CN104231481A - Liquid calcium-zinc phenol-free graphene PVC (polyvinyl chloride) heat stabilizer and preparation method thereof - Google Patents
Liquid calcium-zinc phenol-free graphene PVC (polyvinyl chloride) heat stabilizer and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a liquid calcium-zinc phenol-free graphene PVC (polyvinyl chloride) heat stabilizer. The heat stabilizer comprises the components in parts by weight as follows: 25-45 parts of calcium oxide, 25-45 parts of zinc oxide, 3-8 parts of basic sodium and aluminium carbonate, 5.5-10 parts of beta-diketone, 10-30 parts of oleic acid, 20-40 parts of caprylic acid, 30-60 parts of castor oil, 0.05-1 part of graphene and 0.1-0.3 part of a phenol-free antioxidant, wherein the phenol-free antioxidant is furanone or phthalide or N,N-dibenzylhydroxylamine. According to the heat stabilizer, HCL is captured through calcium and zinc, and in cooperation with the basic sodium and aluminium carbonate and the beta-diketone, short-term and long-term stable effects can be realized under the synergistic effect; a phenol-free and heavy-metal-free formula is used, so that usage pollution and production link pollution are reduced; besides, the graphene is adopted in the formula creatively and matched with a preparation technology, so that the heat resisting and heat conducting performance of the heat stabilizer are improved; in addition, the liquid stabilizer is outstanding in compatibility during usage.
Description
Technical field
The present invention relates to a kind of PVC processing aid and preparation method thereof, particularly a kind of liquid calcium zinc is without phenol Graphene PVC heat stabilizer extremely preparation method.
Background technology
Polyvinyl chloride (PVC) is as one of five large general-purpose plastics, by means of its good flame retardant resistance, resistance to chemical corrosion, wear resistance, electrical insulating property, the advantage such as cheap, develop into one of 21 century main chemical building material gradually, the whole world PVC market requirement increases fast, and the kind of PVC heat stabilizer also continues to bring out.At present, the thermo-stabilizer that PVC is conventional has lead salt, metallic soap, organotin and rare earth thermal stabilizer etc.Recent year is be environment-friendly high-efficiency for the research emphasis of PVC heat stabilizer, the stablizer containing heavy metal such as lead salts uses contaminative due to it and is eliminated gradually to the contaminative of production environment, rare earth class stablizer becomes the emphasis of research gradually, but rare earth class stablizer exist certain toxicity limit its use.
Chinese invention patent application 201310359995.6 is called a kind of PVC liquid composite stabilizing agent and preparation method thereof, this PVC liquid composite stabilizing agent with lipid acid, zinc oxide, hydrated barta, Cadmium oxide, solvent oil, oxidation inhibitor, phosphoric acid ester and epoxy ester for raw material, oxidation inhibitor is dihydroxyphenyl propane, 1010 and 264, adopt the goods of phenolic antioxidant, easy generation oxidation inhibitor moves on packed article from such as packing bag, i.e. qi exhaustion look phenomenon.
Chinese invention patent application 201010156871.4 is called a kind of powdered composite calcium zinc stabilizing agent and preparation method thereof, discloses each component of stablizer to be: polyglycerol fatty acid resin calcium zinc, epoxidised fatty acid calcium-zinc soap, phosphorous acid ester, beta-diketone compounds, be obstructed a point kind antioxidant, lubricant.This stablizer effectively can solve PVC calcium zinc stabilizer in prior art and there is the bad problem of poor compatibility, initial coloring, but adopts Hinered phenols antioxidant to be converted into quinones after peroxide has base by oneself and to make goods yellowing catching in formula.And there is the problem of consistency shortcoming in the stablizer of powder.
The thermal conductivity of macromolecular material is all very little, is generally no more than 1W/m.k, but can become thermally conductive material again after adding thermal conductivity material.Along with the development of national economy, the market requirement of heat-conducting polymer material is increasing, therefore improves the additive of macromolecular material heat conductivility in the urgent need to research.
Summary of the invention
The object of the invention is: solve the deficiencies in the prior art, provide a kind of liquid calcium zinc without phenol Graphene PVC heat stabilizer and preparation method thereof.
