, 2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N' -bis (hydroxyethyl) ethylenediamine, 3-thiaundecanol, 3-thiapentadecanol, 2, 4-trimethyl-1, 6-hexanediol, trimethylolpropane or 4-hydroxymethyl-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane.
o) esters of 3, 5-di-tert-butyl-4-hydroxyphenylacetic acid with monohydric or polyhydric alcohols, for example methanol, ethanol, octanol, octadecanol, 1, 6-hexanediol, 1, 9-nonanediol, ethylene glycol, 1, 2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N' -bis (hydroxyethyl) ethylenediamine, 3-thiaundecanol, 3-thiapentadecanol, 2, 4-trimethyl-1, 6-hexanediol, trimethylolpropane or 4-hydroxymethyl-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane.
p) [ amides of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid, for example N, N '-bis (3, 5-di-tert-butyl-4-hydroxyphenyl propionyl) hexamethylenediamide, N' -bis (3, 5-di-tert-butyl-4-hydroxyphenyl propionyl) trimethylene diamide, N '-bis (3, 5-di-tert-butyl-4-hydroxyphenyl propionyl) hydrazide or N, N' -bis [2- (3- [3, 5-di-tert-butyl-4-hydroxyphenyl ] propionyloxy) ethyl ] oxalyl diamine.
In any or all embodiments of the polymer compositions described herein, the hindered phenol is at least one of the following:
1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione (CYANOX) TM 1790)，
1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione (IRGANOX) TM 3114)，
1, 3-tris (2 ' -methyl-4 ' -hydroxy-5 ' -tert-butylphenyl) butane,
triethylene glycol bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ],
4,4' -thiobis (2-tert-butyl-5-methylphenol),
2,2' -thiodiethylenebis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ],
octadecyl 3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate,
pentaerythritol (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate,
n, N' -hexamethylenebis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propanamide ],
bis (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) thiodipropionate,
pentaerythritol tetrakis (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) (IRGANOX TM 1010)，
Octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (IRGANOX) TM 1076 Or (x)
N, N' -bis (3, 5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine (IRGANOX) TM 1024)。
In any or all embodiments of the polymer composition, the hindered phenol may be at least one of the following: pentaerythritol tetrakis (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) (IRGANOX TM 1010 Octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (IRGANOX) TM 1076 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione (IRGANOX) TM 3114 Or N, N' -bis (3, 5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine (IRGANOX) TM 1024)。
In the same or other embodiments, the antioxidant is selected from the group consisting of hindered phenols, phosphites, and phosphonites, and mixtures thereof. In any or all embodiments, the antioxidant comprises a phosphite or phosphonite. The phosphite or phosphonite may be at least one of the following:
i) A compound according to any one of formulae (1) to (7):
wherein:
the index is an integer and n is 2, 3 or 4; p is 1 or 2; q is 2 or 3; y is 1, 2 or 3; and z is 1 to 6;
if n or q is 2, A 1 Is C 2 -C 18 An alkylene group; by oxygen, sulfur or-NR 4 Interrupted C 2 -C 12 An alkylene group having the formula:
or phenylene;
if n or q is 3, A 1 Is of the formula-C r H 2r-1 -a divalent group, wherein r is an integer from 4 to 12;
if n is 4, A 1 Is that
B is a direct bond, -CH 2 -、-CHR 4 -、-CR 1 R 4 -, sulfur, C (C) 5 -C 7 Cycloalkylene, or from 1 to 4C at the 3, 4 and/or 5 positions 1 -C 4 Alkyl-substituted cyclohexylene;
if p is 1, D 1 Is C 1 -C 4 Alkyl, and if p is 2, is-CH 2 OCH 2 -；
D 2 Is C 1 -C 4 An alkyl group;
if y is 1, E is C 1 -C 18 Alkyl, -OR 1 Or halogen;
if y is 2, E is-O-A 2 -O-, wherein A 2 Is as for A 1 When n isIs defined as 2;
if y is 3, E is a compound of formula R 4 C(CH 2 O) 3 Or N (CH) 2 CH 2 O-) 3 Is a group of (2);
q is a group of at least z-valent mono-or polyhydric alcohol or phenol, which is attached to the phosphorus atom via an oxygen atom of the OH group of the mono-or polyhydric alcohol or phenol;
R 1 、R 2 and R is 3 Each independently is C 1 -C 18 Alkyl, which is unsubstituted or substituted by halogen, -COOR 4 -CN or-CONR 4 R 4 Substitution; by oxygen, sulfur or-NR 4 Interrupted C 2 -C 18 An alkyl group; c (C) 7 -C 9 A phenylalkyl group; c (C) 5 -C 12 Cycloalkyl, phenyl, or naphthyl; by halogen, 1 to 3 alkyl or alkoxy groups having a total of 1 to 18 carbon atoms, or by C 7 -C 9 Phenylalkyl-substituted naphthyl or phenyl; or a group of the formula
Wherein m is an integer from 3 to 6;
R 4 is hydrogen, C 1 -C 8 Alkyl, C 5 -C 12 Cycloalkyl or C 7 -C 9 A phenylalkyl group;
R 5 and R is 6 Each independently is hydrogen, C 1 -C 8 Alkyl or C 5 -C 6 A cycloalkyl group,
if q is 2, R 7 And R is 8 Each independently is C 1 -C 4 Alkyl or together are 2, 3-dehydropentamethylene; and if q is 3, R 7 And R is 8 Each is methyl;
r in each case 14 Independently selected from hydrogen, C 1 -C 9 Alkyl or cyclohexyl;
r in each case 15 Independently hydrogen or methyl;
x and Y are each a direct bond or oxygen;
z is a direct bond, methylene, -C (R) 16 ) 2 -or sulfur, and
R 16 is C 1 -C 8 An alkyl group; or alternatively
ii) a triarylphosphite compound according to formula 8:
wherein:
R 17 is a substituent present in from 0 to 5 instances of an aromatic ring of formula 8 and is independently at each occurrence C 1 -C 20 Alkyl, C 3 -C 20 Cycloalkyl, C 4 -C 20 Alkylcycloalkyl, C 6 -C 10 Aryl or C 7 -C 20 Alkylaryl groups.
In any or all embodiments, the phosphite or phosphonite may be, for example, at least one of the following:
the preparation method comprises the steps of (1) preparing triphenyl phosphite,
diphenyl alkyl phosphite is used as the main component of the composition,
a phenyl dialkyl phosphite is used as a starting material,
the trilauryl phosphite is used as the main ingredient,
a trioctadecyl phosphite ester, wherein the main chain of the phosphite ester is a tri-octadecyl phosphite,
distearyl pentaerythritol phosphite which is used as a main ingredient,
tris (2, 4-di-tert-butylphenyl) phosphite (IRGAFOS) TM 168)，
Tris (4-nonylphenyl) phosphite,
a compound of formula (a), (B), (C), (D), (E), (F), (G), (H), (J), (K) or (L):
/>
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2-butyl-2-ethyl-1, 3-propanediol 2,4, 6-tri-tert-butylphenol phosphite,
bis- (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite,
2-butyl-2-ethyl-1, 3-propanediol 2, 4-di-cumylphenol phosphite,
2-butyl-2-ethyl-1, 3-propanediol 4-methyl-2, 6-di-tert-butylphenol phosphite, or
Bis (2, 4, 6-tri-tert-butyl-phenyl) pentaerythritol diphosphate.
In any or all embodiments, the phosphite or phosphonite is at least one of the following: tris (2, 4-di-tert-butylphenyl) phosphite (IRGAFOS) TM 168 Triphenyl phosphite, tris (4-nonylphenyl) phosphite, bis (2, 4-dicumylphenyl) pentaerythritol Diphosphite (DOVERPHOS) TM S9228) or tetrakis (2, 4-di-tert-butylphenyl) -4,4' -biphenylene-diphosphonite (IRGAFOS) TM P-EPQ)。
The polymer composition according to the present invention further comprises a light stabilizer selected from the group consisting of Hindered Amine Light Stabilizers (HALS), UV absorbers (UVA), hindered benzoates and mixtures thereof. In any or all of the embodiments, the light stabilizer comprises a hindered amine light stabilizer, even in the absence of a UV absorber or other light stabilizer, provided that the HALS is not bis (2, 6, -tetramethyl-4-piperidinyl) sebacate alone (TINUVIN) TM 770). The hindered amine light stabilizer may comprise at least one functional group according to formula (II):
wherein:
R 31 is hydrogen, OH, C 1 -C 20 Hydrocarbyl radicals, -CH 2 CN、C 1 -C 12 Acyl or C 1 -C 18 An alkoxy group;
R 38 is hydrogen or C 1 -C 8 A hydrocarbon group; and is also provided with
R 29 、R 30 、R 32 And R is 33 Each independently is C 1 -C 20 Hydrocarbyl, or R 29 And R is 30 And/or R 32 And R is 33 Together with the carbon to which they are attached form C 5 -C 10 Cycloalkyl; or alternatively
At least one functional group according to formula (IIa):
/>
wherein:
m is an integer from 1 to 2;
R 39 is hydrogen, OH, C 1 -C 20 Hydrocarbyl radicals, -CH 2 CN、C 1 -C 12 Acyl or C 1 -C 18 An alkoxy group; and is also provided with
G 1 -G 4 Each independently is C 1 -C 20 A hydrocarbon group.
In any or all embodiments, the Hindered Amine Light Stabilizer (HALS) may be, for example, at least one of the following:
bis (2, 6-tetramethylpiperidin-4-yl) succinate;
bis (1, 2, 6-pentamethylpiperidin-4-yl) sebacate;
bis (1-octyloxy-2, 6-tetramethylpiperidinyl) succinate;
bis (1-octyloxy-2, 6-tetramethylpiperidin-4-yl) sebacate (TINUVIN) TM 123)；
Bis (1, 2, 6-pentamethylpiperidin-4-yl) n-butyl 3, 5-di-tert-butyl-4-hydroxybenzylmalonate;
condensate of 1- (2-hydroxyethyl) -2, 6-tetramethyl-4-hydroxypiperidine and succinic acid (TINUVIN TM 622)；
2, 6-tetramethylpiperidin-4-yl stearate;
2, 6-tetramethylpiperidin-4-yl dodecanoate;
1,2, 6-pentamethylpiperidin-4-yl stearate;
dodecanoic acid 1,2, 6-pentamethylpiperidin-4-yl ester;
condensate of N, N' -bis (2, 6-tetramethylpiperidin-4-yl) hexamethylenediamine and 4-tert-octylamino-2, 6-dichloro-1, 3, 5-triazine (CHIMASSORB) TM 944)；
Tri (2, 6-tetramethylpiperidin-4-yl) nitrilotriacetic acid ester;
4-stearyloxy-2, 6-tetramethylpiperidine;
condensate of N, N' -bis (2, 6-tetramethylpiperidin-4-yl) hexamethylenediamine and 4-morpholino-2, 6-dichloro-1, 3, 5-triazine (CYASORB) TM UV-3346)；
Methylated condensates of N, N' -bis (2, 6-tetramethylpiperidin-4-yl) hexamethylenediamine and 4-morpholino-2, 6-dichloro-1, 3, 5-triazine (CYASORB) TM UV-3529)；
Condensate of 2-chloro-4, 6-bis (4-n-butylamino-2, 6-tetramethylpiperidinyl) -1,3, 5-triazine and 1, 2-bis (3-aminopropylamino) ethane (CHIMASSORB) TM 119)；
A condensate of 2-chloro-4, 6-bis (4-n-butylamino-1, 2, 6-pentamethylpiperidinyl) -1,3, 5-triazine and 1, 2-bis- (3-aminopropylamino) ethane;
condensate of N, N' -bis (2, 6-tetramethylpiperidin-4-yl) hexamethylenediamine, N-butyl-2, 6-tetramethyl-4-piperidylamine, di-N-butylamine and 2,4, 6-trichloro-1, 3, 5-triazine (CHIMASSORB) TM 2020)；
Mixtures of 4-hexadecyloxy-and 4-stearyloxy-2, 6-tetramethylpiperidine (CYASORB) TM UV-3853)；
A mixture of 4-hexadecyloxy-and 4-stearyloxy-1, 2, 6-pentamethylpiperidine;
condensate of N, N' -bis (2, 6-tetramethylpiperidin-4-yl) hexamethylenediamine and 4-cyclohexylamino-2, 6-dichloro-1, 3, 5-triazine;
Condensates of 1, 2-bis (3-aminopropylamino) ethane, 2,4, 6-trichloro-1, 3, 5-triazine and 4-butylamino-2, 6-tetramethylpiperidine;
condensate of N, N' -bis (2, 6-tetramethylpiperidin-4-yl) hexamethylenediamine and 4-cyclohexylamino-2, 6-dichloro-1, 3, 5-triazine;
tetrakis (2, 6-tetramethylpiperidin-4-yl) -1,2,3, 4-butane tetracarboxylic acid ester;
tetrakis (1, 2, 6-pentamethylpiperidin-4-yl) -1,2,3, 4-butanetetracarboxylate;
1,2,3, 4-butanetetracarboxylic acid, 2, 6-tetramethylpiperidinyl-4-yltridecyl ester;
1,2,3, 4-butanetetracarboxylic acid, 1,2, 6-pentamethylpiperidin-4-yltridecyl ester;
carboxamide, N, N' -1, 6-adipoylbis [ N- (2, 6-tetramethylpiperidin-4-yl) (UVINUL) TM 4050)；
Condensate of N, N' -bis (2, 6-tetramethylpiperidin-4-yl) hexamethylenediamine and 4-tert-octylamino-2, 6-dichloro-1, 3, 5-triazine (CHIMASSORB) TM 944)；
Condensate of N, N' -bis (2, 6-tetramethyl-1- (propoxy) -piperidin-4-yl) hexamethylenediamine, N-butyl-1-propoxy-2, 6-tetramethyl-4-piperidinamine, di-N-butylamine and 2,4, 6-trichloro-1, 3, 5-triazine (TINUVIN TM NOR HALS 371；
Oxidative hydrogenation reaction products of polymers of N, N' -bis (2, 6-tetramethyl-4-piperidin-4-yl) hexamethylenediamine with 2,4, 6-trichloro-1, 3, 5-triazine with 3-bromo-1-propene, di-N-butylamine and N-butyl-2, 6-tetramethyl-4-piperidinamine (TINUVIN TM XT 200)；
TINUVIN TM XT-850/XT-855); or alternatively
N 1 ,N 1' Reaction product of (FLAMETAB) 1, 2-ethanediylbis (1, 3-propanediamine) with cyclohexane and N-butyl-2, 6-tetramethyl-4-piperidinamine-2, 4, 6-trichloro-1, 3, 5-triazine peroxide TM NOR 116)。
It has been described that the polymer composition according to the present invention comprises a light stabilizer selected from the group consisting of Hindered Amine Light Stabilizers (HALS), UV absorbers (UVA), hindered benzoates and mixtures thereof. In any or all embodiments, the light stabilizer comprises a UV absorber (even in the absence of HALS or other light stabilizers) that is at least one 2- (2 '-hydroxyphenyl) -s-triazine, 2-hydroxybenzophenone, 2- (2' -hydroxyphenyl) benzotriazole or benzoxazinone.
In any or all embodiments, the light stabilizer comprises at least one 2- (2' -hydroxyphenyl) -s-triazine. The 2- (2' -hydroxyphenyl) -s-triazine may be a compound according to formula (I):
wherein R is 34 And R is 35 Each of which is independently selected from C 6 -C 10 Aryl, mono-or di-C 1 -C 12 Hydrocarbyl-substituted amino, C 2 -C 12 Alkanoyl, C 1 -C 12 Alkyl, C 1 -C 10 Acyl or C 1 -C 10 An alkoxy group, an amino group,
wherein C is 6 -C 10 Aryl optionally substituted in from 1 to 3 positions with OH, halogen, C 1 -C 12 Alkyl, C 1 -C 12 Alkoxy, C 1-12 Alkoxy esters, C 2-12 At least one substitution of alkanoyl or phenyl, wherein phenyl is optionally substituted at from 1 to 3 substitutable positions with OH, halogen, C 1-12 Alkyl, C 1-12 Alkoxy, C 1-12 Alkoxy esters or C 2-12 At least one substitution in an alkanoyl group; and is also provided with
Each R 36 Independently selected from OH, halogen, C 1 -C 12 Alkyl, C 1 -C 12 Alkoxy, C 1 -C 12 Alkoxy esters, C 2 -C 12 Alkanoyl, phenyl or C 1 -C 12 An acyl group.
