CN110372914B - Calcium-zinc stabilizer for PVC (polyvinyl chloride) pipe and preparation method thereof - Google Patents
Calcium-zinc stabilizer for PVC (polyvinyl chloride) pipe and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of stabilizers, and discloses a calcium-zinc stabilizer for PVC pipes and a preparation method thereof. The calcium zinc stabilizer comprises the following components in parts by weight: 10-30 parts of calcium stearate, 10-30 parts of zinc stearate, 10-20 parts of hydrotalcite, 10-15 parts of zeolite, 1-5 parts of calcium acetylacetonate, 1-5 parts of dibenzoylmethane-quaternary ammonium salt chitosan carrier compound, 1-3 parts of pentaerythritol, 1-3 parts of phosphite ester and 1-3 parts of bisphenol A. According to the invention, the dibenzoyl methane in the stabilizer is compounded with the quaternary ammonium salt, so that the dibenzoyl methane and the quaternary ammonium salt compound are positively charged, and the positively charged dibenzoyl methane and the quaternary ammonium salt compound are repelled from the positively charged ferric ions, thereby preventing the dibenzoyl methane and the ferric ions from being complexed into a red complex and preventing the PVC pipe from being red.
Description
Technical Field
The invention relates to the technical field of stabilizers, in particular to a calcium-zinc stabilizer for PVC pipes and a preparation method thereof.
Background
Polyvinyl chloride (PVC) is one of five general-purpose plastics, and has the advantages that PVC products are wide in application range and mainly used in the fields of industry, building, agriculture and the like, but the PVC resins have the same obvious defects that the PVC resins are poor in thermal stability, the color of products after thermal aging decomposition is dark, various performance indexes are reduced, and direct processing cannot be performed, so that a heat stabilizer must be added in the processing process to improve the aging performance.
At present, the commonly used heat stabilizer mainly comprises inorganic lead salt, metal soap, organic tin and the like, but the inorganic lead salt is toxic, the odor of the organic tin is heavy, and the application range of PVC products is severely limited. In order to improve the health and the sanitation of people and protect the environment, in recent years, developed countries such as Europe and America successively establish and implement a regulation for limiting the use of toxic heat stabilizers, and in China, 7, 1, 7 and 2017, GB/T33284-2017 standards are issued and implemented, and the lead content in PVC-U sectional materials is regulated to be less than or equal to 100 mg/Kg. Environmental protection is a great trend, and the lead inhibition of the remaining products such as PVC pipes is inevitable.
The calcium-zinc stabilizer is a nontoxic environment-friendly stabilizer which is prepared by taking metal soaps such as calcium, zinc and the like as main bodies and matching with a plurality of organic auxiliary heat stabilizers. Beta-diketone compounds such as Dibenzoylmethane (DBM) and the like are used as zinc-based nontoxic auxiliary heat stabilizers with good effects, can obviously improve the initial color and the heat stabilization effect of products, and are now important components of the stabilizers. However, after the calcium zinc stabilizer containing beta-diketone is used, the vacuum tank of the extruder in the production process is made of iron, ferric ions are released into materials in the vacuum tank, and the ferric ions and dibenzoyl methane in the stabilizer form a red complex, so that the materials in the vacuum tank are changed into bloody red, and further, a pipe finished product is also red, and the popularization and application of the product are not facilitated. Chinese patent publication No. CN105315574 discloses a calcium-zinc heat stabilizer for PVC and its application, the main stabilizer and auxiliary stabilizer, the main stabilizer is composed of quinolone zinc salt and quinolone calcium salt, the auxiliary stabilizer is a compound of triphenyl phosphite, epoxidized soybean oil, epoxy octyl stearate, pentaerythritol, dipentaerythritol, sorbitol, trimethylolpropane, dibenzoyl methane, stearoyl benzoyl methane, uracil in any proportion, the stabilizer is used in the PVC plastic production process, the vacuum tank material of the extruder in the production process can not be iron, because ferric iron ions and dibenzoyl methane in the stabilizer can form red complex, the PVC plastic product is red, therefore, only vacuum tank bodies made of other materials with higher cost can be used, and the production line used by enterprises for producing PVC plastics is purchased from the outside, the vacuum tank body is mostly made of iron, and if the stabilizer containing dibenzoyl methane is used, the vacuum tank body needs to be replaced by other materials, so that the operation is troublesome and the cost is increased.
