CN111704774A - Nano-emulsion calcium-zinc stabilizer for PVC (polyvinyl chloride) products and preparation method thereof - Google Patents
Nano-emulsion calcium-zinc stabilizer for PVC (polyvinyl chloride) products and preparation method thereof Download PDFInfo
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- CN111704774A CN111704774A CN202010452577.1A CN202010452577A CN111704774A CN 111704774 A CN111704774 A CN 111704774A CN 202010452577 A CN202010452577 A CN 202010452577A CN 111704774 A CN111704774 A CN 111704774A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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Abstract
The invention discloses a nano-emulsion calcium-zinc stabilizer for PVC (polyvinyl chloride) products, which is prepared from the following raw materials in parts by weight: powder calcium-zinc composite stabilizer: 30-40 parts of liquid calcium-zinc composite stabilizer: 20-30 parts of an emulsifier: 30-40 parts of an auxiliary agent: 10-20 parts; the powder calcium-zinc composite stabilizer comprises: 30-60 parts of a main stabilizer, 10-40 parts of an auxiliary stabilizer, 5-35 parts of an antioxidant, 0.1-2 parts of an ultraviolet absorber, 0.2-1 part of a light stabilizer and 1-15 parts of a lubricant; the nano emulsion calcium zinc stabilizer solves the problems that a single liquid stabilizer has poor lubricity, can reduce the softening point of a product and can deteriorate after long-term storage, a single powder stabilizer has poor compatibility, is easy to precipitate frosting, is easy to absorb moisture, has poor dispersibility, is easy to generate white spots and scratches and the like, solves the problems of fusion and dispersibility of the powder stabilizer and the liquid stabilizer during production, ensures that the product performance is more beneficial, and the surface of a prepared finished product is smoother.
Description
Technical Field
The invention relates to the technical field of PVC heat stabilizers, in particular to a nano-emulsion calcium-zinc stabilizer for PVC products and a preparation method thereof.
Background
Polyvinyl chloride (PVC) is one of five general-purpose plastics, and is widely applied in various fields due to the characteristics of excellent comprehensive performance, low price and the like, and the dosage of the PVC is second to that of polyethylene. However, since PVC has poor thermal stability, a proper amount of thermal stabilizer must be added during the processing to inhibit the degradation of PVC. Currently, the commonly used stabilizers can be roughly classified into lead salts, metallic soaps, organotin stabilizers, rare earth stabilizers, and the like. Under the main melody of global environmental protection, lead salt heat stabilizers with higher toxicity are gradually quitting the market, organic tin heat stabilizers with superior performance are expensive and difficult to popularize, and calcium zinc stabilizers have the advantages of being non-toxic, safe, low in price and the like, so that a wider development space is embodied.
The calcium-zinc stabilizer is prepared by adopting a corresponding composite process by taking calcium salt, zinc salt, a lubricant, an antioxidant and the like as main components, the calcium-zinc stabilizer is generally divided into a powder calcium-zinc stabilizer and a liquid calcium-zinc stabilizer, the liquid calcium-zinc stabilizer has good compatibility with resin and a plasticizer, good transparency and difficult precipitation, but the liquid calcium-zinc stabilizer has poor lubricity, can reduce the softening point of a product and can deteriorate after long-term storage; the solid calcium zinc stabilizer can be divided into powder according to the appearance form, and is characterized by good lubricity, no reduction of the softening point of a PVC hard product, poor compatibility, precipitation of blooming, easy moisture absorption, poor dispersibility, easy occurrence of white points, scratches and the like, and influence on the quality of a PVC product. In order to solve the problems, a nano-emulsion calcium-zinc stabilizer for PVC products is provided.
Disclosure of Invention
The invention aims to solve the defects in the prior art, and provides a nano-emulsion calcium-zinc stabilizer for PVC products and a preparation method thereof.
In order to achieve the purpose, the invention provides the following technical scheme: a nano-emulsion calcium-zinc stabilizer for PVC products,
the powder calcium-zinc composite stabilizer comprises: 30-60 parts of a main stabilizer, 10-40 parts of an auxiliary stabilizer, 5-35 parts of an antioxidant, 0.1-2 parts of an ultraviolet absorber, 0.2-1 part of a light stabilizer and 1-15 parts of a lubricant.
The main stabilizer is calcium stearate, zinc stearate and magnesium stearate, and the mass ratio of the main stabilizer to the main stabilizer is (5-3): (2-1): (1.5-1) the compounded main stabilizer, zinc stearate has the functions of replacing active chlorine and absorbing hydrogen chloride, and the generated metal chloride is Lewis acid and can promote dehydrochlorination reaction. PVC can be maliciously degraded in a short time to cause the phenomenon of 'zinc burning', calcium stearate and magnesium stearate are selected as stearic acid soap synergistic stabilizers to be compounded with zinc soap, the stearic acid soap synergistic stabilizers only have the function of capturing hydrogen chloride and can not replace active chlorine, the generated metal chloride has no catalytic action on dehydrochlorination reaction but can effectively replace chloride generated by the zinc soap, and the derivatives of calcium and magnesium complex ZnCl2Therefore, the HCl removal capability of PVC is reduced to regenerate the PVC.
The auxiliary stabilizer is 4A zeolite, hydrotalcite, stearoylbenzoylmethane, dibenzoylmethane, mosaic and polyhydric alcohol, and the mass ratio of the auxiliary stabilizer to the polyhydric alcohol is (4-8): (2-3): (1-3): (0.5-1.5): (1-2): (2-5) compounding an auxiliary stabilizer.
