TWI408165B - Stabiliser composition for halide-containing polymers - Google Patents

Description

Stabilizer composition containing a halide polymer

The present invention relates to a stabilizer composition for a halide-containing polymer, such as a chlorine-containing polymer.

Halide-containing polymers, such as chlorine-containing polymers such as polyvinyl chloride (PVC), are not thermally stable. PVC is one of the commercially available and very important bulk thermoplastics. In the market, PVC is also one of the heat labile polymers. Therefore, a heat stabilizer is necessary in the process of PVC and the use of its rear end.

Some additives can be used to stabilize PVC, and these PVC stabilizers can be classified into four categories: lead stabilizers; tin stabilizers; mixed metal stabilizers; and organic stabilizers.

A lead stabilizer is a stabilizer having a lead derivative as a main stabilizer, and includes organic salts such as lead trisulfate, lead diphosphite, etc., and lead soaps such as lead stearate, lead laurate, and the like. . Lead stabilizer is currently the most important stabilizer for PVC on the market.

The tin tranquilizer is a stabilizer containing an alkyl-tin thiolate or a carboxylate as a main stabilizer. Tin stabilizers are usually used to stabilize hard PVC.

The mixed metal stabilizer is a composition containing a metal carboxylate such as barium-zinc or calcium-zinc carboxylate. A mixed metal stabilizer containing a calcium-zinc carboxylate is a substitute for a lead stabilizer and/or a tin compound.

The organic stabilizer is an organic compound stabilizer that does not contain a metal as its main stabilizer. Organic stabilizers do not contain lead, calcium, tin, antimony, bismuth, zinc and other heavy metals.

In the market, lead is still the main PVC stabilizer in the world today due to the nature of lead. However, due to the prohibition of the use of lead by environmental regulations, lead stabilizers have gradually been eliminated. Lead-substituents that are less harmful and acceptable for the environment can be divided into two categories, one being a calcium-zinc (Ca/Zn) stabilizer and the other being an organic stabilizer without heavy metals. However, in the PVC process step, the zinc chloride produced when the PVC is stabilized with Ca/Zn stabilizer is a toxic substance.

From the above, it is known to provide a stabilizer to thermally stabilize the chlorine-containing polymer.

Additionally, it would be desirable to provide a stabilizer to overcome or at least ameliorate one or more of the above disadvantages.

Furthermore, it would be desirable to provide an organic stabilizer for a chlorine-containing polymer, such as PVC, which is free of lead, calcium, tin, antimony, bismuth, zinc, and other heavy metals.

According to a first aspect of the present invention, there is provided a stabilizer composition comprising a halide polymer, the composition comprising a compound of the formula (I): Wherein X, Y and Z are each selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an amine group and a functional group having a structure (II), Wherein R ₁ and R ₂ are each independently selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, a phenyl group, a phenylalkyl group, and an aromatic hydrocarbon group, and A is an oxygen atom (O) or a sulfur atom. (S); and the double dashed line above "Expressing a random double bond; and when the above composition is used in combination with a halide-containing polymer, the above composition at least partially inhibits thermal cracking of the halide-containing polymer.

In one embodiment, the halide-containing polymer is a chlorine-containing polymer.

The above composition may further comprise one or more additives selected from the group consisting of polyol compounds, alkali or alkaline earth metal compounds, alkali or alkaline earth metal carboxylic acid compounds, alkali zeolite compounds, fatty acids, hydrotalcite compounds, perchloric acid compounds, A group consisting of a phosphorous acid and a hypophosphorous acid compound, a β-ethanedione compound, a hindered space amine compound, an alkanolamine, a propylene oxide compound, a phenol antioxidant compound, and a combination of one or more thereof.

According to a second aspect of the present invention, there is provided a polymer composition comprising: a halide-containing polymer; and a halide-containing polymer stabilizer composition comprising a compound of the formula (I): Wherein X, Y and Z are each selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an amine group and a functional group having a structure (II), Wherein R ₁ and R ₂ are each independently selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, a phenyl group, a phenylalkyl group, and an aromatic hydrocarbon group, and A is an oxygen atom (O) or a sulfur atom. (S); and the double dashed line above "Expresses a random double bond.

According to a third aspect of the present invention, there is provided a process for the preparation of a stable halide-containing polymer comprising the steps of: mixing a material comprising a halide-containing polymer resin and a stabilizer composition, wherein said stabilizer is comprised The compound includes the compound of the formula (I): Wherein X, Y and Z are each selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an amine group and a functional group having a structure (II), Wherein R ₁ and R ₂ are each independently selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, a phenyl group, a phenylalkyl group, and an aromatic hydrocarbon group, and A is an oxygen atom (O) or a sulfur atom. (S); and the double dashed line above "Expressing a random double bond; and heating the above-described mixed material for a period of time such that the halide-containing resin is at least partially bonded to the stabilizer composition.

According to a fourth aspect of the present invention, there is provided a composition for stabilizing a halide-containing polymer comprising a compound of the formula (I): Wherein X, Y and Z are each selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an amine group and a functional group having a structure (II), Wherein R ₁ and R ₂ are each independently selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, a phenyl group, a phenylalkyl group, and an aromatic hydrocarbon group, and A is an oxygen atom (O) or a sulfur atom. (S); and the double dashed line above "Expresses a random double bond; and a metal perchlorate.

In an embodiment of the second part of the invention, the one or more additives are selected from the group consisting of perchlorinates, hydrotalcites, zeolites, carboxylic acids, hydrocarbons, alkanolamines, and hindered amines.

In one embodiment, it provides a polymer composition comprising: a chlorine-containing polymer; and a stabilizer composition as defined in the first part.

In one embodiment, it provides a polyvinyl chloride resin composition comprising a polyvinyl chloride resin and a stabilizer composition having a heat stable effective level as described in the first part of the present invention.

In one embodiment, there is provided a method of preparing a stable chlorine-containing polymer comprising the steps of: mixing a material comprising a chlorine-containing polymer resin and a stabilizer composition, wherein the stabilizer composition is as described in the first aspect of the present invention Partially defined; and heating the mixed material for a period of time to at least partially bind the polyvinyl chloride-containing resin to the stabilizer composition.

In one embodiment, there is provided a method for stabilizing a chlorine-containing polymer comprising mixing said polymer with a stabilizer composition as defined in the first part of the invention.

In one embodiment, it provides a stabilizer composition as defined in the first part of the invention for stabilizing a chlorine-containing polymer.

definition

The following definitions will be helpful in understanding the description of the invention. The definitions are generally defined and are not intended to limit the scope of the invention, which is intended to provide a better understanding of the invention.

The invention as a whole, a step or an element may be included in the form of a single unit, step or element, unless otherwise required.

Throughout the specification, the word "comprising" is used to interpret a recited step or element or whole, or a set of steps or elements or a whole, and does not exclude other steps or elements or whole or group. Step or component or whole. Therefore, in the context of the present specification, "including" means including in principle, but not necessarily unique.

