CN101914218A - Powdered composite calcium zinc stabilizing agent and preparation method thereof - Google Patents
Powdered composite calcium zinc stabilizing agent and preparation method thereof Download PDFInfo
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- CN101914218A CN101914218A CN2010101568714A CN201010156871A CN101914218A CN 101914218 A CN101914218 A CN 101914218A CN 2010101568714 A CN2010101568714 A CN 2010101568714A CN 201010156871 A CN201010156871 A CN 201010156871A CN 101914218 A CN101914218 A CN 101914218A
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Abstract
The invention relates to a powdered composite calcium zinc stabilizing agent and a preparation method thereof and belongs to the preparation of a stabilizing agent for plastic processing. The stabilizing agent consists of the following components in percentage by weight: 14 to 38 percent of poly-fatty acid resin calcium zinc, 20 to 45 percent of epoxy fatty acid calcium zinc soap, 10 to 15 percent of phosphite ester, 10 to 15 percent of beta-diketone compound, 11 to 23 percent of hindered phenol antioxidant and 10 to 15 percent of lubricant. The preparation method comprises the following steps of: throwing a poly-fatty acid resin, a hydroxide of an alkali-earth metal, an oxide of zinc, high alcohol and oleic acid according to proportion into a reactor to perform salifying reaction to obtain the poly-fatty acid resin calcium zinc; performing epoxidation of the oleic acid, hydrogen peroxide and glacial acetic acid serving as raw materials in the presence of concentrated sulfuric acid serving as a catalyst according to the proportion to generate epoxy fatty acid, directly reacting the epoxy fatty acid with calcium hydroxide to obtain the high-purity epoxy fatty acid calcium soap; and compounding the poly-fatty acid resin calcium zinc with the epoxy fatty acid calcium soap reasonably and then adding other auxiliary agents to obtain the stabilizing agent. The powdered composite calcium zinc stabilizing agent and the preparation method thereof can effectively solve the problems of low compatibility and low dyeing property at an initial stage of the conventional polyvinyl chloride (PVC) calcium zinc stabilizing agent.
Description
Technical field
The invention belongs to the preparation of the stablizer of plastic working, refer in particular to a kind of powdered composite calcium zinc stabilizing agent and preparation method thereof.
Background technology
Since mid-term the 1950's, China has begun independently to form a complete production network since the PVC thermo-stabilizer, and the consumption of thermo-stabilizer increases considerably along with the fast development of PVC industry, and thermo-stabilizer has developed into the second largest series products of additives for plastics.In recent years, China's thermo-stabilizer also has a certain amount of import and export, but because China's thermo-stabilizer product specification is not high, high malicious product is still occupied an leading position, export varieties mainly is the lead salts thermo-stabilizer, annual export volume is about four or five kilotons, and the environment-friendly calcium zinc stabilizer and the organic tin thermo-stabilizer of the some amount of import simultaneously are to satisfy the demand of domestic plastic working industry.Though some import stablizer performances are good in the market, but price is higher, about 3～50,000 yuan/ton as the calcium zinc stabilizer of import, about 4～60,000 yuan/ton of the organotin stabilizer of import.On the other hand, the research of present domestic calcium zinc also is in the exploratory stage, and its stability of home-made calcium soap zinc soap compound stabilizer is relatively poor relatively, and is also bad with the consistency of PVC, and calcium soap consumption poor transparency, easily bloom when big.Just because of domestic no matured product, and imported product price height is restricting China and is prohibiting promotion efficiency plumbous, tin, has formed homemade PVC goods taking environmental conservation into consideration not substantially, and the PVC goods of outlet goods and some higher class have to be with the situation of import thermo-stabilizer.Therefore, in the face of the continuous growth of domestic and international market to nontoxic PVC goods demand, and domestic PVC goods export the unleaded green barrier of global range that is faced, carry out composite calcium zinc PVC thermo-stabilizer tackling of key scientific and technical problems nontoxic, efficient, high stable, realize extensive production domesticization production, promote the product restructuring optimization of China PVC thermo-stabilizer, concerning us, have crucial meaning.The patent of domestic relevant environment-friendly type PVC stablizer is also only just like 03120918.1 (a kind of methyl, the preparation method of zinc isoctyl mercaptoacetate), (200510117186.X containing the double bond organic anion intercalated houghite reaches used as thermo-stabilizer), (200610034532.2 dicarboxylate is as the application of PVC thermo-stabilizer), (200610086380.0 soybean protein in the PVC plastic working as the application of thermostable adjuvant), few reports such as (200410027562.1 a kind of polyvinyl-chloride use rare earth calcium zinc stabilizers and preparation method thereof).About the acid of polyphosphazene polymer fat is not seen document and patent report as yet as the research of the organic anion of calcium/zinc soap class.