The 4A zeolite is porous aluminosilicate mineral containing water, alkali metal or alkaline earth metal, and has alkaline group attached to surfaceThe clusters can quickly neutralize part of HCL generated by PVC degradation, and slow down PVC structural decomposition. The unique pore structure of the active aluminosilicate can effectively restrict HCL generated by degradation; the hydrotalcite is a crystal with a layered structure, H2O and CO2 with ion exchange function exist between layers, and when HCl released in the PVC thermal degradation process is encountered, Cl and CO2 are rapidly replaced, so that the concentration of free HCl in the system is greatly reduced; the hydroxyl groups of the polyol may be reacted with Zn2+The metal ions form colorless and stable ligands, so that the catalytic acceleration effect of the metal ions on the thermal degradation of PVC is passivated, the formation of colored ligands matched by the metal ions and the polyene structure of PVC is prevented, and the stabilizing effect is achieved; the methine sandwiched between two carbonyl groups in the molecule of stearoylbenzoylmethane has quite high activity and is easy to lose protons, so that allyl chloride can be replaced by a carbon alkylation reaction to form a firm carbon-carbon structure, thereby stopping the growth of a conjugated chain caused by HCl removal and achieving a stable effect; the dibenzoyl methane has high transmittance, can greatly improve the initial coloring, transparency and long-term stability of PVC, and is characterized in that the calcium-zinc soap has good synergistic effect, can effectively inhibit 'zinc burning', the dibenzoyl methane can absorb ultraviolet light with the wavelength of more than 290nm, and has light stabilizing effect, thereby providing long-term stability for PVC products; the hydroxyl value of the selected cyazote is 640 +/-10 (KOHmg/g), the acid value is less than or equal to 1.0(KOHmg/g), the pH value is 6.5-7.3, the turbidity is less than or equal to 1.0PPM, the water content is less than or equal to 0.2%, the heat resistance and the mechanical property of the product can be improved, no adverse side effect exists between the cyazote and the product, the cyazote and the product can be complemented greatly after being compounded, and the cyazote and the product have the advantages of short-acting auxiliary stabilizer for improving the initial coloring and long-acting stability of the product.
Wherein the polyalcohol is one or more of pentaerythritol, dipentaerythritol, mannitol and sorbitol.
Preferably, the polyhydric alcohol is pentaerythritol, the molecular structure of the pentaerythritol contains more hydroxyl groups, and the hydroxyl groups can form colorless ligands with metal ions, so that the catalytic acceleration effect of zinc chloride is relieved, and the formation of colored ligands formed by the metal ions and the polyene structure of the polyvinyl chloride is prevented.
The antioxidant comprises a main antioxidant and an auxiliary antioxidant, wherein the main antioxidant is a hindered phenol antioxidant, and the auxiliary antioxidant is a phosphite antioxidant. The hindered phenol type antioxidant of the main antioxidant contains active hydrogen atoms (O-H) which are more active than hydrogen atoms (including hydrogen of double bonds on a carbon chain) on a polymer carbon chain and can be separated out to be combined with a macromolecular chain free radical R-or R00-, and hydrogen peroxide and a stable phenoxy free radical (ArO-) are generated. The number of ortho-position substituent groups of the phenoxy radical is increased or the branching of the phenoxy radical is increased, namely the steric hindrance effect of the phenoxy radical is increased, so that the phenoxy radical can be protected by adjacent groups with larger volume, and the stability of the phenoxy radical is improved. This stability of the phenoxy radical prevents the antioxidant from being consumed too quickly by direct oxidation and also reduces chain transfer reactions, thereby improving its antioxidant properties.
Preferably, the hindered phenol antioxidant is at least one of pentaerythritol tetrakis [ beta-propionate ], n-octadecyl beta-propionate and 4,4' -thiobis (6-tert-butyl-3-methylphenol).
Preferably, the phosphite antioxidant is one or more of monobenzyldiisooctyl phosphite, diphenylisodecyl phosphite, didecylphenyl phosphite, trioctyl phosphite, trinonyl phosphite, etc., triphenyl phosphite, monobenzyldiisooctyl phosphite, triisooctyl phosphate, trinonylphenyl phosphite, tris (2, 4-di-t-butylphenyl) phosphite, 4-diisoidenebisphenol alkyl phosphite, and dipentaerythritol diphosphite.
Wherein the ultraviolet absorbent is one or a mixture of 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2, 4-dihydroxybenzophenone, p-tert-butyl salicylate and bisphenol A salicylate.
Preferably, the light stabilizer is a benzoate light stabilizer.
Preferably, the benzoate light stabilizer is one or more of resorcinol toluate, 3, 5-di-tert-butyl-4-hydroxybenzoic acid-2, 4-di-tert-butylphenyl ester and 3, 5-di-tert-butyl-4-hydroxybenzoic acid n-hexadecyl ester, has high-efficiency free radical capturing capability, has good light stability and also has antioxidant performance.
Preferably, the lubricant is prepared from (1-3): (0.5-1): 3, the oxidized polyethylene wax, the pentaerythritol ester and the glycerin monostearate. The lubricant is mixed with the primary ecological grain size of the main stabilizer, so that the stabilizer can be fully dispersed, and meanwhile, the lubricant and the reaction system of the main stabilizer are co-melted to form particles, so that dust flying is avoided.
The preparation method of the liquid calcium-zinc composite stabilizer comprises the following steps: adding mixed acid into a reaction kettle or a kneading machine, heating to 120-160 ℃, and mixing according to a zinc-calcium molar ratio (1-3): (0.5-2) adding zinc oxide and calcium hydroxide to perform a neutralization reaction, continuously heating for 20-30 min, adding 2-5 parts of solvent, stirring for 10-20 min, finally adding 2-4 parts of phosphite antioxidant, and continuously stirring for 10-15 min to obtain the antioxidant;
the mixed acid is a mixture of two or more of epoxy fatty acid, naphthenic acid, ricinoleic acid, lauric acid, stearic acid, citric acid, adipic acid, nitrilotriacetic acid and p-toluic acid.
The solvent is any one of D40, D70, D80, D90, D110 and D130, and the hydrocarbon content of the solvent is less than 0.1.
The emulsifier is one or more of dodecyl dimethyl benzyl ammonium chloride, cetyl trimethyl ammonium chloride fatty alcohol polyoxyethylene ether series, Arabic gum, isomeric tridecanol polyoxyethylene ether and sodium alkyl benzene sulfonate.
The auxiliary agent is at least one of methyl methacrylate, methyl acrylate and n-butyl stearate.