The technical scheme realizing the object of the invention is: a kind of liquid calcium zinc is without phenol Graphene PVC heat stabilizer, described thermo-stabilizer is made up of following component, count by weight: 25 ~ 45 parts, calcium oxide, preferably 25,26,27,28,29,30,31,32,33,34,35,36,37,38,39,40,41,42,43,44,45 parts; 25 ~ 45 parts, zinc oxide, preferably 25,26,27,28,29,30,31,32,33,34,35,36,37,38,39,40,41,42,43,44,45 parts;
Sodium Aluminium Carbonate Basic 3 ~ 8 parts, preferably 3,4,5,6,7,8 parts, Sodium Aluminium Carbonate Basic is long time type thermo-stabilizer, and it is transparent and electrical insulation capability is more remarkable;
Beta-diketon 5.5 ~ 10 parts, preferably 5.5,6,6.5,7,7.5,8,8.5,9,9.5,10 parts, beta-diketon obviously can improve and suppress first discolouration effect;
Oleic acid 10 ~ 30 parts, preferably 11,12,13,14,15,16,17,18,19,20,21,22,23,24,2526,27,28,29,30 parts;
Sad 20 ~ 40 parts, preferably 20,21,22,23,24,25,26,27,28,29,30,31,32,33,34,35 parts;
Viscotrol C 30 ~ 60 parts, preferably 30,31,32,33,34,35,36,37,38,39,40,41,42,43,44,45,46,47,48,49,50,51,52,53,54,55,56,57,58,59,60 parts; Adopt natural Viscotrol C more environmental protection.
Graphene 0.05 ~ 1 part, preferably 0.05,0.1,0.15,0.2,0.25,0.3,0.35,0.4,0.45,0.5,0.6,0.7,0.8,0.9,1.0 part;
Without 0.1 ~ 0.3 part, phenol oxidation inhibitor, preferably 0.1,0.2,0.3 part;
Described is furanone or phthalide or N, N-dibenzyl hydroxylamine without phenol oxidation inhibitor.
Above-mentioned liquid calcium zinc is without the preparation method of phenol Graphene PVC heat stabilizer, there are following steps: by proportioning by oleic acid, sad, Viscotrol C, stir and constant temperature at 90 ~ 110 DEG C, keep 2 ~ 3 hours, then add calcium oxide, zinc oxide, continue stir and be warming up to 120 ~ 140 DEG C, then by proportioning add Sodium Aluminium Carbonate Basic, beta-diketon, Graphene, without phenol oxidation inhibitor, stir, obtain product.
Above-mentioned liquid calcium zinc is without the preparation method of phenol Graphene PVC heat stabilizer, add Sodium Aluminium Carbonate Basic, beta-diketon, Graphene by proportioning, without phenol oxidation inhibitor, can increase after stirring and carry out the ultrasonic wave dispersion step of 0.5 ~ 2 hour in described preparation method.
A kind of PVC product, add above-mentioned liquid calcium zinc in this PVC product preparation process without phenol Graphene PVC heat stabilizer, add-on is: 0.8 ~ 5wt%, preferably 0.8 ~ 2wt%, more preferably 0.8,0.9,1.0,1.5,2.0,3.0,4.0,5.0wt%.
The present invention has positive effect: adopt calcium, zinc to catch HCL, coordinate the use of Sodium Aluminium Carbonate Basic and beta-diketon, synergy can form short-term and long-term stabilising effect; Adopt without phenol, heavy metal free formula, reduce to use and pollute and production link pollution, more meet environmental requirement; Breakthrough employing Graphene in formula, and prepare technique, increase heat-resisting, the heat conductivility of goods; In addition when liquid stabilisers uses, consistency is given prominence to.
Embodiment
(embodiment 1)
Take calcium oxide 260Kg, zinc oxide 28Kg; Sodium Aluminium Carbonate Basic 75Kg; Beta-diketon 63Kg; Oleic acid 180Kg; Sad 250Kg; Viscotrol C 450Kg; Graphene 0.5Kg; Without phenol oxidation inhibitor N, N-dibenzyl hydroxylamine 2.3Kg;
By above-mentioned oleic acid, sad, Viscotrol C, stir and constant temperature at 90 ~ 110 DEG C, keep 2 hours, then calcium oxide, zinc oxide is added, continue stir and be warming up to 120 ~ 130 DEG C, then by proportioning add Sodium Aluminium Carbonate Basic, beta-diketon, Graphene, without phenol oxidation inhibitor N, N-dibenzyl hydroxylamine, stir, obtain product.