In any or all embodiments, the 2- (2' -hydroxyphenyl) -s-triazine may be at least one of the following:
4, 6-diphenyl-2- (4-hexyloxy-2-hydroxyphenyl) -s-triazine (TINUVIN TM 1577)，
4,6-Bis- (2, 4-dimethylphenyl) -2- (2-hydroxy-4-octyloxyphenyl) -s-triazine (CYASORB) TM 1164)，
2, 4-bis [ 2-hydroxy-4- (2-hydroxyethoxy) phenyl ] -6- (2, 4-dimethylphenyl) -s-triazine,
mixture of 4, 6-bis (2, 4-dimethylphenyl) -2- (2-hydroxy-4- (3-dodecyloxy-2-hydroxypropoxy) phenyl) -s-triazine and 4, 6-bis- (2, 4-dimethylphenyl) -2- (2-hydroxy-4- (3-tridecyloxy-2-hydroxypropoxy) phenyl) -s-Triazine (TINUVIN) TM 400)，
4, 6-bis- (2, 4-dimethylphenyl) -2- (2-hydroxy-4 (3- (2-ethylhexyloxy) -2-hydroxypropoxy) -phenyl) -s-Triazine (TINUVIN) TM 405)，
4, 6-bis- (2, 4-dimethylphenyl) -2- (2-hydroxy-4 (3- (2-ethylhexyloxy) -2-hydroxypropoxy) -phenyl) -s-triazine,
2, 4-bis (2, 4-dimethylphenyl) -6- [ 2-hydroxy-4- [ (octyloxycarbonyl) ethyleneoxy ]Phenyl group]s-Triazine (TINUVIN) TM 479)，
2, 4-bis (4-biphenyl) -6- [ 2-hydroxy-4- [ (octoxycarbonyl) ethyleneoxy ] phenyl ] -s-triazine,
2, 4-bis (4-biphenyl) -6- [ 2-hydroxy-4- (2-ethylhexyloxy) phenyl]s-Triazine (TINUVIN) TM 1600)，
2, 4-bis (2-hydroxy-4-butoxyphenyl) -6- (2, 4-bis-butoxyphenyl) -s-TRIAZINE (triazene) TM 460)，
2,4, 6-tris [ 2-hydroxy-4- (3-sec-butoxy-2-hydroxypropoxy) -phenyl ] -s-triazine, or
2,4, 6-tris [ 2-hydroxy-4- [ (octyloxycarbonyl) ethyleneoxy)]Phenyl group]s-Triazine (TINUVIN) TM 477)。
In the same or other embodiments of the polymer composition according to the invention, the light stabilizer comprises 2-hydroxybenzophenone. The 2-hydroxybenzophenone may be at least one of the following: 2-hydroxy-4-methoxybenzophenone (CYASORB) TM UV-9), 2' -dihydroxy-4-methoxybenzophenone (CYASORB) TM UV-24), 2-hydroxy-4-octoxybenzophenone (CYASORB) TM UV-531), 2 '-dihydroxy-4, 4' -di-methoxy-dibenzoateKetones, 2' -dihydroxybenzophenones, 2',4,4' -tetrahydroxybenzophenone, 2' -dihydroxy-4, 4' -dimethoxybenzophenone, 2' -dihydroxy-4, 4' -diethoxybenzophenone, 2' -dihydroxy-4, 4' -dipropoxybenzophenone, 2' -dihydroxy-4, 4' -dibutoxybenzophenone, 2' -dihydroxy-4-methoxy-4 ' -ethoxybenzophenone, 2' -dihydroxy-4-methoxy-4 ' -propoxybenzophenone 2,2' -dihydroxy-4-methoxy-4 ' -butoxybenzophenone, 2' -dihydroxy-4-ethoxy-4 ' -propoxybenzophenone, 2' -dihydroxy-4-ethoxy-4 ' -butoxybenzophenone, 2,3' -dihydroxy-4, 4' -dimethoxybenzophenone, 2,3' -dihydroxy-4-methoxy-4 ' -butoxybenzophenone, 2-hydroxy-4, 4',5' -trimethoxybenzophenone, 2-hydroxy-4, 4',6' -tributoxybenzophenone, 2-hydroxy-4-butoxy-4 ',5' -dimethoxybenzophenone, 2-hydroxy-4-ethoxy-2 ',4' -dibutylbenzophenone, 2-hydroxy-4-propoxy-4 ',6' -dichlorobenzophenone, and, 2-hydroxy-4-propoxy-4 ',6' -dibromobenzophenone, 2, 4-dihydroxybenzophenone, 2-hydroxy-4-ethoxybenzophenone, 2-hydroxy-4-propoxybenzophenone, 2-hydroxy-4-butoxybenzophenone, 2-hydroxy-4-methoxy-4 ' -methylbenzophenone, 2-hydroxy-4-methoxy-4 ' -ethylbenzophenone, 2-hydroxy-4-methoxy-4 ' -propylbenzophenone, 2-hydroxy-4-methoxy-4 ' -butylbenzophenone, 2-hydroxy-4-methoxy-4 ' -tert-butylbenzophenone, 2-hydroxy-4-methoxy-4 ' -chlorobenzophenone, 2-hydroxy-4-methoxy-2 ' -chlorobenzophenone, 2-hydroxy-4-methoxy-4 ' -bromobenzophenone, 2-hydroxy-4, 4' -dimethoxybenzophenone, 2-hydroxy-4, 4' -dimethoxy-3-methylbenzophenone, 2-hydroxy-4, 4' -dimethoxy-2 ' -ethylbenzophenone, 2-hydroxy-4, 4',5' -trimethoxybenzophenone, 2-hydroxy-4-ethoxy-4 ' -methylbenzophenone, 2-hydroxy-4-ethoxy-4 ' -ethylbenzophenone, 2-hydroxy-4-ethoxy-4 ' -propylbenzophenone, 2-hydroxy-4-ethoxy-4 ' -butylbenzophenone, 2-hydroxy-4-ethoxy-4 ' -methoxybenzophenone, 2-hydroxy-4, 4' -diethoxybenzophenone, 2-hydroxy-4-ethoxy-4 ' -propoxybenzophenone, 2-hydroxy-4-ethoxy-4 ' -butoxybenzophenone, 2-hydroxy-4-ethoxy-4 ' -chlorobenzophenone or 2-hydroxy-4-ethoxy-4 ' -bromobenzophenone.
In the same or other embodiments of the polymer composition according to the invention, the light stabilizer comprises 2- (2' -hydroxyphenyl) benzotriazole. The 2- (2' -hydroxyphenyl) benzotriazole may be at least one of the following: 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole (TINUVIN TM P), 2- (2 '-hydroxy-5' -tert-butylphenyl) benzotriazole, 2- (2 '-hydroxy-3' -methyl-5 '-tert-butylphenyl) benzotriazole, 2- (2' -hydroxy-5 '-cyclohexylphenyl) benzotriazole, 2- (2' -hydroxy-3 ',5' -dimethylphenyl) benzotriazole, 2- (2 '-hydroxy-5' -tert-butylphenyl) -5-chloro-benzotriazole, 2- (2 '-hydroxy-5' -tert-octylphenyl) benzotriazole (cyclic orb) TM UV-5411), 2- (3 ',5' -di-tert-butyl-2 '-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3', 5 '-di-tert-amyl-2' -hydroxyphenyl) benzotriazole (CYASORB) TM UV-2337), 2- (3 ',5' -bis (α, α -dimethylbenzyl) -2' -hydroxyphenyl) benzotriazole (TINUVIN TM 900 2- (3 '-tert-butyl-2' -hydroxy-5 '- (2-octyloxycarbonylethyl) phenyl) benzotriazole, 2' -methylenebis [4- (1, 3-tetramethylbutyl) -6-benzotriazol-2-ylphenol]2- [3' -tert-butyl-5 ' - (2-methoxycarbonylethyl) -2' -hydroxyphenyl]Transesterification product of 2H-benzotriazole with polyethylene glycol 300 (TINUVIN TM 1130 2- [2' -hydroxy-3 ' - (α, α -dimethylbenzyl) -5' - (1, 3-tetramethylbutyl) phenyl]Benzotriazole, 5-trifluoromethyl-2- (2-hydroxy-3-alpha-cumyl-5-tert-octylphenyl) benzotriazole, 2- (2 ' -hydroxy-5 ' - (2-hydroxyethyl) phenyl) benzotriazole, 2- (2 ' -hydroxy-5 ' - (2-methacryloyloxyethyl) phenyl) benzotriazole, 2- (2 ' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-chlorobenzotriazole (TINUVIN) TM 326 2- (3 '-sec-butyl-5' -tert-butyl-2 '-hydroxyphenyl) benzotriazole, 2- (3', 5 '-di-tert-butyl-2' -hydroxyphenyl) benzotriazole, 2- (3 '-dodecyl-5' -methyl-2 '-hydroxyphenyl) -benzotriazole, 2- (3' -tert-butyl-5 '- (2-octoxycarbonylethyl) -2' -hydroxyphenyl) -5-chlorobenzotriazole, 2- (5 '-methyl-2' -hydroxyphenyl) benzotriazole or 2- (5 '-tert-butyl-2' -hydroxyphenyl) benzotriazole.
In the same or other embodiments of the polymer composition according to the invention, the light stabilizer comprises a benzoxazinone. The benzoxazinone may be at least one of the following: 2-methyl-3, 1-benzoxazoleOxazin-4-one, 2-butyl-3, 1-benzoxazine-4-one, 2-phenyl-3, 1-benzoxazine-4-one, 2- (1-or 2-naphthyl) -3, 1-benzoxazine-4-one, 2- (4-biphenyl) -3, 1-benzoxazine-4-one, 2-p-nitrophenyl-3, 1-benzoxazine-4-one, 2-m-nitrophenyl-3, 1-benzoxazine-4-one, 2-p-benzoylphenyl-3, 1-benzoxazine-4-one, 2-p-methoxyphenyl-3, 1-benzoxazine-4-one 2-O-methoxyphenyl-3, 1-benzoxazin-4-one, 2-cyclohexyl-3, 1-benzoxazin-4-one, 2-p (or m) phthalimidophenyl-3, 1-benzoxazin-4-one, N-phenyl-4- (3, 1-benzoxazin-4-one-2-yl) phthalimide, N-benzoyl-4- (3, 1-benzoxazin-4-one-2-yl) aniline, N-benzoyl-N-methyl-4- (3, 1-benzoxazin-4-one-2-yl) -aniline, 2- [ p- (N-phenylcarbamoyl) phenyl ]-3, 1-benzoxazin-4-one, 2- [ p- (N-phenyl N-methylcarbamoyl) phenyl ]]-3, 1-benzoxazin-4-one, 2 '-bis (3, 1-benzoxazin-4-one), 2' -ethylenebis (3, 1-benzoxazin-4-one), 2 '-tetramethylenebis (3, 1-benzoxazin-4-one) 2,2' -hexamethylenebis (3, 1-benzoxazin-4-one), 2 '-decamethylenebis (3, 1-benzoxazin-4-one), 2' -p-phenylenedi (3, 1-benzoxazin-4-one) (CYASORB TM UV-3638), 2 '-m-phenylenebis (3, 1-benzoxazin-4-one), 2' - (4, 4 '-diphenylene) bis (3, 1-benzoxazin-4-one), 2' - (2, 6-or 1, 5-naphtalene) bis (3, 1-benzoxazin-4-one) 2,2'- (2-methyl-p-phenylene) bis (3, 1-benzoxazin-4-one), 2' - (2-nitro-p-phenylene) bis (3, 1-benzoxazin-4-one), 2'- (2-chloro-p-phenylene) bis (3, 1-benzoxazin-4-one) 2,2' - (1, 4-cyclohexylidene) bis (3, 1-benzoxazin-4-one), N-p- (3, 1-benzoxazin-4-one-2-yl) phenyl, 4- (3, 1-benzoxazin-4-one-2-yl) phthalimide, N-p- (3, 1-benzoxazin-4-one-2-yl) benzoyl, 4- (3, 1-benzoxazin-4-one-2-yl) aniline, 1,3, 5-tris (3, 1-benzoxazin-4-one-2-yl) benzene, 1,3, 5-tris (3, 1-benzoxazin-4-one-2-yl) naphthalene or 2,4, 6-tris (3, 1-benzoxazin-4-one-2-yl) naphthalene.
In the same or other embodiments of the polymer composition according to the invention, the light stabilizer comprises a hindered benzoate. In certain embodiments, a hindered benzoate may be present even in the absence of HALS or UV absorbers. The hindered benzoate may be a compound according to formula (VI):
wherein:
R 21 and R is 22 Each of which is independently C 1- C 12 An alkyl group;
t is O or NR 24 Wherein R is 24 Is H or C 1- C 30 A hydrocarbon group; and is also provided with
R 23 Is H or C 1 -C 30 A hydrocarbon group.
The hindered benzoate may be at least one of the following: 3, 5-Di-tert-butyl-4-hydroxybenzoic acid 2, 4-di-tert-butylphenyl ester (TINUVIN TM 120 Cetyl 3, 5-di-tert-butyl-4-hydroxybenzoate (CYASORB) TM UV-2908), octadecyl 3, 5-di-tert-butyl-4-hydroxybenzoate, octyl 3, 5-di-tert-butyl-4-hydroxybenzoate, decyl 3, 5-di-tert-butyl-4-hydroxybenzoate, dodecyl 3, 5-di-tert-butyl-4-hydroxybenzoate, tetradecyl 3, 5-di-tert-butyl-4-hydroxybenzoate, behenyl 3, 5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4, 6-di-tert-butylphenyl 3, 5-di-tert-butyl-4-hydroxybenzoate or phenyl 3- [ 3-tert-butyl-4- (3, 5-di-tert-butyl-4-hydroxybenzoyloxy) ]Butyl propionate.
The polymer compositions described herein may further comprise a thiosynergist. The thio synergist may be at least one of the following: bis-lauryl 3,3 '-thiodipropionate, bis-myristyl 3,3' -thiodipropionate, bis-tridecyl 3,3 '-thiodipropionate, bis-stearyl 3,3' -thiodipropionate, pentaerythritol tetrakis- (3-dodecylthiopropionate), tetraalkylthioethyl thiodisuccinate, 2, 12-dihydroxy-4, 10-dithia-7-oxatridecylmethylenebis [3- (dodecylthio) propionate ], 2-mercaptobenzimidazole, zinc salts, zinc dibutyldithiocarbamate or dioctadecyl disulfide.
The polymer composition according to the present invention may further comprise an inorganic compound. In any or all embodiments, the inorganic compound may be at least one of titanium dioxide, barium sulfate, zinc oxide, or cerium (IV) oxide. The polymer composition may also be free of barium compounds. The barium compound includes, for example, a barium salt such as barium sulfate. By "free" is meant that the polymer compositions described herein have less than 1% by weight, less than 0.1% by weight, less than 0.01% by weight, or less than 0.001% by weight of barium compounds based on the total weight of the polymer composition.
In a second aspect, the present invention provides stable polymeric articles comprising the polymeric compositions described herein, which articles are resistant to discoloration, cracking and/or crazing upon exposure to UV-C (190-280 nm) light. At least one of reduced discoloration, cracking or crazing upon exposure to UV-C light is associated with the use of a light stabilizer in combination with an antioxidant, even in the absence of a barium compound (such as a barium salt) in the stabilizer composition, as compared to an antioxidant in the absence of the light stabilizer.