In addition, the invention also provides a preparation method of the nano-emulsion calcium-zinc stabilizer for PVC products, which comprises the following steps:
A. the raw materials are prepared according to the formula.
B. Injecting the liquid calcium-zinc composite stabilizer, the emulsifier and n-butyl stearate into a high-speed dispersion machine, and stirring and dispersing at the normal temperature at the speed of 800-1200 r/min for 5-10 min.
C. Pouring the prepared powder calcium-zinc composite stabilizer material into a high-speed machine, firstly stirring at a low speed for 2-8 min, and stirring at a high speed of 1000-1500 r/min for 10-20 min until the powder is completely dissolved in the liquid and the dust is prevented from flying.
D. And injecting the uniformly stirred solution into a nano emulsifying machine for emulsifying for 30-60 min.
E. And after emulsification is finished, injecting the emulsion into a high-speed dispersion machine, and dispersing for 5-10 min at the rotating speed of 1000-1500 r/min to obtain the nano-emulsion calcium-zinc stabilizer for PVC products.
Compared with the prior art, the invention has the beneficial effects that:
(1) the nano emulsion calcium-zinc stabilizer disclosed by the invention adopts the mutual matching of the solid-liquid calcium-zinc composite stabilizer, avoids the problems that the single liquid calcium-zinc composite stabilizer is poor in lubricity, so that the softening point of a product is reduced, and the product is easy to deteriorate after being stored for a long time, and also solves the problems that the single powder stabilizer is poor in compatibility, the blooming is separated out, the moisture absorption is easy, the dispersibility is poor, so that white spots and scratches occur on the product, and the like.
(2) The nano emulsion calcium zinc stabilizer prepared by the nano emulsification method solves the problems of compatibility and dispersibility of the powder stabilizer and the liquid stabilizer during production, ensures that the product performance is more beneficial and the surface of the prepared finished product is smoother;
(3) the main stabilizer compounded by calcium stearate, zinc stearate and magnesium stearate can effectively avoid the phenomenon of zinc burning, only has the function of capturing hydrogen chloride and can not replace active chlorine, the generated metal chloride has no catalytic action on dehydrochlorination reaction but can effectively replace the chloride generated by zinc soap, and the calcium magnesium derivative is complexed with ZnCl2Therefore, the HCl removal capability of PVC is reduced to regenerate the PVC.
(4) The auxiliary stabilizer is adopted for compounding, so that the auxiliary stabilizer can be greatly complemented, and has the advantages of short-acting auxiliary stabilizer on the improvement of initial coloring and long-acting stability of products; the 4A zeolite is porous aluminosilicate mineral with a frame structure containing aqueous alkali metal or alkaline earth metal, and alkaline groups attached to the surface can quickly neutralize part of HCL generated by PVC degradation and slow down PVC structural decomposition; the hydroxyl groups of the polyol may be reacted with Zn2+The metal ions form colorless and stable ligands, thereby passivating the catalytic acceleration effect of the metal ions on the thermal degradation of PVC, preventing the formation of colored ligands matched with polyene structures of the PVC and playing a role in stabilization.
(5) The method has the advantages that through the synergistic effect of the hindered phenol antioxidant and the phosphite antioxidant, the number of ortho-position substituents of the phenoxy free radical is increased or the number of branches of the phenoxy free radical is increased, namely the steric hindrance effect of the phenoxy free radical is increased, so that the phenoxy free radical is protected by adjacent groups with larger volume, the stability of the phenoxy free radical is improved, in addition, as the phenoxy free radical and a benzene ring are in a large conjugated system, the stability is high, the activity is low, the chain reaction cannot be initiated, the phenoxy free radical can only be combined with another active free radical, one free radical is terminated again, and a stable compound is generated, so that the; this stability of the phenoxy radical prevents the antioxidant from being consumed too quickly by direct oxidation and also reduces chain transfer reactions, thereby improving its antioxidant properties.
(6) The components of the nano emulsion calcium zinc stabilizer are fully mixed in the production process, and the uniformity of mixing and dispersion with resin is greatly improved.
(7) When the formulas are mixed, the metering times are simplified, and the metering error probability and the loss caused by the metering error probability are reduced.
(8) The supply and storage of auxiliary materials are simple and convenient, and the production and quality management are facilitated.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first embodiment is as follows:
the invention provides a nano-emulsion calcium-zinc stabilizer for PVC (polyvinyl chloride) products, which is prepared from the following raw materials in parts by weight:
the powder calcium-zinc composite stabilizer comprises: 30 parts of main stabilizer, 12 parts of auxiliary stabilizer, 5 parts of antioxidant, 0.2 part of ultraviolet absorber, 0.5 part of light stabilizer and 5 parts of lubricant.
The main stabilizer is compounded by calcium stearate, zinc stearate and magnesium stearate according to the mass ratio of 5:1: 1.
The auxiliary stabilizer is prepared by compounding 4A zeolite, hydrotalcite, stearoylbenzoylmethane, dibenzoylmethane, mosaic and polyhydric alcohol according to a mass ratio of 8:2:1:0.5:1: 5.
The polyalcohol is one or more of pentaerythritol, dipentaerythritol, mannitol and sorbitol.
Preferably, the polyol is pentaerythritol.
The antioxidant comprises a main antioxidant and an auxiliary antioxidant, wherein the main antioxidant is a hindered phenol antioxidant, and the auxiliary antioxidant is a phosphite antioxidant.
Preferably, the hindered phenol antioxidant is at least one of pentaerythritol tetrakis [ beta-propionate ], n-octadecyl beta-propionate and 4,4' -thiobis (6-tert-butyl-3-methylphenol).
Preferably, the phosphite antioxidant is one or more of monobenzyldiisooctyl phosphite, diphenylisodecyl phosphite, didecylphenyl phosphite, trioctyl phosphite, trinonyl phosphite, etc., triphenyl phosphite, monobenzyldiisooctyl phosphite, triisooctyl phosphate, trinonylphenyl phosphite, tris (2, 4-di-t-butylphenyl) phosphite, 4-diisoidenebisphenol alkyl phosphite, and dipentaerythritol diphosphite.
