阅读说明：本技术 钙锌复合稳定剂及其制备方法 (Calcium-zinc composite stabilizer and preparation method thereof ) 是由 单单 单建国 贾爱东 于 2020-06-17 设计创作，主要内容包括：本发明公开了钙锌复合稳定剂及其制备方法,该钙锌复合稳定剂包括：硬脂酸钙10-15份、硬脂酸锌12-18份、改性水滑石15-18、改性助剂5-10份和添加剂组15-35份。本发明具有优异的热稳定性,抑制初期着色能力强,稳定效果佳,剔除了传统热稳定剂存在的铅、镉、汞等有毒重金属成份,可有效改善材料的耐候性,绿色环保。(The invention discloses a calcium-zinc composite stabilizer and a preparation method thereof, wherein the calcium-zinc composite stabilizer comprises the following components: 10-15 parts of calcium stearate, 12-18 parts of zinc stearate, 15-18 parts of modified hydrotalcite, 5-10 parts of modified auxiliary agent and 15-35 parts of additive group. The invention has excellent thermal stability, strong capability of inhibiting initial coloring and good stabilizing effect, eliminates toxic heavy metal components such as lead, cadmium, mercury and the like in the traditional heat stabilizer, can effectively improve the weather resistance of the material, and is green and environment-friendly.)

1. The calcium-zinc composite stabilizer is characterized by comprising the following components in parts by weight: 10-15 parts of calcium stearate, 12-18 parts of zinc stearate, 15-18 parts of modified hydrotalcite, 5-10 parts of modified auxiliary agent and 15-35 parts of additive group.

2. The calcium-zinc composite stabilizer according to claim 1, wherein the modification auxiliary agent comprises 3-4 parts of 1, 3-dimethyl-6-aminouracil, 4-5 parts of lanthanum maleamate and 0.5-1 part of nanotube-shaped modified halloysite.

3. The calcium-zinc composite stabilizer according to claim 2, wherein the nanotube-shaped modified halloysite is a silane coupling agent surface-modified halloysite nanotube, and the preparation method comprises the following steps:

step one, intercalation modification: drying halloysite nanotubes, suspending the halloysite nanotubes in dimethyl sulfoxide solution, stirring, carrying out suction filtration and drying, grinding the obtained solid and lauric acid in a mass ratio of 2: 2-3, and heating to obtain an intercalation modified halloysite nanotube;

step two, surface activity modification: dispersing the intercalated and modified halloysite nanotubes in water to prepare 1-4 mg/ml dispersion, adding a silane coupling agent solution, uniformly mixing, wherein the mass ratio of the silane coupling agent to the halloysite nanotubes in the mixed solution is 1: 1-5, and stirring for reaction to obtain a halloysite nanotube aqueous solution with the surface modified by the silane coupling agent; and cooling, filtering and drying to obtain the modified halloysite nanotube.

4. The calcium-zinc composite stabilizer according to claim 3, wherein in the first step, the concentration of the dimethyl sulfoxide solution is 90-95 wt%; the stirring is carried out for 60-80 h at the temperature of 20-30 ℃; the heating treatment is heating in a water bath at the temperature of 75-85 ℃ for 40-60 h; in the second step, the reaction temperature is 70-90 ℃, and the reaction time is 1-5 h.

5. The calcium-zinc composite stabilizer according to claim 1, wherein the preparation method of the modified hydrotalcite comprises the following steps:

step a: putting hydrotalcite in an ethanol solution, performing ultrasonic treatment for 10-15min under the power of 400-600W, performing centrifugal separation, retaining the bottom solid, repeating for 3-5 times, and then drying and grinding to prepare pretreated hydrotalcite;

step b: adding the pretreated hydrotalcite into water to prepare 10-15% suspension, heating the suspension to 80 ℃ in a water bath, adding hexadecyl dimethyl benzyl quaternary ammonium chloride and isooctyl alcohol polyoxyethylene ether phosphate while stirring, continuously stirring and reacting for 2 hours at constant temperature, carrying out ultrasonic oscillation, carrying out suction filtration, washing the filtrate with deionized water until no precipitate is generated by dropwise adding silver nitrate, and drying, crushing and sieving the filtrate to prepare a modified precursor;

step c: weighing acrylic acid, acrylamide and 2-acrylamidotetradecane sulfonic acid according to a molar ratio of 6:1-3:2, adding a NaOH solution into the acrylic acid for neutralization while stirring under an ice bath condition, controlling the neutralization degree of the acrylic acid to be 75%, then adding the acrylamide and the 2-acrylamidotetradecane sulfonic acid, and fully stirring until a monomer is completely dissolved to prepare a reaction monomer solution;

step d: adding span-80 into cyclopentane according to the mass ratio of 1:5, introducing nitrogen, heating in a water bath to 75 ℃, and stirring until the span-80 is completely dissolved to obtain an oil phase;

step e: adding the modified precursor into a reaction monomer solution, fully stirring, performing ultrasonic dispersion, adding N, N-methylene bisacrylamide and ammonium persulfate, uniformly stirring, adding into an oil phase under a nitrogen atmosphere, introducing nitrogen for 15min, performing reverse phase suspension composite reaction, cooling to room temperature after the reaction is finished, and filtering, washing, drying, grinding and sieving to obtain the modified hydrotalcite.