Disclosure of Invention
The invention aims to overcome the problem that dibenzoyl methane in a calcium stabilizer in the prior art is complexed with ferric ions in an iron vacuum tank to turn red to influence the color of a product, and provides a calcium zinc stabilizer for a PVC pipe.
The invention also provides a preparation method of the calcium-zinc stabilizer for the PVC pipe.
In order to achieve the purpose, the invention adopts the following technical scheme:
the calcium zinc stabilizer for the PVC pipe comprises the following components in parts by weight: 10-30 parts of calcium stearate, 10-30 parts of zinc stearate, 10-20 parts of hydrotalcite, 10-15 parts of zeolite, 1-5 parts of calcium acetylacetonate, 1-5 parts of dibenzoylmethane-quaternary ammonium salt chitosan carrier compound, 1-3 parts of pentaerythritol, 1-3 parts of phosphite ester and 1-3 parts of bisphenol A.
Calcium stearate and zinc stearate are used as main stabilizers, calcium acetylacetonate, dibenzoylmethane-quaternary ammonium salt chitosan carrier complex, pentaerythritol, phosphite and bisphenol A are used as auxiliary stabilizers, hydrotalcite is used for improving the transparency of the stabilizer, and zeolite is favorable for improving the glossiness and the transparency of a product. The main stabilizer, the auxiliary stabilizer, the hydrotalcite and the zeolite are compounded to form the calcium-zinc stabilizer special for the PVC plastic pipeline, so that the thermal stability and the ageing resistance of the PVC plastic pipeline can be improved, and a certain effect of improving the strength of the pipe is achieved.
The vacuum tank material of extruder is iron in PVC tubular product production, can release ferric ion to the material in the vacuum tank, and the red complex is formed with the dibenzoyl methane in the stabilizer to the ferric ion to lead to the material in the vacuum tank to become the red blood, and then lead to the tubular product finished product also can present red, change the colour of PVC tubular product, be unfavorable for the popularization and application of product. The invention improves the dibenzoyl methane in the stabilizer, the dibenzoyl methane in the stabilizer is compounded with the quaternary ammonium salt, the quaternary ammonium salt is connected with four alkyl groups on a nitrogen atom and has a unit positive charge, so that the dibenzoyl methane and the quaternary ammonium salt compound are positively charged, and the positively charged dibenzoyl methane and the quaternary ammonium salt compound are repelled with positively charged ferric ions, thereby preventing the dibenzoyl methane and the ferric ions from being complexed into a red complex and preventing the PVC pipe from being red.
Preferably, the preparation method of the dibenzoylmethane-quaternary ammonium salt chitosan carrier complex comprises the following steps:
adding carboxymethyl chitosan into deionized water to dissolve and prepare a carboxymethyl chitosan solution with the concentration of 2-5 wt%; adding dibenzoyl methane into 10-20wt% sodium hydroxide solution to dissolve to prepare 5-10wt% dibenzoyl methane solution, adding ethyl acetate into the dibenzoyl methane solution, and stirring to obtain mixed solution; dripping carboxymethyl chitosan into the mixed solution and stirring simultaneously to form chitosan microspheres; washing chitosan microspheres with deionized water to neutrality, adding into 3-6wt% sodium tripolyphosphate solution for crosslinking for 2-5h, filtering, and drying to obtain dibenzoylmethane-chitosan compound; adding 2, 3-epoxypropyltrimethyl ammonium chloride into deionized water to prepare a 20-30wt% aqueous solution of 2, 3-epoxypropyltrimethyl ammonium chloride, adding the dibenzoylmethane-chitosan complex into the aqueous solution of 2, 3-epoxypropyltrimethyl ammonium chloride, reacting for 1.5-3h at 40-45 ℃, filtering, washing and drying to obtain the dibenzoylmethane-quaternary ammonium salt chitosan carrier complex.