Wherein the ultraviolet absorbent is one or a mixture of 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2, 4-dihydroxybenzophenone, p-tert-butyl salicylate and bisphenol A salicylate.
Preferably, the light stabilizer is a benzoate light stabilizer.
Preferably, the benzoate light stabilizer is one or more of resorcinol toluate, 2, 4-di-tert-butylphenyl 3, 5-di-tert-butyl-4-hydroxybenzoate and n-hexadecyl 3, 5-di-tert-butyl-4-hydroxybenzoate.
The lubricant is prepared from the following components in a weight ratio of 3: 0.5: 3, the oxidized polyethylene wax, the pentaerythritol ester and the glycerin monostearate are mixed.
The preparation method of the liquid calcium-zinc composite stabilizer comprises the following steps: adding mixed acid into a reaction kettle or a kneading machine, heating to 120 ℃, adding zinc oxide and calcium hydroxide according to the zinc-calcium molar ratio of 3:1 for neutralization reaction, continuously heating for 20min, adding 3 parts of solvent, stirring for 20min, finally adding 3 parts of phosphite antioxidant, and continuously stirring for 10min to obtain the product;
the mixed acid is a mixture of two or more of epoxy fatty acid, naphthenic acid, ricinoleic acid, lauric acid, stearic acid, citric acid, adipic acid, nitrilotriacetic acid and p-toluic acid.
The solvent is any one of D40, D70, D80, D90, D110 and D130, and the hydrocarbon content of the solvent is less than 0.1.
The emulsifier is one or more of dodecyl dimethyl benzyl ammonium chloride, cetyl trimethyl ammonium chloride fatty alcohol polyoxyethylene ether series, Arabic gum, isomeric tridecanol polyoxyethylene ether and sodium alkyl benzene sulfonate.
The auxiliary agent is at least one of methyl methacrylate, methyl acrylate and n-butyl stearate.
The preparation method of the nano-emulsion calcium-zinc stabilizer for PVC products comprises the following steps:
A. the raw materials are prepared according to the formula.
B. Injecting the liquid calcium-zinc composite stabilizer, the emulsifier and the n-butyl stearate into a high-speed dispersion machine, and stirring and dispersing at the normal temperature at the speed of 800r/min for 5 min.
C. Pouring the prepared powdery calcium-zinc composite stabilizer material into a high-speed machine, firstly stirring at a low speed for 4min, and then stirring at a high speed of 1000r/min for 10min until the powder is fully dissolved in the liquid (so as to avoid flying of powder and water dust) until the powder is fully stirred uniformly.
D. And injecting the uniformly stirred solution into a nano emulsifying machine for emulsifying for 30 min.
E. And after emulsification is finished, injecting the emulsion into a high-speed dispersion machine, and dispersing for 5min at the rotating speed of 1000r/min to obtain the nano-emulsion calcium-zinc stabilizer for PVC products.
Example two:
the invention provides a nano-emulsion calcium-zinc stabilizer for PVC (polyvinyl chloride) products, which is prepared from the following raw materials in parts by weight:
the powder calcium-zinc composite stabilizer comprises: 45 parts of main stabilizer, 15 parts of auxiliary stabilizer, 30 parts of antioxidant, 1 part of ultraviolet absorbent, 0.5 part of light stabilizer and 5 parts of lubricant.
The main stabilizer is compounded by calcium stearate, zinc stearate and magnesium stearate according to the mass ratio of 4:1.5: 1.2.
The auxiliary stabilizer is prepared by compounding 4A zeolite, hydrotalcite, stearoylbenzoylmethane, dibenzoylmethane, mosaic and polyhydric alcohol according to a mass ratio of 4:2:2:1:1.5: 4.
The polyalcohol is one or more of pentaerythritol, dipentaerythritol, mannitol and sorbitol.
Preferably, the polyol is pentaerythritol.
The antioxidant comprises a main antioxidant and an auxiliary antioxidant, wherein the main antioxidant is a hindered phenol antioxidant, and the auxiliary antioxidant is a phosphite antioxidant.
Preferably, the hindered phenol antioxidant is at least one of pentaerythritol tetrakis [ beta-propionate ], n-octadecyl beta-propionate and 4,4' -thiobis (6-tert-butyl-3-methylphenol).
Preferably, the phosphite antioxidant is one or more of monobenzyldiisooctyl phosphite, diphenylisodecyl phosphite, didecylphenyl phosphite, trioctyl phosphite, trinonyl phosphite, etc., triphenyl phosphite, monobenzyldiisooctyl phosphite, triisooctyl phosphate, trinonylphenyl phosphite, tris (2, 4-di-t-butylphenyl) phosphite, 4-diisoidenebisphenol alkyl phosphite, and dipentaerythritol diphosphite.
Wherein the ultraviolet absorbent is one or a mixture of 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2, 4-dihydroxybenzophenone, p-tert-butyl salicylate and bisphenol A salicylate.
Preferably, the light stabilizer is a benzoate light stabilizer.
Preferably, the benzoate light stabilizer is one or more of resorcinol toluate, 2, 4-di-tert-butylphenyl 3, 5-di-tert-butyl-4-hydroxybenzoate and n-hexadecyl 3, 5-di-tert-butyl-4-hydroxybenzoate.
The lubricant is prepared from the following components in a weight ratio of 2: 0.8: 3, the oxidized polyethylene wax, the pentaerythritol ester and the glycerin monostearate are mixed.
The preparation method of the liquid calcium-zinc composite stabilizer comprises the following steps: adding mixed acid into a reaction kettle or a kneading machine, heating to 140 ℃, adding zinc oxide and calcium hydroxide according to the zinc-calcium molar ratio of 2:1 for neutralization reaction, continuously heating for 25min, adding 4 parts of solvent, stirring for 15min, finally adding 4 parts of phosphite antioxidant, and continuously stirring for 15min to obtain the product;
the mixed acid is a mixture of two or more of epoxy fatty acid, naphthenic acid, ricinoleic acid, lauric acid, stearic acid, citric acid, adipic acid, nitrilotriacetic acid and p-toluic acid.