Develop powdered composite calcium zinc PVC stablizer cheap, production domesticization, nontoxic, efficient, high stable, effectively import substitutes reduce cost.The shortcoming of calcium/zinc soap class maximum is that initial coloring is big, dispersiveness is also undesirable, and powdered composite calcium zinc stabilizing agent can overcome above shortcoming, advantages the such as wherein calcium zinc stabilizer of powder has satisfactory stability and lubricity, and vicat softening temperature, the cost that does not reduce PVC simultaneously is low, VOC content is low.At present, research to calcium/zinc soap class concentrates on the texture improvement and formulation optimization of organic anion mostly, the present invention adopts the polyglycerol fatty acid of acrylate functionalization of autonomous design as the anionic group of calcium zinc soap, simultaneously epoxide group is incorporated on the lipid acid, give full play to the high-compatibility of polyglycerol fatty acid and PVC, the efficient auxiliary stabilization of epoxy compounds, can effectively solve the problem that consistency is poor, initial coloring is bad that current home-made PVC calcium-zinc composite stabilizing agent exists.
Summary of the invention
The invention discloses a kind of efficient powdered composite calcium zinc stabilizing agent and preparation method thereof, the polyglycerol fatty acid of the acrylate functionalization of employing autonomous design is as the negatively charged ion combination of calcium zinc soap.This polyglycerol fatty acid and PVC have consistency preferably, can solve present PVC calcium zinc stabilizer effectively and exist consistency poor, the problem that initial coloring is bad.On this basis, epoxide group is incorporated on the lipid acid, the auxiliary stabilization of epoxy compounds can be combined with the stability of fatty acid soaps salt, improve the thermostability of one package stabilizer effectively.
One of purpose of the present invention provides that a kind of consistency is good, high effect nontoxic, initial coloring is good and have a kind of efficient powdered composite calcium zinc stabilizing agent of good environmental-protecting performance.
Efficient powdered composite calcium zinc stabilizing agent is made up of the component of following weight part: polyglycerol fatty acid resin calcium zinc 14～38%, epoxyfatty acid calcium zinc soap 20～45%, phosphorous acid ester 10～15%, beta-diketone compounds 10～15%, Hinered phenols antioxidant 11～23%, lubricant 10～15%.
Described beta-diketone compounds is liquid beta-diketon or methyl ethyl diketone.
Described Hinered phenols antioxidant be 2,6 di t butyl phenol (2,6-DTBP), 3,5-di-tert-butyl-4-hydroxyl benzyl dimethylamine (benzyl methylamine) or 3,5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphonate (1222).
Described lubricant is ethylene bis stearamide (EBS).
The preparation method of the polyglycerol fatty acid resin calcium zinc of described acrylate functionalization is as follows: add oleic acid earlier, under at the uniform velocity stirring, slowly heat up, when temperature is raised to 55～65 ℃, add the polyglycerol fatty acid resin again, calcium hydroxide, zinc oxide and higher alcohols are carried out to reactant salt, by controlling reaction time 2～3h, 65～70 ℃ of temperature of reaction, pressure is normal pressure, obtain the polyglycerol fatty acid resin of acrylate functionalization, wherein the add-on of polyglycerol fatty acid resin is 18～38 weight parts, the add-on of calcium hydroxide is 15～35 weight parts, the add-on of zinc oxide is 10～16 weight parts, the add-on of higher alcohols is 15～20 weight parts, oleic add-on is 17～28 weight parts.
Described higher alcohols is the mixture that contains six carbon atom～eight a carbon atom monohydroxy-alcohol.