Here, "alkyl" includes its original monovalent "alkyl" and divalent "alkylene" which have 1 to 10 carbon atoms (for example, 1, 2, 3, 4, 5, 6, 7, 8, A saturated aliphatic group of a straight or branched chain of 9 or 10 carbon atoms. For example, alkyl groups include, but are not limited to, methyl, ethyl, -propyl, isopropyl, -butyl, 2-butyl, isobutyl, tert-butyl, pentyl, 1,2-di Methylpropyl, 1,1-dimethylpropyl, pentyl, isopentyl, hexyl, 4-methylpentyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl Base, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 1,2,2-trimethyl Propyl, 1,1,2-trimethylpropyl, 2-ethylpentyl, 3-ethylpentyl, heptyl, 1-methylhexyl, 2,2-dimethylpentyl, 3 ,3-dimethylpentyl, 4,4-dimethylpentyl, 1,2-dimethylpentyl, 1,3-dimethylpentyl, 1,4-dimethylpentyl, 1 , 2,3-trimethylbutyl, 1,1,2-trimethylbutyl, 1,1,3-trimethylbutyl, 5-methylheptyl, 1-methylheptyl, octyl Base, sulfhydryl, sulfhydryl and the like.

The "low alkyl group" includes an alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms.

"Alkenyl" includes its original monovalent "alkenyl" and divalent "alkenylene" which have 2 to 10 carbon atoms (eg 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbons). An unsaturated fatty hydrocarbon group of a straight or branched chain of an atom, and having at least one double bond in the alkyl chain, and which may be E, Z, cis or trans stereochemistry. Examples of alkenyl groups include, but are not limited to, ethenyl, vinyl, allyl, 1-methylvinyl, 1-propenyl, 2-propenyl, 2-methyl-1- Propylene, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1,3-butadienyl, 1-pentenyl, 2-pentene , 3-pentenyl, 4-pentenyl, 1,3-pentadienyl, 2,4-pentadienyl, 1,4-pentadienyl, 3-methyl-2-butene , 1-hexenyl, 2-hexenyl, 3-hexenyl, 1,3-hexadienyl, 1,4-hexadienyl, 2-methylpentenyl, 1-heptene Base, 2-heptenyl, 3-heptenyl, 1-octenyl, 1-decenyl, 1-decenyl and the like.

The "low alkenyl group" as used herein includes an alkenyl group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms.

As used herein, "alkynyl" includes its original monovalent "alkynyl" and divalent "alkynylene" which are linear or branched unsaturated fatty hydrocarbon groups having 2 to 10 carbon atoms, and There is at least one triple bond on the carbon chain. Examples of alkynyl groups include, but are not limited to, ethynyl, 1-propynyl, 1-butynyl, 2-butenyl, 1-methyl-2-butynyl, 3-methyl-1-butene Alkynyl, 1-pentynyl, 1-hexynyl, methylpentynyl, 1-heptynyl, 2-heptynyl, 1-octynyl, 1-decynyl, 1-decynyl And similar.

The "low alkynyl group" as used herein includes an alkynyl group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms.

As used herein, "cycloalkyl" refers to a cyclic saturated aliphatic group, including the original monovalent "cycloalkyl" and divalent "cycloalkylene" which have from 3 to 10 carbon atoms (eg, 3, 4, A saturated, monocyclic, bicyclic, polycyclic or fused polycyclic hydrocarbon residue of 5, 6, 7, 8, 9 or 10 carbon atoms. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, 2-methylcyclopropyl, cyclobutyl, cyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, cyclohexyl, and analog.

As used herein, "cycloalkenyl" refers to a cyclic unsaturated aliphatic group, including the original monovalent "cycloalkenyl" and divalent "cycloalkenylene" having from 3 to 10 carbon atoms (eg, 3, 4). a monocyclic, bicyclic, polycyclic or fused polycyclic hydrocarbon residue of 5, 6, 7, 8, 9 or 10 carbon atoms, and having at least one double bond in the alkyl chain, and which may be E , Z, cis or trans stereochemistry. Examples of cycloalkenyl groups include, but are not limited to, cyclopropenyl, cyclopentenyl, cyclohexenyl, and the like.

As used herein, "cycloalkynyl" refers to a cyclic unsaturated aliphatic group, including the original monovalent "cycloalkynyl" and divalent "cycloalkynylene" which are monocyclic and bicyclic having 3 to 10 carbon atoms. a polycyclic or fused polycyclic hydrocarbon residue having at least one triple bond on the alkyl chain. Examples of cycloalkynyl groups include, but are not limited to, cyclopentynyl, cyclohexynyl, and the like.

As used herein, "phenyl" refers to a randomly substituted phenyl group.

As used herein, "phenylalkyl" refers to a phenyl group plus a lower alkyl residue including, but not limited to, benzyl, 4-hydroxybenzyl, 4-chlorobenzyl, 1-Naphthylmethyl and the like.

As used herein, "aromatic hydrocarbon group" refers to an optionally substituted monocyclic or polycyclic aromatic group which includes carbon and hydrogen atoms. Examples of suitable aromatic hydrocarbon groups include, but are not limited to, phenyl, tolyl, yl, fluorenyl, fluorenyl, fluorenyl, naphthyl, and benzene-fused carbon rings.

As used herein, "optional substitution" refers to the attachment of an unsaturated or saturated functional group having one or more functional groups selected from the group consisting of alkyl, alkenyl, alkynyl, thioalkyl, Cycloalkyl, cycloalkenyl, isocycloalkyl, halo, carboxy, haloalkyl, haloalkenyl, hydroxy, oxyalkyl, thiooxyalkyl, oxyalkenyl, halooxyalkyl, halooxyalkylene Base, nitrogen group, amino group, nitrogen alkyl group, nitrogen alkenyl group, azaynyl group, nitrogen heterocyclic group, alkylamino group, dialkylamino group, olefinic group, alkynyl group, decyl group, enone group, alkynyl group, fluorenyl group , dinonylamino, decyloxy, alkyl sulfoneoxy, iso-epoxy, isocyclic amino, halocycloalkyl, alkylsulfonyl, alkylcarbonyl, alkylthio, fluorenyl a thio group, a phosphorus-containing group (such as a phosphinylene group and a phosphino group), an aromatic hydrocarbon group, an isoaromatic hydrocarbon group, an alkyl aromatic hydrocarbon group, an alkylisoaromatic hydrocarbon group, a cyano group, a cyanate group, an isocyanate group, a -C ( O) NH(alkyl) and -C(O)N(alkyl) ₂ .

As used herein, "halide" refers to fluorine, chlorine, bromine, and iodine.

As used herein, "halide-containing polymer" refers to a polymeric material that is a solid form at 20 degrees Celsius and which contains a halide as defined above.

As used herein, the term "stabilized halide-containing polymer" or "stabilized polymer" is broadly interpreted to include any chlorine-containing polymer having a stabilizer composition therein.

The broad definition of "inevitable impurities" as used herein is a material that does not contain a chlorine-containing polymer or a stable composition, which may be produced during the manufacture of a stabilizer composition or a stable chlorine-containing polymer material. .

As used herein, "amino" refers to a structure having -NRaRb, wherein Ra and Rb are each selected from, but not limited to, a hydrogen atom, an optionally substituted alkyl group, preferably a randomly substituted lower alkyl group, optionally The substituted alkenyl group is preferably an optionally substituted lower alkenyl group, an optionally substituted alkynyl group, preferably a randomly substituted lower alkynyl group and an optionally substituted aromatic hydrocarbon group.

The invention will be further described in the following examples, which are intended to illustrate the invention, but not to limit the scope claimed by the applicant.