The solvent is any one of D40, D70, D80, D90, D110 and D130, and the hydrocarbon content of the solvent is less than 0.1.
The emulsifier is one or more of dodecyl dimethyl benzyl ammonium chloride, cetyl trimethyl ammonium chloride fatty alcohol polyoxyethylene ether series, Arabic gum, isomeric tridecanol polyoxyethylene ether and sodium alkyl benzene sulfonate.
The auxiliary agent is at least one of methyl methacrylate, methyl acrylate and n-butyl stearate.
A nano-emulsion calcium-zinc stabilizer for PVC products comprises the following steps:
A. the raw materials are prepared according to the formula.
B. Injecting the liquid calcium-zinc composite stabilizer, the emulsifier and the n-butyl stearate into a high-speed dispersion machine, and stirring and dispersing at the speed of 1000r/min for 8min at normal temperature.
C. Pouring the prepared powdery calcium-zinc composite stabilizer material into a high-speed machine, firstly stirring at a low speed for 5min, and then stirring at a high speed of 1200r/min for 15min until the powder is completely dissolved in the liquid (so as to avoid flying of powder and water dust) until the powder is fully stirred uniformly.
D. And injecting the uniformly stirred solution into a nano emulsifying machine for emulsification, wherein the emulsifying time is 50 min.
E. And after emulsification is finished, injecting the emulsion into a high-speed dispersion machine, and dispersing for 10min at the rotating speed of 1200r/min to obtain the nano-emulsion calcium-zinc stabilizer for PVC products.
Example three:
the invention provides a nano-emulsion calcium-zinc stabilizer for PVC (polyvinyl chloride) products, which is prepared from the following raw materials in parts by weight:
the powder calcium-zinc composite stabilizer comprises: 55 parts of main stabilizer, 38 parts of auxiliary stabilizer, 21 parts of antioxidant, 0.8 part of ultraviolet absorber, 0.3 part of light stabilizer and 12 parts of lubricant.
The main stabilizer is compounded by calcium stearate, zinc stearate and magnesium stearate according to the mass ratio of 5:2: 1.
The auxiliary stabilizer is prepared by compounding 4A zeolite, hydrotalcite, stearoylbenzoylmethane, dibenzoylmethane, mosaic and polyhydric alcohol according to a mass ratio of 5:2.5:3:1:1: 3.
The polyalcohol is one or more of pentaerythritol, dipentaerythritol, mannitol and sorbitol.
Preferably, the polyol is pentaerythritol.
The antioxidant comprises a main antioxidant and an auxiliary antioxidant, wherein the main antioxidant is a hindered phenol antioxidant, and the auxiliary antioxidant is a phosphite antioxidant.
Preferably, the hindered phenol antioxidant is at least one of pentaerythritol tetrakis [ beta-propionate ], n-octadecyl beta-propionate and 4,4' -thiobis (6-tert-butyl-3-methylphenol).
Preferably, the phosphite antioxidant is one or more of monobenzyldiisooctyl phosphite, diphenylisodecyl phosphite, didecylphenyl phosphite, trioctyl phosphite, trinonyl phosphite, etc., triphenyl phosphite, monobenzyldiisooctyl phosphite, triisooctyl phosphate, trinonylphenyl phosphite, tris (2, 4-di-t-butylphenyl) phosphite, 4-diisoidenebisphenol alkyl phosphite, and dipentaerythritol diphosphite.
Wherein the ultraviolet absorbent is one or a mixture of 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2, 4-dihydroxybenzophenone, p-tert-butyl salicylate and bisphenol A salicylate.
Preferably, the light stabilizer is a benzoate light stabilizer.
Preferably, the benzoate light stabilizer is one or more of resorcinol toluate, 2, 4-di-tert-butylphenyl 3, 5-di-tert-butyl-4-hydroxybenzoate and n-hexadecyl 3, 5-di-tert-butyl-4-hydroxybenzoate.
The lubricant is prepared from the following components in a weight ratio of 1.8: 0.6: 3, the oxidized polyethylene wax, the pentaerythritol ester and the glycerin monostearate are mixed.
The preparation method of the liquid calcium-zinc composite stabilizer comprises the following steps: adding mixed acid into a reaction kettle or a kneading machine, heating to 140 ℃, adding zinc oxide and calcium hydroxide according to the zinc-calcium molar ratio of 2:1 for neutralization reaction, continuously heating for 25min, adding 4 parts of solvent, stirring for 15min, finally adding 4 parts of phosphite antioxidant, and continuously stirring for 15min to obtain the product;
the mixed acid is a mixture of two or more of epoxy fatty acid, naphthenic acid, ricinoleic acid, lauric acid, stearic acid, citric acid, adipic acid, nitrilotriacetic acid and p-toluic acid.
The solvent is any one of D40, D70, D80, D90, D110 and D130, and the hydrocarbon content of the solvent is less than 0.1.
The emulsifier is one or more of dodecyl dimethyl benzyl ammonium chloride, cetyl trimethyl ammonium chloride fatty alcohol polyoxyethylene ether series, Arabic gum, isomeric tridecanol polyoxyethylene ether and sodium alkyl benzene sulfonate.
The auxiliary agent is at least one of methyl methacrylate, methyl acrylate and n-butyl stearate.
A nano-emulsion calcium-zinc stabilizer for PVC products comprises the following steps:
A. the raw materials are prepared according to the formula.
B. Injecting the liquid calcium-zinc composite stabilizer, the emulsifier and the n-butyl stearate into a high-speed dispersion machine, and stirring and dispersing at the speed of 1000r/min for 8min at normal temperature.
C. Pouring the prepared powdery calcium-zinc composite stabilizer material into a high-speed machine, firstly stirring at a low speed for 5min, and then stirring at a high speed of 1200r/min for 15min until the powder is completely dissolved in the liquid (so as to avoid flying of powder and water dust) until the powder is fully stirred uniformly.
D. And injecting the uniformly stirred solution into a nano emulsifying machine for emulsification, wherein the emulsifying time is 50 min.
