CN102070858A - Sodium-zinc compound stabilizer for PVC and preparation method thereof - Google Patents
Sodium-zinc compound stabilizer for PVC and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of chemistry and relates to a sodium-zinc compound stabilizer for PVC. The stabilizer consists of the following components in part by weight: 55 to 80 parts of main stabilizer and 20 to 45 parts of auxiliary stabilizer, wherein the main stabilizer is the compound of maleic acid sodium and maleic acid zinc. The preparation method comprises two steps of the preparation of the main stabilizer and the preparation of the auxiliary stabilizer, wherein the main stabilizer is prepared by reacting maleic acid with sodium compounds and reacting the maleic acid with zinc compounds in sequence, or by mixing maleic acid and the reaction liquid of the sodium compounds and the zinc compounds in a certain ratio respectively for reaction and drying, or by mixing maleic acid and the solid reaction products of the sodium compounds and the zinc compounds in a certain ratio respectively. The sodium-zinc compound stabilizer for PVC has high thermal stability, the preparation method is simple, raw materials are readily available, the yield is high, the cost is low, and the sodium-zinc compound stabilizer is environmentally-friendly.
Description
Technical field
The invention belongs to chemical field, relate to a kind of polyvinyl chloride (PVC) thermo-stabilizer and preparation method thereof, particularly a kind of PVC sodium zinc composite stabilizer and preparation method thereof.
Background technology
PVC is the general-purpose plastics that a class is widely used in fields such as building, light industry, chemical industry, electronics, space flight, automobile, agricultural.China PVC industry in recent years presents flourish situation, and the domestic production amount had reached more than 2,000 ten thousand tons in 2009.The disadvantage of PVC is a poor heat stability.In order to suppress the degraded of PVC in the course of processing, need in the PVC course of processing, add thermo-stabilizer usually.Existing P VC thermo-stabilizer mainly is lead salt stabilizer, organotin stabilizer, barium cadmium one package stabilizer, calcium-zinc composite stabilizing agent etc., and the consumption maximum is to have supervirulent lead salt stabilizer at present.In recent years, constantly perfect along with the enhancing of environmental consciousness and various rules, the application of lead salt stabilizer progressively is restricted, and enterprise has shown intensive interest to the exploitation of environment-friendly type PVC thermo-stabilizer.
The environment-friendly type PVC thermo-stabilizer mainly is organotin stabilizer and calcium-zinc composite stabilizing agent at present.Organotin stabilizer has remarkable stability and transparent, but the cost height, application is very limited.And advantage such as that calcium-zinc composite stabilizing agent has is cheap, oilness is good has utmost point vast potential for future development.But the calcium-zinc composite stabilizing agent of Xiao Shouing is that the calcium/zinc salt with organic monoacids such as stearic acid, lauric acid, oleic acid, isocaprylic acid, phenylformic acid is a main component in the market, its stabilization effect is compared with lead salt stabilizer and is still had big gap, and heat-stable time is shorter.In recent years, lot of domestic and international scholar has synthesized calcium salt, the high zinc compound of macromole of some new calcium zinc complexes such as epoxyfatty acid calcium zinc, glycerin zinc, unsymmetric structure etc., and be that main component has been prepared efficient PVC thermo-stabilizer with this class mixture, but this class stablizer costs an arm and a leg, and development prospect also is subjected to bigger restriction.Therefore, deficiency such as price height, the thermostability that exists at present environment-friendly type PVC thermo-stabilizer is relatively poor, develop a kind of efficiently, the environment-friendly type PVC thermo-stabilizer is very necessary cheaply.
The sodium zinc composite stabilizer also is a class environment-friendly type PVC thermo-stabilizer.Publication number is that the Chinese patent application of CN101712771A discloses a kind of Sodium isooctanoate zinc composite stabilizer, and points out that this one package stabilizer has good PVC heat stabilization.But the research of at present relevant sodium zinc composite stabilizer report seldom, also do not have the sodium zinc composite stabilizer to sell on the market.
Summary of the invention
In view of this, one of purpose of the present invention is to provide a kind of novel PVC sodium zinc composite stabilizer, has good thermostable effect.
For achieving the above object, the invention provides following technical scheme:
A kind of PVC sodium zinc composite stabilizer is made up of for 20 ~ 45 parts 55 ~ 80 parts of main stabilizers and auxiliary stabilizer by weight; Described main stabilizer is the mixture of maleic acid sodium and maleic acid zinc.