Liquid calcium zinc polyvinyl chloride resin, the present embodiment prepared is without phenol Graphene PVC heat stabilizer, and add-on is after 0.8wt% and other auxiliary agent high-speed mixing, after mixing in two roller mill, plasticizing, bottom sheet, section, be cut into the small pieces of 5mm*5mm, obtain PVC style, test.
(embodiment 2)
Take calcium oxide 305Kg, zinc oxide 318Kg; Sodium Aluminium Carbonate Basic 64Kg; Beta-diketon 75Kg; Oleic acid 210Kg; Sad 310Kg; Viscotrol C 535Kg; Graphene 0.5Kg; Without phenol oxidation inhibitor N, N-dibenzyl hydroxylamine 2.5Kg;
By above-mentioned oleic acid, sad, Viscotrol C, stir and constant temperature at 90 ~ 100 DEG C, keep 2 hours, then calcium oxide, zinc oxide is added, continue stir and be warming up to 120 ~ 130 DEG C, then by proportioning add Sodium Aluminium Carbonate Basic, beta-diketon, Graphene, without phenol oxidation inhibitor N, N-dibenzyl hydroxylamine, stir, obtain product.
Liquid calcium zinc polyvinyl chloride resin, the present embodiment prepared is without phenol Graphene PVC heat stabilizer, and add-on is after 2.5wt% and other auxiliary agent high-speed mixing, after mixing in two roller mill, plasticizing, bottom sheet, section, be cut into the small pieces of 5mm*5mm, obtain PVC style, test.
(embodiment 3)
Take calcium oxide 280Kg, zinc oxide 275Kg; Sodium Aluminium Carbonate Basic 54Kg; Beta-diketon 67Kg; Oleic acid 230Kg; Sad 360Kg; Viscotrol C 542Kg; Graphene 1Kg; Without phenol oxidation inhibitor furanone 1.5Kg;
By above-mentioned oleic acid, sad, Viscotrol C, stir and constant temperature at 90 ~ 100 DEG C, keep 2 hours, then calcium oxide, zinc oxide is added, continue stir and be warming up to 130 ~ 140 DEG C, then add Sodium Aluminium Carbonate Basic, beta-diketon, Graphene g by proportioning, without phenol oxidation inhibitor furanone, stir, obtain product.
Liquid calcium zinc polyvinyl chloride resin, the present embodiment prepared is without phenol Graphene PVC heat stabilizer, and add-on is after 0.9wt% and other auxiliary agent high-speed mixing, after mixing in two roller mill, plasticizing, bottom sheet, section, be cut into the small pieces of 5mm*5mm, obtain PVC style, test.
(embodiment 4)
Take calcium oxide 420Kg, zinc oxide 430Kg; Sodium Aluminium Carbonate Basic 75Kg; Beta-diketon 70Kg; Oleic acid 210Kg; Sad 320Kg; Viscotrol C 520Kg; Graphene 1Kg; Without phenol oxidation inhibitor furans ketoamine 1.6Kg;
By above-mentioned oleic acid, sad, Viscotrol C, stir and constant temperature at 100 ~ 110 DEG C, keep 2 hours, then calcium oxide, zinc oxide is added, continue stir and be warming up to 120 ~ 130 DEG C, then add Sodium Aluminium Carbonate Basic, beta-diketon, Graphene by proportioning, without phenol oxidation inhibitor furanone, stir, then carry out ultrasonic wave and disperse 30 minutes, obtain final product.
Liquid calcium zinc polyvinyl chloride resin, the present embodiment prepared is without phenol Graphene PVC heat stabilizer, and add-on is after 5wt% and other auxiliary agent high-speed mixing, after mixing in two roller mill, plasticizing, bottom sheet, section, be cut into the small pieces of 5mm*5mm, obtain PVC style, test.
(embodiment 5)
Take calcium oxide 440Kg, zinc oxide 430Kg; Sodium Aluminium Carbonate Basic 70Kg; Beta-diketon 95Kg; Oleic acid 310Kg; Sad 360Kg; Viscotrol C 570Kg; Graphene 1Kg; Without phenol oxidation inhibitor N, N-dibenzyl hydroxylamine 3Kg;
By above-mentioned oleic acid, sad, Viscotrol C, stir and constant temperature at 95 ~ 100 DEG C, keep 3 hours, then add calcium oxide, zinc oxide, continue stir and be warming up to 125 ~ 130 DEG C, then by proportioning add Sodium Aluminium Carbonate Basic, beta-diketon, Graphene, without phenol oxidation inhibitor N, N-dibenzyl hydroxylamine, stir, then carry out ultrasonic wave and disperse 60 minutes, obtain product.