E. And after emulsification is finished, injecting the emulsion into a high-speed dispersion machine, and dispersing for 10min at the rotating speed of 1200r/min to obtain the nano-emulsion calcium-zinc stabilizer for PVC products.
Example four:
the invention provides a nano-emulsion calcium-zinc stabilizer for PVC (polyvinyl chloride) products, which is prepared from the following raw materials in parts by weight:
the powder calcium-zinc composite stabilizer comprises: 42 parts of main stabilizer, 15 parts of auxiliary stabilizer, 20 parts of antioxidant, 0.8 part of ultraviolet absorber, 0.3 part of light stabilizer and 12 parts of lubricant.
The main stabilizer is compounded by calcium stearate, zinc stearate and magnesium stearate according to the mass ratio of 4:2: 1.3.
The auxiliary stabilizer is prepared by compounding 4A zeolite, hydrotalcite, stearoylbenzoylmethane, dibenzoylmethane, mosaic and polyhydric alcohol according to a mass ratio of 6:2.5:1.5:0.8:1.3: 2.5.
The polyalcohol is one or more of pentaerythritol, dipentaerythritol, mannitol and sorbitol.
Preferably, the polyol is pentaerythritol.
The antioxidant comprises a main antioxidant and an auxiliary antioxidant, wherein the main antioxidant is a hindered phenol antioxidant, and the auxiliary antioxidant is a phosphite antioxidant.
Preferably, the hindered phenol antioxidant is at least one of pentaerythritol tetrakis [ beta-propionate ], n-octadecyl beta-propionate and 4,4' -thiobis (6-tert-butyl-3-methylphenol).
Preferably, the phosphite antioxidant is one or more of monobenzyldiisooctyl phosphite, diphenylisodecyl phosphite, didecylphenyl phosphite, trioctyl phosphite, trinonyl phosphite, etc., triphenyl phosphite, monobenzyldiisooctyl phosphite, triisooctyl phosphate, trinonylphenyl phosphite, tris (2, 4-di-t-butylphenyl) phosphite, 4-diisoidenebisphenol alkyl phosphite, and dipentaerythritol diphosphite.
Wherein the ultraviolet absorbent is one or a mixture of 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2, 4-dihydroxybenzophenone, p-tert-butyl salicylate and bisphenol A salicylate.
Preferably, the light stabilizer is a benzoate light stabilizer.
Preferably, the benzoate light stabilizer is one or more of resorcinol toluate, 2, 4-di-tert-butylphenyl 3, 5-di-tert-butyl-4-hydroxybenzoate and n-hexadecyl 3, 5-di-tert-butyl-4-hydroxybenzoate.
The lubricant is prepared from the following components in a weight ratio of 2.5: 0.7: 3, the oxidized polyethylene wax, the pentaerythritol ester and the glycerin monostearate are mixed.
The preparation method of the liquid calcium-zinc composite stabilizer comprises the following steps: adding mixed acid into a reaction kettle or a kneading machine, heating to 150 ℃, adding zinc oxide and calcium hydroxide according to the zinc-calcium molar ratio of 2:1.5 for neutralization reaction, continuously heating for 30min, adding 5 parts of solvent, stirring for 18min, finally adding 3 parts of phosphite antioxidant, and continuously stirring for 12min to obtain the product;
the mixed acid is a mixture of two or more of epoxy fatty acid, naphthenic acid, ricinoleic acid, lauric acid, stearic acid, citric acid, adipic acid, nitrilotriacetic acid and p-toluic acid.
The solvent is any one of D40, D70, D80, D90, D110 and D130, and the hydrocarbon content of the solvent is less than 0.1.
The emulsifier is one or more of dodecyl dimethyl benzyl ammonium chloride, cetyl trimethyl ammonium chloride fatty alcohol polyoxyethylene ether series, Arabic gum, isomeric tridecanol polyoxyethylene ether and sodium alkyl benzene sulfonate.
The auxiliary agent is at least one of methyl methacrylate, methyl acrylate and n-butyl stearate.
A nano-emulsion calcium-zinc stabilizer for PVC products comprises the following steps:
A. the raw materials are prepared according to the formula.
B. Injecting the liquid calcium-zinc composite stabilizer, the emulsifier and the n-butyl stearate into a high-speed dispersion machine, and stirring and dispersing at the normal temperature at the speed of 900r/min for 6 min.
C. Pouring the prepared powdery calcium-zinc composite stabilizer material into a high-speed machine, firstly stirring at a low speed for 5min, and then stirring at a high speed of 1200r/min for 15min until the powder is completely dissolved in the liquid (so as to avoid flying of powder and water dust) until the powder is fully stirred uniformly.
D. And injecting the uniformly stirred solution into a nano emulsifying machine for emulsification, wherein the emulsifying time is 50 min.
E. And after emulsification is finished, injecting the emulsion into a high-speed dispersion machine, and dispersing for 8min at the rotating speed of 1200r/min to obtain the nano-emulsion calcium-zinc stabilizer for PVC products.
Example five:
the invention provides a nano-emulsion calcium-zinc stabilizer for PVC (polyvinyl chloride) products, which is prepared from the following raw materials in parts by weight:
the powder calcium-zinc composite stabilizer comprises: 58 parts of main stabilizer, 36 parts of auxiliary stabilizer, 31 parts of antioxidant, 1.8 parts of ultraviolet absorber, 0.2 part of light stabilizer and 10 parts of lubricant.
The main stabilizer is compounded by calcium stearate, zinc stearate and magnesium stearate according to the mass ratio of 3:1.6: 1.4.
The auxiliary stabilizer is prepared by compounding 4A zeolite, hydrotalcite, stearoylbenzoylmethane, dibenzoylmethane, mosaic and polyhydric alcohol according to a mass ratio of 5:3:2:1:1.5: 3.
The polyalcohol is one or more of pentaerythritol, dipentaerythritol, mannitol and sorbitol.
Preferably, the polyol is pentaerythritol.