As can be seen from the examples of the present invention, at least one of reduced discoloration or reduced cracking and/or crazing after exposure to UV-C light is associated with the use of a light stabilizer in combination with an antioxidant, even in the absence of a barium compound (such as a barium salt) in the stabilizer composition, as compared to an antioxidant in the absence of the light stabilizer. Thus, the stabilizer compositions described herein advantageously serve to reduce discoloration and/or reduce cracking or crazing of the organic polymeric material upon exposure to UV-C (190-280 nm) light, as compared to polymeric compositions comprising an antioxidant alone. Thus, a method of stabilizing an organic polymeric material against the effects of UV-C (190-280 nm) light comprises adding to the organic polymeric material a stabilizer composition having: an antioxidant selected from the group consisting of hindered phenols, phosphites and phosphonites and mixtures thereof; and a light stabilizer selected from the group consisting of Hindered Amine Light Stabilizers (HALS), UV absorbers (UVA), hindered benzoates, and mixtures thereof, even in the absence of a barium compound (e.g., barium Salts), and provided that the HALS is not bis (2, 6, -tetramethyl-4-piperidinyl) sebacate alone (TINUVIN TM 770). At least one of reduced discoloration, cracking or crazing after exposure to UV-C light is associated with the use of the light stabilizer in combination with the antioxidant, as compared to the antioxidant in the absence of the light stabilizer.
As discussed above, to determine the reduced discoloration, the color change associated with the combination of light stabilizer and antioxidant is compared to the same amount of the same antioxidant in the absence of light stabilizer. In particular, as shown in the examples of the present invention, 1200. Mu.W/cm at 254nm exposure 2 After 24 hours of UV-C light of average irradiance, reduced discoloration is measured by comparing Δe and/or Δyellow index (YI). ΔE is measured according to ASTM D2244-16 and ΔYI is measured according to ASTM E313-20.
Also, to determine the reduced cracking or crazing, the amount of cracking or crazing associated with the combination of light stabilizer and antioxidant is compared to the same amount of the same antioxidant in the absence of light stabilizer. In particular, as shown in examples 5-10 of the present invention and FIGS. 1A-C, 1200 μW/cm at 254nm exposure 2 After 24 hours of UV-C light of average irradiance, the cracks or crazes were determined by visual inspection or by inspection at 20 x magnification using a digital stereo microscope.
All embodiments of the polymer compositions described herein are equally applicable to methods of stabilizing organic polymer materials. Thus, in the method of stabilizing a polymeric organic material, the total amount of antioxidants is from 0.001% to 5.0% by weight and the total amount of light stabilizers is from 0.01% to 2.0% by weight, both based on the total weight of the polymer composition.
Antioxidants, light stabilizers and optionally other additives may be added to the polymeric organic material by any suitable method known to those skilled in the art, for example by direct mixing, dry mixing, melting or by extrusion, pelletization, milling and shaping. Pure additives may be added, i.e. in the absence of solvents or polymeric carriers. The additives may also be added as a solution or dispersion in a solvent, optionally followed by evaporation of the solvent. The additives may also be added as a masterbatch, i.e. as a concentrate in the polymeric organic material. Additives in particulate form may also be encapsulated with waxes, oils or polymers for addition to the polymeric organic material.
The polymer compositions described herein may be included in a kit. The kit may have a single or multiple components, each component selected from the group consisting of the organic polymeric materials described herein, antioxidants, light stabilizers, and other additives, and combinations thereof. Thus, one or more components of the polymer composition may be in a first container, and one or more other components of the polymer composition may optionally be in a second or more containers. The containers may be packaged together and the kit may include instructions for administration or mixing on a label or on an insert included in the kit, optionally with a website or bar code to obtain further information. In addition to the components of the polymer composition, the kit may also include additional features or devices for administering or mixing the components (including solvents).
Antioxidants, light stabilizers and optionally other additives may be added before or during the formation of the organic polymeric material from the monomers by polymerization or before crosslinking of the polymeric organic material. The additives may be pre-mixed or pre-blended prior to addition to the polymeric organic material. Additives in the form of a melt, or a solution or dispersion in a solvent, may also be sprayed onto the polymeric organic material.
The polymer composition as defined herein may be used in an industrial manufacturing process to produce a stable polymer article. Thus, a method of making a stabilized polymeric article includes adding to an organic polymeric material a stabilizer composition having: an antioxidant selected from the group consisting of hindered phenols, phosphites and phosphonites and mixtures thereof; and a light stabilizer selected from the group consisting of Hindered Amine Light Stabilizers (HALS), UV absorbers (UVA), hindered benzoates, and mixtures thereof; and shaping the organic polymeric material containing the stabilizer composition into the stabilized polymeric article. Shaping may be performed, for example, by molding, extrusion, blowing, casting, thermoforming, compaction, or variations or combinations thereof. The molding may be, for example, injection molding, rotational molding, blow molding, roll-to-roll molding, metal injection molding, compression molding, transfer molding, dip molding, gas assist molding, insert injection molding, micro-molding, reaction injection molding, dual shot injection molding, or variations or combinations thereof.
The polymer compositions described herein are advantageously used to make stable polymer articles that are more resistant to discoloration, cracking or crazing upon exposure to UV-C (190-280 nm) light (e.g., from a disinfecting (germicidal) light source) than polymer compositions comprising other hindered phenols and organophosphites. Thus, a stable polymer article resistant to discoloration, cracking or crazing upon exposure to UV-C (190-280 nm) light comprises a polymer composition having an antioxidant selected from the group consisting of hindered phenols, phosphites and phosphonites and mixtures thereof; and a light stabilizer selected from the group consisting of Hindered Amine Light Stabilizers (HALS), UV absorbers (UVA), hindered benzoates, and mixtures thereof, even in the absence of a barium compound (such as a barium salt) in the stabilizer composition, and provided that the HALS is not bis (2, 6, -tetramethyl-4-piperidinyl) sebacate alone (TINUVIN TM 770). At least one of reduced discoloration, cracking or crazing upon exposure to UV-C light is associated with the use of a light stabilizer in combination with an antioxidant, even in the absence of a barium compound (such as a barium salt) in the stabilizer composition, as compared to an antioxidant in the absence of the light stabilizer. All embodiments of the polymer compositions described herein are equally applicable to stable polymer articles containing such compositions. Thus, in a stabilized polymer article that is resistant to discoloration, cracking or crazing, the total amount of antioxidants can be from 0.001% to 5.0% by weight and the total amount of light stabilizers can be from 0.01% to 2.0% by weight, both based on the total weight of the polymer composition.
As described herein, the present disclosure includes at least the following embodiments:
a polymer composition for use in the manufacture of a stabilized polymer article that is resistant to at least one of discoloration, cracking, and/or crazing upon exposure to UV-C (190-280 nm) light, the polymer composition comprising:
i) An organic polymeric material; and
ii) a stabilizer composition comprising:
an antioxidant selected from the group consisting of hindered phenols, phosphites and phosphonites and mixtures thereof; and
A light stabilizer selected from the group consisting of Hindered Amine Light Stabilizers (HALS), UV absorbers (UVA), hindered benzoates and mixtures thereof,
even in the absence of a barium compound (e.g., a barium salt) in the stabilizer composition, and provided that the HALS is not bis (2, 6, -tetramethyl-4-piperidinyl) sebacate alone (TINUVIN TM 770)。
In the same (i.e., the foregoing) or other embodiments of the polymer composition, even in the absence of a barium compound (e.g., a barium salt) in the stabilizer composition, at least one of reduced discoloration, cracking, and/or crazing upon exposure to UV-C light has a detrimental effect associated with the use of the light stabilizer in combination with the antioxidant, as compared to the antioxidant in the absence of the light stabilizer.
In any of the foregoing or other embodiments of the polymer composition, the organic polymeric material comprises at least one of: polyolefins, thermoplastic olefins (TPO), poly (ethylene-vinyl acetate) (EVA), polyesters, polyethers, polyketones, polyamides, natural and synthetic rubbers, polyurethanes, polystyrenes, polyacrylates, polymethacrylates, polybutyl acrylates, polyacetals, polyacrylonitriles, polybutadiene, acrylonitrile-butadiene-styrene (ABS), styrene-acrylonitrile (SAN), acrylonitrile-styrene-acrylate (ASA), cellulose acetate butyrate, cellulosic polymers, polyimides, polyamideimides, polyetherimides, polyphenylene sulfides, polyphenylene oxides, polysulfones, polyethersulfones, polyvinylchlorides, amino resin crosslinked polyacrylates and polyesters, polyisocyanate crosslinked polyesters and polyacrylates, phenol/formaldehyde, urea/formaldehyde and melamine/formaldehyde resins alkyd resins, polyester resins, acrylate resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, urethanes or epoxy resins, crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic and aromatic glycidyl ethers crosslinked with anhydrides or amines, polysiloxanes, michael addition polymers, addition polymers of amines or blocked amines with activated unsaturated and activated methylene compounds, addition polymers of ketimines with activated unsaturated and activated methylene compounds, combinations of polyketimines with unsaturated acrylic polyacetoacetate resins, coating compositions, radiation curable compositions, epoxy melamine resins, organic dyes, cosmetics, cellulose-based papers, photographic film papers, fibers, and the like, wax or ink.
In any of the foregoing or other embodiments of the polymer composition, the organic polymeric material comprises at least one of: (i) Polyethylene, polypropylene, polyisobutylene, polybut-1-ene or poly-4-methylpent-1-ene; (ii) polyisoprene or polybutadiene; (iii) cyclopentene or norbornene; (iv) Optionally crosslinked polyethylene, high Density Polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultra high molecular weight polyethylene (HDPE-UHMW), medium Density Polyethylene (MDPE), low Density Polyethylene (LDPE), linear Low Density Polyethylene (LLDPE), very Low Density Polyethylene (VLDPE), or Ultra Low Density Polyethylene (ULDPE); (v) thermoplastic olefins (TPOs); or (vi) copolymers of at least one of a mono-, di-or cyclic olefin.
In any of the foregoing or other embodiments of the polymer composition, the antioxidant is present at from 0.001% to 5.0%, preferably from 0.005% to 3.0%, and more preferably from 0.01% to 1.0% by weight based on the total weight of the polymer composition.
In any of the foregoing or other embodiments of the polymer composition, the light stabilizer is present at from 0.005% to 5.0% by weight, preferably from 0.01% to 2.0% by weight, based on the total weight of the polymer composition.
In any of the foregoing or other embodiments of the polymer composition, the antioxidant comprises a hindered phenol having at least one group according to formula (IVa), (IVb), or (IVc):
wherein:
indicating the attachment point of the molecular fragment to the parent compound (via a carbon-carbon single bond);
r in formula (IVa), (IVb) or (IVc) 18 Is hydrogen or C 1-12 A hydrocarbon group;
r in formula (IVa), (IVb) or (IVc) 19 And R is 20 Each of which is independently hydrogen or C 1 -C 20 A hydrocarbon group; and is also provided with
R in formula (IVa), (IVb) or (IVc) 37 Is C 1 -C 12 A hydrocarbon group.
In the same or other embodiments, R in formula (IVa), (IVb) or (IVc) 18 And R is 37 Each independently is methyl or tert-butyl.
In any of the same or other embodiments of the polymer composition, the hindered phenol comprises at least one of:
1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione (CYANOX) TM 1790)，
1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione (IRGANOX) TM 3114)，
1, 3-tris (2 ' -methyl-4 ' -hydroxy-5 ' -tert-butylphenyl) butane,
triethylene glycol bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ],
4,4' -thiobis (2-tert-butyl-5-methylphenol),
2,2' -thiodiethylenebis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ],
Octadecyl 3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate,
pentaerythritol (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate,
n, N' -hexamethylenebis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propanamide ],
bis (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) thiodipropionate,
pentaerythritol tetrakis (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) (IRGANOX TM 1010)，
Octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (IRGANOX) TM 1076 Or (x)
N, N' -bis (3, 5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine (IRGANOX) TM 1024)。
In any of the same or other embodiments of the polymer composition, the hindered phenol comprises at least one of: pentaerythritol tetrakis (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) (IRGANOX TM 1010 Octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (IRGANOX) TM 1076 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione (IRGANOX) TM 3114 Or N, N' -bis (3, 5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine (IRGANOX) TM 1024)。
In any of the same or other embodiments of the polymer composition, the antioxidant comprises a phosphite or phosphonite, and the phosphite or phosphonite comprises at least one of:
i) A compound according to any one of formulae (1) to (7):
wherein:
the index is an integer and n is 2, 3 or 4; p is 1 or 2; q is 2 or 3; y is 1, 2 or 3; and z is 1 to 6;
if n or q is 2, A 1 Is C 2 -C 18 An alkylene group; by oxygen, sulfur or-NR 4 Interrupted C 2 -C 12 An alkylene group having the formula:
or phenylene;
if n or q is 3, A 1 Is of the formula-C r H 2r-1 -a divalent group, wherein r is an integer from 4 to 12;
if n is 4, A 1 Is that
B is a direct bond, -CH 2 -、-CHR 4 -、-CR 1 R 4 -, sulfur, C (C) 5 -C 7 Cycloalkylene, or from 1 to 4C at the 3, 4 and/or 5 positions 1 -C 4 Alkyl-substituted cyclohexylene;
if p is 1, D 1 Is C 1 -C 4 Alkyl, and if p is 2, is-CH 2 OCH 2 -；
D 2 Is C 1 -C 4 An alkyl group;
if y is 1, E is C 1 -C 18 Alkyl, -OR 1 Or halogen;
if y is 2, E is-O-A 2 -O-, wherein A 2 Is as for A 1 Defined when n is 2;
if y is 3, E is a compound of formula R 4 C(CH 2 O) 3 Or N (CH) 2 CH 2 O-) 3 Is a group of (2);
q is a group of at least z-valent mono-or polyhydric alcohol or phenol, which is attached to the phosphorus atom via an oxygen atom of the OH group of the mono-or polyhydric alcohol or phenol;
R 1 、R 2 and R is 3 Each independently is C 1 -C 18 Alkyl, which is unsubstituted or substituted by halogen, -COOR 4 -CN or-CONR 4 R 4 Substitution; by oxygen, sulfur or-NR 4 Interrupted C 2 -C 18 An alkyl group; c (C) 7 -C 9 A phenylalkyl group; c (C) 5 -C 12 Cycloalkyl, phenyl, or naphthyl; by halogen, 1 to 3 alkyl or alkoxy groups having a total of 1 to 18 carbon atoms, or by C 7 -C 9 Phenylalkyl-substituted naphthyl or phenyl; or a group of the formula
Wherein m is an integer in the range of 3 to 6;
R 4 is hydrogen, C 1 -C 8 Alkyl, C 5 -C 12 Cycloalkyl or C 7 -C 9 A phenylalkyl group;
R 5 and R is 6 Each independently is hydrogen, C 1 -C 8 Alkyl or C 5 -C 6 A cycloalkyl group,
if q is 2, R 7 And R is 8 Each independently is C 1 -C 4 Alkyl or together are 2, 3-dehydropentamethylene; and if q is 3, R 7 And R is 8 Each is methyl;
r in each case 14 Independently selected from hydrogen, C 1 -C 9 Alkyl or cyclohexyl;
r in each case 15 Independently hydrogen or methyl;
x and Y are each a direct bond or oxygen;
z is a direct bond, methylene, -C (R) 16 ) 2 -or sulfur, and
R 16 is C 1 -C 8 An alkyl group; or alternatively
ii) a triarylphosphite according to formula 8:
wherein:
R 17 is a substituent present in from 0 to 5 instances of an aromatic ring of formula 8 and is independently at each occurrence C 1 -C 20 Alkyl, C 3 -C 20 Cycloalkyl, C 4 -C 20 Alkylcycloalkyl, C 6 -C 10 Aryl or C 7 -C 20 Alkylaryl groups.
In the same or other embodiments of the polymer composition, the phosphite or phosphonite comprises at least one of:
The preparation method comprises the steps of (1) preparing triphenyl phosphite,
diphenyl alkyl phosphite is used as the main component of the composition,
a phenyl dialkyl phosphite is used as a starting material,
the trilauryl phosphite is used as the main ingredient,
a trioctadecyl phosphite ester, wherein the main chain of the phosphite ester is a tri-octadecyl phosphite,
distearyl pentaerythritol phosphite which is used as a main ingredient,
tris (2, 4-di-tert-butylphenyl) phosphite (IRGAFOS) TM 168)，
Tris (4-nonylphenyl) phosphite,
a compound of formula (a), (B), (C), (D), (E), (F), (G), (H), (J), (K) or (L):
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2-butyl-2-ethyl-1, 3-propanediol 2,4, 6-tri-tert-butylphenol phosphite,
bis- (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite,
2-butyl-2-ethyl-1, 3-propanediol 2, 4-di-cumylphenol phosphite,
2-butyl-2-ethyl-1, 3-propanediol 4-methyl-2, 6-di-tert-butylphenol phosphite, or
Bis (2, 4, 6-tri-tert-butyl-phenyl) pentaerythritol diphosphate.