An example of a stabilizer composition for thermally stabilizing a halide-containing polymer such as a chlorine-containing polymer will be described below. Hereinafter, for convenience of explanation, a description will be made by taking "chlorinated polymer" or "chloride-containing polymer" as an example. However, the disclosed compositions can be used in any type of halide-containing polymer.

The disclosed embodiment describes a novel stabilizer composition comprising a compound of the formula (I): Wherein X, Y and Z are each selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an amine group and a functional group having a structure (II), Wherein R ₁ and R ₂ are each independently selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, a phenyl group, a phenylalkyl group, and an aromatic hydrocarbon group, and A is an oxygen atom (O) or a sulfur atom. (S); and the double dashed line therein "Expressing a random double bond. Preferably, the above formula (I) does not have more than three double bonds in its aromatic ring structure.

In one embodiment, the above compound has the structure shown in the general formula (IA):

In another embodiment, the above compound has the structure of formula (IB):

In one embodiment, X, Y, Z, R ₁ and R ₂ are each selected from the group consisting of a lower alkyl group, a lower alkenyl group, and a lower alkynyl group.

This stabilizer composition can be used as a thermal stabilizer to stabilize a chlorine-containing polymer.

The stabilizer composition may include two or more compounds of the formula (I), and the A atoms are linked by a covalent bond. In one embodiment, when one of X, Y, Z is an amino group or has structure (II), two or more compounds of formula (I) are linked by a covalent bond between the nitrogen atoms. together.

The stabilizer composition may comprise two or more compounds of formula (I) and which are linked by a covalent bond.

This stabilizer may include one or more additional compounds. The stabilizer may also contain one or more lubricants.

The stabilizer composition can be combined with a chlorine-containing polymer to form a stable chlorine-containing polymer. The stabilized chlorine-containing polymer may comprise a compound of formula I, and the content of the compound of formula I may be selected from the group consisting of 0.01% to 20%, 0.01% to 16%, 0.1% to 15%, 0.15. Groups consisting of %~10%, 0.2%~8%, 0.2%~6%, and 0.2%~4%.

In one embodiment, the chlorine-containing polymer having a compound of formula I in an amount of from 0.05% to 1% can be extruded into a granule.

In another embodiment, a chlorine-containing polymer having a compound of formula I in an amount of from 0.1% to 3.5% can be injection molded into a molded shape.

The stabilized chlorine-containing polymer may include one or more additives, and the content of the additive is selected from the group consisting of 0.09% to 16%, 0.1% to 15%, 0.15% to 10%, 0.2% to 8%, and 0.2%. Groups of ~6% and 0.2%~4%.

In one embodiment, the chlorine-containing polymer having from 0.1% to 2% of one or more additive compounds can be extruded into a single particle.

In another embodiment, the chlorine-containing polymer having one or more additive compounds in an amount of from 0.3% to 3% can be injection molded into a molded shape.

The stabilized chlorine-containing polymer may include one or more lubricants, and the content of the lubricant is selected from the group consisting of 0.09% to 21%, 0.1% to 20%, 0.15% to 10%, 0.2% to 8%, and 0.3%. A group consisting of ~6% and 0.4%~4%.

In one embodiment, the chlorine-containing polymer having a lubricant content of from 0.5% to 2% can be extruded into a pellet.

In another embodiment, the chlorine-containing polymer having one or more lubricants in an amount of from 0.8% to 3% can be injection molded into a molded shape.

Amino-substituted pyrimidine compound

The amino-substituted pyrimidine compound may be an amino-substituted hydroxy-pyrimidine or an amino-substituted thiol-pyrimidine.

The amino-substituted pyrimidine compound may be selected from the group consisting of 2-amino-6-hydroxypyrimidine, 2-amino-6-hydrothiopyrimidine, 2-N-methylamino-6-hydroxypyrimidine, 2 -N-2-propylamino-6-hydroxypyrimidine, 4-amino-6-hydroxypyrimidine, 4-amino-6-hydrothiopyrimidine, 4-N-phenylamino-6-hydroxypyrimidine, 4-methyl Amino-6-hydroxypyrimidine, 4-octylmethylamino-6-hydroxypyrimidine, 5-amino-6-hydroxypyrimidine, 5-amino-6-hydrothiopyrimidine, 5-N-butylamino-6-hydroxypyrimidine , 5-N-methylamino-6-hydrothiopyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4-diamino-6-hydrothiopyrimidine, 2,4-N,N' -Dimethyldiamino-6-hydroxypyrimidine, 4,5-diamino-6-hydroxypyrimidine, 4,5-diamino-6-hydrothiopyrimidine, 4,5-N,N'-dipropyl Diamino-6-hydroxypyrimidine, 4-N-methylamino-5-N-octylamino-6-hydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,6-diamino-6- Hydroxypyrimidine, 2,6-diamino-6-hydrogen Thiopyrimidine, 2,6-N,N'-dibutyldiamino-6-hydroxypyrimidine, 2,4,5-triamino-6-hydroxypyrimidine, 2,4,5-triamino-6-hydrogen Thiopyrimidine, 2-N-methylamino-4-N-butylamino-5-N-phenylamino-6-hydroxypyrimidine, and combinations of one or more thereof.

Additive compound

The stabilizer compound is more bitter and comprises one or more additives selected from the group consisting of polyhydric alcohols, alkali or alkaline earth metal compounds, alkali or alkaline earth metal carboxylic acid compounds, alkali zeolite compounds, fatty acids, hydrotalcite compounds, perchloric acid compounds, sub- A group consisting of phosphoric acid and a hypophosphorous acid compound, a β-ethylenedione compound, a hindered space amine compound, an alkanolamine, a propylene oxide compound, a phenol antioxidant compound, and a combination of one or more thereof.

The content of the additive compound in the stabilized chlorine-containing polymer may be a group selected from the group consisting of 0.001% to 15%, 0.01% to 10%, 0.1% to 8%, 0.1% to 6%, and 0.1%. ~5%, 0.1%~4%, 0.1%~3%, 0.1%~2%, 0.1%~0.6%.

Polyol

The polyol may be selected from the group consisting of pentaerythritol, dipentaerythritol, tripentaerythritol, ditrimethylolpropane, ditrimethylolethane, trimethylolpropane, polyvinyl alcohol, sorbitol, mannitol. Alcohol, tetramethylolcyclohexane alcohol, tetramethylol cyclopentanol, tetramethylolcycloalkanol, glycerin, diglycerin, polyglycerol, thiodiglycerol, tris(hydroxyethyl)isotrimer Polycyanate, tris(hydroxypropyl)isocyanate, and combinations of one or more thereof.

Alkaline or alkaline earth metal compound

The alkali or alkaline earth metal compound may be selected from the group consisting of oxides, hydroxides, sulfides, citrates, phosphates, borates, alkali metal or alkaline earth metal carbonates, and the like. Or a combination of multiples.

The alkali metal may be selected from the group consisting of lithium, sodium, potassium, and combinations of one or more thereof.

The alkaline earth metal may be selected from the group consisting of magnesium, calcium, strontium, barium, and combinations of one or more thereof.

The alkali or alkaline earth metal compound may be a basic alkali or alkaline earth metal, which may be selected from the group consisting of calcium hydroxide, magnesium hydroxide, lithium hydroxide, sodium borate, sodium citrate and one or more thereof. combination.