The antioxidant comprises a main antioxidant and an auxiliary antioxidant, wherein the main antioxidant is a hindered phenol antioxidant, and the auxiliary antioxidant is a phosphite antioxidant.
Preferably, the hindered phenol antioxidant is at least one of pentaerythritol tetrakis [ beta-propionate ], n-octadecyl beta-propionate and 4,4' -thiobis (6-tert-butyl-3-methylphenol).
Preferably, the phosphite antioxidant is one or more of monobenzyldiisooctyl phosphite, diphenylisodecyl phosphite, didecylphenyl phosphite, trioctyl phosphite, trinonyl phosphite, etc., triphenyl phosphite, monobenzyldiisooctyl phosphite, triisooctyl phosphate, trinonylphenyl phosphite, tris (2, 4-di-t-butylphenyl) phosphite, 4-diisoidenebisphenol alkyl phosphite, and dipentaerythritol diphosphite.
Wherein the ultraviolet absorbent is one or a mixture of 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2, 4-dihydroxybenzophenone, p-tert-butyl salicylate and bisphenol A salicylate.
Preferably, the light stabilizer is a benzoate light stabilizer.
Preferably, the benzoate light stabilizer is one or more of resorcinol toluate, 2, 4-di-tert-butylphenyl 3, 5-di-tert-butyl-4-hydroxybenzoate and n-hexadecyl 3, 5-di-tert-butyl-4-hydroxybenzoate.
Preferably, the benzoate light stabilizer is one or more of resorcinol toluate, 2, 4-di-tert-butylphenyl 3, 5-di-tert-butyl-4-hydroxybenzoate and n-hexadecyl 3, 5-di-tert-butyl-4-hydroxybenzoate.
The lubricant is prepared from the following components in a weight ratio of 2.1: 0.9: 3, the oxidized polyethylene wax, the pentaerythritol ester and the glycerin monostearate are mixed.
The preparation method of the liquid calcium-zinc composite stabilizer comprises the following steps: adding mixed acid into a reaction kettle or a kneading machine, heating to 130 ℃, adding zinc oxide and calcium hydroxide according to the zinc-calcium molar ratio of 2.8:1.7 for neutralization reaction, continuously heating for 30min, adding 3.5 parts of solvent, stirring for 16min, finally adding 3.7 parts of phosphite ester antioxidant, and continuously stirring for 11min to obtain the product;
the mixed acid is a mixture of two or more of epoxy fatty acid, naphthenic acid, ricinoleic acid, lauric acid, stearic acid, citric acid, adipic acid, nitrilotriacetic acid and p-toluic acid.
The solvent is any one of D40, D70, D80, D90, D110 and D130, and the hydrocarbon content of the solvent is less than 0.1.
The emulsifier is one or more of dodecyl dimethyl benzyl ammonium chloride, cetyl trimethyl ammonium chloride fatty alcohol polyoxyethylene ether series, Arabic gum, isomeric tridecanol polyoxyethylene ether and sodium alkyl benzene sulfonate.
The auxiliary agent is at least one of methyl methacrylate, methyl acrylate and n-butyl stearate.
A nano-emulsion calcium-zinc stabilizer for PVC products comprises the following steps:
A. the raw materials are prepared according to the formula.
B. Injecting the liquid calcium-zinc composite stabilizer, the emulsifier and the n-butyl stearate into a high-speed dispersion machine, and stirring and dispersing at the speed of 1100r/min for 8min at normal temperature.
C. Pouring the prepared powdery calcium-zinc composite stabilizer material into a high-speed machine, firstly stirring at a low speed for 4min until the powder is completely dissolved in the liquid to avoid the flying of the powder, and then stirring at a high speed of 1300r/min for 18min until the powder is fully stirred uniformly.
D. And injecting the uniformly stirred solution into a nano emulsifying machine for emulsification, wherein the emulsifying time is 33 min.
E. And after emulsification is finished, injecting the emulsion into a high-speed dispersion machine, and dispersing for 6min at the rotating speed of 1400r/min to obtain the nano-emulsion calcium-zinc stabilizer for PVC products.
Performance testing
The components (except the plasticizer) are put into a high-speed mixer according to the following table 1 (wherein the stabilizer is the stabilizer prepared in the first to fifth embodiments, and the single powder calcium zinc composite stabilizer and the single liquid calcium zinc composite stabilizer in the fourth embodiment are respectively used as the first test control group and the second test control group), mixed for 15 minutes at a high speed, then the plasticizer is added to be mixed uniformly at a low speed, the mixture is tabletted on a two-roll plasticator at 160 ℃, the temperature of the constant roll is continuously refined, the timing is started after the roll holding, the sampling is carried out after 10 minutes, and the 20mm × 20mm long strips are respectively taken to be used for an aging test and the small strips are taken to be used for a Congo red test.
TABLE 1
The aging test was carried out in an aging oven at 200 ℃ and examined with reference to ASTM D2115-04. Color-coded (0-white; 1-yellowish; 2-pale yellow; 3-yellow; 4-brownish yellow; 5-brown; 6-reddish brown; 7-dark brown; etc.) results are given in Table 2 below:
TABLE 2
| Categories | 30min | 60min | 90min | 120min | 150min | 180min |
| Example one | White colour | White colour | Light yellow | Yellow colour | Brown colour | Deep brown |
| Example two | White colour | White colour | Light yellow | Light yellow | Yellow colour | Brown colour |
| EXAMPLE III | White colour | White colour | Light yellow | Yellow colour | Yellow colour | Brown colour |
| Example four | White colour | White colour | Light yellow | Yellow colour | Yellow colour | Brown colour |
| ExamplesFive of them | White colour | White colour | Light yellow | Yellow colour | Yellow brown | Red palm |
| Control group one | White colour | Light yellow | Yellow colour | Yellow brown | Red palm | Deep brown |
| Control group two | White colour | Light yellow | Yellow colour | Yellow colour | Brown colour | Deep brown |
Static Congo Red tests were performed at 200 ℃ in an oil bath, according to the national standard GB/T2917-2002, and the results are given in Table 3 below:
TABLE 3
| Group of | Example one | Example two | EXAMPLE III | Example four | EXAMPLE five | Control group one | Control group two |
| min | 85 | 94 | 87 | 105 | 99 | 66 | 71 |
According to the results of the static Congo red and aging tests in the table above, compared with a single powder calcium-zinc stabilizer and a single liquid calcium-zinc stabilizer, the nano-emulsion calcium-zinc stabilizer for PVC products has excellent thermal stability for PVC, has good synergistic effect among the components, can be well used in PVC extrusion and injection molding processing industries, and has performance reaching relevant industrial standards of European Union and China.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The nano-emulsion calcium-zinc stabilizer for PVC products is characterized by comprising the following raw materials in parts by weight:
2. the nano-emulsion calcium-zinc stabilizer for PVC products as claimed in claim 1, wherein the powder calcium-zinc composite stabilizer comprises: 30-60 parts of a main stabilizer, 10-40 parts of an auxiliary stabilizer, 5-35 parts of an antioxidant, 0.1-2 parts of an ultraviolet absorber, 0.2-1 part of a light stabilizer and 1-15 parts of a lubricant.