According to the invention, carboxymethyl chitosan is dripped into a mixed solution, sodium hydroxide in the mixed solution is not only used as a solvent of dibenzoyl methane, but also compounded with ethyl acetate to be used as a condensation liquid of the carboxymethyl chitosan, a carboxymethyl chitosan solution is dripped into the mixed solution, the drops of the carboxymethyl chitosan slowly become microspheres, the dibenzoyl methane gradually diffuses into the carboxymethyl chitosan under the stirring action, then sodium tripolyphosphate cross-linking agent is used for carrying out cross-linking treatment on the carboxymethyl chitosan, so that the carboxymethyl chitosan forms a three-dimensional reticular cross-linking structure, and the dibenzoyl methane is embedded into the interior of three-dimensional reticular carboxymethyl chitosan macromolecules and is not easy to separate from the carboxymethyl chitosan microspheres; and then adding the carboxymethyl chitosan microspheres into 2, 3-epoxypropyl trimethyl ammonium chloride quaternary ammonium salt solution, wherein an epoxy group on the 2, 3-epoxypropyl trimethyl ammonium chloride and a carboxyl group or a hydroxyl group on the carboxymethyl chitosan microspheres undergo a ring opening reaction, so that the 2, 3-epoxypropyl trimethyl ammonium chloride is grafted to the surfaces of the carboxymethyl chitosan microspheres, the carboxymethyl chitosan plays a role of bridging, and the 2, 3-epoxypropyl trimethyl ammonium chloride and the dibenzoyl methane are compounded to form the dibenzoyl methane-quaternary ammonium salt chitosan carrier compound.
Preferably, the ethyl acetate is added in an amount of 2 to 5wt% based on the dibenzoylmethane solution.
Preferably, the dropping amount of the carboxymethyl chitosan is 15 to 30wt% of the mixed solution.
Preferably, the mass ratio of the dibenzoylmethane-chitosan complex to the 2, 3-epoxypropyltrimethylammonium chloride is 1: 0.3-0.6.
The preparation method of the calcium-zinc stabilizer for the PVC pipe comprises the following steps:
1) weighing the formula components according to the proportion of the raw materials, adding the hydrotalcite and the zeolite into a high-speed stirrer, and stirring for 1-3h at the temperature of 60-80 ℃;
2) adding calcium stearate and zinc stearate into the stirred material in the step 1), and stirring for 20-30min at 50-60 ℃;
3) adding calcium acetylacetonate, dibenzoylmethane-quaternary ammonium salt chitosan carrier complex, pentaerythritol, phosphite ester and bisphenol A into the stirred material obtained in the step 2), and stirring for 2-4h at 50-60 ℃ to obtain the chitosan/bisphenol A composite material.
Preferably, the stirring speed in the step 1) is controlled at 1400-1500 r/min; the stirring speed in the step 2) is controlled at 1200-1400 r/min; the stirring speed in the step 3) is controlled at 1000-1100 r/min.
Therefore, the invention has the following beneficial effects: (1) the main stabilizer, the auxiliary stabilizer, the hydrotalcite and the zeolite are compounded to form the calcium-zinc stabilizer special for the PVC plastic pipeline, so that the thermal stability and the ageing resistance of the PVC plastic pipeline can be improved, and the strength of the pipe is improved to a certain extent; (2) the dibenzoyl methane in the stabilizer is compounded with the quaternary ammonium salt, the quaternary ammonium salt is connected with four alkyl groups on a nitrogen atom, and has a unit positive charge, so that the dibenzoyl methane and the quaternary ammonium salt compound are positively charged, and the positively charged dibenzoyl methane and the quaternary ammonium salt compound are repelled from the positively charged ferric ions, thereby preventing the dibenzoyl methane and the ferric ions from being complexed into a red complex and preventing the PVC pipe from being red.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
In the present invention, unless otherwise specified, all the raw materials and equipment used are commercially available or commonly used in the art, and the methods in the examples are conventional in the art unless otherwise specified.
Example 1
The preparation method of the dibenzoylmethane-quaternary ammonium salt chitosan carrier compound comprises the following steps:
adding carboxymethyl chitosan into deionized water to dissolve and prepare a carboxymethyl chitosan solution with the concentration of 3 wt%; adding dibenzoyl methane into a sodium hydroxide solution with the mass concentration of 15 wt% to dissolve and prepare a dibenzoyl methane solution with the concentration of 8 wt%, adding ethyl acetate into the dibenzoyl methane solution, wherein the addition amount of the ethyl acetate is 4 wt% of the dibenzoyl methane solution, and stirring to obtain a mixed solution; dropping carboxymethyl chitosan into the mixed solution and stirring simultaneously to form chitosan microspheres, wherein the dropping amount of the carboxymethyl chitosan is 20wt% of the mixed solution; washing chitosan microspheres to be neutral by using deionized water, adding the chitosan microspheres into a sodium tripolyphosphate solution with the concentration of 5wt% for crosslinking for 4 hours, filtering, and drying to obtain a dibenzoylmethane-chitosan compound; adding 2, 3-epoxypropyltrimethylammonium chloride into deionized water to prepare a 25 wt% aqueous solution of 2, 3-epoxypropyltrimethylammonium chloride, adding a dibenzoylmethane-chitosan composite into the aqueous solution of 2, 3-epoxypropyltrimethylammonium chloride, wherein the mass ratio of the dibenzoylmethane-chitosan composite to the 2, 3-epoxypropyltrimethylammonium chloride is 1:0.5, carrying out heat preservation reaction at 40 ℃ for 3 hours, filtering, washing and drying to obtain the dibenzoylmethane-quaternary ammonium salt chitosan carrier composite.