6. The calcium-zinc composite stabilizer according to claim 5, wherein the amount of the hexadecyl dimethyl benzyl quaternary ammonium chloride in the step b is 35 to 40 percent of the mass of the pretreated hydrotalcite, and the amount of the isooctanol polyoxyethylene ether phosphate ester is 8 to 12 percent of the mass of the pretreated hydrotalcite; the amount of span-80 is 0.2-0.8% of the total mass of the three reaction monomers, the amount of N, N-methylene bisacrylamide is 0.01-0.02% of the total mass of the three reaction monomers, the amount of ammonium persulfate is 0.05-0.2% of the total mass of the three reaction monomers, and the amount of the modified precursor is 45-60% of the total mass of the three reaction monomers; the conditions of the reversed phase suspension composite reaction are as follows: reacting at 35-40 deg.C for 20min, reacting at 45-50 deg.C for 25min, reacting at 55-60 deg.C for 60min, and reacting at 68-72 deg.C for 90 min.

7. The calcium-zinc composite stabilizer according to claim 1, wherein the additive group comprises 2-5 parts of a dispersant, 2-5 parts of a surfactant, 8-15 parts of an external lubricant, 3-5 parts of an internal lubricant and 0.5-1.5 parts of an antioxidant.

8. The calcium-zinc composite stabilizer according to claim 7, wherein the dispersant comprises one or more of stearic acid monoglyceride, oleic acid acyl, polyethylene glycol and stearamide, the surfactant is polyoxyethylene lauryl ether, the internal lubricant is fatty alcohol dicarboxylate, the external lubricant is one or two of polyethylene wax and Fischer-Tropsch wax, and the antioxidant is one or two of n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and antioxidant 1010.

9. A method for preparing a calcium-zinc composite stabilizer according to any one of claims 1 to 8, which comprises the following steps:

step (1): preparing the following components in parts by weight: 10-15 parts of calcium stearate, 12-18 parts of zinc stearate, 15-18 parts of modified hydrotalcite, 3-4 parts of 1, 3-dimethyl-6-aminouracil, 4-5 parts of lanthanum maleamate, 0.5-1 part of nano-tubular modified halloysite, 2-5 parts of a dispersing agent, 2-5 parts of a surfactant, 8-15 parts of an external lubricant, 3-5 parts of an internal lubricant and 0.5-1.5 parts of an antioxidant;

step (2): mixing calcium stearate, zinc stearate, modified hydrotalcite, 1, 3-dimethyl-6-aminouracil, lanthanum maleamide and nano-tube-shaped modified halloysite according to parts by weight, stirring and heating to 45-60 ℃, sequentially adding a dispersing agent, a surfactant and an antioxidant according to parts by weight while stirring, stirring at a constant temperature for 30-60min, finally adding an external lubricant and an internal lubricant, continuously stirring at a constant temperature for 25-35min, and cooling to room temperature.

10. The calcium-zinc composite stabilizer and the preparation method thereof as claimed in claim 1, wherein the stirring rate in step (2) is controlled to 2000-4000 r/min.

Technical Field

The invention relates to the technical field of stabilizers, in particular to a calcium-zinc composite stabilizer and a preparation method thereof.

Background

Polyvinyl chloride (PVC) is one of five common plastics in the world, and has the advantages of high strength, low price, good chemical corrosion resistance, good electrical insulation, difficult combustion and the like. The special structure of PVC makes it easy to remove hydrogen chloride on the molecule to cause polymer degradation when processed under high temperature and high shear conditions, which causes product discoloration and product mechanical property reduction, and affects the service life, therefore, the processing process needs to add heat stabilizer to increase the stability.

The most used heat stabilizers in the traditional PVC production mainly comprise lead salts and organic tin, but have the problems of high toxicity, high price and the like. The novel environment-friendly calcium-zinc composite stabilizer has the advantages of environmental protection, no toxicity, high efficiency and the like, and is a variety with the greatest development prospect. At present, the imported calcium zinc stabilizer is expensive, the domestic calcium zinc stabilizer is mostly used in a specific PVC industry, and most of the components have diketone compounds which easily cause the discoloration of PVC products and have potential danger.