3. The nano-emulsion calcium-zinc stabilizer for PVC products as claimed in claim 2, wherein the main stabilizer comprises calcium stearate, zinc stearate, magnesium stearate prepared from (5-3): (2-1): (1.5-1) by mass.
4. The nano-emulsion calcium-zinc stabilizer for PVC products as claimed in claim 2, wherein the auxiliary stabilizer comprises 4A zeolite, hydrotalcite, stearoylbenzoylmethane, dibenzoylmethane, mosaic, polyol, and the mass ratio of (4-8): (2-3): (1-3): (0.5-1.5): (1-2): (2-5), wherein the polyhydric alcohol is one or more of pentaerythritol, dipentaerythritol, mannitol and sorbitol.
5. The nanoemulsion calcium zinc stabilizer for PVC products as claimed in claim 2, wherein the antioxidant comprises a primary antioxidant and a secondary antioxidant, the primary antioxidant is a hindered phenol antioxidant, the secondary antioxidant is a phosphite antioxidant, the hindered phenol antioxidant is at least one of pentaerythritol tetrakis [ beta-propionate ], n-octadecyl beta-propionate and 4,4' -thiobis (6-tert-butyl-3-methylphenol), and the phosphite antioxidant is diisooctyl monobenzene phosphite, diphenylisodecyl phosphite, didecyl phenyl phosphite, trioctyl phosphite, trinonyl phosphite, triphenyl phosphite, diisooctyl monobenzene phosphite, triisooctyl phosphate, trisnonylphenyl phosphite, tris (2, 4-di-tert-butylphenyl) phosphite, 4, 4-diiso-bisphenol alkyl phosphite and dipentaerythritol diphosphite.
6. The nano-emulsion calcium-zinc stabilizer for PVC (polyvinyl chloride) products as claimed in claim 2, wherein the ultraviolet absorber is one or more of 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2, 4-dihydroxybenzophenone, p-tert-butyl salicylate and bisphenol A salicylate, the light stabilizer is benzoate light stabilizer, the benzoate light stabilizer is one or more of resorcinol toluate, 2, 4-di-tert-butylphenyl 3, 5-di-tert-butyl-4-hydroxybenzoate and n-hexadecyl 3, 5-di-tert-butyl-4-hydroxybenzoate, and the lubricant is prepared from (1-3): (0.5-1): 3, the oxidized polyethylene wax, the pentaerythritol ester and the glycerin monostearate.
7. The nano-emulsion calcium-zinc stabilizer for PVC products as claimed in claim 1, wherein the preparation method of the liquid calcium-zinc composite stabilizer is to add mixed acid into a reaction kettle or a kneader, heat the mixture to 120-160 ℃, add zinc oxide and calcium hydroxide according to the zinc-calcium molar ratio (1-3) (0.5-2) for neutralization reaction, continuously heat the mixture for 20-30 min, add 2-5 parts of solvent, stir the mixture for 10-20 min, finally add 2-4 parts of phosphite antioxidant, and continuously stir the mixture for 10-15 min; the mixed acid is a mixture of two or more of epoxy fatty acid, naphthenic acid, ricinoleic acid, lauric acid, stearic acid, citric acid, adipic acid, nitrilotriacetic acid and p-methylbenzoic acid, the solvent is any one of D40, D70, D80, D90, D110 and D130, and the hydrocarbon content of the solvent is less than 0.1.
8. The nano-emulsion calcium-zinc stabilizer for PVC products as claimed in claim 1, wherein the emulsifier is one or more of dodecyl dimethyl benzyl ammonium chloride, hexadecyl trimethyl ammonium chloride, fatty alcohol-polyoxyethylene ether, gum arabic, isomeric tridecanol polyoxyethylene ether, and sodium alkyl benzene sulfonate.
9. The nano-emulsion calcium-zinc stabilizer for PVC products as claimed in claim 1, wherein the assistant is at least one of methyl methacrylate, methyl acrylate and n-butyl stearate.
10. A method for preparing the nanoemulsion calcium zinc stabilizer for PVC products according to any one of claims 1 to 9, characterized by comprising the following steps:
A. preparing raw materials according to the formula;
B. injecting the liquid calcium-zinc composite stabilizer, the emulsifier and n-butyl stearate into a high-speed dispersion machine, and stirring and dispersing at the normal temperature at the speed of 800-1200 r/min for 5-10 min;
C. pouring the prepared powder calcium-zinc composite stabilizer material into a high-speed machine, firstly stirring at a low speed for 2-8 min, and then stirring at a high speed of 1000-1500 r/min for 10-20 min until the powder is fully dissolved in the liquid;
D. injecting the uniformly stirred solution into a nano emulsifying machine for emulsifying for 30-60 min;
E. and after emulsification is finished, injecting the emulsion into a high-speed dispersion machine, and dispersing for 5-10 min at the rotating speed of 1000-1500 r/min to obtain the nano-emulsion calcium-zinc stabilizer for PVC products.
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