Further, 20 ~ 45 parts of described auxiliary stabilizers are composed of the following components by weight:
Component A: be selected from stearoyl benzoyl methane, diphenylpropane-1,3-dione(DPPO), isobutyl phenyl ketone formyl methane and the decoyl benzoyl methane one or more, 10 ~ 20 parts;
B component: be selected from glycidyl ether, cycloaliphatic epoxy resin, trimellitic acid three-glycidyl ester and the diglycidyl terephthalate of glycidyl ether, tetraphenyl ethane of epoxy soybean oil, epoxy sunflower oil, bisphenol A diglycidyl ether, Bisphenol F diglycidylether, resol one or more, 6 ~ 15 parts;
Component C: be selected from ultrafine zeolite and/or hydrotalcite, 3 ~ 5 parts;
Component D: be selected from paraffin, polyethylene wax, oxidized polyethlene wax, stearic acid, butyl stearate and the XU 61518.10 one or more, 1 ~ 5 part.
Further, described B component is selected from one or more in epoxy soybean oil, epoxy sunflower oil and the bisphenol A diglycidyl ether; Component D is selected from one or more in polyethylene wax, oxidized polyethlene wax, stearic acid and the XU 61518.10.
Two of purpose of the present invention is to provide the preparation method of above-mentioned PVC with the sodium zinc composite stabilizer, and easy and simple to handle, raw material is cheap and easy to get, the productive rate height, and cost is low, environmental friendliness.
For achieving the above object, the invention provides following three kinds of technical schemes:
First kind of technical scheme: described PVC may further comprise the steps with the preparation method of sodium zinc composite stabilizer:
The preparation of a, main stabilizer: count by molar and take by weighing 5 ~ 45 parts of 15 ~ 55 parts of 40 ~ 55 parts of maleic acids, compounds containing sodium and zinc compounds respectively, described compounds containing sodium is one or more in sodium hydroxide, yellow soda ash and the sodium bicarbonate, and described zinc compound is one or more in zinc oxide, zinc carbonate, zinc subcarbonate and the zinc hydroxide; Maleic acid is dissolved in the water, adds compounds containing sodium under agitation condition, finish and be warming up to 80 ~ 95 ℃, add zinc compound under the insulated and stirred condition, finish the insulated and stirred reaction to fully, get solid product, drying promptly gets main stabilizer;
B, auxiliary stabilizer composite: take by weighing 20 ~ 45 parts of 55 ~ 80 parts of step a gained main stabilizers and auxiliary stabilizers by weight respectively, fully mixing promptly gets PVC sodium zinc composite stabilizer.
Second kind of technical scheme: described PVC may further comprise the steps with the preparation method of sodium zinc composite stabilizer:
The preparation of a, main stabilizer: count by molar and take by weighing 50 ~ 60 parts of 40 ~ 50 parts of maleic acids and compounds containing sodiums respectively, described compounds containing sodium is one or more in sodium hydroxide, yellow soda ash and the sodium bicarbonate, maleic acid is dissolved in the water, be warming up to 80 ~ 95 ℃, under the insulated and stirred condition, add compounds containing sodium again, finish the insulated and stirred reaction to fully, obtain the maleic acid sodium solution; Count by molar and take by weighing 50 ~ 60 parts of 40 ~ 50 parts of maleic acids and zinc compounds respectively, described zinc compound is one or more in zinc oxide, zinc carbonate, zinc subcarbonate and the zinc hydroxide, maleic acid is dissolved in the water, under agitation condition, add zinc compound again, finish stirring reaction to fully, obtain the maleic acid zinc solution; Is that 3:1 ~ 1:3 mixes with maleic acid sodium solution and maleic acid zinc solution according to the solute mol ratio, and stirring reaction is got solid product to fully, and drying promptly gets main stabilizer;
B, auxiliary stabilizer composite: take by weighing 20 ~ 45 parts of 55 ~ 80 parts of step a gained main stabilizers and auxiliary stabilizers by weight respectively, fully mixing promptly gets PVC sodium zinc composite stabilizer.