The preparation method of described epoxyfatty acid calcium soap is as follows: with oleic acid, hydrogen peroxide, Glacial acetic acid is a raw material, with the vitriol oil is that catalyzer carries out epoxidation reaction, the epoxyfatty acid that generates, directly and calcium hydroxide reaction, reaction times 3～4h, 70～80 ℃ of temperature of reaction, pressure is normal pressure, obtain epoxy group(ing) and keep intact high purity epoxyfatty acid calcium soap, wherein oleic add-on is 30～48 weight parts, the add-on of hydrogen peroxide is 20～40 weight parts, the add-on of Glacial acetic acid is 10～35 weight parts, the add-on of the vitriol oil is 1.3～1.4 weight parts, the add-on of calcium hydroxide is 10～16 weight parts.
Among the preparation method of above-mentioned epoxyfatty acid calcium soap, the actual conditions of epoxidation reaction is: reaction times 3～4h, 65 ℃ of temperature of reaction, pressure are normal pressure.
Second purpose of the present invention provides the preparation method of above-mentioned efficient powdered composite calcium zinc stabilizing agent, is specially:
1) in proportion the oxyhydroxide of polyglycerol fatty acid resin and alkaline-earth metal, oxide compound, higher alcohols and the oleic acid of zinc are dropped into reactor, be carried out to reactant salt, by controlling reaction time, temperature, pressure and catalyzer, obtain the polyglycerol fatty acid resin calcium zinc of acrylate functionalization.
2) be raw material with oleic acid, hydrogen peroxide, Glacial acetic acid in proportion, the vitriol oil is that catalyzer carries out epoxidation reaction, the epoxyfatty acid that generates is under the effect of catalyzer, and direct and calcium hydroxide reaction can obtain epoxy group(ing) and keep intact high purity epoxyfatty acid calcium soap.
3) polyglycerol fatty acid resin calcium zinc and the epoxyfatty acid calcium soap with acrylate functionalization carries out rationally composite, be aided with organic auxiliary stabilizer such as phosphorous acid ester, beta-diketone compounds again, reach other auxiliary agents such as Hinered phenols antioxidant, lubricant, obtain composite calcium zinc stabilizing agent efficient, high stability.
The present invention proposes this polyglycerol fatty acid and PVC has consistency preferably, can solve present PVC calcium zinc stabilizer effectively and exist consistency poor, and the bad theory problem foundation of initial coloring is:
Promptly this polyglycerol fatty acid resin has the similar macromolecular structure with PVC, and more polar functional group is arranged, and can increase the consistency of thermo-stabilizer and PVC effectively.
Epoxyfatty acid calcium zinc soap in the efficient powdered composite calcium zinc stabilizing agent provided by the invention, structure with close diene reagent, the function of existing absorption HCl, simultaneously again can be to a certain extent with the PVC chain on the conjugated polyene segment DielsAlder reaction takes place, increase thereby block it, suppress the degraded of PVC.
Embodiment
Embodiment one: efficient powdered composite calcium zinc stabilizing agent
1, the preparation of the polyglycerol fatty acid resin of acrylate functionalization
In reactive tank, add the oleic acid of 893kg, under at the uniform velocity stirring, slowly heat up.When temperature is raised to 65 ℃, add the polyglycerol fatty acid resin of 180kg, the calcium hydroxide of 150kg, the zinc oxide of 100kg, the higher alcohols of 950kg is carried out to reactant salt, stirs insulation, and temperature remains on 65～70 ℃, and constant temperature is two hours under the normal pressure.Material in the reactive tank is beaten to letdown tank.
2, the preparation of high purity epoxyfatty acid calcium
In reactive tank, add the oleic acid of 1786kg, under at the uniform velocity stirring, slowly heat up.When temperature is raised to 55～65 ℃, stop heating, add the Glacial acetic acid of 200kg, vitriol oil 30kg.Begin to drip hydrogen peroxide 1040kg.The control rate of addition, about 1h dropwises, and continues to stir 3h, and temperature is controlled at 65 ℃, and the epoxyoleic acid of generation washes with water to neutrality, dewaters under the vacuum.Be heated to 70～80 ℃, add the calcium hydroxide of 150kg, stir insulation 3h.Material in the reactive tank is beaten to letdown tank.
3, the preparation of efficient powdered composite calcium zinc stabilizing agent
With the polyglycerol fatty acid resin of 170kg acrylate functionalization, the epoxyfatty acid calcium soap of 350kg, the organic auxiliary stabilizer that adds other again, that is, the liquid beta-diketon of the phosphorous acid ester of 100kg and 135kg adds 125kg2 simultaneously, 6-DI-tert-butylphenol compounds (2,6-DTBP), the EBS of 100kg puts into compound still in order and carries out compound, stir after one hour, after drying under 50 ℃ of normal pressures, obtain efficient powder calcium zinc stabilizer.
