CN112143040A - Novel sustained-release environment-friendly stabilizer applied to PVC double-layer shaft hollow tube - Google Patents
Novel sustained-release environment-friendly stabilizer applied to PVC double-layer shaft hollow tube Download PDFInfo
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08K5/00—Use of organic ingredients
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- C08K5/053—Polyhydroxylic alcohols
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- C08K5/34—Heterocyclic compounds having nitrogen in the ring
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Abstract
The invention discloses a novel sustained-release environment-friendly stabilizer applied to PVC double-layer shaft hollow tubes, which comprises the following components, by weight, 20% of zinc stearate, 5% of calcium stearate, 10% of cypress, 2% of uracil, 36% of zeolite, 8% of calcium hydroxide, 3% of an antioxidant, 10% of a synergistic heat stabilizer and 6% of polyol. The invention relates to the technical field of hollow tube stabilizers. This new slowly-releasing type is applied to double-deck axle hollow tube environmental protection stabilizer of PVC, has solved current calcium zinc stabilizer and has used in the double-deck axle hollow tube raw materials production process of PVC, and the double-deck axle hollow tube performance of PVC after the production is single, and degradation speed is fast simultaneously, and thermal stability is poor, influences the problem of the stability ability of follow-up pipeline in the reality.
Description
Technical Field
The invention relates to the technical field of hollow tube stabilizers, in particular to a novel slow-release environment-friendly stabilizer applied to PVC double-layer shaft hollow tubes.
Background
Municipal rainwater and sewage separation, drainage pipeline reconstruction engineering and sponge city construction are increasing, and the demands on drainage pipes and inspection wells are increasing. Compared with cement pipes and inspection wells, the rigid polyvinyl chloride (PVC-U) double-layer axial hollow wall pipe and the polyvinyl chloride (PVC) inspection well have the obvious advantages of good connection sealing performance, corrosion resistance, convenience in transportation, quickness in construction and reduction of construction period. Is increasingly used in drainage engineering in China.
The existing calcium-zinc stabilizer is applied to the production process of the PVC double-layer shaft hollow tube raw material, the produced PVC double-layer shaft hollow tube has single performance, and meanwhile, the degradation speed is high, the thermal stability is poor, and the stability of a subsequent pipeline in practice is influenced.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a novel sustained-release environment-friendly stabilizer applied to a PVC double-layer shaft hollow tube, and solves the problems that when the existing calcium-zinc stabilizer is applied to the production process of a PVC double-layer shaft hollow tube raw material, the produced PVC double-layer shaft hollow tube has single performance, high degradation speed and poor thermal stability, and the stability of a subsequent pipeline in practice is influenced.
(II) technical scheme
In order to achieve the purpose, the invention is realized by the following technical scheme: a novel sustained-release environment-friendly stabilizer applied to PVC double-layer shaft hollow tubes comprises, by weight, 20% of zinc stearate, 5% of calcium stearate, 10% of cypress, 2% of uracil, 36% of zeolite, 8% of calcium hydroxide, 3% of an antioxidant, 10% of a synergistic heat stabilizer and 6% of polyol.
And is prepared by the following steps:
step one, uniformly stirring zinc stearate, calcium stearate, saxok, uracil and polyhydric alcohol for 10min at the temperature of 28 ℃;
step two, adding zeolite and calcium hydroxide, mixing and stirring for 17 min;
thirdly, adding a synergistic stabilizer, an antioxidant and a high-performance graphene oxide calcium zinc stabilizer, stirring for 6min at 75 ℃ under the condition of matching with nitrogen protection, and cooling to obtain a PVC stabilizer;
and step four, modifying the PVC stabilizer obtained in the step three to obtain the slow-release environment-friendly stabilizer applied to the PVC double-layer shaft hollow tube.
Preferably, the synergistic stabilizer is prepared by compounding metal soap ZN/Ca salt, phosphorous acid auxiliary stabilizer, epoxy compound and polyol according to a certain proportion.
Preferably, in the fourth step, the outer diameter is 600-1900nm, and the inner hole is
The ring cage material of (1).
Preferably, the ring cage-shaped material is 800nm in outer diameter
A material.