The calcium zinc stabilizer for the PVC pipe comprises the following components in parts by weight: 15 parts of calcium stearate, 20 parts of zinc stearate, 15 parts of hydrotalcite, 12 parts of zeolite, 3 parts of calcium acetylacetonate, 3 parts of dibenzoylmethane-quaternary ammonium salt chitosan carrier compound, 2 parts of pentaerythritol, 2 parts of phosphite ester and 1 part of bisphenol A; wherein the hydrotalcite is MgO/Al2O3Magnesium-aluminum binary hydrotalcite with a molar ratio of 4: 1.
The preparation method of the calcium-zinc stabilizer for the PVC pipe comprises the following steps:
1) weighing the formula components according to the proportion of the raw materials, adding the hydrotalcite and the zeolite into a high-speed stirrer, and stirring for 2 hours at 70 ℃, wherein the stirring speed is controlled at 1400 r/min;
2) adding calcium stearate and zinc stearate into the stirred material in the step 1), and stirring at 55 ℃ for 25min at the stirring speed of 1300 r/min;
3) adding calcium acetylacetonate, dibenzoylmethane-quaternary ammonium salt chitosan carrier compound, pentaerythritol, phosphite ester and bisphenol A into the stirred material obtained in the step 2), stirring for 3 hours at 55 ℃, and controlling the stirring speed at 1000r/min to obtain the nano-composite material.
Example 2
The preparation method of the dibenzoylmethane-quaternary ammonium salt chitosan carrier compound comprises the following steps:
adding carboxymethyl chitosan into deionized water to be dissolved and prepared into a carboxymethyl chitosan solution with the concentration of 2 wt%; adding dibenzoyl methane into a sodium hydroxide solution with the mass concentration of 15 wt% to dissolve and prepare a dibenzoyl methane solution with the concentration of 6wt%, adding ethyl acetate into the dibenzoyl methane solution, wherein the addition amount of the ethyl acetate is 3 wt% of the dibenzoyl methane solution, and stirring to obtain a mixed solution; dropping carboxymethyl chitosan into the mixed solution and stirring simultaneously to form chitosan microspheres, wherein the dropping amount of the carboxymethyl chitosan is 15 wt% of the mixed solution; washing chitosan microspheres to be neutral by using deionized water, adding the chitosan microspheres into a sodium tripolyphosphate solution with the concentration of 5wt% for crosslinking for 3 hours, filtering, and drying to obtain a dibenzoylmethane-chitosan compound; adding 2, 3-epoxypropyltrimethylammonium chloride into deionized water to prepare a 30wt% aqueous solution of 2, 3-epoxypropyltrimethylammonium chloride, adding a dibenzoylmethane-chitosan composite into the aqueous solution of 2, 3-epoxypropyltrimethylammonium chloride, wherein the mass ratio of the dibenzoylmethane-chitosan composite to the 2, 3-epoxypropyltrimethylammonium chloride is 1:0.5, carrying out heat preservation reaction at 45 ℃ for 1.5h, filtering, washing and drying to obtain the dibenzoylmethane-quaternary ammonium salt chitosan carrier composite.
The calcium zinc stabilizer for the PVC pipe comprises the following components in parts by weight: 20 parts of calcium stearate, 10 parts of zinc stearate, 15 parts of hydrotalcite, 10 parts of zeolite, 3 parts of calcium acetylacetonate, 3 parts of dibenzoylmethane-quaternary ammonium salt chitosan carrier compound, 2 parts of pentaerythritol, 1 part of phosphite ester and 2 parts of bisphenol A; wherein the hydrotalcite is MgO/Al2O3Magnesium-aluminum binary hydrotalcite with a molar ratio of 4: 1.