Alkaline or alkaline earth metal carboxylic acid compound

The alkali or alkaline earth metal carboxylic acid compound may be selected from the group consisting of sodium palmitate, potassium palmitate, magnesium palmitate, sodium hydroxystearate, calcium hydroxystearate, magnesium hydroxystearate. , sodium stearate, lithium stearate, potassium stearate, magnesium stearate, calcium stearate, sodium acetate, potassium acetate, lithium acetate, sodium propionate, potassium propionate, sodium butyrate, malonic acid Sodium, sodium adipate, sodium benzoate, and combinations of one or more thereof.

Alkali zeolite compound

The alkali zeolite compound may be selected from the group consisting of sodium aluminosilicate, potassium aluminosilicate, lithium aluminosilicate, and combinations of one or more thereof.

fatty acid

What can be used is an aliphatic carboxylic acid having at least one carboxyl group in the molecule. Examples of carboxylic acids are glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, di- or tri-linolenic acid, acrylic acid, and methacrylic acid, caproic acid, caprylic acid, and laurel. Acid, myristic acid, palmitic acid, stearic acid, citric acid, behenic acid, oleic acid, etc., and any salt of the above fatty acids.

Hydrotalcite compound

Any hydrotalcite compound can be used. Examples of hydrotalcites include, but are not limited to, Al ₂ O ₃ 6MgO.CO ₂ .12H ₂ O, Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ .3.5H ₂ O, 4MgO.Al ₂ O ₃ .CO ₂ .9H ₂ O, 4MgO.Al ₂ O ₃ .CO ₂ .6H ₂ O, Mg ₆ .Al ₂ (CO ₃ )(OH) ₁₆ .4H ₂ O, Mg _4.5 .Al ₂ (CO ₃ )(OH) ₁₃ .3H ₂ O and its anhydrous form.

Perchloric acid compound

The perchloric acid compound may be selected from compounds having the general formula M(ClO ₄ ) _n , wherein M is a metal selected from Li, Na, K, Mg, Ca, Sr, Zn, Al, La or Ce, and n Is 1, 2 or 3.

The perchloric acid compound may be complexed with an alcohol (polyol, cyclodextrin), an ether alcohol or an ester alcohol. Ester alcohols also include partial esters of polyols. Of course, the polyols used herein are di-, tri-, oligo, polymers such as di-, tri-, tetra-, and poly-ethylene glycols and di-, tri-, and tetra-pentaerythritol or various Polymer grade grade of polyvinyl alcohol.

The perchloric acid compound may be in various forms, such as in the form of a salt or in the form of an aqueous solution applied to a substrate, such as PVC, calcium silicate, zeolite or hydrotalcite or by chemical reaction with water. Talc combined.

Phosphorous acid and hypophosphorous acid compounds

The phosphorous acid may be selected from the group consisting of triphenylphosphite, diphenylalkylphosphite, phenyldialkylphosphite, tris-(nonylphenyl)phosphoric acid, trilaury Phosphoric acid, trioctylmercaptophosphite, distearyl-pentaerythritol phosphorous acid, tris(2,4,-di-tetra-butylphenyl)phosphoric acid, diisodecyl pentaerythritol phosphorous acid, bis (2, 4,-di-tetra-butylphenyl)pentaerythritol phosphorous acid, bis(2,6,-di-tetra-butyl-4-methylphenyl)pentaerythritol phosphorous acid, bis-isodecyl epoxy-pentaerythritol Phosphorous acid, bis(2,4,-di-tetra-butyl-6-methylphenyl)pentaerythritol phosphorous acid, tris(2,4,6-tri-tetra-butylphenyl)pentaerythritol pyrite, three Stearyl-sorbitol phosphorous acid, bis(2,4,-di-tri-butyl-6-methylphenyl)phosphoric acid, bis(2,4,-di-tri-butyl-6-methyl Phenyl phenyl)ethyl phosphite, phenyl dimercaptophosphite, (2,4,-di-tri-butylphenyl)-di-dodecylphosphite, (2,6,-di- Tri-butylphenyl)-di-dodecylphosphite and a combination of one or more thereof .

The hypophosphorous acid may be selected from the group consisting of sodium hypophosphite, lithium hypophosphite, potassium hypophosphite, magnesium hypophosphite, calcium hypophosphite, zinc hypophosphite, titanium hypophosphite, secondary Vanadium phosphite, molybdenum hypophosphite, manganese hypophosphite, cobalt hypophosphite, amine hypophosphite, butylamine hypophosphite, tetraethylamine hypophosphite, N-hexadecylphosphite, Tetraphenylphosphonium hypophosphite and a combination of one or more thereof.

--ethylenedione compound

The β-ethanedione compound may be selected from the group consisting of benzoic acid methane, octadecyl benzamidine methane, benzamidine 2,4-methylenedioxybenzamide, benzene. Mercapto 3,5-methylenedioxybenzamide, benzhydryl 3-methylbenzhydryl methane, benzhydryl 4-methylbenzhydryl methane, 3-methylbenzhydryl 4-methylbenzhydryl methane, benzhydryl 4-chlorobenzhydryl methane, benzhydryl 2-bromobenzamide methane, benzhydryl 3,5-dichlorobenzamide methane, benzyl Indenyl 2-azabenzamide, benzhydryl 2,3,4-trimethylbenzhydryl methane, benzamidine 2,3,5-trichlorobenzamide methane, benzhydrazinyl Octanemethyl methane, 3-methylbenzhydryl octadecyl methane, 3,4-dichlorobenzhydryl octadecyl methane, benzamidine heptadecyl methane, 3-methyl benzoyl Mercaptotetramethane, 2-methylbenzhydryl-laurel, methane, 3-azabenzyl-myristyl methane, 2,3-ethoxybenzimidylhexadecanyl methane, 2- Methyl benzhydrazinyl octadecyl methane and combinations of one or more thereof.