The third technical scheme: described PVC may further comprise the steps with the preparation method of sodium zinc composite stabilizer:
The preparation of a, main stabilizer: count by molar and take by weighing 50 ~ 60 parts of 40 ~ 50 parts of maleic acids and compounds containing sodiums respectively, described compounds containing sodium is one or more in sodium hydroxide, yellow soda ash and the sodium bicarbonate, maleic acid is dissolved in the water, be warming up to 80 ~ 95 ℃, under the insulated and stirred condition, add compounds containing sodium again, finish the insulated and stirred reaction, get solid product to fully, drying obtains maleic acid sodium; Count by molar and take by weighing 50 ~ 60 parts of 40 ~ 50 parts of maleic acids and zinc compounds respectively, described zinc compound is one or more in zinc oxide, zinc carbonate, zinc subcarbonate and the zinc hydroxide, maleic acid is dissolved in the water, under agitation condition, add zinc compound again, finish stirring reaction to complete, get solid product, drying obtains maleic acid zinc; Is that 2:1 ~ 1:2 mixes with maleic acid sodium and maleic acid zinc according to mol ratio, promptly gets main stabilizer;
B, auxiliary stabilizer composite: take by weighing 20 ~ 45 parts of 55 ~ 80 parts of step a gained main stabilizers and auxiliary stabilizers by weight respectively, fully mixing promptly gets PVC sodium zinc composite stabilizer.
The main stabilizer that makes according to above-mentioned three kinds of technical schemes is the mixture of maleic acid sodium and maleic acid zinc.Because a little less than the mutual associativity of main stabilizer maleic acid sodium/zinc soap, stabilising effect is not good when using separately, needs to add auxiliary stabilizer usually and carry out composite with it to improve its performance.Auxiliary stabilizer of the present invention mainly comprises several classes such as beta-diketon, epoxy compounds, mineral compound and lubricant.It is to improve the tinctorial property of PVC goods that beta-diketon has vital role, outstanding role to raising thermostability, light stability and inhibition " zinc burning ", and general and other components do not have the antagonism effect.In the present invention, can be selected from stearoyl benzoyl methane, diphenylpropane-1,3-dione(DPPO), isobutyl phenyl ketone formyl methane and the decoyl benzoyl methane one or more as the beta-diketon of auxiliary stabilizer.Epoxy compounds and hcl reaction generate chloroethanol, under metallic soap katalysis such as calcium, zinc, can replace unsettled chlorine atom among the PVC and the effect of playing stably.In the present invention, can be selected from glycidyl ether, cycloaliphatic epoxy resin, trimellitic acid three-glycidyl ester and the diglycidyl terephthalate of glycidyl ether, tetraphenyl ethane of epoxy soybean oil, epoxy sunflower oil, bisphenol A diglycidyl ether, Bisphenol F diglycidylether, resol one or more, one or more in preferred epoxy soybean oil, epoxy sunflower oil and the bisphenol A diglycidyl ether as the epoxy compounds of auxiliary stabilizer.Mineral compound as auxiliary stabilizer mainly contains zeolite and hydrotalcite.Zeolite is the effective acid scavenger of halogen containing polymers, and has good long term stability, but its particle diameter is heated in the course of processing when big and degassing phenomenon can occurs and make the product rerum natura and surface property descends, so preferred ultrafine zeolite.Hydrotalcite has the transparency and thermostability preferably, and the common drawback of itself and zeolite is that the initial stage color and luster is relatively poor, and generally adding beta-diketon can solve.Lubricant can reduce that PVC is intermolecular, the friction between intramolecularly or molecule and the metal specific surface, and the material temperature when reducing forming process can produce good effect to thermostability.In the present invention, can be selected from paraffin, polyethylene wax, oxidized polyethlene wax, stearic acid, butyl stearate and the XU 61518.10 one or more, one or more in preferably polyethylene wax, oxidized polyethlene wax, stearic acid and the XU 61518.10 as the lubricant of auxiliary stabilizer.
Beneficial effect of the present invention is: the invention provides a kind of sodium zinc composite stabilizer of PVC with good thermostable effect, the dynamic stability time that it is tested with the banburying of Haake rheometer under 200 ℃ of conditions of temperature and the steady stability time of static Congo red experiment test all are better than other PVC sodium zinc composite stabilizer of present bibliographical information.And this PVC is simple and easy to do with the preparation method of sodium zinc composite stabilizer, and raw material is cheap and easy to get, the productive rate height, and cost is low, environmental friendliness.PVC of the present invention is applicable to the sodium zinc composite stabilizer and has broad application prospects soft, the boardy product of PVC of the multiple trade mark.
Embodiment
In order to make the purpose, technical solutions and advantages of the present invention clearer, below the preferred embodiments of the present invention are described in detail.