In the same or other embodiments of the polymer composition, the phosphite or phosphonite comprises at least one of: tris (2, 4-di-tert-butylphenyl) phosphite (IRGAFOS) TM 168 Triphenyl phosphite, tris (4-nonylphenyl) phosphite, bis (2, 4-dicumylphenyl) pentaerythritol Diphosphite (DOVERPHOS) TM S9228) or tetrakis (2, 4-di-tert-butylphenyl) -4,4' -biphenylene-diphosphonite (IRGAFOS) TM P-EPQ)。
In any of the same or other embodiments of the polymer composition, the light stabilizer comprises a Hindered Amine Light Stabilizer (HALS) comprising at least one functional group according to formula (II):
wherein:
R 31 is hydrogen, OH, C 1 -C 20 Hydrocarbyl radicals, -CH 2 CN、C 1 -C 12 Acyl or C 1 -C 18 An alkoxy group;
R 38 is hydrogen or C 1 -C 8 A hydrocarbon group; and is also provided with
R 29 、R 30 、R 32 And R is 33 Each independently is C 1 -C 20 Hydrocarbyl, or R 29 And R is 30 And/or R 32 And R is 33 Together with the carbon to which they are attached form C 5 -C 10 Cycloalkyl; or alternatively
At least one functional group according to formula (IIa):
wherein:
m is an integer from 1 to 2;
R 39 is hydrogen, OH, C 1 -C 20 Hydrocarbyl radicals, -CH 2 CN、C 1 -C 12 Acyl or C 1 -C 18 An alkoxy group; and is also provided with
G 1 -G 4 Each independently is C 1 -C 20 A hydrocarbon group.
In the same or other embodiments of the polymer composition, the Hindered Amine Light Stabilizer (HALS) is at least one of the following:
bis (2, 6-tetramethylpiperidin-4-yl) succinate;
bis (1, 2, 6-pentamethylpiperidin-4-yl) sebacate;
bis (1-octyloxy-2, 6-tetramethylpiperidinyl) succinate;
bis (1-octyloxy-2, 6-tetramethylpiperidin-4-yl) sebacate (TINUVIN) TM 123)；
Bis (1, 2, 6-pentamethylpiperidin-4-yl) n-butyl 3, 5-di-tert-butyl-4-hydroxybenzylmalonate;
condensate of 1- (2-hydroxyethyl) -2, 6-tetramethyl-4-hydroxypiperidine and succinic acid (TINUVIN TM 622)；
2, 6-tetramethylpiperidin-4-yl stearate;
2, 6-tetramethylpiperidin-4-yl dodecanoate;
1,2, 6-pentamethylpiperidin-4-yl stearate;
dodecanoic acid 1,2, 6-pentamethylpiperidin-4-yl ester;
condensate of N, N' -bis (2, 6-tetramethylpiperidin-4-yl) hexamethylenediamine and 4-tert-octylamino-2, 6-dichloro-1, 3, 5-triazine (CHIMASSORB) TM 944)；
Tri (2, 6-tetramethylpiperidin-4-yl) nitrilotriacetic acid ester;
4-stearyloxy-2, 6-tetramethylpiperidine;
n, N' -bis (2, 6-tetramethylpiperidine-4)-yl) condensate of hexamethylenediamine and 4-morpholino-2, 6-dichloro-1, 3, 5-triazine (CYASORB) TM UV-3346)；
Methylated condensates of N, N' -bis (2, 6-tetramethylpiperidin-4-yl) hexamethylenediamine and 4-morpholino-2, 6-dichloro-1, 3, 5-triazine (CYASORB) TM UV-3529)；
Condensate of 2-chloro-4, 6-bis (4-n-butylamino-2, 6-tetramethylpiperidinyl) -1,3, 5-triazine and 1, 2-bis (3-aminopropylamino) ethane (CHIMASSORB) TM 119)；
A condensate of 2-chloro-4, 6-bis (4-n-butylamino-1, 2, 6-pentamethylpiperidinyl) -1,3, 5-triazine and 1, 2-bis- (3-aminopropylamino) ethane;
condensate of N, N' -bis (2, 6-tetramethylpiperidin-4-yl) hexamethylenediamine, N-butyl-2, 6-tetramethyl-4-piperidylamine, di-N-butylamine and 2,4, 6-trichloro-1, 3, 5-triazine (CHIMASSORB) TM 2020)；
Mixtures of 4-hexadecyloxy-and 4-stearyloxy-2, 6-tetramethylpiperidine (CYASORB) TM UV-3853)；
A mixture of 4-hexadecyloxy-and 4-stearyloxy-1, 2, 6-pentamethylpiperidine;
condensate of N, N' -bis (2, 6-tetramethylpiperidin-4-yl) hexamethylenediamine and 4-cyclohexylamino-2, 6-dichloro-1, 3, 5-triazine;
condensates of 1, 2-bis (3-aminopropylamino) ethane, 2,4, 6-trichloro-1, 3, 5-triazine and 4-butylamino-2, 6-tetramethylpiperidine;
condensate of N, N' -bis (2, 6-tetramethylpiperidin-4-yl) hexamethylenediamine and 4-cyclohexylamino-2, 6-dichloro-1, 3, 5-triazine;
tetrakis (2, 6-tetramethylpiperidin-4-yl) -1,2,3, 4-butane tetracarboxylic acid ester;
tetrakis (1, 2, 6-pentamethylpiperidin-4-yl) -1,2,3, 4-butanetetracarboxylate;
1,2,3, 4-butanetetracarboxylic acid, 2, 6-tetramethylpiperidinyl-4-yltridecyl ester;
1,2,3, 4-butanetetracarboxylic acid, 1,2, 6-pentamethylpiperidin-4-yltridecyl ester;
the reaction product of formamide, N,n' -1, 6-adipoylbis [ N- (2, 6-tetramethylpiperidin-4-yl) (UVINUL) TM 4050)；
Condensate of N, N' -bis (2, 6-tetramethylpiperidin-4-yl) hexamethylenediamine and 4-tert-octylamino-2, 6-dichloro-1, 3, 5-triazine (CHIMASSORB) TM 944)；
Condensate of N, N' -bis (2, 6-tetramethyl-1- (propoxy) -piperidin-4-yl) hexamethylenediamine, N-butyl-1-propoxy-2, 6-tetramethyl-4-piperidinamine, di-N-butylamine and 2,4, 6-trichloro-1, 3, 5-triazine (TINUVIN TM NOR HALS 371；
Oxidative hydrogenation reaction products of polymers of N, N' -bis (2, 6-tetramethyl-4-piperidin-4-yl) hexamethylenediamine with 2,4, 6-trichloro-1, 3, 5-triazine with 3-bromo-1-propene, di-N-butylamine and N-butyl-2, 6-tetramethyl-4-piperidinamine (TINUVIN TM XT 200)；
TINUVIN TM XT-850/XT-855); or alternatively
N 1 ,N 1 Reaction product of' -1, 2-ethanediylbis (1, 3-propanediamine) with cyclohexane and N-butyl-2, 6-tetramethyl-4-piperidylamine-2, 4, 6-trichloro-1, 3, 5-triazine peroxide (FLAMETAB TM NOR 116)。
In any of the same or other embodiments of the polymer composition, the light stabilizer comprises a UV absorber that is at least one 2- (2 '-hydroxyphenyl-s-triazine, 2-hydroxybenzophenone, 2- (2' -hydroxyphenyl) benzotriazole or benzoxazinone.
In the same or other embodiments of the polymer composition, the light stabilizer comprises at least one 2- (2' -hydroxyphenyl) -s-triazine according to formula (I):
wherein R is 34 And R is 35 Each of which is independently C 6 -C 10 Aryl, mono-or di-C 1 -C 12 Hydrocarbyl-substituted amino, C 2 -C 12 Alkanoyl, C 1 -C 12 Alkyl, C 1 -C 10 Acyl or C 1 -C 10 An alkoxy group, an amino group,
wherein C is 6 -C 10 Aryl optionally substituted in from 1 to 3 positions with OH, halogen, C 1 -C 12 Alkyl, C 1 -C 12 Alkoxy, C 1-12 Alkoxy esters, C 2-12 At least one substitution of alkanoyl or phenyl, wherein phenyl is optionally substituted at from 1 to 3 substitutable positions with OH, halogen, C 1-12 Alkyl, C 1-12 Alkoxy, C 1-12 Alkoxy esters or C 2-12 At least one substitution in an alkanoyl group; and is also provided with
Each R 36 Independently OH, halogen, C 1 -C 12 Alkyl, C 1 -C 12 Alkoxy, C 1 -C 12 Alkoxy esters, C 2 -C 12 Alkanoyl, phenyl or C 1 -C 12 An acyl group.
In the same or other embodiments of the polymer composition, the 2- (2' -hydroxyphenyl) -s-triazine comprises at least one of:
4, 6-diphenyl-2- (4-hexyloxy-2-hydroxyphenyl) -s-triazine (TINUVIN TM 1577)，
4, 6-bis- (2, 4-dimethylphenyl) -2- (2-hydroxy-4-octyloxyphenyl) -s-triazine (CYASORB) TM 1164)，
2, 4-bis [ 2-hydroxy-4- (2-hydroxyethoxy) phenyl ] -6- (2, 4-dimethylphenyl) -s-triazine,
mixture of 4, 6-bis (2, 4-dimethylphenyl) -2- (2-hydroxy-4- (3-dodecyloxy-2-hydroxypropoxy) phenyl) -s-triazine and 4, 6-bis- (2, 4-dimethylphenyl) -2- (2-hydroxy-4- (3-tridecyloxy-2-hydroxypropoxy) phenyl) -s-Triazine (TINUVIN) TM 400)，
4, 6-bis- (2, 4-dimethylphenyl) -2- (2-hydroxy-4 (3- (2-ethylhexyloxy) -2-hydroxypropoxy) -phenyl) -s-Triazine (TINUVIN) TM 405)，
4, 6-bis- (2, 4-dimethylphenyl) -2- (2-hydroxy-4 (3- (2-ethylhexyloxy) -2-hydroxypropoxy) -phenyl) -s-triazine,
2, 4-bis (2, 4-dimethylphenyl) -6- [ 2-hydroxy-4- [ (octyloxycarbonyl) ethyleneoxy ]Phenyl group]s-Triazine (TINUVIN) TM 479)，
2, 4-bis (4-biphenyl) -6- [ 2-hydroxy-4- [ (octoxycarbonyl) ethyleneoxy ] phenyl ] -s-triazine,
2, 4-bis (4-biphenyl) -6- [ 2-hydroxy-4- (2-ethylhexyloxy) phenyl]s-Triazine (TINUVIN) TM 1600)，
2, 4-bis (2-hydroxy-4-butoxyphenyl) -6- (2, 4-bis-butoxyphenyl) -s-TRIAZINE (triazene) TM 460)，
2,4, 6-tris [ 2-hydroxy-4- (3-sec-butoxy-2-hydroxypropoxy) -phenyl ] -s-triazine, or
2,4, 6-tris [ 2-hydroxy-4- [ (octyloxycarbonyl) ethyleneoxy)]Phenyl group]s-Triazine (TINUVIN) TM 477)。
In any of the same or other embodiments of the polymer composition, the light stabilizer comprises a 2-hydroxybenzophenone comprising at least one of: 2-hydroxy-4-methoxybenzophenone (CYASORB) TM UV-9), 2' -dihydroxy-4-methoxybenzophenone (CYASORB) TM UV-24), 2-hydroxy-4-octoxybenzophenone (CYASORB) TM UV-531), 2' -dihydroxy-4, 4' -di-methoxybenzophenone, 2' -dihydroxybenzophenone, 2',4,4' -tetrahydroxybenzophenone, 2' -dihydroxy-4, 4' -dimethoxybenzophenone, 2' -dihydroxy-4, 4' -diethoxybenzophenone, 2' -dihydroxy-4, 4' -dipropoxybenzophenone, 2' -dihydroxy-4, 4' -dibutoxybenzophenone, 2' -dihydroxy-4-methoxy-4 ' -ethoxybenzophenone, 2' -dihydroxy-4-methoxy-4 ' -propoxybenzophenone 2,2' -dihydroxy-4-methoxy-4 ' -butoxybenzophenone, 2' -dihydroxy-4-ethoxy-4 ' -propoxybenzophenone, 2' -dihydroxy-4-ethoxy-4 ' -butoxybenzophenone, 2,3' -dihydroxy-4, 4' -dimethoxybenzophenone, 2,3' -dihydroxy-4-methoxy-4 ' -butoxybenzophenone, 2-hydroxy-4, 4',5' -trimethoxybenzophenone, 2-hydroxy-4, 4',6' -tributoxybenzophenone, 2-hydroxy-4-butoxy-4 ',5' -dimethoxybenzophenone, 2-hydroxy-4-ethoxy-2 ',4' -dibutylbenzophenone, 2-hydroxy-4-propoxy-4 ',6' -dichlorobenzophenone, 2-hydroxy-4-propoxy-4 ',6' -dibromobenzophenone, 2, 4-dihydroxybenzophenone 2-hydroxy-4-ethoxybenzophenone, 2-hydroxy-4-propoxybenzophenone, 2-hydroxy-4-butoxybenzophenone, 2-hydroxy-4-methoxy-4 '-methylbenzophenone, 2-hydroxy-4-methoxy-4' -ethylbenzophenone, 2-hydroxy-4-methoxy-4 '-propylbenzophenone, 2-hydroxy-4-methoxy-4' -butylbenzophenone, 2-hydroxy-4-methoxy-4 '-tert-butylbenzophenone, 2-hydroxy-4-methoxy-4' -chlorobenzophenone, 2-hydroxy-4-methoxy-2 '-chlorobenzophenone, 2-hydroxy-4-methoxy-4' -bromobenzophenone, 2-hydroxy-4, 4 '-dimethoxybenzophenone, 2-hydroxy-4, 4' -dimethoxy-3-methylbenzophenone, 2-hydroxy-4, 4 '-dimethoxy-2' -ethylbenzophenone, 2-hydroxy-4, 4',5' -trimethoxybenzophenone, 2-hydroxy-4-ethoxy-4 '-methylbenzophenone, 2-hydroxy-4' -ethoxy-4 '-ethylbenzophenone, 2-hydroxy-4-ethoxy-4' -propylbenzophenone, 2-hydroxy-4-ethoxy-4 ' -butylbenzophenone, 2-hydroxy-4-ethoxy-4 ' -methoxybenzophenone, 2-hydroxy-4, 4' -diethoxybenzophenone, 2-hydroxy-4-ethoxy-4 ' -propoxybenzophenone, 2-hydroxy-4-ethoxy-4 ' -butoxybenzophenone, 2-hydroxy-4-ethoxy-4 ' -chlorobenzophenone or 2-hydroxy-4-ethoxy-4 ' -bromobenzophenone.