Embodiment two: efficient powdered composite calcium zinc stabilizing agent
1, the preparation of the polyglycerol fatty acid resin of acrylate functionalization
In reactive tank, the oleic acid of inferior adding 129kg slowly heats up under at the uniform velocity stirring.When temperature is raised to 60 ℃, add the polyglycerol fatty acid resin of 17.5kg, the calcium hydroxide of 15.6kg, the zinc oxide of 10.5kg, the higher alcohols of 94kg is carried out to reactant salt, stirs insulation, and temperature remains on 65～70 ℃, and constant temperature is 3 hours under the normal pressure.Material in the reactive tank is beaten to letdown tank.
2, the preparation of high purity epoxyfatty acid calcium
In reactive tank, add the oleic acid of 258kg, under at the uniform velocity stirring, slowly heat up.When temperature is raised to 55～65 ℃, stop heating, add the Glacial acetic acid of 20.6kg, vitriol oil 3kg.Begin to drip hydrogen peroxide 104kg.The control rate of addition, about 1h dropwises, and continues to stir 4h, and temperature is controlled at 65 ℃, and the epoxyoleic acid of generation washes with water to neutrality, dewaters under the vacuum.Be heated to 70～80 ℃, add the calcium hydroxide of 14.5kg, stir insulation 4h.Material in the reactive tank is beaten to letdown tank.
3, the preparation of efficient powdered composite calcium zinc stabilizing agent
With the polyglycerol fatty acid resin of 17.5kg acrylate functionalization, the epoxyfatty acid calcium soap of 35.7kg, the organic auxiliary stabilizer that adds other again, that is, the liquid beta-diketon of the phosphorous acid ester of 10kg and 13.5kg adds 12.5kg2 simultaneously, 6-DI-tert-butylphenol compounds (2,6-DTBP), the EBS of 9kg puts into compound still in order and carries out compound, stir after one hour, after drying under 50 ℃ of normal pressures, obtain efficient powder calcium zinc stabilizer.
Embodiment three: efficient powdered composite calcium zinc stabilizing agent
1, the preparation of the polyglycerol fatty acid resin of acrylate functionalization
In reactive tank, the oleic acid of inferior adding 155kg slowly heats up under at the uniform velocity stirring.When temperature is raised to 55 ℃, add the polyglycerol fatty acid resin of 21kg, the calcium hydroxide of 18.72kg, the zinc oxide of 12.6kg, the higher alcohols of 112.8kg is carried out to reactant salt, stirs insulation, and temperature remains on 65～70 ℃, and constant temperature is two hours under the normal pressure.Material in the reactive tank is beaten to letdown tank.
2, the preparation of high purity epoxyfatty acid calcium
In reactive tank, add the oleic acid of 213kg, under at the uniform velocity stirring, slowly heat up.When temperature is raised to 55～65 ℃, stop heating, add the Glacial acetic acid of 24.72kg, vitriol oil 3.6kg.Begin to drip hydrogen peroxide 125kg.The control rate of addition, about 1h dropwises, and continues to stir 3h, and temperature is controlled at 65 ℃, and the epoxyoleic acid of generation washes with water to neutrality, dewaters under the vacuum.Be heated to 70～80 ℃, add the calcium hydroxide of 17.4kg, stir insulation 3h.Material in the reactive tank is beaten to letdown tank.
3, the preparation of efficient powdered composite calcium zinc stabilizing agent
With the polyglycerol fatty acid resin of 21kg acrylate functionalization, the epoxyfatty acid calcium soap of 45kg, the organic auxiliary stabilizer that adds other again, that is, the liquid beta-diketon of the phosphorous acid ester of 12kg and 16.2kg adds 15kg2 simultaneously, 6-DI-tert-butylphenol compounds (2,6-DTBP), the EBS of 10.8kg puts into compound still in order and carries out compound, stir after one hour, after drying under 50 ℃ of normal pressures, obtain efficient powder calcium zinc stabilizer.