Embodiment 1
The preparation of a, main stabilizer: count by molar and take by weighing 20 parts in 50 parts of maleic acids, 30 parts in yellow soda ash and zinc oxide respectively, be dissolved in maleic acid in the deionized water fully, be to add yellow soda ash under 1000 ~ 1500rpm condition several times in stir speed (S.S.) again, finish and be warming up to 80 ~ 95 ℃, under the insulated and stirred condition, add zinc oxide several times, finish the insulated and stirred reaction to complete, solvent evaporated, take out solid product, under 130 ~ 150 ℃ of conditions of temperature, dry, promptly get main stabilizer, productive rate reaches more than 97%;
B, auxiliary stabilizer composite: take by weighing 65 parts of step a gained main stabilizers, 15 parts of stearoyl benzoyl methanes, 15 parts of epoxy soybean oils, 2 parts of ultrafine zeolites, 1 part of hydrotalcite, 1 part of oxidized polyethlene wax, 1 part of XU 61518.10 by weight respectively, fully mixing promptly gets PVC sodium zinc composite stabilizer.
The PVC that present embodiment is made with sodium zinc composite stabilizer and polyvinyl chloride resin by weight for after 5:95 mixes, the dynamic stability time with Haake rheometer banburying test under 200 ℃ of conditions of temperature was not less than 15 minutes, and the steady stability time of static Congo red experiment test was not less than 80 minutes.
Embodiment 2
The preparation of a, main stabilizer: count by molar and take by weighing 20 parts of 50 parts of maleic acids, 30 parts in yellow soda ash and zinc hydroxides respectively, be dissolved in maleic acid in the deionized water fully, be to add yellow soda ash under 1000 ~ 1500rpm condition several times in stir speed (S.S.) again, finish and be warming up to 80 ~ 95 ℃, under the insulated and stirred condition, add zinc hydroxide several times, finish the insulated and stirred reaction to complete, solvent evaporated, take out solid product, under 130 ~ 150 ℃ of conditions of temperature, dry, promptly get main stabilizer, productive rate reaches more than 95%;
B, auxiliary stabilizer composite: take by weighing 55 parts of step a gained main stabilizers, 20 parts of stearoyl benzoyl methanes, 15 parts of epoxy soybean oils, 2 parts of ultrafine zeolites, 3 parts of hydrotalcites, 2 parts of oxidized polyethlene wax, 3 parts of XU 61518.10 by weight respectively, fully mixing promptly gets PVC sodium zinc composite stabilizer.
The PVC that present embodiment is made with sodium zinc composite stabilizer and polyvinyl chloride resin by weight for after 10:90 mixes, the dynamic stability time with Haake rheometer banburying test under 200 ℃ of conditions of temperature was not less than 17 minutes, and the steady stability time of static Congo red experiment test was not less than 80 minutes.
Embodiment 3
The preparation of a, main stabilizer: count by molar and take by weighing 5 parts of 40 parts of maleic acids, 55 parts in sodium hydroxide and zinc carbonates respectively, be dissolved in maleic acid in the deionized water fully, be to add sodium hydroxide under 1000 ~ 1500rpm condition several times in stir speed (S.S.) again, finish and be warming up to 80 ~ 95 ℃, under the insulated and stirred condition, add zinc carbonate several times, finish the insulated and stirred reaction to complete, solvent evaporated, take out solid product, under 130 ~ 150 ℃ of conditions of temperature, dry, promptly get main stabilizer, productive rate reaches more than 97%;
B, auxiliary stabilizer composite: take by weighing 80 parts of step a gained main stabilizers, 5 parts of stearoyl benzoyl methanes, 5 parts in isobutyl phenyl ketone formyl methane, 6 parts of epoxy soybean oils, 1 part of ultrafine zeolite, 2 parts of hydrotalcites, 0.5 part of oxidized polyethlene wax, 0.5 part of XU 61518.10 by weight respectively, fully mixing promptly gets PVC sodium zinc composite stabilizer.
The PVC that present embodiment is made with sodium zinc composite stabilizer and polyvinyl chloride resin by weight for after 5:95 mixes, the dynamic stability time with Haake rheometer banburying test under 200 ℃ of conditions of temperature was not less than 10 minutes, and the steady stability time of static Congo red experiment test was not less than 60 minutes.
Embodiment 4
The preparation of a, main stabilizer: count by molar and take by weighing 45 parts of 40 parts of maleic acids, 15 parts of sodium bicarbonates and zinc subcarbonates respectively, be dissolved in maleic acid in the deionized water fully, be to add sodium bicarbonate under 1000 ~ 1500rpm condition several times in stir speed (S.S.) again, finish and be warming up to 80 ~ 95 ℃, under the insulated and stirred condition, add zinc subcarbonate several times, finish the insulated and stirred reaction to complete, solvent evaporated, take out solid product, under 130 ~ 150 ℃ of conditions of temperature, dry, promptly get main stabilizer, productive rate reaches more than 90%;
B, auxiliary stabilizer composite: take by weighing 60 parts of step a gained main stabilizers, 10 parts of stearoyl benzoyl methanes, 5 parts in isobutyl phenyl ketone formyl methane, 15 parts of epoxy soybean oils, 5 parts of ultrafine zeolites, 3 parts of polyethylene waxs, 1 part of oxidized polyethlene wax, 1 part of XU 61518.10 by weight respectively, fully mixing promptly gets PVC sodium zinc composite stabilizer.