Hindering space amine compounds

The hindered space amine compound may be selected from the group consisting of bis(2,2,6,6-tetramethyl-4-pyridine)sebacate, bis(2,2,6,6-tetramethyl) 4-pyridine) succinate, bis(1,2,2,6,6-pentamethyl-4-pyridine)sebacate, bis(1-octyl-2,2,6,6-tetra Methyl 4-pyridine) sebacate, bis(1,2,2,6,6-pentamethyl 4-pyridyl)n-butyl-3,5-di-tetra-butyl-4-hydroxybenzene Concentrate of propylmalonate, 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypyridine and succinic acid, N,N'-bis (2,2 , 6,6-tetramethyl-4-pyridine)hexamethylenediamine and 4-tetra-octyl-amino-2,6-dichloro-1,3,5-trinitrogen concentrate, three ( 2,2,6,6-tetramethyl-4-pyridine)-1,2,3,4-butane tetracarboxylate, 1,1'-(1,2-ethanediyl)-bis-(3, 3,5,5-tetramethylpiperazinone), 4-benzylidene-2,2,6,6-tetramethylpyridine, 4-octadecylalkyl-2,2,6,6-tetramethyl Alkyl, bis(1,2,2,6,6-pentamethylpyridine)-2-n-butyl-2-(2-hydroxy-3,5-di-tetra-butylphenyl)propane Acid, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-three azasp Iro[4.5]undecane-2,4-dione, bis(1-octyloxy-2,2,6,6-tetramethylpyridine)sebacic acid, bis(1-octyloxy-2, 2,6,6-tetramethylpyridine)succinic acid, N,N'-bis(2,2,6,6-tetramethyl-4-pyridine)hexamethylenediamine and 4-end-2 , a concentrate of 6-dichloro-1,3,5-trinitrogen, 2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethyl-4- Concentrate of pyridine)-1,3,5-triazo and 1,2-bis(3-aminopropylamino)ethane, 2-chloro-4,6-bis(4-n-butylamino-1 , 2,2,6,6-pentamethylpyridine)-1,3,5-triazo and 1,2-bis(3-aminopropylamino)ethane concentrate, 8-acetic acid thiol-3 -dodecyl-7,7,9,9-trimethyl-1,3,8-triazaspiro[4.5]undecane-2,4-dione, 3-dodecyl-(2, 2,6,6-tetramethyl-4-pyridine)pyrrolidine-2,5-dione, 3-dodecyl-1-(1,2,2,6,6-pentamethyl-4- Mixture of pyridinium-2,5-dione, 4-hexadecene oxide and 4-octadecane-2,2,6,6-tetramethylpyridine, N,N'-double ( 2,2,6,6-tetramethyl-4-pyridine)hexamethylenediamine and 4-cyclohexaneamino-2 , a concentrate of 6-dichloro-1,3,5-trinitrogen, 1,2-bis(3-aminopropylamino)ethane, and 2,4,6-trichloro-1,3,5-three A concentrated product of nitrogen and 4-butylamino-2,2,6,6-tetramethylpyridine, N-(2,2,6,6-tetramethyl-4-pyridine)-n-dodecyl Butanediamine, N-(1,2,2,6,6-pentamethyl-4-pyridine)-n-dodecylbutanediamine, 2-undecyl-7,7,9 , 9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4.5]decane and a combination of one or more thereof.

Alkanolamine

The alkanolamine may be selected from the group consisting of ethanolamine, triethanolamine, propanolamine, tri-propanolamine, butanolamine, tris(2-hydroxy-1-propyl)amine, tris(2) -hydroxy-ethyl)amine, bis(2-hydroxy-1-propyl)(2-hydroxyethyl)amine, mono(2-hydroxy-ethyl)amine, bis(2-hydroxy-ethyl)amine, Mono(2-hydroxy-propyl)amine, bis(2-hydroxy-propyl)amine.

Propylene oxide compound

The propylene oxide compound may be selected from the group consisting of liquid bisphenol-A-propylene oxide, solid bisphenol-A-propylene oxide, liquid bisphenol-F-propylene oxide, tetraphenyl Solid polyoxypropylene ether of ethane, solid and liquid polyoxypropylene ether of phenol/formaldehyde phenolic resin, solid and liquid polyoxypropylene ether of o-cresol/formaldehyde phenolic resin, liquid oxypropylene ether of alcohol, carboxylic acid Liquid oxypropylene ether, solid heterocyclic epoxy resin (tripropylene oxide isocyanuric acid), liquid cycloaliphatic epoxy resin, liquid N, N, O-tris oxide ether, tetra-oxidation of p-aminophenol Propylene-4,4'-methyleneaniline or N,N,N',N'-tetrapropenyl-diamino-phenylmethane.

Phenolic antioxidant compound

The phenolic antioxidant compound may be selected from the group consisting of 2,2-bis(4-hydroxyphenyl)propane, 3,5-di-tri-4-hydroxyphenylpropionic acid and stearyl alcohol or pentaerythritol. Esters, tris(2,4-di-tri-butylphenyl)phosphite, tetrakis[methylidene-3-(3',5'-di-tributyl-4-hydroxyphenyl)propane Acid]methane, octadecyl 3-(3',5'-di-tributyl-4-hydroxyphenyl)propionate, octadecyl 3,5-di-tributyl-4-hydroxyl Hydrogenated cinnamate, di-n-octadecyl 3,5-di-tributyl-4-hydroxybenzyl phosphate, tris-2,4,6-(3,5-di-tributyl) 4-hydroxybenzyl)isomeric cyanurate and combinations of one or more thereof.

And can be used commercially available phenolic antioxidant can be obtained from Great Lakes Chemical Corporation of Indianapolis, Indiana USA, under the trade name Anox ^TM and Lowinox ^TM.

Lubricant

The lubricant may be selected from the group consisting of glycerol monooleate, glyceryl monostearate, glyceryl dioleate, glyceryl monostearate, fat having a C ₁₆ to C ₁₈ chain length. An alcohol, a phthalic acid ester of a fatty alcohol having a C ₁₆ to C ₁₈ chain length, a hydrogenated kumquat oil (for example, a glyceride of 12-hydroxystearic acid), an ester of a polyhydric alcohol and a short-chain monocarboxylic acid (for example) Glyceryl monostearate), ethylene glycol dilaurate, 2-ethylhexanediol-1,3-distearate, ethylene glycol di-2-ethylhexanoate, Octene glycol dioctanoate, ester of dicarboxylic acid with short chain monohydroxy-alcohol (eg diisooctyl stearate), dilaurate stearate, oxidized polyethylene wax, polyethylene Wax, paraffin, carboxylic acid (such as stearic acid, 12-hydroxystearic acid and octadecanoic acid), carboxylic acid (such as calcium stearate, magnesium stearate, sodium stearate), amines (such as ethylene) Bis-stearic acid amine) and one or more combinations thereof.

The content of the lubricant in the stabilized halide-containing polymer is selected from the group consisting of 0.01% to 2%, 0.05% to 1.8%, 0.1% to 1.5%, 0.15% to 1.45%, 0.2%. 1.4%, 0.5%~1.35%, 1%~1.3%, 1.1%~1.3%, 1.2%~1.3%, 1.25%~1.28%.

Chlorinated polymer

The chlorine-containing polymer may be stabilized by the disclosed stabilizer composition, which may be selected from the group consisting of chlorinated polyolefin resins, chlorinated polyolefin resin copolymers, and chlorinated polyolefin resins. Polymer mixture of homopolymer or copolymer, homopolymer of vinyl chloride, homopolymer of vinylidene chloride, copolymer of vinyl chloride, copolymer of vinylidene chloride, same with vinyl chloride A polymer mixture of a metapolymer or a copolymer and one or more combinations thereof.

The polymer mixture of the homopolymer of vinyl chloride, the copolymer of vinyl chloride, and the homopolymer or copolymer containing vinyl chloride may be selected from the group consisting of polyvinyl chloride, polyvinyl dichloride, a copolymer of vinyl chloride with a copolymerizable and ethylenically unsaturated monomer (for example, dichloroethylene), methyl chloroacrylate, vinyl vinyl chloride, 1-fluoro-1-chloroethylene, chloroacrylonitrile, sub Propylene diacetate, chloropropylene propylene diacetate, a mixture of polymers, such as a mixture of polyvinyl chloride and polyethylene, a mixture of polyvinyl chloride and chlorinated polyethylene, polyvinyl chloride and polymethyl methyl a mixture of acrylic acid, a mixture of polyvinyl chloride and polybutyl methacrylic acid, a mixture of polyvinyl chloride and polystyrene, a mixture of polyvinyl chloride and acrylonitrile-butylene-styrene copolymer, polyvinyl chloride and polyvinylidene, and A mixture of polymethyl methacrylic acid and one or more combinations thereof.