In any of the same or other embodiments of the polymer composition, the light stabilizer comprises 2- (2' -hydroxyphenyl) benzotriazole comprising at least one of the following: 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole (TINUVIN TM P), 2- (2 '-hydroxy-5' -tert-butylphenyl) benzotriazole, 2- (2 '-hydroxy-3' -methyl-5 '-tert-butylphenyl) benzotriazole, 2- (2' -hydroxy-5 '-cyclohexylphenyl) benzotriazole, 2- (2' -hydroxy-3 ',5' -dimethylphenyl) benzotriazole, 2- (2 '-hydroxy-5' -tert-butylphenyl) -5-chloro-benzotriazole, 2- (2 '-hydroxy-5' -tert-octylphenyl) benzotriazole (cyclic orb) TM UV-5411), 2- (3 ',5' -di-tert-butyl-2 '-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3', 5 '-di-tert-amyl-2' -hydroxyphenyl) benzotriazole (CYASORB) TM UV-2337), 2- (3 ',5' -bis (α, α -dimethylbenzyl) -2' -hydroxyphenyl) benzotriazole (TINUVIN TM 900 2- (3 '-tert-butyl-2' -hydroxy-5 '- (2-octyloxycarbonylethyl) phenyl) benzotriazole, 2' -methylenebis [4- (1, 3-tetramethylbutyl) -6-benzotriazole-2-ylphenol]2- [3' -tert-butyl-5 ' - (2-methoxycarbonylethyl) -2' -hydroxyphenyl]Transesterification product of 2H-benzotriazole with polyethylene glycol 300 (TINUVIN TM 1130 2- [2' -hydroxy-3 ' - (α, α -dimethylbenzyl) -5' - (1, 3-tetramethylbutyl) phenyl ]Benzotriazole, 5-trifluoromethyl-2- (2-hydroxy-3-alpha-cumyl-5-tert-octylphenyl) benzotriazole, 2- (2 ' -hydroxy-5 ' - (2-hydroxyethyl) phenyl) benzotriazole, 2- (2 ' -hydroxy-5 ' - (2-methacryloyloxyethyl) phenyl) benzotriazole, 2- (2 ' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-chlorobenzotriazole (TINUVIN) TM 326 2- (3 '-sec-butyl-5' -tert-butyl-2 '-hydroxyphenyl) benzotriazole, 2- (3', 5 '-di-tert-butyl-2' -hydroxyphenyl) benzotriazole, 2- (3 '-dodecyl-5' -methyl-2 '-hydroxyphenyl) -benzotriazole, 2- (3' -tert-butyl-5 '- (2-octoxycarbonylethyl) -2' -hydroxyphenyl) -5-chlorobenzotriazole, 2- (5 '-methyl-2' -hydroxyphenyl) benzotriazole or 2- (5 '-tert-butyl-2' -hydroxyphenyl) benzotriazole.
In any of the same or other embodiments of the polymer composition, the light stabilizer comprises a benzoxazinone comprising at least one of the following: 2-methyl-3, 1-benzoxazin-4-one, 2-butyl-3, 1-benzoxazin-4-one, 2-phenyl-3, 1-benzoxazin-4-one, 2- (1-or 2-naphthyl) -3, 1-benzoxazin-4-one, 2- (4-biphenyl) -3, 1-benzoxazin-4-one, 2-p-nitrophenyl-3, 1-benzoxazin-4-one, 2-m-nitrophenyl-3, 1-benzoxazin-4-one, 2-p-benzoylphenyl-3, 1-benzoxazin-4-one, 2-p-methoxyphenyl-3, 1-benzoxazin-4-one, 2-O-methoxyphenyl-3, 1-benzoxazin-4-one, 2-cyclohexyl-3, 1-benzoxazin-4-one, 2-p (or m) phthalimidophenyl-3, 1-benzoxazin-4-one, N- (2, 1-benzoylphenyl-4-oxazin-4-one, N-2-benzoylanilide, N- (2-methyl) -2-4-benzoylanilide, 2- [ p- (N-phenylcarbamoyl) phenyl ]-3, 1-benzoxazin-4-one, 2- [ p- (N-phenyl N-methylcarbamoyl) phenyl ]]-3, 1-benzoxazin-4-one, 2 '-bis (3, 1-benzoxazin-4-one), 2' -ethylenebis (3, 1-benzoxazin-4-one), 2 '-tetramethylenebis (3, 1-benzoxazin-4-one), 2' -hexamethylenebis (3, 1-benzoxazin-4-one), 22 '-decamethylenebis (3, 1-benzoxazin-4-one), 2' -p-phenylenebis (3, 1-benzoxazin-4-one) (CYASORB TM UV-3638), 2 '-m-phenylenebis (3, 1-benzoxazin-4-one), 2' - (4, 4 '-diphenylene) bis (3, 1-benzoxazin-4-one), 2' - (2, 6-or 1, 5-naphtalene) bis (3, 1-benzoxazin-4-one) 2,2'- (2-methyl-p-phenylene) bis (3, 1-benzoxazin-4-one), 2' - (2-nitro-p-phenylene) bis (3, 1-benzoxazin-4-one), 2'- (2-chloro-p-phenylene) bis (3, 1-benzoxazin-4-one) 2,2' - (1, 4-cyclohexylidene) bis (3, 1-benzoxazin-4-one), N-p- (3, 1-benzoxazin-4-one-2-yl) phenyl, 4- (3, 1-benzoxazin-4-one-2-yl) phthalimide, N-p- (3, 1-benzoxazin-4-one-2-yl) benzoyl, 4- (3, 1-benzoxazin-4-one-2-yl) aniline, 1,3, 5-tris (3, 1-benzoxazin-4-one-2-yl) benzene, 1,3, 5-tris (3, 1-benzoxazin-4-one-2-yl) naphthalene or 2,4, 6-tris (3, 1-benzoxazin-4-one-2-yl) naphthalene.
In any of the same or other embodiments of the polymer composition, the light stabilizer comprises a hindered benzoate according to formula (VI):
wherein:
R 21 and R is 22 Each of which is independently C 1- C 12 An alkyl group;
t is O or NR 24 Wherein R is 24 Is H or C 1- C 30 A hydrocarbon group; and is also provided with
R 23 Is H or C 1- C 30 A hydrocarbon group.
In the same or other embodiments of the polymer composition, the hindered benzoate comprises at least one of the following: 3, 5-Di-tert-butyl-4-hydroxybenzoic acid 2, 4-di-tert-butylphenyl ester (TINUVIN TM 120 Cetyl 3, 5-di-tert-butyl-4-hydroxybenzoate (CYASORB) TM UV-2908), octadecyl 3, 5-di-tert-butyl-4-hydroxybenzoate, octyl 3, 5-di-tert-butyl-4-hydroxybenzoate, decyl 3, 5-di-tert-butyl-4-hydroxybenzoate, and 3, 5-di- -Dodecyl tert-butyl-4-hydroxybenzoate, tetradecyl 3, 5-di-tert-butyl-4-hydroxybenzoate, behenyl 3, 5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4, 6-di-tert-butylphenyl 3, 5-di-tert-butyl-4- (3, 5-di-tert-butyl-4-hydroxybenzoyloxy) phenyl]Butyl propionate.
In any of the same or other embodiments, the polymer composition further comprises a thiosynergist comprising at least one of: bis-lauryl 3,3 '-thiodipropionate, bis-myristyl 3,3' -thiodipropionate, bis-tridecyl 3,3 '-thiodipropionate, bis-stearyl 3,3' -thiodipropionate, pentaerythritol tetrakis- (3-dodecylthiopropionate), tetraalkylthioethyl thiodisuccinate, 2, 12-dihydroxy-4, 10-dithia-7-oxatridecylmethylenebis [3- (dodecylthio) propionate ], 2-mercaptobenzimidazole, zinc salts, zinc dibutyldithiocarbamate or dioctadecyl disulfide.
In any of the same or other embodiments, the polymer composition further comprises an inorganic compound comprising at least one of titanium dioxide, barium sulfate, zinc oxide, or cerium (IV) oxide.
In any of the same or other embodiments of the polymer composition, the polymer composition is free of a barium compound.
The present invention also provides a stabilized polymer article comprising a polymer composition of any of the preceding embodiments described herein that is resistant to the deleterious effects of at least one of discoloration, cracking, and/or crazing upon repeated or prolonged exposure to UV-C (190-280 nm) light.
In the same or other embodiments of the stabilized polymer article, at least one of reduced discoloration, cracking or crazing upon exposure to UV-C light has a detrimental effect associated with the use of a light stabilizer in combination with an antioxidant, even in the absence of a barium compound (such as a barium salt) in the stabilizer composition, as compared to an antioxidant in the absence of the light stabilizer.
The present invention also provides a method of making a stabilized polymer article as described in any one of the embodiments herein, such method comprising:
Adding to the organic polymeric material a stabilizer composition comprising:
an antioxidant selected from the group consisting of hindered phenols, phosphites and phosphonites and mixtures thereof; and
a light stabilizer selected from the group consisting of Hindered Amine Light Stabilizers (HALS), UV absorbers (UVA), hindered benzoates, and mixtures thereof, even in the absence of a barium compound, such as a barium salt, in the stabilizer composition, and provided that the HALS is not bis (2, 6, -tetramethyl-4-piperidinyl) sebacate alone (TINUVIN TM 770 A) is provided; and
the organic polymeric material containing the stabilizer composition is formed into the stabilized polymeric article.
Similarly, methods of stabilizing an organic polymeric material against the deleterious effects of repeated or prolonged exposure to UV-C (190-280 nm) light are also provided, such methods comprising adding to the organic polymeric material a stabilizer composition comprising:
an antioxidant selected from the group consisting of hindered phenols, phosphites and phosphonites and mixtures thereof; and
a light stabilizer selected from the group consisting of Hindered Amine Light Stabilizers (HALS), UV absorbers (UVA), hindered benzoates, and mixtures thereof, even in the absence of a barium compound, such as a barium salt, in the stabilizer composition, and provided that the HALS is not bis (2, 6, -tetramethyl-4-piperidinyl) sebacate alone (TINUVIN TM 770)；
Wherein at least one of reduced discoloration or reduced cracking or crazing after repeated or prolonged exposure to UV-C light, as compared to an antioxidant in the absence of the light stabilizer, is associated with the use of the light stabilizer in combination with the antioxidant.
In the same or other embodiments for stabilizing an organic polymeric material against the deleterious effects of UV-C light, the total amount of antioxidants comprises from 0.001% to 5.0% by weight and the total amount of light stabilizers comprises from 0.01% to 2.0% by weight, both based on the total weight of the polymeric composition.
Examples
The following examples are provided to assist those of ordinary skill in the art in further understanding certain embodiments defined herein. These examples are intended for illustrative purposes and should not be construed as limiting the scope of the various embodiments as defined by the claims.
The performance of various individual additive materials and specific combinations thereof in protecting polymers from UV-C induced discoloration and photodegradation was evaluated. Polypropylene homopolymer (PRO-FAX) from Liandebarsel company (LyondellBasell) was selected TM 6301 NT) as polymer matrix for the weathering study in the examples. Table 1 lists information about suppliers, commercial names, and chemical names of various additive materials in the formulation examples. In some cases, these same chemicals may be available from other suppliers under different trade names. All additive materials were used as received.
TABLE 1 additive types, trade names, chemical names and suppliers of additives
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The general procedure for preparing the additive-containing plaques is as follows. 1,000 g of the powder mixture of each formulation was prepared by dry blending the additives with the polypropylene resin. The mixture was then compounded at 230℃using a Werner & Pfleiderer twin screw extruder. After extrusion, a standard rectangular plate (2×2.5×0.125 inch) was injection molded into a rectangular plate using an Auburg injection molding machine at 200 ℃.
For the UV-C weathering study, UV-C weathering devices were developed and assembled internally. The device comprisesThere are two low-pressure narrow-band UV-C lamps (254 nm), with an average irradiance at the plate surface of about 1200. Mu.W/cm 2 (at 254 nm), and an automatic fan controller to maintain the test temperature below 40 ℃. During UV-C weathering tests, the plates were placed in the apparatus and frequently repositioned to ensure that all samples received an equal amount of radiation exposure.
The color change (ΔE) and yellowness index change (ΔYI) of the panel surface after UV-C exposure were used to evaluate surface discoloration. Both Color and YI measurements were made using an X-Rite Color i7 spectrophotometer using the Hunter L, a, b Color scale (for Color). ΔE is measured according to ASTM D2244-16 and ΔYI is measured according to ASTM E313-20. Δe is calculated by subtracting the initial color reading (time=0 hours) from the color reading after the UV-C exposure for the specified number of hours. Δyi is calculated by subtracting the initial YI reading (time=0 hours) from the YI reading after a specified number of hours of UV-C exposure. For example, the number of hours may be 24, 42, or 250. 24 hours is a convenient time scale.
The development of cracks and/or crazes on the surface of the polymer article after UV-C exposure was used to evaluate photodegradation. Within each test interval, polypropylene plaques were inspected visually and with a Leica S9i digital stereo microscope (at 20 x magnification) for cracks or crazes. The images are taken using a camera integrated in the microscope.
Example 1-UV-C weathering Properties of Polypropylene containing phosphite and other additives (. DELTA.E and. DELTA.YI)
TABLE 2 UV-C weathering Properties of Polypropylene containing phosphites and other additives
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The data in table 2 shows that polypropylene formulated with the common phosphite antioxidants experienced significant discoloration after UV-C exposure compared to pure, unstable polypropylene. (compare sample 2-2 with sample 2-1.) however, certain light stabilizers in combination with phosphites reduced discoloration after UV-C exposure, as indicated by the lower Δyi and Δe values presented in table 2 (samples 2-2 to 2-8).
EXAMPLE 2 UV-C weathering Properties of polypropylene containing hindered phenols and other additives (ΔE and ΔYI)
TABLE 3 UV-C weathering Properties of polypropylene containing hindered phenols and other phosphites
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The data in table 3 shows that polypropylene formulated with common hindered phenols undergoes significant discoloration upon UV-C exposure. (compare sample 3-2 with sample 3-1.) however, certain light stabilizers in combination with hindered phenols reduced discoloration after UV-C exposure, as indicated by the lower Δyi and Δe values presented in table 3 (samples 3-3 to 3-7).
Example 3-UV-C weathering Properties of Polypropylene containing phosphite and other additives (. DELTA.E and. DELTA.YI)
TABLE 4 UV-C weathering Properties of Polypropylene containing phosphites and other additives
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The data in table 4 shows that polypropylene formulated with common phosphite antioxidants experienced significant discoloration after UV-C exposure. (compare sample 4-2 with sample 4-1.) however, certain combinations of UV absorbers, hindered amine light stabilizers, and hindered benzoates used in combination with phosphites reduced discoloration after UV-C exposure, as indicated by the lower Δyi and Δe values presented in table 4 (samples 4-3 through 4-6).
Example 4-UV-C weathering Properties of polypropylene containing hindered phenols and other additives (. DELTA.E and. DELTA.YI)
TABLE 5 UV-C weathering Properties of polypropylene containing hindered phenols and other additives
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The data in table 5 shows that polypropylene formulated with common hindered phenol antioxidants undergoes significant discoloration after UV-C exposure. (comparison of sample 5-2 with sample 5-1.) however, certain combinations of UV absorbers, hindered amine light stabilizers, and hindered benzoates used in combination with hindered phenols reduced discoloration after UV-C exposure, as indicated by the lower Δyi and Δe values presented in table 5. (samples 5-3 to 5-6)
Example 5-UV-C weathering Properties of antioxidant-only Polypropylene (ΔE, ΔYI and crazing/crazing)
TABLE 6 UV-C weathering Properties of antioxidant-only Polypropylene
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The data for sample 6-1 in table 6 shows that the unstable polypropylene undergoes severe photodegradation after UV-C irradiation, as evidenced by the development of significant surface cracks and/or crazes as shown in fig. 1A. Samples 6-2 through 6-4 demonstrate that polypropylene containing only an antioxidant (hindered phenol alone, or a combination of hindered phenol and phosphite) undergoes severe surface discoloration (as indicated by Δe and Δyi results), photodegradation (as indicated by surface cracking/crazing shown in table 6 and fig. 1B and 1C), or a combination of both discoloration and photodegradation.
Example 6-UV-C weathering Properties of polypropylene containing a combination of antioxidant and hindered amine light stabilizer (ΔE, ΔA) YI and cracking/crazing)
Table 7. UV-C weathering properties of polypropylene containing a combination of antioxidants and hindered amine light stabilizers.
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Samples 7-3 and 7-4 demonstrate that polypropylene containing both antioxidants and hindered amine light stabilizers showed less discoloration after UV-C irradiation than sample 7-2 containing only antioxidants, as demonstrated by the Δe and Δyi results shown in table 7. Samples 7-5, 7-6 and 7-7 demonstrate that polypropylene containing both antioxidants and hindered amine light stabilizers showed less surface photodegradation after UV-C irradiation than both the unstable polypropylene (sample 7-1) and the polypropylene containing only antioxidants (sample 7-2), as demonstrated by the surface crack/crazing observations in table 7.