Claims (9)
1. powdered composite calcium zinc stabilizing agent, it is characterized in that: the component by following weight part is formed: polyglycerol fatty acid resin calcium zinc 14～38%, epoxyfatty acid calcium soap 20～45%, phosphorous acid ester 10～15%, beta-diketone compounds 10～15%, Hinered phenols antioxidant 11～23%, lubricant 10～15%.
2. the described powdered composite calcium zinc stabilizing agent of claim 1, it is characterized in that: described beta-diketone compounds is liquid beta-diketon or methyl ethyl diketone.
3. the described powdered composite calcium zinc stabilizing agent of claim 1, it is characterized in that: described Hinered phenols antioxidant is a 2,6 di t butyl phenol, 3,5-di-tert-butyl-4-hydroxyl benzyl dimethylamine or 3,5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphonate.
4. the described powdered composite calcium zinc stabilizing agent of claim 1, it is characterized in that: described lubricant is an ethylene bis stearamide.
5. the described powdered composite calcium zinc stabilizing agent of claim 1, it is characterized in that: the preparation method of the polyglycerol fatty acid resin calcium zinc of described acrylate functionalization is as follows: add oleic acid earlier, under at the uniform velocity stirring, slowly heat up, when temperature is raised to 55～65 ℃, add the polyglycerol fatty acid resin again, calcium hydroxide, zinc oxide and higher alcohols are carried out to reactant salt, by controlling reaction time 2～3h, 65～70 ℃ of temperature of reaction, pressure is normal pressure, obtain the polyglycerol fatty acid resin of acrylate functionalization, wherein the add-on of polyglycerol fatty acid resin is 18～38 weight parts, the add-on of calcium hydroxide is 15～35 weight parts, the add-on of zinc oxide is 10～16 weight parts, the add-on of higher alcohols is 15～20 weight parts, oleic add-on is 17～28 weight parts.
6. the described powdered composite calcium zinc stabilizing agent of claim 5, it is characterized in that: described higher alcohols is the mixture that contains six carbon atom～eight a carbon atom monohydroxy-alcohol.
7. the described powdered composite calcium zinc stabilizing agent of claim 1, it is characterized in that: the preparation method of described epoxyfatty acid calcium soap is as follows: with oleic acid, hydrogen peroxide, Glacial acetic acid is a raw material, with the vitriol oil is that catalyzer carries out epoxidation reaction, the epoxyfatty acid that generates, directly and calcium hydroxide reaction, reaction times 3～4h, 70～80 ℃ of temperature of reaction, pressure is normal pressure, obtain epoxy group(ing) and keep intact high purity epoxyfatty acid calcium, wherein oleic add-on is 30～48 weight parts, the add-on of hydrogen peroxide is 20～40 weight parts, the add-on of Glacial acetic acid is 10～35 weight parts, the add-on of the vitriol oil is 1.3～1.4 weight parts, the add-on of calcium hydroxide is 10～16 weight parts.
8. the described powdered composite calcium zinc stabilizing agent of claim 7, it is characterized in that: among the preparation method of above-mentioned epoxyfatty acid calcium soap, the actual conditions of epoxidation reaction is: reaction times 3～4h, 65 ℃ of temperature of reaction, pressure are normal pressure.
9. the preparation method of the described powdered composite calcium zinc stabilizing agent of claim 1 is specially:
1) in proportion polyglycerol fatty acid resin and calcium hydroxide, zinc oxide, higher alcohols and oleic acid are dropped into reactor, be carried out to reactant salt,, obtain the polyglycerol fatty acid resin calcium zinc of acrylate functionalization by controlling reaction time, temperature, pressure and catalyzer;
2) be raw material with oleic acid, hydrogen peroxide, Glacial acetic acid in proportion, the vitriol oil is that catalyzer carries out epoxidation reaction, the epoxyfatty acid that generates is under the effect of catalyzer, and direct and calcium hydroxide reaction obtains epoxy group(ing) and keeps intact high purity epoxyfatty acid calcium soap;
3) the polyglycerol fatty acid resin calcium zinc of acrylate functionalization and epoxyfatty acid calcium soap are carried out composite, be aided with phosphorous acid ester, beta-diketone compounds, Hinered phenols antioxidant and lubricant again, obtain powdered composite calcium zinc stabilizing agent.
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| CN102604295A (en) * | 2012-01-12 | 2012-07-25 | 河北大学 | Polymer calcium zinc complex soap heat stabilizer, preparation method thereof and application thereof |
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Application publication date: 20101215 |