Preferably, the light stabilizer and the ultraviolet absorber are added in the third step and are stirred synchronously.
Preferably, the addition amount of the high-performance graphene oxide calcium zinc stabilizer is as follows: 0.8 wt%.
Preferably, in the fourth step, the PVC stabilizer is modified by a coating, intercalation or adsorption process.
Advantageous effects
The invention provides a novel sustained-release environment-friendly stabilizer applied to PVC double-layer shaft hollow tubes. The method has the following beneficial effects:
the novel sustained-release environment-friendly stabilizer applied to the PVC double-layer shaft hollow tube avoids the traditional high-valence hydrotalcite material in the preparation process, is prepared from the raw materials of zinc stearate, calcium stearate, cypress, uracil, zeolite, calcium hydroxide, an antioxidant, a synergistic heat stabilizer and polyol, has high cost performance, and simultaneously has stronger thermal stability of the whole stabilizer by adopting a metal soap ZN/Ca salt, matching with a phosphorous acid auxiliary stabilizer and an epoxy compound, and compounding the polyol according to a certain proportion to form the synergistic stabilizer, so that the color of the whole stabilizer is not easy to change in the PVC processing process, and the continuous production period is long; the specific raw materials are selected and matched according to a certain proportion, so that the raw materials are not easy to separate out in production, the production efficiency and the economic benefit are improved due to the long production period, the appearance quality of the product is also ensured due to the difficult separation, the synergistic effect of the raw materials is enhanced by adopting the specific formula proportion, the surface separation of the liquid calcium zinc stabilizer can be improved by adopting the high-performance graphene oxide, and the compatibility of the liquid calcium zinc stabilizer is improved. Meanwhile, the heat resistance and the heat conduction performance of the product can be improved by adding the graphene, so that the physical performance of the produced product is better, and compared with the PVC raw material of the PVC double-layer shaft hollow tube after the slow-release type PVC double-layer shaft hollow tube environment-friendly stabilizer is applied to the PVC double-layer shaft hollow tube environment-friendly stabilizer in the conventional system, the PVC double-layer shaft hollow tube environment-friendly stabilizer has slower degradation speed and better thermal stability, and is more favorable for the stability of the PVC double-layer shaft hollow tube in practical life.
Drawings
FIG. 1 is a schematic diagram showing the test results of a pvc specimen using the stabilizer of the present invention and an old system stabilizer.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1, the present invention provides a technical solution: the novel slow-release environment-friendly stabilizer applied to the PVC double-layer shaft hollow tube comprises, by weight, 20% of zinc stearate, 5% of calcium stearate, 10% of cypress, 2% of uracil, 36% of zeolite, 8% of calcium hydroxide, 3% of an antioxidant, 10% of a synergistic thermal stabilizer and 6% of polyol.
And is prepared by the following steps:
step one, uniformly stirring zinc stearate, calcium stearate, saxok, uracil and polyhydric alcohol for 10min at the temperature of 28 ℃;
step two, adding zeolite and calcium hydroxide, mixing and stirring for 17 min;
thirdly, adding a synergistic stabilizer, an antioxidant and a high-performance graphene oxide calcium zinc stabilizer, stirring for 6min at 75 ℃ under the condition of matching with nitrogen protection, and cooling to obtain a PVC stabilizer;
and step four, modifying the PVC stabilizer obtained in the step three to obtain the slow-release environment-friendly stabilizer applied to the PVC double-layer shaft hollow tube.