The Chinese patent with the publication number of CN108586991A discloses an environment-friendly liquid calcium zinc stabilizer and a preparation method thereof, which comprises the following components: maleic anhydride, isooctanol, plasticizer, calcium oxide, isooctanoic acid, zinc oxide, beta-diketone and antioxidant 1010. The environment-friendly liquid calcium zinc stabilizer is formed by combining maleic anhydride, isooctanol, plasticizer, calcium oxide, isooctanoic acid, zinc oxide, beta-diketone and antioxidant 1010, and has the effect of being difficult to discolor. However, the stability of the environment-friendly liquid calcium-zinc stabilizer is poor, and the environment-friendly liquid calcium-zinc stabilizer is mostly used for PVC soft products with low requirements on thermal stability, so that the application field of the calcium-zinc heat stabilizer is limited.

Disclosure of Invention

In order to solve the defect of poor stability in the prior art, the invention provides a calcium-zinc composite stabilizer.

The invention adopts the technical scheme that a calcium-zinc composite stabilizer comprises the following components in parts by weight: 10-15 parts of calcium stearate, 12-18 parts of zinc stearate, 15-18 parts of modified hydrotalcite, 5-10 parts of modified auxiliary agent and 15-35 parts of additive group.

Preferably, the modification auxiliary agent comprises 3-4 parts of 1, 3-dimethyl-6-aminouracil, 4-5 parts of lanthanum maleamide and 0.5-1 part of nanotube-shaped modified halloysite.

Preferably, the nanotube-shaped modified halloysite is a silane coupling agent surface-modified halloysite nanotube, and the preparation method comprises the following steps:

step one, intercalation modification: drying halloysite nanotubes, suspending the halloysite nanotubes in dimethyl sulfoxide solution, stirring, carrying out suction filtration and drying, grinding the obtained solid and lauric acid in a mass ratio of 2: 2-3, and heating to obtain an intercalation modified halloysite nanotube;

step two, surface activity modification: dispersing the intercalated and modified halloysite nanotubes in water to prepare 1-4 mg/ml dispersion, adding a silane coupling agent solution, uniformly mixing, wherein the mass ratio of the silane coupling agent to the halloysite nanotubes in the mixed solution is 1: 1-5, and stirring for reaction to obtain a halloysite nanotube aqueous solution with the surface modified by the silane coupling agent; and cooling, filtering and drying to obtain the modified halloysite nanotube.

Preferably, in the step one, the concentration of the dimethyl sulfoxide solution is 90-95 wt%; the stirring is carried out for 60-80 h at the temperature of 20-30 ℃; the heating treatment is heating in a water bath at the temperature of 75-85 ℃ for 40-60 h; in the second step, the reaction temperature is 70-90 ℃, and the reaction time is 1-5 h.

Preferably, the preparation method of the modified hydrotalcite comprises the following steps:

step a: putting hydrotalcite in an ethanol solution, performing ultrasonic treatment for 10-15min under the power of 400-600W, performing centrifugal separation, retaining the bottom solid, repeating for 3-5 times, and then drying and grinding to prepare pretreated hydrotalcite;

step b: adding the pretreated hydrotalcite into water to prepare 10-15% suspension, heating the suspension to 80 ℃ in a water bath, adding hexadecyl dimethyl benzyl quaternary ammonium chloride and isooctyl alcohol polyoxyethylene ether phosphate while stirring, continuously stirring and reacting for 2 hours at constant temperature, carrying out ultrasonic oscillation, carrying out suction filtration, washing the filtrate with deionized water until no precipitate is generated by dropwise adding silver nitrate, and drying, crushing and sieving the filtrate to prepare a modified precursor;

step c: weighing acrylic acid, acrylamide and 2-acrylamidotetradecane sulfonic acid according to a molar ratio of 6:1-3:2, adding a NaOH solution into the acrylic acid for neutralization while stirring under an ice bath condition, controlling the neutralization degree of the acrylic acid to be 75%, then adding the acrylamide and the 2-acrylamidotetradecane sulfonic acid, and fully stirring until a monomer is completely dissolved to prepare a reaction monomer solution;

step d: adding span-80 into cyclopentane according to the mass ratio of 1:5, introducing nitrogen, heating in a water bath to 75 ℃, and stirring until the span-80 is completely dissolved to obtain an oil phase;

step e: adding the modified precursor into a reaction monomer solution, fully stirring, performing ultrasonic dispersion, adding N, N-methylene bisacrylamide and ammonium persulfate, uniformly stirring, adding into an oil phase under a nitrogen atmosphere, introducing nitrogen for 15min, performing reverse phase suspension composite reaction, cooling to room temperature after the reaction is finished, and filtering, washing, drying, grinding and sieving to obtain the modified hydrotalcite.