The preparation method of the calcium-zinc stabilizer for the PVC pipe comprises the following steps:
1) weighing the formula components according to the proportion of the raw materials, adding the hydrotalcite and the zeolite into a high-speed stirrer, and stirring for 2 hours at the temperature of 60 ℃, wherein the stirring speed is controlled at 1500 r/min;
2) adding calcium stearate and zinc stearate into the stirred material in the step 1), and stirring at 55 ℃ for 25min at the stirring speed of 1300 r/min;
3) adding calcium acetylacetonate, dibenzoylmethane-quaternary ammonium salt chitosan carrier compound, pentaerythritol, phosphite ester and bisphenol A into the stirred material obtained in the step 2), stirring for 3 hours at 55 ℃, and controlling the stirring speed at 1100r/min to obtain the nano-composite material.
Example 3
The preparation method of the dibenzoylmethane-quaternary ammonium salt chitosan carrier compound comprises the following steps:
adding carboxymethyl chitosan into deionized water to dissolve and prepare a carboxymethyl chitosan solution with the concentration of 3 wt%; adding dibenzoyl methane into a sodium hydroxide solution with the mass concentration of 20wt% to dissolve and prepare a 10wt% dibenzoyl methane solution, adding ethyl acetate into the dibenzoyl methane solution, wherein the addition amount of the ethyl acetate is 3 wt% of the dibenzoyl methane solution, and stirring to obtain a mixed solution; dripping carboxymethyl chitosan into the mixed solution and stirring simultaneously to form chitosan microspheres, wherein the dripping amount of the carboxymethyl chitosan is 25 wt% of the mixed solution; washing chitosan microspheres to be neutral by using deionized water, adding the chitosan microspheres into a sodium tripolyphosphate solution with the concentration of 5wt% for crosslinking for 5 hours, filtering, and drying to obtain a dibenzoylmethane-chitosan compound; adding 2, 3-epoxypropyltrimethylammonium chloride into deionized water to prepare a 25 wt% aqueous solution of 2, 3-epoxypropyltrimethylammonium chloride, adding a dibenzoylmethane-chitosan composite into the aqueous solution of 2, 3-epoxypropyltrimethylammonium chloride, wherein the mass ratio of the dibenzoylmethane-chitosan composite to the 2, 3-epoxypropyltrimethylammonium chloride is 1:0.3, carrying out heat preservation reaction at 40 ℃ for 3 hours, filtering, washing and drying to obtain the dibenzoylmethane-quaternary ammonium salt chitosan carrier composite.
The calcium zinc stabilizer for the PVC pipe comprises the following components in parts by weight: 25 parts of calcium stearate, 25 parts of zinc stearate, 15 parts of hydrotalcite, 10 parts of zeolite, 4 parts of calcium acetylacetonate, 3 parts of dibenzoylmethane-quaternary ammonium salt chitosan carrier compound, 2 parts of pentaerythritol, 2 parts of phosphite ester and 2 parts of bisphenol A; wherein the hydrotalcite is MgO/Al2O3Magnesium-aluminum binary hydrotalcite with a molar ratio of 4: 1.
The preparation method of the calcium-zinc stabilizer for the PVC pipe comprises the following steps:
1) weighing the formula components according to the proportion of the raw materials, adding the hydrotalcite and the zeolite into a high-speed stirrer, and stirring for 1h at the temperature of 80 ℃, wherein the stirring speed is controlled at 1400 r/min;
2) adding calcium stearate and zinc stearate into the stirred material in the step 1), and stirring at 55 ℃ for 25min at the stirring speed of 1300 r/min;
3) adding calcium acetylacetonate, dibenzoylmethane-quaternary ammonium salt chitosan carrier compound, pentaerythritol, phosphite ester and bisphenol A into the stirred material obtained in the step 2), stirring for 3 hours at 55 ℃, and controlling the stirring speed at 1100r/min to obtain the nano-composite material.