The PVC that present embodiment is made with sodium zinc composite stabilizer and polyvinyl chloride resin by weight for after 10:90 mixes, the dynamic stability time with Haake rheometer banburying test under 200 ℃ of conditions of temperature was not less than 15 minutes, and the steady stability time of static Congo red experiment test was not less than 80 minutes.
Embodiment 5
The preparation of a, main stabilizer: count by molar and take by weighing 60 parts in 40 parts of maleic acids and sodium hydroxide respectively, be dissolved in maleic acid in the deionized water fully, be warming up to 80 ~ 95 ℃, be to add sodium hydroxide under 800 ~ 1500rpm condition several times in insulation, stir speed (S.S.) again, finish the insulated and stirred reaction to fully, obtain the maleic acid sodium solution; Count by molar and take by weighing 50 parts of 50 parts of maleic acids and zinc subcarbonates respectively, be dissolved in maleic acid in the deionized water fully, be to add zinc subcarbonate under 1000 ~ 1500rpm condition several times in stir speed (S.S.) again, finish stirring reaction, obtain the maleic acid zinc solution to fully; Is that 1:1 mixes with the maleic acid sodium solution and the maleic acid zinc solution of above-mentioned preparation according to the solute mol ratio, and stirring reaction is extremely complete, solvent evaporated, take out solid product, dry under 130 ~ 150 ℃ of conditions of temperature, promptly get main stabilizer, productive rate reaches more than 95%;
B, auxiliary stabilizer composite: take by weighing 70 parts of step a gained main stabilizers, 10 parts in isobutyl phenyl ketone formyl methane, 15 parts in epoxy sunflower oil, 3 parts of hydrotalcites, 1 part of stearic acid, 1 part of XU 61518.10 by weight respectively, fully mixing promptly gets PVC sodium zinc composite stabilizer.
The PVC that present embodiment is made with sodium zinc composite stabilizer and polyvinyl chloride resin by weight for after 10:90 mixes, the dynamic stability time with Haake rheometer banburying test under 200 ℃ of conditions of temperature was not less than 10 minutes, and the steady stability time of static Congo red experiment test was not less than 60 minutes.
Embodiment 6
The preparation of a, main stabilizer: count by molar and take by weighing 50 parts in 50 parts of maleic acids and sodium hydroxide respectively, be dissolved in maleic acid in the deionized water fully, be warming up to 80 ~ 95 ℃, be to add sodium hydroxide under 800 ~ 1500rpm condition several times in insulation, stir speed (S.S.) again, finish the insulated and stirred reaction to fully, obtain the maleic acid sodium solution; Count by molar and take by weighing 60 parts of 40 parts of maleic acids and zinc subcarbonates respectively, be dissolved in maleic acid in the deionized water fully, be to add zinc subcarbonate under 1000 ~ 1500rpm condition several times in stir speed (S.S.) again, finish stirring reaction, obtain the maleic acid zinc solution to fully; Is that 1:3 mixes with the maleic acid sodium solution and the maleic acid zinc solution of above-mentioned preparation according to the solute mol ratio, and stirring reaction is extremely complete, solvent evaporated, take out solid product, dry under 130 ~ 150 ℃ of conditions of temperature, promptly get main stabilizer, productive rate reaches more than 95%;
B, auxiliary stabilizer composite: take by weighing 65 parts of step a gained main stabilizers, 20 parts in isobutyl phenyl ketone formyl methane, 6 parts of epoxy soybean oils, 5 parts of ultrafine zeolites, 2 parts of stearic acid, 2 parts of XU 61518.10 by weight respectively, fully mixing promptly gets PVC sodium zinc composite stabilizer.
The PVC that present embodiment is made with sodium zinc composite stabilizer and polyvinyl chloride resin by weight for after 10:90 mixes, the dynamic stability time with Haake rheometer banburying test under 200 ℃ of conditions of temperature was not less than 10 minutes, and the steady stability time of static Congo red experiment test was not less than 60 minutes.