In the embodiment, the synergistic stabilizer is prepared by compounding metal soap ZN/Ca salt, phosphorous acid auxiliary stabilizer, epoxy compound and polyol according to a certain proportion. Phosphite is the most widely used auxiliary stabilizer in Ca/Zn composite stabilizer, and is an indispensable component in the composite stabilizer. The phosphite esters used as the auxiliary stabilizer mainly include triphenyl phosphite, tridecyl phosphite, trisnonylphenyl phosphite, trioctyl phosphite, and the like. For soft PVC, the phosphite is generally used in combination with β -diketone, epoxidized soybean oil, and the like. Phosphite has a plasticizing effect and is not suitable for rigid PVC; has antioxidant capacity, can capture hydrogen chloride, add polyene, and greatly improve the stability of a PVC stabilizing system. Among the epoxy compounds, epoxidized soybean oil has traditionally been used as an auxiliary stabilizer. Recent studies have shown that bisphenol a diglycidyl ether, bisphenol F diglycidyl ether, glycidyl ether of phenol resin, glycidyl ether of tetraphenylethane, alicyclic epoxy resin, triglycidyl trimellitate, diglycidyl terephthalate, and the like all have high stabilization efficiency. Epoxide reacts with hydrogen chloride to generate chlorohydrin which replaces unstable chlorine atoms in PVC to play a stabilizing role under the catalytic action of metal soaps such as calcium, zinc and the like. In the static stability test, the epoxy compound acts to inhibit yellowing of PVC.
In the fourth step of the present embodiment, the outer diameter is 600-1900nm, and the inner hole is
The ring cage material of (1).
In this embodiment, the ring cage material has an outer diameter of 800nm
A material. By adopting the outer diameter of 800mm and the inner hole of
The ring cage material carries out modification treatment on the PVC stabilizer, so that the stabilizer is hollow and perforated, the stabilizer is equivalently released in the actual use process, and the protection effect on the PVC pipe is improved.
In this example, the light stabilizer and the ultraviolet absorber are added in the third step and are stirred synchronously. On one hand, the light stabilizer is added in the raw materials, and has the functions of shielding or absorbing the energy of ultraviolet rays, quenching singlet oxygen, decomposing hydroperoxide into inactive substances and the like, so that the possibility of photochemical reaction can be eliminated or slowed down and the process of photoaging can be prevented or delayed under the radiation of light, thereby achieving the purpose of prolonging the service life of a high molecular polymer product, and further assisting the ultraviolet absorber to improve the oxidation resistance of the stabilizer.
In this embodiment, the addition amount of the high-performance graphene oxide calcium zinc stabilizer is as follows: 0.8 wt%. By adopting the high-performance graphene oxide, the surface precipitation of the liquid calcium-zinc stabilizer can be improved, and the compatibility of the liquid calcium-zinc stabilizer can be improved. Meanwhile, the heat resistance and the heat conduction performance of the product can be improved by adding the graphene.
In this embodiment, in the fourth step, the PVC stabilizer is modified by a coating, intercalation, or adsorption process.
Examples
A novel sustained-release environment-friendly stabilizer applied to PVC double-layer shaft hollow tubes adopts the following raw materials by weight percent:
20% of zinc stearate;
5% of calcium stearate;
10% of mosaic;
2% of uracil;
36% of zeolite;
8% of calcium hydroxide;
3% of antioxidant;
10% of synergistic heat stabilizer;
6% of polyol.
The preparation method comprises the following steps:
step one, uniformly stirring zinc stearate, calcium stearate, saxok, uracil and polyhydric alcohol for 10min at the temperature of 28 ℃;
step two, adding zeolite and calcium hydroxide, mixing and stirring for 17 min;
thirdly, adding a synergistic stabilizer, an antioxidant and a high-performance graphene oxide calcium zinc stabilizer, stirring for 6min at 75 ℃ under the condition of matching with nitrogen protection, and cooling to obtain a PVC stabilizer;
step four, adopting the PVC stabilizer obtained in the step three, wherein the outer diameter is 800mm, and the inner hole is
The ring cage material is modified, so that the stabilizer is hollow and perforated, and the slow-release type PVC double-layer shaft hollow tube environment-friendly stabilizer is obtained.