Example 4
The preparation method of the dibenzoylmethane-quaternary ammonium salt chitosan carrier compound comprises the following steps:
adding carboxymethyl chitosan into deionized water to dissolve and prepare 5wt% carboxymethyl chitosan solution; adding dibenzoyl methane into a sodium hydroxide solution with the mass concentration of 20wt% to dissolve and prepare a 10wt% dibenzoyl methane solution, adding ethyl acetate into the dibenzoyl methane solution, wherein the addition amount of the ethyl acetate is 5wt% of the dibenzoyl methane solution, and stirring to obtain a mixed solution; dripping carboxymethyl chitosan into the mixed solution and stirring simultaneously to form chitosan microspheres, wherein the dripping amount of the carboxymethyl chitosan is 30wt% of the mixed solution; washing chitosan microspheres to be neutral by using deionized water, adding the chitosan microspheres into a sodium tripolyphosphate solution with the concentration of 6wt% for crosslinking for 5 hours, filtering, and drying to obtain a dibenzoylmethane-chitosan compound; adding 2, 3-epoxypropyltrimethylammonium chloride into deionized water to prepare a 30wt% aqueous solution of 2, 3-epoxypropyltrimethylammonium chloride, adding a dibenzoylmethane-chitosan composite into the aqueous solution of 2, 3-epoxypropyltrimethylammonium chloride, wherein the mass ratio of the dibenzoylmethane-chitosan composite to the 2, 3-epoxypropyltrimethylammonium chloride is 1:0.6, carrying out heat preservation reaction at 45 ℃ for 1.5h, filtering, washing and drying to obtain the dibenzoylmethane-quaternary ammonium salt chitosan carrier composite.
The calcium zinc stabilizer for the PVC pipe comprises the following components in parts by weight: 30 parts of calcium stearate, 30 parts of zinc stearate, 20 parts of hydrotalcite, 15 parts of zeolite, 5 parts of calcium acetylacetonate, 5 parts of dibenzoylmethane-quaternary ammonium salt chitosan carrier compound, 3 parts of pentaerythritol, 3 parts of phosphite ester and 3 parts of bisphenol A; wherein the hydrotalcite is MgO/Al2O3Magnesium-aluminum binary hydrotalcite with a molar ratio of 4: 1.
The preparation method of the calcium-zinc stabilizer for the PVC pipe comprises the following steps:
1) weighing the formula components according to the proportion of the raw materials, adding the hydrotalcite and the zeolite into a high-speed stirrer, and stirring for 1h at the temperature of 80 ℃, wherein the stirring speed is controlled at 1500 r/min;
2) adding calcium stearate and zinc stearate into the stirred material in the step 1), and stirring for 20min at 60 ℃, wherein the stirring speed is controlled at 1400 r/min;
3) adding calcium acetylacetonate, dibenzoylmethane-quaternary ammonium salt chitosan carrier compound, pentaerythritol, phosphite ester and bisphenol A into the stirred material obtained in the step 2), stirring for 2 hours at 60 ℃, and controlling the stirring speed at 1100r/min to obtain the nano-composite material.
Example 5
The preparation method of the dibenzoylmethane-quaternary ammonium salt chitosan carrier compound comprises the following steps:
adding carboxymethyl chitosan into deionized water to be dissolved and prepared into a carboxymethyl chitosan solution with the concentration of 2 wt%; adding dibenzoyl methane into 10wt% sodium hydroxide solution to dissolve to prepare 5wt% dibenzoyl methane solution, adding ethyl acetate into the dibenzoyl methane solution, wherein the addition amount of the ethyl acetate is 2 wt% of the dibenzoyl methane solution, and stirring to obtain a mixed solution; dropping carboxymethyl chitosan into the mixed solution and stirring simultaneously to form chitosan microspheres, wherein the dropping amount of the carboxymethyl chitosan is 15 wt% of the mixed solution; washing chitosan microspheres to be neutral by using deionized water, adding the chitosan microspheres into a sodium tripolyphosphate solution with the concentration of 3 wt% for crosslinking for 2 hours, filtering, and drying to obtain a dibenzoylmethane-chitosan compound; adding 2, 3-epoxypropyltrimethylammonium chloride into deionized water to prepare a 20wt% aqueous solution of 2, 3-epoxypropyltrimethylammonium chloride, adding a dibenzoylmethane-chitosan composite into the aqueous solution of 2, 3-epoxypropyltrimethylammonium chloride, wherein the mass ratio of the dibenzoylmethane-chitosan composite to the 2, 3-epoxypropyltrimethylammonium chloride is 1:0.3, carrying out heat preservation reaction at 40 ℃ for 3 hours, filtering, washing and drying to obtain the dibenzoylmethane-quaternary ammonium salt chitosan carrier composite.