Embodiment 7
The preparation of a, main stabilizer: count by molar and take by weighing 50 parts in 50 parts of maleic acids and yellow soda ash respectively, be dissolved in maleic acid in the deionized water fully, be warming up to 80 ~ 95 ℃, be to add yellow soda ash under 800 ~ 1500rpm condition several times in insulation, stir speed (S.S.) again, finish the insulated and stirred reaction to fully, obtain the maleic acid sodium solution; Count by molar and take by weighing 50 parts in 50 parts of maleic acids and zinc oxide respectively, be dissolved in maleic acid in the deionized water fully, be to add zinc oxide under 1000 ~ 1500rpm condition several times in stir speed (S.S.) again, finish stirring reaction, obtain the maleic acid zinc solution to fully; Is that 3:1 mixes with the maleic acid sodium solution and the maleic acid zinc solution of above-mentioned preparation according to the solute mol ratio, and stirring reaction is extremely complete, solvent evaporated, take out solid product, dry under 130 ~ 150 ℃ of conditions of temperature, promptly get main stabilizer, productive rate reaches more than 95%;
B, auxiliary stabilizer composite: take by weighing 70 parts of step a gained main stabilizers, 10 parts in isobutyl phenyl ketone formyl methane, 10 parts in epoxy sunflower oil, 5 parts of ultrafine zeolites, 2 parts of stearic acid, 3 parts of XU 61518.10 by weight respectively, fully mixing promptly gets PVC sodium zinc composite stabilizer.
The PVC that present embodiment is made with sodium zinc composite stabilizer and polyvinyl chloride resin by weight for after 10:90 mixes, the dynamic stability time with Haake rheometer banburying test under 200 ℃ of conditions of temperature was not less than 15 minutes, and the steady stability time of static Congo red experiment test was not less than 80 minutes.
Embodiment 8
The preparation of a, main stabilizer: count by molar and take by weighing 60 parts in 40 parts of maleic acids and sodium hydroxide respectively, be dissolved in maleic acid in the deionized water fully, be warming up to 80 ~ 95 ℃, be to add sodium hydroxide under 800 ~ 1500rpm condition several times in insulation, stir speed (S.S.) again, finish the insulated and stirred reaction to complete, solvent evaporated is taken out solid product, under 130 ~ 150 ℃ of conditions of temperature, dry, obtain maleic acid sodium; Count by molar and take by weighing 30 parts in 40 parts of maleic acids, 30 parts of zinc carbonates and zinc oxide respectively, be dissolved in maleic acid in the deionized water fully, be to add zinc carbonate and zinc oxide under 1000 ~ 1500rpm condition several times in stir speed (S.S.) again, finish stirring reaction to complete, solvent evaporated, take out solid product, under 130 ~ 150 ℃ of conditions of temperature, dry, obtain maleic acid zinc; Is that 1:2 mixes with maleic acid sodium and maleic acid zinc according to mol ratio, promptly gets main stabilizer, and productive rate reaches more than 90%;
B, auxiliary stabilizer composite: take by weighing 65 parts of step a gained main stabilizers, 10 parts of stearyl benzoyls, 5 parts of diphenylpropane-1,3-dione(DPPO)s, 5 parts in decoyl benzoyl methane, 5 parts of epoxy soybean oils, 3 parts of bisphenol A diglycidyl ethers, 3 parts of ultrafine zeolites, 2 parts of hydrotalcites, 1 part of oxidized polyethlene wax, 1 part of XU 61518.10 by weight respectively, fully mixing promptly gets PVC sodium zinc composite stabilizer.
The PVC that present embodiment is made with sodium zinc composite stabilizer and polyvinyl chloride resin by weight for after 5:95 mixes, the dynamic stability time with Haake rheometer banburying test under 200 ℃ of conditions of temperature was not less than 10 minutes, and the steady stability time of static Congo red experiment test was not less than 60 minutes.