The vinyl chloride copolymer may be selected from the group consisting of vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinylvinylidene copolymer, vinyl chloride-trichloroethylene copolymer, and vinyl chloride-2-acetic acid ethylhexyl copolymer. Things.

Preparation of stable chlorine-containing polymer

The stabilizer composition and the chlorine-containing polymer (e.g., polyvinyl chloride (PVC)) are mixed in a mixing device to form a homogeneous mixture.

The content of the stabilizer composition in the homogeneous mixture is selected from the group consisting of 0.5% to 10%, 1% to 7.5%, 1.2% to 6%, 1.5% to 5%, and 1.7% to 4.5%. 2%~4%, 2%~3.5%, 2%~3%, 2.3%~2.7%. In one embodiment, the level of the stabilizer composition in the homogeneous mixture is about 2.4%.

The initial stabilizer composition and the chlorine-containing polymer may be in the form of a powder to facilitate subsequent uniform mixing.

The homogeneous mixture can be heated to a predetermined temperature to at least partially bind the stabilizer composition powder to the chlorine-containing polymer powder. The heating temperature can be from 90 ° C to 120 ° C or from 100 ° C to 110 ° C.

The heating time may be selected from the group consisting of: 10 to 1000 minutes, 20 to 800 minutes, 25 to 600 minutes, 30 to 400 minutes, 35 to 300 minutes, 40 to 200 minutes, 45 to 120 minutes, and 50 to 90. minute.

The stabilized chlorine-containing polymer can be cooled to serve as a material for subsequent processes.

In one embodiment, the chlorine-containing polymer may be placed in a press apparatus such as a TWP-110-PVC twin screw extruder manufactured by Foshan Plastic Machinery Co., Ltd. Foshan, Guangdong Province, China. .

In another embodiment, the chlorine-containing polymer may be placed in an injection molding apparatus such as IS-GS/GT manufactured by Toshiba Machine Co., Ltd. Of Numazu-shi, Shizuoka-ken, Japan. Injection molding machine.

Mode for carrying out the invention

Non-limiting examples of the invention are described below.

Organic stabilizer composition

Amino substituted pyrimidine compounds are commercially available from Sigma-Aldrich Company of St. Louis, Missouri, United States of America and include: 2-amino-6-hydroxypyrimidine, 2-amino-6-hydrothiopyrimidine, 2 -N-methylamino-6-hydroxypyrimidine, 2-N-2-propylamino-6-hydroxypyrimidine, 4-amino-6-hydroxypyrimidine, 4-amino-6-hydrothiopyrimidine, 4-N -Phenylamino-6-hydroxypyrimidine, 4-methylamino-6-hydroxypyrimidine, 4-octylmethylamino-6-hydroxypyrimidine, 5-amino-6-hydroxypyrimidine, 5-amino-6-hydrothiopyrimidine , 5-N-butylamino-6-hydroxypyrimidine, 5-N-methylamino-6-hydrothiopyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4-diamino-6- Hydrothiopyrimidine, 2,4-N,N'-dimethyldiamino-6-hydroxypyrimidine, 4,5-diamino-6-hydroxypyrimidine, 4,5-diamino-6-hydrothiopyrimidine , 4,5-N,N'-dipropyldiamino-6-hydroxypyrimidine, 4-N-methylamino-5-N-octylamino-6-hydroxypyrimidine, 2,4-diamino-6 -hydroxypyrimidine, 2,6 Diamino-6-hydroxypyrimidine, 2,6-diamino-6-hydrothiopyrimidine, 2,6-N,N'-dibutyldiamino-6-hydroxypyrimidine, 2,4,5-triamino -6-hydroxypyrimidine, 2,4,5-triamino-6-hydrothiopyrimidine, 2-N-methylamino-4-N-butylamino-5-N-phenylamino-6-hydroxypyrimidine.

Example 1

The stabilizer composition was prepared by agitating the following appropriate amounts of the compound together: 0.3 parts of 2,4-diamino-6-hydroxypyrimidine, taken from ScienceLab.com, Inc. of Kingwood, Texas, USA; 0.2 parts Pentaerythritol is added to a stabilizer, which is taken from US Petrochemical Industries, Inc., of Houston, Texas, USA; 0.45 parts of hydrotalcite added stabilizer, taken from Minerals Technology Inc. of New York, USA; 0.05 parts octadecyl-3,5-di - three - butyl-4-hydroxy cinnamic acid ester hydrogenation stabilizer is added, which is taken from Ciba Specialty Chemicals Corporation of Tarrytown, New York, USA, under the trade name is Irganox 1076 ^TM; 0.1 part oxidized polyethylene wax, taken from Clariant Corporation, of Charlotte, North Carolina, USA; 0.1 part polyethylene wax, taken from Clariant Corporation, of Charlotte, North Carolina, USA; 0.4 parts of stearin Calcium acid, taken from Astro Chemicals, Inc., of Springfield Massachusettes; and 0.4 parts of glyceryl monostearate, taken from Acme-Hardesty of Blue Bell, Pennsylvania, USA.

The stabilizer composition was prepared by mixing the mixture in a mixer at normal temperature and normal pressure for 30 minutes. Thereafter, this stabilizer composition was mixed with 100 parts by weight of a PVC resin, 0.3 parts of CaCO ₃ , 1.2 parts of TiO ₂ and 0.001 parts of a pigment at 105 ° C to prepare a PVC compound (PVC 1A). Further, a comparative PVC (Comparative PVC 1B) having a stabilizer composition and having a Pb stabilizer was prepared, which was mixed at 105 °C.

The composition of PVC 1A and comparative PVC 1B is shown in Table I:

Mechanical treatment of hard granule extrusion of PVC 1A with comparative PVC B to produce 40 mm (diameter) pressurized granules, KMD2-90 extruder manufactured by Krauss-Maffei Process technology AG of Munich, Germany To execute, and its process parameters are as shown in Table II:

The visual effect of PVC 1A and comparative PVC 1 is shown in Figure 1. Figure 1 shows that PVC 1A has a good color which is comparable to PVC 1B containing lead.

As can be seen from the above, the visual effect of the PVC product of the present invention is comparable to that of PVC containing lead as a stabilizer. Therefore, the stabilizer composition used in PVC A can be used as a stabilizer for the replacement of lead.

Product test result

Granular products made from PVA 1A will be tested according to standard methods known in the art, and the test results are listed in Table III:

Example 2

Hard injection molding will be performed herein to demonstrate the effectiveness of comparing the stabilizer composition of the present invention with a commercially available Pb stabilizer. 0.5 parts of 2,4-diamino-6-hydroxypyrimidine, taken from ScienceLab.com, Inc. of Kingwood, Texas, USA, mixed with 0.3 parts of pentaerythritol plus stabilizer, taken from US Petrochemical Industries, Inc., of Houston, Texas, USA; 0.7 part hydrotalcite addition stabilizer, taken from Minerals Technology Inc. of New York, USA; 0.8 part zeolite addition stabilizer, taken from Zeoite Australia Ltd of South Melbourne, Victoria, Australia; and 0.1 part of octadecyl-3,5-di-tri-butyl-4-hydroxyhydrocinnamate added stabilizer, taken from Ciba Specialty Chemicals Corporation of Tarrytown , New York, USA, under the trade name is Irganox 1076 ^TM; 0.3 parts of oxidized polyethylene wax, which is taken from Clariant Corporation, of Charlotte, North Carolina , USA; 1.5 parts of polyethylene wax, which is taken from Clariant Corporation, Of Charlotte, North Carolina, USA; 0.8 parts calcium stearate, taken from Astro Chemicals, Inc., of Springfield Massachusettes.