Example 7-UV-C weathering Properties of Polypropylene containing a combination of antioxidant and UV absorber (ΔE, ΔYI and Kelvin) Cracking/crazing
TABLE 8 UV-C weathering Properties of Polypropylene containing a combination of antioxidant and UV absorber
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Samples 8-3 through 8-9 demonstrate that polypropylene containing both antioxidants and UV absorbers (benzophenone, benzotriazole, or triazine) showed less discoloration after UV-C irradiation than both the unstable polypropylene (sample 8-1) and the polypropylene containing only antioxidants (sample 8-2), as demonstrated by the Δe and Δyi results presented in table 8. In addition, formulations 8-3 to 8-9 demonstrate that polypropylene containing both antioxidants and UV absorbers showed less photodegradation than both the unstable polypropylene (sample 8-1) and the polypropylene containing only antioxidants (sample 8-2), as demonstrated by the surface crack/crazing observations.
Example 8-UV-C weathering Properties of Polypropylene containing a combination of antioxidant and hindered benzoate (ΔE, ΔYI) And cracking/crazing
TABLE 9 UV-C weathering Properties of polypropylene stabilized by a combination of antioxidants and hindered benzoates
Samples 9-3 and 9-4 demonstrate that polypropylene containing both antioxidants and hindered benzoates showed less discoloration after UV-C irradiation than polypropylene containing only antioxidants (sample 9-2), as indicated by the Δe and Δyi results of table 9. Sample 9-4 shows that polypropylene containing both antioxidant and hindered benzoate showed less surface photodegradation after UV-C irradiation than both the unstable polypropylene (sample 9-1) and the polypropylene containing only antioxidant (sample 9-2), as indicated by the surface crack/crazing observations of table 9.
Example 9-UV-C weatherability of Polypropylene containing a combination of antioxidant, UV absorber and hindered amine light stabilizer Energy (. DELTA.E)ΔYI and cracking/crazing)
TABLE 10 UV-C weathering properties of polypropylene stabilized by a combination of antioxidants, UV absorbers and hindered amine light stabilizers
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Samples 10-3 to 10-8 demonstrate that polypropylene containing an antioxidant in combination with a UV absorber and a hindered amine light stabilizer shows less discoloration and less surface photodegradation after UV-C irradiation than both the unstable polypropylene (sample 10-1) and the polypropylene containing only the antioxidant (sample 10-2), as demonstrated by the Δe and Δyi results in table 10 and the observations of surface crack/crazing development.
Example 10-Polypropylene containing a combination of antioxidants, UV absorbers, hindered benzoates and hindered amine light stabilizers UV-C weathering Properties of the alkene (ΔE, ΔYI and cracking/crazing)
TABLE 11 UV-C weathering Properties of polypropylene stabilized by a combination of antioxidants, UV absorbers, hindered benzoates and hindered amine light stabilizers
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Samples 11-3 through 11-10 demonstrate that polypropylene containing an antioxidant in combination with a UV absorber, a hindered benzoate, and a hindered amine light stabilizer shows less discoloration and less photodegradation after UV-C irradiation than the unstable polypropylene (sample 11-1) and the polypropylene containing only an antioxidant (sample 11-2), as indicated by the Δe and Δyi results in table 11 and the observations of surface cracking/crazing.
EXAMPLE 11 UV-C weathering Properties of Polypropylene containing antioxidants and other additives (ΔE and ΔYI)
The results are presented in table 12 below.
Table 12.
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Table 12 shows that WESTON TM 618 shows minimal discoloration in polypropylene after UV-C exposure (sample 12-2 (WESTON TM 618 Sample 2-2 (IRGAFOS) TM 168 A) to compare. The addition of various UV stabilizers increased the initial YI, but maintained/reduced the color change (ΔE) after UV-C exposure, as demonstrated by samples 12-3 and 12-4. IRGANOX is treated TM 1010 was added to the formulation to make the panel more susceptible to discoloration from UV-C exposure (see samples 12-5 and 12-6).
Example 12-UV-C weathering Properties of Polypropylene containing hindered phenols and other additives (. DELTA.E and. DELTA.YI)
This study is generally based on example 2 above, but the UV loading (% by weight) is higher. The results are shown in table 13 below.
Table 13.
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Similar to the data in table 3, the data in table 13 shows that polypropylene formulated with common hindered phenols undergoes discoloration upon UV-C exposure. (comparison of samples 13-2 and 3-2 with samples 13-1 and 3-1.) however, certain light stabilizers in combination with hindered phenols reduced discoloration after UV-C exposure, as indicated by the lower Δyi and Δe values presented in table 13 (see samples 13-3 to 13-6). Higher UV loadings do appear to have a slight benefit on ΔYI (samples 13-2 to 13-6 compared to 3-2 to 3-6).
Example 13 UV-C weathering Properties (ΔE and ΔYI) of polyethylene containing phosphite and other additives
The performance of various individual additive materials and specific combinations thereof in protecting polymers from UV-C induced discoloration and photodegradation was evaluated. Selecting high density polyethylene from Norva Chemicals @2909 As polymer matrix for weathering studies in these examples. Table 1 above lists information about suppliers, commercial names, and chemical names of the various additive materials in the formulation examples. All additive materials were used as received.
The general procedure for preparing the additive-containing plaques is as follows. 1,000 g of the powder mixture of each formulation was prepared by dry blending the additives with the polyethylene resin. The mixture was then compounded at 190℃using a Werner & Pfleiderer twin screw extruder. After extrusion, a standard rectangular plate (2×2.5×0.125 inch) was injection molded into a rectangular plate using an Engel injection molding machine at 190 ℃.
As detailed in the previous examples, UV-C weathering studies were performed using UV-C weathering devices as described. The color change (ΔE) and yellowness index change (ΔYI) of the plate surface after UV-C exposure were also measured in the same manner. The UV-C weathering results for polyethylenes with phosphite and other additives are presented in table 12 below.
Table 14. UV-C weathering properties of polypropylene containing phosphite and other additives.
The data in table 14 shows that polyethylene formulated with the common phosphite antioxidants experienced significant discoloration after UV-C exposure compared to pure, unstable polyethylene. (e.g., comparing sample 14-2 with sample 14-1). However, certain light stabilizers in combination with phosphites reduced discoloration after UV-C exposure, as indicated by the lower Δyi and Δe values presented in table 14 (see samples 14-2 through 14-6).
EXAMPLE 14 UV-C weathering Properties of polyethylene containing hindered phenols and other additives (. DELTA.E and. DELTA.YI)
The results are presented in table 15 below.
Table 15.
The data in table 15 shows that polyethylene formulated with common hindered phenols undergoes significant discoloration upon UV-C exposure. (compare sample 15-2 with sample 15-1). However, certain light stabilizers in combination with hindered phenols reduced discoloration after UV-C exposure, as indicated by the lower Δyi and Δe values presented in table 15 (samples 15-3 through 15-5).
EXAMPLE 15 222nm UV-C weathering Properties (ΔE and ΔE) of polyethylene containing phosphite and other additives YI)
The study conducted in example 13 was repeated, but instead of performing UV-C weathering at 254nm, the weathering apparatus was modified to contain three KrCl excimer UV-C lamps (222 nm), with an average irradiance at the panel surface of about 190. Mu.W/cm 2 (at 222 nm), and an automatic fan controller to maintain the test temperature below 40 ℃. During UV-C weathering test, the plates were placed in the apparatus and frequently repositioned to ensure that all samples were dockedAn amount of radiation exposure was received.
The color change (ΔE) and the yellowness index change (ΔYI) of the plate surface after UV-C exposure were measured in the same manner as in the previous examples. The UV-C weathering results for polyethylenes with phosphite and other additives are presented in table 16 below.
Table 16. 222nm UV-C weathering properties of polyethylene containing phosphite and other additives.
The data in Table 16 shows that polyethylene formulated with conventional phosphites undergoes discoloration upon UV-C exposure. (compare sample 16-2 with sample 16-1.) however, certain light stabilizers in combination with phosphites reduced discoloration after UV-C exposure, as indicated by the lower Δyi and Δe values presented in table 16 (samples 16-3 to 16-6).
These results presented in the foregoing examples generally demonstrate that the stabilizer compositions disclosed herein for use in making polymeric articles are effective in providing resistance to the deleterious effects of discoloration, cracking and/or crazing when the polymeric articles are subjected to repeated or prolonged exposure to UV-C (190-280 nm) disinfecting (sterilizing) light sources. Bis (2, 6, -tetramethyl-4-piperidinyl) sebacate (TINUVIN) TM 770 Data relating to the use of the same as an additive for combating the detrimental effects of polymer compositions after exposure to UV-C radiation is not fully supported and the inventors accordingly have abandoned it from the present application. Nevertheless, the datSup>A is provided to demonstrate that it cannot be inferred only that stabilizer additives that are beneficial or useful for preventing the detrimental effects of the polymer composition after exposure to UV-Sup>A and/or UV-B would also be beneficial or useful for preventing the polymer composition from such detrimental effects of UV-C exposure. To further support the concept that the use of stabilizer additives for UV-A/UV-B cannot be inferred to be useful for UV-C, the following presents Sup>A study of the effect of various UV stabilizers and antioxidants on polycarbonate after UV-C exposure.
EXAMPLE 16 after 254nm UV-C exposureEffect of Standard UV stabilizers/antioxidants on polycarbonate materials
Polycarbonates are known to be high performance engineering thermoplastics for a variety of applications including, but not limited to, compact discs, safety helmets, bullet-proof glass, safety glasses, and automotive headlamp lenses. Although any polymer linked together by carbonate groups (-O- (c=o) -O-) can be considered a polycarbonate, the most common polycarbonate used is based on bisphenol a (BPA). Polycarbonates have many advantageous properties including high impact strength, high toughness, optical clarity, chemical resistance, heat resistance, high dimensional stability, good electrical properties, and low weight. It is known to use various stabilizer compositions well known to those skilled in the art to protect polycarbonates from the deleterious effects of UV-Sup>A and/or UV-B radiation. Therefore, it would be desirable if the polycarbonate material was resistant to discoloration due to UV radiation at wavelengths below 300 nm.
The purpose of this experiment was to investigate whether a similar trend was observed from the polypropylene study exemplified above.
The study in this example was to use LUPOY TM 1201 10P Natural polycarbonate (LG Chemical Co., ltd. (LG Chemical)) (PC) was used as the base resin. The amount of additive used in PC is described in weight percent (wt.%) and is described in this manner throughout. Extrusion was performed on a Killion single screw at 550°f (about 290 ℃) melt temperature. The temperature zones at the nozzles were 480°f, 525°f, 550°f, and 550°f. Injection molding was performed on an Engel machine at 295 ℃. The temperature zones at the nozzles were 275 ℃, 285 ℃, 295 ℃ and 295 ℃. All samples were dried in a vacuum oven for a minimum of 4 hours and cooled in a sealed glass jar for 1 hour before being mixed with additives and added to the extruder. Samples were prepared and exposed as 2 x 0.125 inch plates.
UVC exposure at 254nm was performed with an internal chamber equipped with two low-pressure mercury light sources and a calibrated radiometer (to measure irradiance over time). The average irradiance of the exposed sample was about 1.5mW/cm 2 . The average temperature is about 30 ℃. Measurement on a Ci7800 SpectrophotometerColor measurement the spectrophotometer was calibrated for the Hunter LAB color scale using a D65 light source at an observation angle of 10 °. The colors were measured on a Ci7800 spectrophotometer calibrated for the Hunter LAB color scale using a D65 light source at an observation angle of 10 °.
Table 17 lists the various formulations considered in the study.
Table 17. Evaluation of standard UV absorbers, hindered amine light stabilizers, hindered benzoates and antioxidants on polycarbonate after 254nm UV-C exposure.
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Although a series of different samples were put together for testing, the results show that all of the stabilizers evaluated had relatively little effect on reducing the discoloration of the polycarbonate after 254nm UV-C exposure. Interestingly, the formulation comprising UV-1164 appears to contribute additional color to the PC sample, especially in formulation 17-6 in combination with AO-618. When UV-1164 was combined with AO-168 (formulations 17-23), the initial discoloration was lower. This discoloration is also noted in UV-1577, but typically to a lesser extent. Higher initial yellowness was also observed for UV-3346 in combination with AO-618. Polycarbonates are sensitive to alkaline substances and therefore it is possible that UV-3346 leads to initial degradation of PC before UV-C exposure.
With respect to the total color change, formulation 17-6 (UV-1164+AO-618) showed the lowest change technically. However, the initial color in this formulation is highest, so discoloration due to UV-C exposure is likely to be masked by the high initial color. The remaining formulations tested showed a color change of approximately 4 units (±0.5 units) after 12 hours, with only a minimal color increase from 12 hours to 30 hours.

Claims (32)

1. A polymer composition for use in the manufacture of a stabilized polymer article that is resistant to at least one of discoloration, cracking or crazing upon exposure to UV-C (190-280 nm) light, the polymer composition comprising:
i) An organic polymeric material; and
ii) a stabilizer composition comprising:
an antioxidant selected from the group consisting of hindered phenols, phosphites and phosphonites and mixtures thereof; and
light stabilizers selected from the group consisting of Hindered Amine Light Stabilizers (HALS), UV absorbers (UVA), hindered benzoates and mixtures thereof
Even in the absence of a barium compound (e.g., a barium salt) in the stabilizer composition, and provided that the HALS is not bis (2, 6, -tetramethyl-4-piperidinyl) sebacate alone (TINUVIN TM 770)。
2. The polymer composition of claim 1, wherein at least one of reduced discoloration, cracking or crazing after exposure to UV-C light is associated with the use of the light stabilizer in combination with the antioxidant, as compared to the antioxidant in the absence of the light stabilizer.
3. The polymer composition of claim 1 or claim 2, wherein the organic polymer material comprises at least one of: polyolefins, thermoplastic olefins (TPO), poly (ethylene-vinyl acetate) (EVA), polyesters, polyethers, polyketones, polyamides, natural and synthetic rubbers, polyurethanes, polystyrenes, polyacrylates, polymethacrylates, polybutyl acrylates, polyacetals, polyacrylonitriles, polybutadiene, acrylonitrile-butadiene-styrene (ABS), styrene-acrylonitrile (SAN), acrylonitrile-styrene-acrylate (ASA), cellulose acetate butyrate, cellulosic polymers, polyimides, polyamideimides, polyetherimides, polyphenylene sulfides, polyphenylene oxides, polysulfones, polyethersulfones, polyvinylchlorides, amino resin crosslinked polyacrylates and polyesters, polyisocyanate crosslinked polyesters and polyacrylates, phenol/formaldehyde, urea/formaldehyde and melamine/formaldehyde resins alkyd resins, polyester resins, acrylate resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, urethanes or epoxy resins, crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic and aromatic glycidyl ethers crosslinked with anhydrides or amines, polysiloxanes, michael addition polymers, addition polymers of amines or blocked amines with activated unsaturated and activated methylene compounds, addition polymers of ketimines with activated unsaturated and activated methylene compounds, combinations of polyketimines with unsaturated acrylic polyacetoacetate resins, coating compositions, radiation curable compositions, epoxy melamine resins, organic dyes, cosmetics, cellulose-based papers, photographic film papers, fibers, and the like, wax or ink.
4. The polymer composition of claim 1 or claim 2, wherein the organic polymer material comprises at least one of: (i) Polyethylene, polypropylene, polyisobutylene, polybut-1-ene or poly-4-methylpent-1-ene; (ii) polyisoprene or polybutadiene; (iii) cyclopentene or norbornene; (iv) Optionally crosslinked polyethylene, high Density Polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultra high molecular weight polyethylene (HDPE-UHMW), medium Density Polyethylene (MDPE), low Density Polyethylene (LDPE), linear Low Density Polyethylene (LLDPE), very Low Density Polyethylene (VLDPE), or Ultra Low Density Polyethylene (ULDPE); (v) thermoplastic olefins (TPOs); or (vi) copolymers of at least one of a mono-, di-or cyclic olefin.