A calcium-zinc stabilizer for PVC pipe material comprisesThe composition comprises the following components in parts by weight: 10 parts of calcium stearate, 10 parts of zinc stearate, 10 parts of hydrotalcite, 10 parts of zeolite, 1 part of calcium acetylacetonate, 1 part of dibenzoylmethane-quaternary ammonium salt chitosan carrier compound, 1 part of pentaerythritol, 1 part of phosphite ester and 1 part of bisphenol A; wherein the hydrotalcite is MgO/Al2O3Magnesium-aluminum binary hydrotalcite with a molar ratio of 4: 1.
The preparation method of the calcium-zinc stabilizer for the PVC pipe comprises the following steps:
1) weighing the formula components according to the proportion of the raw materials, adding the hydrotalcite and the zeolite into a high-speed stirrer, and stirring for 3 hours at the temperature of 60 ℃, wherein the stirring speed is controlled at 1400 r/min;
2) adding calcium stearate and zinc stearate into the stirred material in the step 1), and stirring for 30min at 50 ℃, wherein the stirring speed is controlled at 1200 r/min;
3) adding calcium acetylacetonate, dibenzoylmethane-quaternary ammonium salt chitosan carrier compound, pentaerythritol, phosphite ester and bisphenol A into the stirred material obtained in the step 2), stirring for 4 hours at 50 ℃, and controlling the stirring speed at 1000r/min to obtain the nano-composite material.
Test and test:
1g of the calcium-zinc stabilizer in the examples 1 to 5 is weighed respectively and added into a beaker, then 50mL of absolute ethyl alcohol is taken and fully stirred evenly, the mixture is kept stand for 10min, 5mL of supernatant is taken and added into a test tube, then a drop of ferric ammonium sulfate solution is added dropwise, and the color change is observed.
For the comparison of the test effects, a control group 1 and a control group 2 were provided, and the calcium zinc stabilizer of the control group 1 was different from that of example 1 in that the dibenzoylmethane-quaternary ammonium salt chitosan carrier complex was replaced with an equal amount of dibenzoylmethane; control 2 the calcium zinc stabilizer differed from example 1 in that it did not contain dibenzoylmethane. Respectively weighing 1g of calcium-zinc stabilizer of the control group 1 and the control group 2, adding the weighed 1g of calcium-zinc stabilizer into a beaker, then taking 50mL of absolute ethyl alcohol, fully and uniformly stirring, standing for 10min, taking 5mL of supernatant, adding the supernatant into a test tube, then dropwise adding a drop of ferric ammonium sulfate solution, and observing color change.
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Control group 1 | Control group 2 | |
| Colour(s) | Is transparent | Is transparent | Is transparent | Is transparent | Is transparent | Reddening with yellow | Is transparent |
The test result proves that the calcium zinc stabilizer containing dibenzoyl methane is combined with iron ions to turn red, the dibenzoyl methane in the stabilizer is compounded with quaternary ammonium salt, the quaternary ammonium salt is connected with four alkyl groups on a nitrogen atom, and has a unit positive charge, so that the dibenzoyl methane and the quaternary ammonium salt compound are positively charged, and the positively charged dibenzoyl methane and the quaternary ammonium salt compound repel positively charged ferric ions, thereby preventing the dibenzoyl methane and the ferric ions from being complexed to turn into a red complex.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (6)
1. The calcium-zinc stabilizer for the PVC pipe is characterized by comprising the following components in parts by weight: 10-30 parts of calcium stearate, 10-30 parts of zinc stearate, 10-20 parts of hydrotalcite, 10-15 parts of zeolite, 1-5 parts of calcium acetylacetonate, 1-5 parts of dibenzoylmethane-quaternary ammonium salt chitosan carrier compound, 1-3 parts of pentaerythritol, 1-3 parts of phosphite ester and 1-3 parts of bisphenol A;
the preparation method of the dibenzoylmethane-quaternary ammonium salt chitosan carrier compound comprises the following steps:
adding carboxymethyl chitosan into deionized water to dissolve and prepare a carboxymethyl chitosan solution with the concentration of 2-5 wt%; adding dibenzoyl methane into 10-20wt% sodium hydroxide solution to dissolve to prepare 5-10wt% dibenzoyl methane solution, adding ethyl acetate into the dibenzoyl methane solution, and stirring to obtain mixed solution; dripping carboxymethyl chitosan into the mixed solution and stirring simultaneously to form chitosan microspheres; washing chitosan microspheres with deionized water to neutrality, adding into 3-6wt% sodium tripolyphosphate solution for crosslinking for 2-5h, filtering, and drying to obtain dibenzoylmethane-chitosan compound; adding 2, 3-epoxypropyltrimethyl ammonium chloride into deionized water to prepare a 20-30wt% aqueous solution of 2, 3-epoxypropyltrimethyl ammonium chloride, adding the dibenzoylmethane-chitosan complex into the aqueous solution of 2, 3-epoxypropyltrimethyl ammonium chloride, reacting for 1.5-3h at 40-45 ℃, filtering, washing and drying to obtain the dibenzoylmethane-quaternary ammonium salt chitosan carrier complex.