Liquid calcium zinc polyvinyl chloride resin, the present embodiment prepared is without phenol Graphene PVC heat stabilizer, and add-on is after 2wt% and other auxiliary agent high-speed mixing, after mixing in two roller mill, plasticizing, bottom sheet, section, be cut into the small pieces of 5mm*5mm, obtain PVC style, test.
Above-described specific embodiment; object of the present invention, technical scheme and beneficial effect are further described; be understood that; the foregoing is only specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any amendment made, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (6)
1. liquid calcium zinc is without a phenol Graphene PVC heat stabilizer, it is characterized in that: described thermo-stabilizer is made up of following component, counts by weight:
25 ~ 45 parts, calcium oxide;
25 ~ 45 parts, zinc oxide;
Sodium Aluminium Carbonate Basic 3 ~ 8 parts;
Beta-diketon 5.5 ~ 10 parts;
Oleic acid 10 ~ 30 parts;
Sad 20 ~ 40 parts;
Viscotrol C 30 ~ 60 parts;
Graphene 0.05 ~ 1 part;
Without 0.1 ~ 0.3 part, phenol oxidation inhibitor;
Described is furanone or phthalide or N, N-dibenzyl hydroxylamine without phenol oxidation inhibitor.
2. liquid calcium zinc according to claim 1 is without phenol Graphene PVC heat stabilizer, it is characterized in that: each component of described thermo-stabilizer is counted by weight:
30 ~ 35 parts, calcium oxide;
30 ~ 35 parts, zinc oxide;
Sodium Aluminium Carbonate Basic 5 ~ 7 parts;
Beta-diketon 5.5 ~ 10 parts;
Oleic acid 15 ~ 25 parts;
Sad 25 ~ 35 parts;
Viscotrol C 45 ~ 60 parts;
Graphene 0.05 ~ 1 part;
Without 0.1 ~ 0.3 part, phenol oxidation inhibitor.
3. the liquid calcium zinc as described in 1 or 2 is without the preparation method of phenol Graphene PVC heat stabilizer, it is characterized in that: there are following steps: by proportioning by oleic acid, sad, Viscotrol C, stir and constant temperature at 90 ~ 110 DEG C, keep 2 ~ 3 hours, then add calcium oxide, zinc oxide, continue stir and be warming up to 120 ~ 140 DEG C, then by proportioning add Sodium Aluminium Carbonate Basic, beta-diketon, Graphene, without phenol oxidation inhibitor, stir, obtain product.
4. liquid calcium zinc according to claim 3 is without the preparation method of phenol Graphene PVC heat stabilizer, it is characterized in that: described preparation method adds Sodium Aluminium Carbonate Basic, beta-diketon, Graphene by proportioning, without phenol oxidation inhibitor, increases and carry out the ultrasonic wave dispersion step of 0.5 ~ 2 hour after stirring.
5. a PVC product, is characterized in that: add liquid calcium zinc as claimed in claim 1 or 2 in this PVC product preparation process without phenol Graphene PVC heat stabilizer, add-on is: 0.8 ~ 5wt%.
6. PVC product according to claim 5, is characterized in that: in this PVC product preparation process, liquid calcium zinc without the add-on of phenol Graphene PVC heat stabilizer is: 0.8 ~ 2wt%.
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| CN201410476715.4A CN104231481B (en) | 2014-09-17 | 2014-09-17 | Liquid calcium-zinc phenol-free graphene PVC (polyvinyl chloride) heat stabilizer and preparation method thereof |
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| CN201410476715.4A CN104231481B (en) | 2014-09-17 | 2014-09-17 | Liquid calcium-zinc phenol-free graphene PVC (polyvinyl chloride) heat stabilizer and preparation method thereof |
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Cited By (1)
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| CN106243741A (en) * | 2016-08-23 | 2016-12-21 | 深圳市志海实业股份有限公司 | A kind of preparation method of High-performance graphite oxide alkene modified calcium zinc stabilizer |
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Address after: 213331 Dai Bei Cun, Dai Town, Liyang, Jiangsu, Changzhou Patentee after: Jiangsu carinver Technology Co., Ltd. Address before: 213331 Changzhou Province, Liyang City Port Industrial Park, the new road, No. 1 Patentee before: Changzhou Carinver Chemistry Co., Ltd. |