Embodiment 9
The preparation of a, main stabilizer: count by molar and take by weighing 50 parts of 50 parts of maleic acids and sodium bicarbonates respectively, be dissolved in maleic acid in the deionized water fully, be warming up to 80 ~ 95 ℃, be to add sodium bicarbonate under 800 ~ 1500rpm condition several times in insulation, stir speed (S.S.) again, finish the insulated and stirred reaction to complete, solvent evaporated is taken out solid product, under 130 ~ 150 ℃ of conditions of temperature, dry, obtain maleic acid sodium; Count by molar and take by weighing 50 parts in 50 parts of maleic acids and zinc oxide respectively, be dissolved in maleic acid in the deionized water fully, be to add zinc oxide under 1000 ~ 1500rpm condition several times in stir speed (S.S.) again, finish stirring reaction to complete, solvent evaporated, take out solid product, under 130 ~ 150 ℃ of conditions of temperature, dry, obtain maleic acid zinc; Is that 2:1 mixes with maleic acid sodium and maleic acid zinc according to mol ratio, promptly gets main stabilizer, and productive rate reaches more than 90%;
B, auxiliary stabilizer composite: take by weighing 1 part of 65 parts of step a gained main stabilizers, 5 parts of stearyl benzoyls, 5 parts of diphenylpropane-1,3-dione(DPPO)s, 5 parts in decoyl benzoyl methane, 8 parts of epoxy soybean oils, 7 parts of bisphenol A diglycidyl ethers, 2 parts of ultrafine zeolites, 1 part of hydrotalcite, 1 part of oxidized polyethlene wax and XU 61518.10 by weight respectively, fully mixing promptly gets PVC sodium zinc composite stabilizer.
The PVC that present embodiment is made with sodium zinc composite stabilizer and polyvinyl chloride resin by weight for after 10:90 mixes, the dynamic stability time with Haake rheometer banburying test under 200 ℃ of conditions of temperature reached more than 15 minutes, and the steady stability time of static Congo red experiment test reached more than 80 minutes.
Explanation is at last, above preferred embodiment is only unrestricted in order to technical scheme of the present invention to be described, although by invention has been described with reference to the preferred embodiments of the present invention, but those of ordinary skill in the art is to be understood that, can make various changes to it in the form and details, and the spirit and scope of the present invention that do not depart from appended claims and limited.
Claims (6)
1.PVC use the sodium zinc composite stabilizer, it is characterized in that: form for 20 ~ 45 parts by 55 ~ 80 parts of main stabilizers and auxiliary stabilizer by weight; Described main stabilizer is the mixture of maleic acid sodium and maleic acid zinc.
2. PVC sodium zinc composite stabilizer according to claim 1 is characterized in that: 20 ~ 45 parts of described auxiliary stabilizers are composed of the following components by weight:
Component A: be selected from stearoyl benzoyl methane, diphenylpropane-1,3-dione(DPPO), isobutyl phenyl ketone formyl methane and the decoyl benzoyl methane one or more, 10 ~ 20 parts;
B component: be selected from glycidyl ether, cycloaliphatic epoxy resin, trimellitic acid three-glycidyl ester and the diglycidyl terephthalate of glycidyl ether, tetraphenyl ethane of epoxy soybean oil, epoxy sunflower oil, bisphenol A diglycidyl ether, Bisphenol F diglycidylether, resol one or more, 6 ~ 15 parts;
Component C: be selected from ultrafine zeolite and/or hydrotalcite, 3 ~ 5 parts;
Component D: be selected from paraffin, polyethylene wax, oxidized polyethlene wax, stearic acid, butyl stearate and the XU 61518.10 one or more, 1 ~ 5 part.
3. PVC sodium zinc composite stabilizer according to claim 2, it is characterized in that: described B component is selected from one or more in epoxy soybean oil, epoxy sunflower oil and the bisphenol A diglycidyl ether; Component D is selected from one or more in polyethylene wax, oxidized polyethlene wax, stearic acid and the XU 61518.10.
4. the described PVC of claim 1 is characterized in that: may further comprise the steps with the preparation method of sodium zinc composite stabilizer:
The preparation of a, main stabilizer: count by molar and take by weighing 5 ~ 45 parts of 15 ~ 55 parts of 40 ~ 55 parts of maleic acids, compounds containing sodium and zinc compounds respectively, described compounds containing sodium is one or more in sodium hydroxide, yellow soda ash and the sodium bicarbonate, and described zinc compound is one or more in zinc oxide, zinc carbonate, zinc subcarbonate and the zinc hydroxide; Maleic acid is dissolved in the water, adds compounds containing sodium under agitation condition, finish and be warming up to 80 ~ 95 ℃, add zinc compound under the insulated and stirred condition, finish the insulated and stirred reaction to fully, get solid product, drying promptly gets main stabilizer;
B, auxiliary stabilizer composite: take by weighing 20 ~ 45 parts of 55 ~ 80 parts of step a gained main stabilizers and auxiliary stabilizers by weight respectively, fully mixing promptly gets PVC sodium zinc composite stabilizer.