5. The polymer composition of claim 4, wherein the organic polymeric material is polypropylene, polyethylene, or a thermoplastic olefin.
6. The polymer composition of any of claims 1 to 5, wherein the antioxidant is present at from 0.001% to 5.0%, preferably from 0.005% to 3.0%, and more preferably from 0.01% to 1.0% by weight based on the total weight of the polymer composition.
7. The polymer composition of any of claims 1 to 6, wherein the light stabilizer is present at from 0.005% to 5.0% by weight, preferably from 0.01% to 2.0% by weight, based on the total weight of the polymer composition.
8. The polymer composition of any one of claims 1 to 7, wherein the antioxidant comprises a hindered phenol having at least one group according to formula (IVa), (IVb) or (IVc):
wherein:
indicating the attachment point of the molecular fragment to the parent compound (via a carbon-carbon single bond);
r in formula (IVa), (IVb) or (IVc) 18 Is hydrogen or C 1-12 A hydrocarbon group;
r in formula (IVa), (IVb) or (IVc) 19 And R is 20 Each independently is hydrogen or C 1 -C 20 A hydrocarbon group; and is also provided with
R in formula (IVa), (IVb) or (IVc) 37 Is C 1 -C 12 A hydrocarbon group.
9. The polymer composition of claim 8, wherein R in formula (IVa), (IVb) or (IVc) 18 And R is 37 Each independently is methyl or tert-butyl.
10. The polymer composition of claim 8 or claim 9, wherein the hindered phenol comprises at least one of:
1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione (CYANOX) TM 1790)，
1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione (IRGANOX) TM 3114)，
1, 3-tris (2 ' -methyl-4 ' -hydroxy-5 ' -tert-butylphenyl) butane,
triethylene glycol bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ],
4,4' -thiobis (2-tert-butyl-5-methylphenol),
2,2' -thiodiethylenebis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ],
octadecyl 3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate,
pentaerythritol (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate,
n, N' -hexamethylenebis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propanamide ],
bis (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) thiodipropionate,
pentaerythritol tetrakis (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) (IRGANOX TM 1010)，
Octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (IRGANOX) TM 1076 Or (x)
N, N' -bis (3, 5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine (IRGANOX) TM 1024)。
11. The polymer composition of any of claims 8 to 10, wherein the hindered phenol comprises at least one of: pentaerythritol tetrakis (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) (IRGANOX TM 1010 Octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (IRGANOX) TM 1076 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione (IRGANOX) TM 3114 Or N, N' -bis (3, 5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine (IRGANOX) TM 1024)。
12. The polymer composition of any one of claims 1 to 11, wherein the antioxidant comprises the phosphite or phosphonite, and the phosphite or phosphonite is at least one of:
i) A compound according to any one of formulae (1) to (7):
wherein:
the index is an integer and n is 2, 3 or 4; p is 1 or 2; q is 2 or 3; y is 1, 2 or 3; and z is 1 to 6;
if n or q is 2, A 1 Is C 2 -C 18 An alkylene group; by oxygen, sulfur or-NR 4 Interrupted C 2 -C 12 An alkylene group having the formula:
or phenylene;
if n or q is 3, A 1 Is of the formula-C r H 2r-1 -a divalent group, wherein r is an integer from 4 to 12;
if n is 4, A 1 Is that
B is a direct bond, -CH 2 -、-CHR 4 -、-CR 1 R 4 -, sulfur, C (C) 5 -C 7 Cycloalkylene, or from 1 to 4C at the 3, 4 and/or 5 positions 1 -C 4 Alkyl-substituted cyclohexylene;
if p is 1, D 1 Is C 1 -C 4 Alkyl, and if p is 2is-CH 2 OCH 2 -；
D 2 Is C 1 -C 4 An alkyl group;
if y is 1, E is C 1 -C 18 Alkyl, -OR 1 Or halogen;
if y is 2, E is-O-A 2 -O-, wherein A 2 Is as for A 1 Defined when n is 2;
if y is 3, E is a compound of formula R 4 C(CH 2 O) 3 Or N (CH) 2 CH 2 O-) 3 Is a group of (2);
Q is a group of at least z-valent mono-or polyhydric alcohol or phenol, which is attached to the phosphorus atom via an oxygen atom of the OH group of the mono-or polyhydric alcohol or phenol;
R 1 、R 2 and R is 3 Each independently is C 1 -C 18 Alkyl, which is unsubstituted or substituted by halogen, -COOR 4 -CN or-CONR 4 R 4 Substitution; by oxygen, sulfur or-NR 4 Interrupted C 2 -C 18 An alkyl group; c (C) 7 -C 9 A phenylalkyl group; c (C) 5 -C 12 Cycloalkyl, phenyl, or naphthyl; by halogen, 1 to 3 alkyl or alkoxy groups having a total of 1 to 18 carbon atoms, or by C 7 -C 9 Phenylalkyl-substituted naphthyl or phenyl; or a group of the formula
Wherein m is an integer in the range of 3 to 6;
R 4 is hydrogen, C 1 -C 8 Alkyl, C 5 -C 12 Cycloalkyl or C 7 -C 9 A phenylalkyl group;
R 5 and R is 6 Each independently is hydrogen, C 1 -C 8 Alkyl or C 5 -C 6 A cycloalkyl group,
if q is 2, R 7 And R is 8 Each independently is C 1 -C 4 Alkyl or together are 2, 3-dehydropentamethylene; and if q is 3, R 7 And R is 8 Each is methyl;
r in each case 14 Independently selected from hydrogen, C 1 -C 9 Alkyl or cyclohexyl;
r in each case 15 Independently hydrogen or methyl;
x and Y are each a direct bond or oxygen;
z is a direct bond, methylene, -C (R) 16 ) 2 -or sulfur, and
R 16 is C 1 -C 8 An alkyl group; or alternatively
ii) a triarylphosphite according to formula 8:
wherein:
R 17 is a substituent present in from 0 to 5 instances of an aromatic ring of formula 8 and is independently selected in each occurrence from C 1 -C 20 Alkyl, C 3 -C 20 Cycloalkyl, C 4 -C 20 Alkylcycloalkyl, C 6 -C 10 Aryl or C 7 -C 20 Alkylaryl groups.
13. The polymer composition of claim 12, wherein the phosphite or phosphonite comprises at least one of:
the preparation method comprises the steps of (1) preparing triphenyl phosphite,
diphenyl alkyl phosphite is used as the main component of the composition,
a phenyl dialkyl phosphite is used as a starting material,
the trilauryl phosphite is used as the main ingredient,
a trioctadecyl phosphite ester, wherein the main chain of the phosphite ester is a tri-octadecyl phosphite,
distearyl pentaerythritol phosphite which is used as a main ingredient,
tris (2, 4-di-tert-butylphenyl) phosphite (IRGAFOS) TM 168)，
Tris (4-nonylphenyl) phosphite,
a compound of formula (a), (B), (C), (D), (E), (F), (G), (H), (J), (K) or (L):
2-butyl-2-ethyl-1, 3-propanediol 2,4, 6-tri-tert-butylphenol phosphite,
bis- (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite,
2-butyl-2-ethyl-1, 3-propanediol 2, 4-di-cumylphenol phosphite,
2-butyl-2-ethyl-1, 3-propanediol 4-methyl-2, 6-di-tert-butylphenol phosphite, or
Bis (2, 4, 6-tri-tert-butyl-phenyl) pentaerythritol diphosphate.
14. The polymer composition of claim 12 or claim 13, wherein the phosphite or phosphonite comprises at least one of: tris (2, 4-di-tert-butylphenyl) phosphite (IRGAFOS) TM 168 Triphenyl phosphite, tris (4-nonylphenyl) phosphite, bis (2, 4-dicumylphenyl) pentaerythritol Diphosphite (DOVERPHOS) TM S9228) or tetrakis (2, 4-di-tert-butylphenyl) -4,4' -biphenylene-diphosphonite (IRGAFOS) TM P-EPQ)。
15. The polymer composition of any of claims 1 to 14, wherein the light stabilizer comprises a Hindered Amine Light Stabilizer (HALS) comprising at least one functional group according to formula (II):
wherein:
R 31 is hydrogen, OH, C 1 -C 20 Hydrocarbyl radicals, -CH 2 CN、C 1 -C 12 Acyl or C 1 -C 18 An alkoxy group;
R 38 is hydrogen or C 1 -C 8 A hydrocarbon group; and is also provided with
R 29 、R 30 、R 32 And R is 33 Each independently is C 1 -C 20 Hydrocarbyl, or R 29 And R is 30 And/or R 32 And R is 33 Together with the carbon to which they are attached form C 5 -C 10 Cycloalkyl; or alternatively
At least one functional group according to formula (IIa):
wherein:
m is an integer from 1 to 2;
R 39 is hydrogen, OH, C 1 -C 20 Hydrocarbyl radicals, -CH 2 CN、C 1 -C 12 Acyl or C 1 -C 18 An alkoxy group; and is also provided with
G 1 -G 4 Each independently is C 1 -C 20 A hydrocarbon group.
16. The polymer composition of claim 15, wherein the Hindered Amine Light Stabilizer (HALS) comprises at least one of:
bis (2, 6-tetramethylpiperidin-4-yl) succinate;
bis (1, 2, 6-pentamethylpiperidin-4-yl) sebacate;
bis (1-octyloxy-2, 6-tetramethylpiperidinyl) succinate;
Bis (1-octyloxy-2, 6-tetramethylpiperidin-4-yl) sebacate (TINUVIN) TM 123)；
Bis (1, 2, 6-pentamethylpiperidin-4-yl) n-butyl 3, 5-di-tert-butyl-4-hydroxybenzylmalonate;
condensate of 1- (2-hydroxyethyl) -2, 6-tetramethyl-4-hydroxypiperidine and succinic acid (TINUVIN TM 622)；
2, 6-tetramethylpiperidin-4-yl stearate;
2, 6-tetramethylpiperidin-4-yl dodecanoate;
1,2, 6-pentamethylpiperidin-4-yl stearate;
dodecanoic acid 1,2, 6-pentamethylpiperidin-4-yl ester;
condensate of N, N' -bis (2, 6-tetramethylpiperidin-4-yl) hexamethylenediamine and 4-tert-octylamino-2, 6-dichloro-1, 3, 5-triazine (CHIMASSORB) TM 944)；
Tri (2, 6-tetramethylpiperidin-4-yl) nitrilotriacetic acid ester;
4-stearyloxy-2, 6-tetramethylpiperidine;
condensate of N, N' -bis (2, 6-tetramethylpiperidin-4-yl) hexamethylenediamine and 4-morpholino-2, 6-dichloro-1, 3, 5-triazine (CYASORB) TM UV-3346)；
Methylated condensates of N, N' -bis (2, 6-tetramethylpiperidin-4-yl) hexamethylenediamine and 4-morpholino-2, 6-dichloro-1, 3, 5-triazine (CYASORB) TM UV-3529)；
Condensate of 2-chloro-4, 6-bis (4-n-butylamino-2, 6-tetramethylpiperidinyl) -1,3, 5-triazine and 1, 2-bis (3-aminopropylamino) ethane (CHIMASSORB) TM 119)；
A condensate of 2-chloro-4, 6-bis (4-n-butylamino-1, 2, 6-pentamethylpiperidinyl) -1,3, 5-triazine and 1, 2-bis- (3-aminopropylamino) ethane;
condensate of N, N' -bis (2, 6-tetramethylpiperidin-4-yl) hexamethylenediamine, N-butyl-2, 6-tetramethyl-4-piperidylamine, di-N-butylamine and 2,4, 6-trichloro-1, 3, 5-triazine (CHIMASSORB) TM 2020)；
4-hexadecyloxy-and 4-stearyloxy-2, 6-tetramethylpiperi-dineMixtures of pyridines (CYASORB TM UV-3853)；
A mixture of 4-hexadecyloxy-and 4-stearyloxy-1, 2, 6-pentamethylpiperidine;
condensate of N, N' -bis (2, 6-tetramethylpiperidin-4-yl) hexamethylenediamine and 4-cyclohexylamino-2, 6-dichloro-1, 3, 5-triazine;
condensates of 1, 2-bis (3-aminopropylamino) ethane, 2,4, 6-trichloro-1, 3, 5-triazine and 4-butylamino-2, 6-tetramethylpiperidine;
condensate of N, N' -bis (2, 6-tetramethylpiperidin-4-yl) hexamethylenediamine and 4-cyclohexylamino-2, 6-dichloro-1, 3, 5-triazine;
tetrakis (2, 6-tetramethylpiperidin-4-yl) -1,2,3, 4-butane tetracarboxylic acid ester;
tetrakis (1, 2, 6-pentamethylpiperidin-4-yl) -1,2,3, 4-butanetetracarboxylate;
1,2,3, 4-butanetetracarboxylic acid, 2, 6-tetramethylpiperidinyl-4-yltridecyl ester;
1,2,3, 4-butanetetracarboxylic acid, 1,2, 6-pentamethylpiperidin-4-yltridecyl ester;
Carboxamide, N, N' -1, 6-adipoylbis [ N- (2, 6-tetramethylpiperidin-4-yl) (UVINUL) TM 4050)；
Condensate of N, N' -bis (2, 6-tetramethylpiperidin-4-yl) hexamethylenediamine and 4-tert-octylamino-2, 6-dichloro-1, 3, 5-triazine (CHIMASSORB) TM 944)；
Condensate of N, N' -bis (2, 6-tetramethyl-1- (propoxy) -piperidin-4-yl) hexamethylenediamine, N-butyl-1-propoxy-2, 6-tetramethyl-4-piperidinamine, di-N-butylamine and 2,4, 6-trichloro-1, 3, 5-triazine (TINUVIN TM NOR HALS 371；
Oxidative hydrogenation reaction products of polymers of N, N' -bis (2, 6-tetramethyl-4-piperidin-4-yl) hexamethylenediamine with 2,4, 6-trichloro-1, 3, 5-triazine with 3-bromo-1-propene, di-N-butylamine and N-butyl-2, 6-tetramethyl-4-piperidinamine (TINUVIN TM XT 200)；
TINUVIN TM XT-850/XT-855); or alternatively
N 1 ,N 1' -1, 2-ethanediylbis (1, 3-propanediamine) with cyclohexane and N-butyl peroxideReaction products of (FLAMETAB) 2, 6-tetramethyl-4-piperidinamine-2, 4, 6-trichloro-1, 3, 5-triazine TM NOR 116)。
17. The polymer composition of any one of claims 1 to 16, wherein the light stabilizer comprises a UV absorber comprising at least one 2- (2 '-hydroxyphenyl-s-triazine, 2-hydroxybenzophenone, 2- (2' -hydroxyphenyl) benzotriazole or benzoxazinone.
18. The polymer composition of claim 17, wherein the light stabilizer comprises at least one 2- (2' -hydroxyphenyl) -s-triazine according to formula (I):
Wherein R is 34 And R is 35 Each of which is independently C 6 -C 10 Aryl, mono-or di-C 1 -C 12 Hydrocarbyl-substituted amino, C 2 -C 12 Alkanoyl, C 1 -C 12 Alkyl, C 1 -C 10 Acyl or C 1 -C 10 An alkoxy group, an amino group,
wherein C is 6 -C 10 Aryl optionally substituted in from 1 to 3 positions with OH, halogen, C 1 -C 12 Alkyl, C 1 -C 12 Alkoxy, C 1-12 Alkoxy esters, C 2-12 At least one substitution of alkanoyl or phenyl, wherein phenyl is optionally substituted at from 1 to 3 substitutable positions with OH, halogen, C 1-12 Alkyl, C 1-12 Alkoxy, C 1-12 Alkoxy esters or C 2-12 At least one substitution in an alkanoyl group; and is also provided with
Each R 36 Independently OH, halogen, C 1 -C 12 Alkyl, C 1 -C 12 Alkoxy, C 1 -C 12 Alkoxy esters, C 2 -C 12 Alkanoyl, phenyl or C 1 -C 12 An acyl group.