The heated stabilizer composition is made by stirring the ingredients and contents shown in Table IV:

The composition 2A and the composition 2B were mixed in a stirred tank reactor at a temperature of 105 ° C for 5 minutes under normal pressure to form PVC polymers 2A and 2B, respectively.

The PVC polymers 2A and 2B were subjected to hard injection molding using an injection molding machine (NC-8300) supplied by NISSEI Plastic Industrial Co. Ltd.

Injection molding test

The test results of PVC polymers 2A and 2B are listed in the following Table V:

It can be seen from Table V that the mechanical stability properties of PVC 2A and PVC 2B are similar. Therefore, the stabilizer composition of PVC 2A can directly replace the lead stabilizer which is commercially available for PVC.

Example 3

Part A: Experimental Procedure Roller Milling The ingredients shown in Table VI of Part B were thoroughly mixed at room temperature to form a powder mixture. This mixture was then milled in a pair of roller mills at 180 ° C for 5 minutes to form a PVC milled sheet.

The abrasive sheets formed by the Congo red test procedure will be cut into small pieces, and these small pieces will be placed in the test tube, and the opening of the test tube will be plugged with cotton. Thereafter, a piece of Congo red test paper (Whatman PLC, United Kingdom) was inserted into the test tube via cotton. Thereafter, the test tube containing the sample will be immersed in an oil bath and heated to 190 °C.

The time from when the test tube is inserted to when the color of the bottom of the Congo red test strip becomes a distinct blue color will be recorded. The recorded time is hereafter referred to as Congo Red Time. In general, the longer the Congo red time, the better the thermal stability of the PVC stabilizer composition for PVC samples.

The mixing of Table VI of the Dynamic Color Test Step B section should not be thoroughly mixed to form a powder mixture. Next, the machine Brabender ^TM Plasticorder (Brabender GmbHund Co.KG, Germany) on a compound of this mixture was pressed into a wafer fusion. After that, the color of the fused wafer is called "dynamic color", which indicates the color retention effect of the PVC sample stabilized by the special PVC thermal stabilizer.

Part B

Part C

As can be seen from Table VII, for the comparative stabilizer composition containing DAHP, the thermal stability effect can be remarkably improved by additionally adding a small amount of sodium perchlorate (metal perchlorate).

Example 4

Part A: The ingredients in Table VIII of Part B of the experiment will be subjected to the “roller grinding”, “dynamic color test” and “Congo red test” as described in Experiment 3 above. The heating temperature is 200 except for the Congo red test. °C.

Part B: Formula

Part C: Results

For the comparative stabilizer composition containing DAHP and sodium perchlorate, the color retention effect can be remarkably enhanced by additionally adding triethanolamine (alkyl alcohol amine).

Example 5

Part A: The ingredients in Table X of Part B of the experiment will be subjected to the "roller grinding", "dynamic color test" and "Congo red test" as described in Experiment 3 above. The heating temperature is 200 except for the Congo red test. °C.

Part B: Formula

Part C: Results ^* Dynamic color indication: 1- Excellent; 2-Good; 3-Fair; 4-Inferior; 5--Very poor Table XI

For the comparative stabilizer composition containing DAHP and sodium perchlorate, the color retention effect can be remarkably enhanced by additionally adding THEIC (polyol) and TNPP (phosphite).

Example 6

Part A: The components in Table VXII of Part B of the experiment will be subjected to "Roller Milling", "Dynamic Color Test" and "Congo Red Test" as described in Experiment 3 above.

Part B: Formula

Part C: Results ^* Dynamic color indication: 1- Excellent; 2-Good; 3-Fair; 4-Inferior; 5--Very poor Table XI

For the comparative stabilizer composition containing DAHP and sodium perchlorate, the color retention effect and the longer-term stability effect can be remarkably improved by additionally adding sodium acetate (metal carboxylate).

Example 7

Part A: The components in Table VXIV of Part B of the experiment will be subjected to "Roller Milling", "Dynamic Color Test" and "Congo Red Test" as described in Experiment 3 above.

Part B: Formula

Part C: Results

For the comparative stabilizer composition containing DAHP and sodium perchlorate, the color retention effect can be remarkably improved by additionally adding a trace amount of HTMPD (space-blocking amine).

The stabilizer composition disclosed above can be used as a stabilizer to stabilize a halide-containing polymer (e.g., polyvinyl chloride). Advantageously, the stabilizer composition at least partially inhibits the thermal entanglement of the polymer when the stabilizer is mixed with a halogen-containing polymer.

The stabilizer compositions disclosed above do not contain metals such as lead, cadmium, tin, antimony, bismuth, and zinc.

The stabilizer compositions disclosed above can be used in place of lead stabilizers, tin stabilizers, mixed metal stabilizers, and known organic stabilizers.

While the present invention has been described in its preferred embodiments, the present invention is not intended to limit the invention, and the present invention may be modified and modified without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application.

Figure 1 is a picture of a chlorine-containing polymer (PVC 1A) with a stable composition and a lead-containing chlorine polymer (compared PVC 1B) with lead.

Claims (41)