Preferably, the amount of the cetyl dimethyl benzyl quaternary ammonium chloride in the step b is 35-40% of the mass of the pretreated hydrotalcite, and the amount of the isooctanol polyoxyethylene ether phosphate ester is 8-12% of the mass of the pretreated hydrotalcite; the amount of span-80 is 0.2-0.8% of the total mass of the three reaction monomers, the amount of N, N-methylene bisacrylamide is 0.01-0.02% of the total mass of the three reaction monomers, the amount of ammonium persulfate is 0.05-0.2% of the total mass of the three reaction monomers, and the amount of the modified precursor is 45-60% of the total mass of the three reaction monomers; the conditions of the reversed phase suspension composite reaction are as follows: reacting at 35-40 deg.C for 20min, reacting at 45-50 deg.C for 25min, reacting at 55-60 deg.C for 60min, and reacting at 68-72 deg.C for 90 min.

Preferably, the additive group comprises 2-5 parts of a dispersant, 2-5 parts of a surfactant, 8-15 parts of an external lubricant, 3-5 parts of an internal lubricant and 0.5-1.5 parts of an antioxidant.

Preferably, the dispersant comprises one or more of stearic acid monoglyceride, oleic acid acyl, polyethylene glycol or stearamide, the surfactant is polyoxyethylene lauryl ether, the internal lubricant is fatty alcohol dicarboxylate, the external lubricant is one or two of polyethylene wax or Fischer-Tropsch wax, and the antioxidant is one or two of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate or antioxidant 1010.

The invention also provides a preparation method of the calcium-zinc coincidence stabilizer, which comprises the following steps:

step (1): preparing the following components in parts by weight: 10-15 parts of calcium stearate, 12-18 parts of zinc stearate, 15-18 parts of modified hydrotalcite, 3-4 parts of 1, 3-dimethyl-6-aminouracil, 4-5 parts of lanthanum maleamate, 0.5-1 part of nano-tubular modified halloysite, 2-5 parts of a dispersing agent, 2-5 parts of a surfactant, 8-15 parts of an external lubricant, 3-5 parts of an internal lubricant and 0.5-1.5 parts of an antioxidant;

step (2): mixing calcium stearate, zinc stearate, modified hydrotalcite, 1, 3-dimethyl-6-aminouracil, lanthanum maleamide and nano-tube-shaped modified halloysite according to parts by weight, stirring and heating to 45-60 ℃, sequentially adding a dispersing agent, a surfactant and an antioxidant according to parts by weight while stirring, stirring at a constant temperature for 30-60min, finally adding an external lubricant and an internal lubricant, continuously stirring at a constant temperature for 25-35min, and cooling to room temperature.

Preferably, the stirring rate in step (2) is controlled to 2000-.

Compared with the prior art, the invention has the following beneficial effects:

1. in the aspect of modified hydrotalcite, an acrylic acid/acrylamide/2-acrylamidotetradecane sulfonic acid terpolymer is grafted on the surface of hydrotalcite through an inverse suspension polymerization method, and a monomer 2-acrylamidotetradecane sulfonic acid capable of providing a large side group is introduced into a molecular chain of the acrylic acid/acrylamide copolymer, so that the thermal stability of the acrylic acid/acrylamide copolymer can be obviously improved, the modified hydrotalcite has excellent dispersibility, the agglomeration of hydrotalcite particles is effectively prevented, a surfactant can be coated on the surface of the hydrotalcite, the surface performance of the hydrotalcite is effectively improved, and the dispersibility and compatibility of the modified hydrotalcite in a PVC product are further improved;

2. the halloysite nanotube is subjected to intercalation modification, and then is subjected to surface activity modification by using a silane coupling agent, so that the modified halloysite nanotube has good compatibility with PVC, and the network structure of the halloysite nanotube can enhance the strength and stability of the PVC material;

3. the 1, 3-dimethyl-6-aminouracil has the capacity of replacing unstable chlorine atoms in PVC, improves the stability of the PVC and reduces the discoloration phenomenon of the PVC; and lanthanum maleamate can overcome the problem of 'zinc burning' of PVC containing calcium zinc stabilizer in the using process, and the two aspects of improving the PVC stability and overcoming the zinc burning are combined, so that the PVC is effectively prevented from discoloring in the processing process, and a good zinc burning inhibiting effect is achieved. In addition, the lanthanum maleamate in the formula also has the functions of promoting melting, coupling, internal plasticization, toughening, brightening and the like, so that the PVC mixture can be uniformly plasticized and is easy to process;

4. the stabilizer disclosed by the invention has excellent thermal stability, strong initial coloring inhibition capability and good stabilizing effect, eliminates toxic heavy metal components such as lead, cadmium, mercury and the like existing in the traditional heat stabilizer, can effectively improve the weather resistance of the material, is green and environment-friendly, is suitable for hard PVC pipes and profiles, has wide product applicability and is not easy to cause the color change of hard PVC products.

Detailed Description