5. the described PVC of claim 1 is characterized in that: may further comprise the steps with the preparation method of sodium zinc composite stabilizer:
The preparation of a, main stabilizer: count by molar and take by weighing 50 ~ 60 parts of 40 ~ 50 parts of maleic acids and compounds containing sodiums respectively, described compounds containing sodium is one or more in sodium hydroxide, yellow soda ash and the sodium bicarbonate, maleic acid is dissolved in the water, be warming up to 80 ~ 95 ℃, under the insulated and stirred condition, add compounds containing sodium again, finish the insulated and stirred reaction to fully, obtain the maleic acid sodium solution; Count by molar and take by weighing 50 ~ 60 parts of 40 ~ 50 parts of maleic acids and zinc compounds respectively, described zinc compound is one or more in zinc oxide, zinc carbonate, zinc subcarbonate and the zinc hydroxide, maleic acid is dissolved in the water, under agitation condition, add zinc compound again, finish stirring reaction to fully, obtain the maleic acid zinc solution; Is that 3:1 ~ 1:3 mixes with maleic acid sodium solution and maleic acid zinc solution according to the solute mol ratio, and stirring reaction is got solid product to fully, and drying promptly gets main stabilizer;
B, auxiliary stabilizer composite: take by weighing 20 ~ 45 parts of 55 ~ 80 parts of step a gained main stabilizers and auxiliary stabilizers by weight respectively, fully mixing promptly gets PVC sodium zinc composite stabilizer.
6. the described PVC of claim 1 is characterized in that: may further comprise the steps with the preparation method of sodium zinc composite stabilizer:
The preparation of a, main stabilizer: count by molar and take by weighing 50 ~ 60 parts of 40 ~ 50 parts of maleic acids and compounds containing sodiums respectively, described compounds containing sodium is one or more in sodium hydroxide, yellow soda ash and the sodium bicarbonate, maleic acid is dissolved in the water, be warming up to 80 ~ 95 ℃, under the insulated and stirred condition, add compounds containing sodium again, finish the insulated and stirred reaction, get solid product to fully, drying obtains maleic acid sodium; Count by molar and take by weighing 50 ~ 60 parts of 40 ~ 50 parts of maleic acids and zinc compounds respectively, described zinc compound is one or more in zinc oxide, zinc carbonate, zinc subcarbonate and the zinc hydroxide, maleic acid is dissolved in the water, under agitation condition, add zinc compound again, finish stirring reaction to complete, get solid product, drying obtains maleic acid zinc; Is that 2:1 ~ 1:2 mixes with maleic acid sodium and maleic acid zinc according to mol ratio, promptly gets main stabilizer;
B, auxiliary stabilizer composite: take by weighing 20 ~ 45 parts of 55 ~ 80 parts of step a gained main stabilizers and auxiliary stabilizers by weight respectively, fully mixing promptly gets PVC sodium zinc composite stabilizer.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103571108A (en) * | 2013-11-25 | 2014-02-12 | 西南大学 | Oxidized graphene salt-based PVC environment-friendly composite stabilizer and preparation method thereof |
| CN103665671A (en) * | 2013-12-13 | 2014-03-26 | 重庆莘然高分子材料有限公司 | Compound stabilizer for polyvinyl chloride (PVC) and preparation method thereof |
| CN106519127A (en) * | 2016-12-01 | 2017-03-22 | 贵州华锐达环保装饰材料有限公司 | Method for preparing calcium-zinc epoxy copolymer core-shell emulsion and modified wood plastic material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1590437A (en) * | 2004-04-29 | 2005-03-09 | 北京化工大学 | Hgdrotalcite base chlorine containing high polymer composite heat stabilizing agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1590437A (en) * | 2004-04-29 | 2005-03-09 | 北京化工大学 | Hgdrotalcite base chlorine containing high polymer composite heat stabilizing agent |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103571108A (en) * | 2013-11-25 | 2014-02-12 | 西南大学 | Oxidized graphene salt-based PVC environment-friendly composite stabilizer and preparation method thereof |
| CN103571108B (en) * | 2013-11-25 | 2015-08-12 | 西南大学 | Based on the PVC environment-friendlycomposite one package stabilizer and preparation method thereof of graphene oxide salt |
| CN103665671A (en) * | 2013-12-13 | 2014-03-26 | 重庆莘然高分子材料有限公司 | Compound stabilizer for polyvinyl chloride (PVC) and preparation method thereof |
| CN106519127A (en) * | 2016-12-01 | 2017-03-22 | 贵州华锐达环保装饰材料有限公司 | Method for preparing calcium-zinc epoxy copolymer core-shell emulsion and modified wood plastic material |
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