A stabilizer composition containing a halide polymer, the composition comprising a compound of the formula (I): Wherein X, Y and Z are each selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an amine group and a functional group having a structure (II), Wherein R ₁ and R ₂ are each independently selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, a phenyl group, a phenylalkyl group, and an aromatic hydrocarbon group, and A is an oxygen atom (O) or a sulfur atom. (S); and the double dashed line therein "" indicates a random double bond; and when the composition is used in combination with the halide-containing polymer, the composition at least partially inhibits thermal cracking of the halide-containing polymer. The stabilizer composition of the halide-containing polymer according to claim 1, further comprising one or more additives selected from the group consisting of a polyol compound, an alkali or alkaline earth metal compound, an alkali or alkaline earth metal carboxylic acid compound. , alkali zeolite compound, fatty acid, hydrotalcite compound, perchloric acid compound, phosphorous acid and hypophosphorous acid compound, β-ethanedione compound, hindered space amine compound, alkanolamine, propylene oxide compound, phenol antioxidant compound and A group of one or more combinations. The stabilizer composition containing a halide polymer as described in claim 1 further includes a lubricant. The stabilizer composition containing a halide polymer according to claim 3, wherein the lubricant is selected from the group consisting of glycerol monooleate, glyceryl monostearate, glyceryl dioleate, and single hard. glyceryl fatty acid having C ₁₆ to C ₁₈ long chain fatty alcohols having C ₁₆ to C ₁₈ chain length of the fatty alcohol phthalate, Queensland hydrogenated linseed oil, esters of polyhydric alcohols, monocarboxylic acids, Ethylene glycol dilaurate, 2-ethylhexanediol-1,3-distearate, ethylene glycol di-2-ethylhexanoate, octene glycol dioctanoic acid Esters, esters of dicarboxylic acids having short chain monohydroxy-alcohols, polyethylene wax, paraffin wax, carboxylic acid, stearic acid, calcium carboxylic acid stearate, magnesium stearate, sodium stearate, amines and a group consisting of one or more combinations thereof. A stabilizer composition containing a halide polymer as described in claim 1, wherein the two or more compounds of the formula (I) are linked together by a covalent bond. The stabilizer composition containing a halide polymer according to claim 5, wherein the A atoms of the two or more compounds of the formula (I) are linked by a covalent bond. The stabilizer composition containing a halide polymer according to claim 5, wherein the nitrogen atoms of X, Y or Z of the two or more compounds of the formula (I) are covalently bonded. A stabilizer composition containing a halide polymer as described in claim 1, wherein the compound of the formula (I) is an amino-substituted hydroxy-pyrimidine compound. A stabilizer composition containing a halide polymer as described in claim 8 wherein the compound of formula (I) is diamino-hydroxyuracil. The stabilizer composition containing a halide polymer according to claim 9, wherein the compound of the formula (I) is 2,4-diamino-6-hydroxyoxypyrimidine. A stabilizer composition containing a halide polymer as described in claim 1, wherein X, Y, Z, R ₁ and R ₂ are each selected from the group consisting of a lower alkyl group, a lower alkenyl group and a lower alkynyl group. A stabilizer composition containing a halide polymer as described in claim 1, wherein the halide-containing polymerization is a chlorine-containing polymer. The stabilizer composition containing a halide polymer according to claim 1, wherein the compound has a structure represented by the formula (IA): The stabilizer composition containing a halide polymer according to claim 1, wherein the compound has a structure represented by the formula (IB): A polymer composition comprising: a halide-containing polymer; and a stabilizer composition comprising a compound of the formula (I): Wherein X, Y and Z are each selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an amine group and a functional group having a structure (II), Wherein R ₁ and R ₂ are each independently selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, a phenyl group, a phenylalkyl group, and an aromatic hydrocarbon group, and A is an oxygen atom (O) or a sulfur atom. (S); where the double dashed line" "Expresses a random double bond. The polymer composition of claim 15, wherein the compound of the formula (I) is contained in the polymer composition in an amount of from 0.01% to 20% by weight. The polymer composition of claim 15, wherein the compound of the formula (I) is present in the polymer composition in an amount of from 0.05% to 1% by weight. The polymer composition of claim 15, wherein the stabilizer composition comprises one or more additives selected from the group consisting of a polyol compound, an alkali or alkaline earth metal compound, an alkali or alkaline earth metal carboxylic acid compound, and a base. a zeolite compound, a fatty acid, a hydrotalcite compound, a perchloric acid compound, a phosphorous acid and a hypophosphorous acid compound, a β-ethylenedione compound, a hindered space amine compound, an alkanolamine, a propylene oxide compound, a phenol antioxidant compound, and one or A group of multiple combinations. The polymer composition of claim 18, wherein the additive is present in the polymer composition in an amount between 0.1% and 15% by weight. The polymer composition of claim 18, wherein the stabilizer composition comprises one or more lubricants. The polymer composition of claim 20, wherein the lubricant is present in the polymer composition in an amount between 0.1% and 20% by weight. The polymer composition of claim 18, wherein the halide-containing polymer is a chlorine-containing polymer. The polymer composition of claim 22, wherein the chlorine-containing polymer is polyvinyl chloride. The polymer composition of claim 15, wherein the compound has the structure represented by the formula (IA): The polymer composition of claim 15, wherein the compound has the structure represented by the formula (IB): A polyvinyl chloride resin composition comprising a polyvinyl chloride resin and a composition as claimed in claim 1, wherein the composition has a heat stable effective content. A method of preparing a stable halide-containing polymer, comprising the steps of: mixing a material comprising a halide-containing polymer resin and a stabilizer composition, wherein the stabilizer composition is as described in claim 1 And heating the mixed material for a period of time to at least partially bind the halide-containing resin to the stabilizer composition. A method for stabilizing a halide-containing polymer comprising mixing the polymer with a compound of formula (I): Wherein X, Y and Z are each selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an amine group and a functional group having a structure (II), Wherein R ₁ and R ₂ are each independently selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, a phenyl group, a phenylalkyl group, and an aromatic hydrocarbon group, and A is an oxygen atom (O) or a sulfur atom. (S); and the double dashed line above "Expresses a random double bond. A stabilizer composition containing a halide polymer as described in claim 1 for use in stabilizing a chlorine-containing polymer. A stable chlorine-containing polymer produced by the method of claim 28 of the patent application. A composition for stabilizing a halide-containing polymer comprising a compound of the formula (I): Wherein X, Y and Z are each selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an amine group and a functional group having a structure (II), Wherein R ₁ and R ₂ are each independently selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, a phenyl group, a phenylalkyl group, and an aromatic hydrocarbon group, and A is an oxygen atom (O) or a sulfur atom. (S); and the double dashed line above "Expresses a random double bond; and a metal perchlorate. A composition for stabilizing a halide-containing polymer as described in claim 31 of the patent application, further comprising a monoalkanolamine. The composition for stabilizing a halide-containing polymer according to claim 31, wherein the metal perchlorate has the formula: M(ClO ₄ ) _n M is a metal selected from Li, Na, K, Mg, Ca, Sr, Zn, Al, La or Ce, and n is 1, 2 or 3. The composition for stabilizing a halide-containing polymer according to claim 31, wherein the metal perchlorate is at least one of sodium perchlorate and potassium perchlorate. The composition for calming a halide-containing polymer as described in claim 32, wherein the alkanolamine is selected from the group consisting of ethanolamine, triethanolamine, propanolamine, tripropanolamine, butanolamine, Tris(2-hydroxy-1-propyl)amine, bis(2-hydroxyethyl)(2-hydroxy-1-propyl)amine, bis(2-hydroxy-1-ethyl)(2-hydroxypropyl) a group consisting of an amine, bis(2-hydroxy-ethyl)amine, mono(2-hydroxy-1-propyl)amine, bis(2-hydroxy-1-propyl)amine, and mixtures thereof. A composition for stabilizing a halide-containing polymer as described in claim 31, wherein the compound has a structure represented by the formula (IA): A composition for stabilizing a halide-containing polymer as described in claim 31, wherein the compound has a structure represented by the formula (IB): A composition for stabilizing a halide-containing polymer as described in claim 31 or 32, further comprising a polyol. A composition for stabilizing a halide-containing polymer as described in claim 31 or 32, further comprising a metal carboxylic acid. A composition for stabilizing a halide-containing polymer as described in claim 31 or 32, which further comprises a hindered space amine. A composition for stabilizing a halide-containing polymer comprising a compound of the formula (I): Wherein X, Y and Z are each selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an amine group and a functional group having a structure (II), Wherein R ₁ and R ₂ are each independently selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, a phenyl group, a phenylalkyl group, and an aromatic hydrocarbon group, and A is an oxygen atom (O) or a sulfur atom. (S); and the double dashed line above ” denotes a random double bond; and one or more additives selected from the group consisting of polyol compounds, alkali or alkaline earth metal compounds, alkali or alkaline earth metal carboxylic acid compounds, alkali zeolite compounds, fatty acids, hydrotalcite compounds, perchloric acid A group consisting of a compound, a phosphorous acid and a hypophosphorous acid compound, a β-ethanedione compound, a hindered space amine compound, an alkanolamine, a propylene oxide compound, a phenol antioxidant compound, and a combination of one or more thereof.