2. The calcium zinc stabilizer for PVC pipe according to claim 1, characterized in that the ethyl acetate is added in an amount of 2-5wt% of the dibenzoylmethane solution.
3. The calcium-zinc stabilizer for PVC pipes as claimed in claim 1, wherein the carboxymethyl chitosan is added in an amount of 15-30wt% of the mixed solution.
4. The calcium-zinc stabilizer for PVC pipes as claimed in claim 1, wherein the mass ratio of dibenzoylmethane-chitosan complex to 2, 3-epoxypropyltrimethylammonium chloride is 1: 0.3-0.6.
5. The process for the preparation of the calcium zinc stabilizer for PVC pipes according to any of claims 1 to 4, characterized in that it comprises the following steps:
1) weighing the formula components according to the proportion of the raw materials, adding the hydrotalcite and the zeolite into a high-speed stirrer, and stirring for 1-3h at the temperature of 60-80 ℃;
2) adding calcium stearate and zinc stearate into the stirred material in the step 1), and stirring for 20-30min at 50-60 ℃;
3) adding calcium acetylacetonate, dibenzoylmethane-quaternary ammonium salt chitosan carrier complex, pentaerythritol, phosphite ester and bisphenol A into the stirred material obtained in the step 2), and stirring for 2-4h at 50-60 ℃ to obtain the chitosan/bisphenol A composite material.
6. The method for preparing the calcium-zinc stabilizer for the PVC pipe as recited in claim 5, wherein the stirring speed in step 1) is controlled at 1400-1500 r/min; the stirring speed in the step 2) is controlled at 1200-1400 r/min; the stirring speed in the step 3) is controlled at 1000-1100 r/min.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101066460A (en) * | 2007-06-07 | 2007-11-07 | 上海交通大学 | Synthesis of quaternary ammonium salt modified nucleophilic NO donor |
| WO2009027971A3 (en) * | 2007-08-27 | 2009-04-30 | H2Q Water Ind Ltd | Antimicrobial polymers |
| CN102321276A (en) * | 2011-07-29 | 2012-01-18 | 广东若天新材料科技有限公司 | Transparent environment-friendly calcium zinc stabilizer and preparation method thereof |
| CN105802192A (en) * | 2016-04-29 | 2016-07-27 | 苏州林华医疗器械股份有限公司 | Novel material applied to indwelling needle catheter and preparation method thereof |
| CN106478990A (en) * | 2016-09-26 | 2017-03-08 | 深圳市志海实业股份有限公司 | A kind of novel melting one-step method prepares hydroxy fatty acid calcium zinc PVC stabilizer |
-
2019
- 2019-06-27 CN CN201910568230.0A patent/CN110372914B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101066460A (en) * | 2007-06-07 | 2007-11-07 | 上海交通大学 | Synthesis of quaternary ammonium salt modified nucleophilic NO donor |
| WO2009027971A3 (en) * | 2007-08-27 | 2009-04-30 | H2Q Water Ind Ltd | Antimicrobial polymers |
| CN102321276A (en) * | 2011-07-29 | 2012-01-18 | 广东若天新材料科技有限公司 | Transparent environment-friendly calcium zinc stabilizer and preparation method thereof |
| CN105802192A (en) * | 2016-04-29 | 2016-07-27 | 苏州林华医疗器械股份有限公司 | Novel material applied to indwelling needle catheter and preparation method thereof |
| CN106478990A (en) * | 2016-09-26 | 2017-03-08 | 深圳市志海实业股份有限公司 | A kind of novel melting one-step method prepares hydroxy fatty acid calcium zinc PVC stabilizer |
Non-Patent Citations (1)
| Title |
|---|
| 含β-二酮填充PVC塑料发红现象的原因与解决办法;吴茂英;《塑料工业》;20110630;第39卷(第6期);74-76,86 * |
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