19. The polymer composition of claim 18, wherein the 2- (2' -hydroxyphenyl) -s-triazine comprises at least one of:
4, 6-diphenyl-2- (4-hexyloxy-2-hydroxyphenyl) -s-triazine (TINUVIN TM 1577)，
4, 6-bis- (2, 4-dimethylphenyl) -2- (2-hydroxy-4-octyloxyphenyl) -s-triazine (CYASORB) TM 1164)，
2, 4-bis [ 2-hydroxy-4- (2-hydroxyethoxy) phenyl ] -6- (2, 4-dimethylphenyl) -s-triazine,
mixture of 4, 6-bis (2, 4-dimethylphenyl) -2- (2-hydroxy-4- (3-dodecyloxy-2-hydroxypropoxy) phenyl) -s-triazine and 4, 6-bis- (2, 4-dimethylphenyl) -2- (2-hydroxy-4- (3-tridecyloxy-2-hydroxypropoxy) phenyl) -s-Triazine (TINUVIN) TM 400)，
4, 6-bis- (2, 4-dimethylphenyl) -2- (2-hydroxy-4 (3- (2-ethylhexyloxy) -2-hydroxypropoxy) -phenyl) -s-Triazine (TINUVIN) TM 405)，
4, 6-bis- (2, 4-dimethylphenyl) -2- (2-hydroxy-4 (3- (2-ethylhexyloxy) -2-hydroxypropoxy) -phenyl) -s-triazine,
2, 4-bis (2, 4-dimethylphenyl) -6- [ 2-hydroxy-4- [ (octyloxycarbonyl) ethyleneoxy]Phenyl group]s-Triazine (TINUVIN) TM 479)，
2, 4-bis (4-biphenyl) -6- [ 2-hydroxy-4- [ (octoxycarbonyl) ethyleneoxy ] phenyl ] -s-triazine,
2, 4-bis (4-biphenyl) -6- [ 2-hydroxy-4- (2-ethylhexyloxy) phenyl]s-Triazine (TINUVIN) TM 1600)，
2, 4-bis (2-hydroxy-4-butoxyphenyl) -6- (2, 4-bis-butoxyphenyl) -s-TRIAZINE (triazene) TM 460)，
2,4, 6-tris [ 2-hydroxy-4- (3-sec-butoxy-2-hydroxypropoxy) -phenyl ] -s-triazine, or
2,4, 6-tris [ 2-hydroxy-4- [ (octyloxycarbonyl) ethyleneoxy)]Phenyl group]s-Triazine (TINUVIN) TM 477)。
20. The polymer composition of claim 17, wherein theThe light stabilizer comprises a 2-hydroxybenzophenone comprising at least one of the following: 2-hydroxy-4-methoxybenzophenone (CYASORB) TM UV-9), 2' -dihydroxy-4-methoxybenzophenone (CYASORB) TM UV-24), 2-hydroxy-4-octoxybenzophenone (CYASORB) TM UV-531), 2' -dihydroxy-4, 4' -di-methoxybenzophenone, 2' -dihydroxybenzophenone, 2',4,4' -tetrahydroxybenzophenone, 2' -dihydroxy-4, 4' -dimethoxybenzophenone, 2' -dihydroxy-4, 4' -diethoxybenzophenone, 2' -dihydroxy-4, 4' -dipropoxybenzophenone, 2' -dihydroxy-4, 4' -dibutoxybenzophenone, 2' -dihydroxy-4-methoxy-4 ' -ethoxybenzophenone, 2' -dihydroxy-4-methoxy-4 ' -propoxybenzophenone 2,2' -dihydroxy-4-methoxy-4 ' -butoxybenzophenone, 2' -dihydroxy-4-ethoxy-4 ' -propoxybenzophenone, 2' -dihydroxy-4-ethoxy-4 ' -butoxybenzophenone, 2,3' -dihydroxy-4, 4' -dimethoxybenzophenone, 2,3' -dihydroxy-4-methoxy-4 ' -butoxybenzophenone, 2-hydroxy-4, 4',5' -trimethoxybenzophenone, 2-hydroxy-4, 4',6' -tributoxybenzophenone, 2-hydroxy-4-butoxy-4 ',5' -dimethoxybenzophenone, 2-hydroxy-4-ethoxy-2 ',4' -dibutylbenzophenone, 2-hydroxy-4-propoxy-4 ',6' -dichlorobenzophenone, 2-hydroxy-4-propoxy-4 ',6' -dibromobenzophenone, 2, 4-dihydroxybenzophenone, 2-hydroxy-4-ethoxybenzophenone, 2-hydroxy-4-propoxybenzophenone, 2-hydroxy-4-butoxybenzophenone, 2-hydroxy-4-methoxy-4 ' -methylbenzophenone, 2-hydroxy-4-methoxy-4 ' -ethylbenzophenone, 2-hydroxy-4-methoxy-4 ' -propylbenzophenone, 2-hydroxy-4-methoxy-4 ' -butylbenzophenone, 2-hydroxy-4-methoxy-4 ' -tert-butylbenzophenone, 2-hydroxy-4-methoxy-4 ' -chlorobenzophenone, 2-hydroxy-4-methoxy-4 ' -bromobenzophenone, 2-hydroxy-4, 4' -dimethoxybenzophenone, 2-hydroxy-4, 4' -dimethoxy-3-methylbenzophenone, 2-hydroxy-4, 4' -dimethoxy-2 ' -ethylbenzophenone, 2-hydroxy-4, 4' -trimethoxy-5 ' -trimethoxy benzophenone, 2-hydroxy-4-ethoxy-4 ' -methylbenzophenone, 2-hydroxy-4-ethoxy-4 ' -ethylbenzophenone, 2-hydroxy-4-ethoxy-4 ' -propylbenzophenone, 2-hydroxy-4-ethyl-benzophenone Oxy-4 ' -butylbenzophenone, 2-hydroxy-4-ethoxy-4 ' -methoxybenzophenone, 2-hydroxy-4, 4' -diethoxybenzophenone, 2-hydroxy-4-ethoxy-4 ' -propoxybenzophenone, 2-hydroxy-4-ethoxy-4 ' -butoxybenzophenone, 2-hydroxy-4-ethoxy-4 ' -chlorobenzophenone or 2-hydroxy-4-ethoxy-4 ' -bromobenzophenone.
21. The polymer composition of claim 17, wherein the light stabilizer comprises 2- (2' -hydroxyphenyl) benzotriazole comprising at least one of the following: 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole (TINUVIN TM P), 2- (2 '-hydroxy-5' -tert-butylphenyl) benzotriazole, 2- (2 '-hydroxy-3' -methyl-5 '-tert-butylphenyl) benzotriazole, 2- (2' -hydroxy-5 '-cyclohexylphenyl) benzotriazole, 2- (2' -hydroxy-3 ',5' -dimethylphenyl) benzotriazole, 2- (2 '-hydroxy-5' -tert-butylphenyl) -5-chloro-benzotriazole, 2- (2 '-hydroxy-5' -tert-octylphenyl) benzotriazole (cyclic orb) TM UV-5411), 2- (3 ',5' -di-tert-butyl-2 '-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3', 5 '-di-tert-amyl-2' -hydroxyphenyl) benzotriazole (CYASORB) TM UV-2337), 2- (3 ',5' -bis (α, α -dimethylbenzyl) -2' -hydroxyphenyl) benzotriazole (TINUVIN TM 900 2- (3 '-tert-butyl-2' -hydroxy-5 '- (2-octyloxycarbonylethyl) phenyl) benzotriazole, 2' -methylenebis [4- (1, 3-tetramethylbutyl) -6-benzotriazol-2-ylphenol ]2- [3' -tert-butyl-5 ' - (2-methoxycarbonylethyl) -2' -hydroxyphenyl]Transesterification product of 2H-benzotriazole with polyethylene glycol 300 (TINUVIN TM 1130 2- [2' -hydroxy-3 ' - (α, α -dimethylbenzyl) -5' - (1, 3-tetramethylbutyl) phenyl]Benzotriazole, 5-trifluoromethyl-2- (2-hydroxy-3-alpha-cumyl-5-tert-octylphenyl) benzotriazole, 2- (2 ' -hydroxy-5 ' - (2-hydroxyethyl) phenyl) benzotriazole, 2- (2 ' -hydroxy-5 ' - (2-methacryloyloxyethyl) phenyl) benzotriazole, 2- (2 ' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-chlorobenzotriazole (TINUVIN) TM 326 2- (3 '-sec-butyl-5' -tert-butyl-2 '-hydroxyphenyl) benzotriazole, 2- (3', 5 '-di-tert-butyl-2' -hydroxyphenyl) benzotriazole, 2- (3 '-dodecyl-5' -methyl-2 '-hydroxyphenyl) -benzotriazole, 2- (3' -tert-butyl-5 '- (2-octoxycarbonylethyl) -2' -hydroxyphenyl) -5-chloroBenzotriazole, 2- (5 '-methyl-2' -hydroxyphenyl) benzotriazole or 2- (5 '-tert-butyl-2' -hydroxyphenyl) benzotriazole.
22. The polymer composition of claim 17, wherein the light stabilizer comprises a benzoxazinone comprising at least one of: 2-methyl-3, 1-benzoxazin-4-one, 2-butyl-3, 1-benzoxazin-4-one, 2-phenyl-3, 1-benzoxazin-4-one, 2- (1-or 2-naphthyl) -3, 1-benzoxazin-4-one, 2- (4-biphenyl) -3, 1-benzoxazin-4-one, 2-p-nitrophenyl-3, 1-benzoxazin-4-one, 2-m-nitrophenyl-3, 1-benzoxazin-4-one, 2-p-benzoylphenyl-3, 1-benzoxazin-4-one, 2-p-methoxyphenyl-3, 1-benzoxazin-4-one, 2-O-methoxyphenyl-3, 1-benzoxazin-4-one, 2-cyclohexyl-3, 1-benzoxazin-4-one, 2-p (or m) phthalimidophenyl-3, 1-benzoxazin-4-one, N- (2, 1-benzoylphenyl-4-oxazin-4-one, N-2-benzoylanilide, N- (2-methyl) -2-4-benzoylanilide, 2- [ p- (N-phenylcarbamoyl) phenyl ]-3, 1-benzoxazin-4-one, 2- [ p- (N-phenyl N-methylcarbamoyl) phenyl ]]-3, 1-benzoxazin-4-one, 2 '-bis (3, 1-benzoxazin-4-one), 2' -ethylenebis (3, 1-benzoxazin-4-one), 2 '-tetramethylenebis (3, 1-benzoxazin-4-one) 2,2' -hexamethylenebis (3, 1-benzoxazin-4-one), 2 '-decamethylenebis (3, 1-benzoxazin-4-one), 2' -p-phenylenedi (3, 1-benzoxazin-4-one) (CYASORB TM UV-3638), 2 '-m-phenylenebis (3, 1-benzoxazin-4-one), 2' - (4, 4 '-diphenylene) bis (3, 1-benzoxazin-4-one), 2' - (2, 6-or 1, 5-naphthalene) bis (3, 1-benzoxazin-4-one), 2'- (2-methyl-p-phenylene) bis (3, 1-benzoxazin-4-one), 2' - (2-nitro-p-phenylene) bis (3, 1-benzoxazin-4-one) 2,2'- (2-chloro-p-phenylene) bis (3, 1-benzoxazin-4-one), 2' - (1, 4-cyclohexylene) bis (3, 1-benzoxazin-4-one), N-p- (3, 1-benzoxazin-4-one-2-yl) phenyl, 4- (3, 1-benzoxazin-4-one-2-yl) phthalimide, N-p- (3, 1-benzoxazin-4-one-2-yl) benzoyl, 4- (3, 1-benzoxazin-4-one-2-yl) aniline, 1,3, 5-tris (3, 1-benzoxa-N-3-1-eOxazin-4-one-2-yl) benzene, 1,3, 5-tris (3, 1-benzoxazin-4-one-2-yl) naphthalene or 2,4, 6-tris (3, 1-benzoxazin-4-one-2-yl) naphthalene.
23. The polymer composition of any one of claims 1 to 22, wherein the light stabilizer comprises a hindered benzoate according to formula (VI):
wherein:
R 21 and R is 22 Each of which is independently C 1- C 12 An alkyl group;
t is O or NR 24 Wherein R is 24 Is H or C 1 -C 30 A hydrocarbon group; and is also provided with
R 23 Is H or C 1 -C 30 A hydrocarbon group.
24. The polymer composition of claim 23, wherein the hindered benzoate comprises at least one of: 3, 5-Di-tert-butyl-4-hydroxybenzoic acid 2, 4-di-tert-butylphenyl ester (TINUVIN TM 120 Cetyl 3, 5-di-tert-butyl-4-hydroxybenzoate (CYASORB) TM UV-2908), octadecyl 3, 5-di-tert-butyl-4-hydroxybenzoate, octyl 3, 5-di-tert-butyl-4-hydroxybenzoate, decyl 3, 5-di-tert-butyl-4-hydroxybenzoate, dodecyl 3, 5-di-tert-butyl-4-hydroxybenzoate, tetradecyl 3, 5-di-tert-butyl-4-hydroxybenzoate, behenyl 3, 5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4, 6-di-tert-butylphenyl 3, 5-di-tert-butyl-4-hydroxybenzoate or phenyl 3- [ 3-tert-butyl-4- (3, 5-di-tert-butyl-4-hydroxybenzoyloxy)]Butyl propionate.
25. The polymer composition of any one of claims 1 to 24, further comprising a thiosynergist comprising at least one of: bis-lauryl 3,3 '-thiodipropionate, bis-myristyl 3,3' -thiodipropionate, bis-tridecyl 3,3 '-thiodipropionate, bis-stearyl 3,3' -thiodipropionate, pentaerythritol tetrakis- (3-dodecylthiopropionate), tetraalkylthioethyl thiodisuccinate, 2, 12-dihydroxy-4, 10-dithia-7-oxatridecylmethylenebis [3- (dodecylthio) propionate ], 2-mercaptobenzimidazole, zinc salts, zinc dibutyldithiocarbamate or dioctadecyl disulfide.
26. The polymer composition of any one of claims 1 to 25, further comprising an inorganic compound comprising at least one of titanium dioxide, barium sulfate, zinc oxide, or cerium (IV) oxide.
27. The polymer composition of any one of claims 1 to 25, wherein the polymer composition is free of barium compounds.
28. A stable polymeric article resistant to discoloration, cracking and/or crazing upon exposure to UV-C (190-280 nm) light comprising the polymer composition of any one of claims 1-27.
29. The stabilized polymer article of claim 28, wherein at least one of reduced discoloration, cracking or crazing after exposure to UV-C light is associated with the use of the light stabilizer in combination with the antioxidant, as compared to the antioxidant in the absence of the light stabilizer.
30. A method of making the stabilized polymer article of claim 28, the method comprising:
adding to the organic polymeric material a stabilizer composition comprising:
an antioxidant selected from the group consisting of hindered phenols, phosphites and phosphonites and mixtures thereof; and
A light stabilizer selected from the group consisting of Hindered Amine Light Stabilizers (HALS), UV absorbers (UVA), hindered benzoates, and mixtures thereof; and
the organic polymeric material containing the stabilizer composition is formed into the stabilized polymeric article.
31. A method of stabilizing an organic polymeric material against the deleterious effects of UV-C (190-280 nm) light, the method comprising adding to the organic polymeric material a stabilizer composition comprising:
an antioxidant selected from the group consisting of hindered phenols, phosphites and phosphonites and mixtures thereof; and
a light stabilizer selected from the group consisting of Hindered Amine Light Stabilizers (HALS), UV absorbers (UVA), hindered benzoates, and mixtures thereof;
wherein at least one of reduced discoloration or reduced cracking or crazing after exposure to UV-C light is associated with the use of the light stabilizer in combination with the antioxidant, as compared to the antioxidant in the absence of the light stabilizer.
32. The method of claim 31, wherein the total amount of antioxidants is from 0.001% to 5.0% by weight and the total amount of light stabilizers is from 0.01% to 2.0% by weight, both based on the total weight of the polymer composition.
CN202180091292.2A 2020-11-27 2021-11-24 Compositions and methods for protecting organic polymeric materials from the deleterious effects of UV-C light exposure Pending CN116745353A (en)

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