The slow-release type environment-friendly stabilizer applied to PVC double-layer shaft hollow tubes and the commercially available composite stabilizer prepared in the embodiment are uniformly mixed with 110g of PVC powder, 2g of DOP, 2g of titanium dioxide and 21g of light calcium of the raw materials of the PVC double-layer shaft hollow tubes respectively, the temperature of front and back rollers is 190 ℃, the gap between the front and back rollers is 0.5 +/-0.1, the rotating speed of the front roller is 18R, the rotating speed of the back roller is 20R, tabletting is carried out for 8min, a PVC sample is obtained, the PVC sample is tested for 90min in an aging tester at the temperature of 185 ℃, and the color of the PVC sample is recorded every 15 min. The following table is recorded. Generally, when PVC is heated, the color of the PVC can be changed from light to dark in a series of changes from white-yellow-brown-black, and the degradation condition can be judged according to the color of the PVC in a certain time. (darker colors indicate closer to black, lighter colors indicate closer to white, and intermediate colors are yellow, brown, and brown)
In the table shown in fig. 1, it can be seen that the PVC double-layer hollow tube raw material PVC sample sheet under the condition of using the old system environment-friendly calcium zinc stabilizer, the color changes greatly after 30min under the experimental conditions, the color tends to be black in 90min, the degradation speed is high, on the contrary, the slow-release type PVC sample wafer applied to the PVC double-layer shaft hollow tube environment-friendly stabilizer in the invention, under the experimental conditions, the color basically tends to be stable within 30mim to 90min, no large color change occurs, therefore, compared with the PVC raw material of the PVC double-layer shaft hollow tube which is applied to the PVC double-layer shaft hollow tube environment-friendly stabilizer in the prior system, the PVC raw material of the PVC double-layer shaft hollow tube has slower degradation speed and better thermal stability, and is more favorable for the stability performance of the PVC double-layer shaft hollow tube in practical life.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation. The use of the phrase "comprising one of the elements does not exclude the presence of other like elements in the process, method, article, or apparatus that comprises the element.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. The novel sustained-release environment-friendly stabilizer applied to PVC double-layer shaft hollow tubes is characterized by comprising the following components, by weight, 20% of zinc stearate, 5% of calcium stearate, 10% of cypress, 2% of uracil, 36% of zeolite, 8% of calcium hydroxide, 3% of an antioxidant, 10% of a synergistic heat stabilizer and 6% of polyol.
2. The novel sustained-release environment-friendly stabilizer applied to the PVC double-layer shaft hollow tube according to claim 1 is prepared by the following steps:
step one, uniformly stirring zinc stearate, calcium stearate, saxok, uracil and polyhydric alcohol for 10min at the temperature of 28 ℃;
step two, adding zeolite and calcium hydroxide, mixing and stirring for 17 min;
thirdly, adding a synergistic stabilizer, an antioxidant and a high-performance graphene oxide calcium zinc stabilizer, stirring for 6min at 75 ℃ under the condition of matching with nitrogen protection, and cooling to obtain a PVC stabilizer;
and step four, modifying the PVC stabilizer obtained in the step three to obtain the slow-release environment-friendly stabilizer applied to the PVC double-layer shaft hollow tube.
3. The novel sustained-release environment-friendly stabilizer applied to PVC double-layer shaft hollow tubes according to claim 1 is characterized in that: the synergistic stabilizer is prepared by compounding metal soap ZN/Ca salt, phosphorous acid auxiliary stabilizer, epoxy compound and polyol according to a certain proportion.
4. The novel sustained-release environment-friendly stabilizer applied to PVC double-layer shaft hollow tubes according to claim 1 is characterized in that: in the fourth step, the outer diameter is 600-1900nm, and the inner hole is
The ring cage material of (1).
5. The novel sustained-release environment-friendly stabilizer applied to PVC double-layer shaft hollow tubes according to claim 4 is characterized in that: the ring cage-shaped material has an outer diameter of 800nm
A material.
6. The novel sustained-release environment-friendly stabilizer applied to PVC double-layer shaft hollow tubes according to claim 1 is characterized in that: and adding a light stabilizer and an ultraviolet absorbent into the third step for synchronous stirring.
7. The novel sustained-release environment-friendly stabilizer applied to PVC double-layer shaft hollow tubes according to claim 1 is characterized in that: the high-performance graphene oxide calcium zinc stabilizer is prepared from the following components in parts by weight: 0.8 wt%.
8. The novel sustained-release environment-friendly stabilizer applied to PVC double-layer shaft hollow tubes according to claim 2 is characterized in that: and in the fourth step, the PVC stabilizer is modified through a coating, intercalation or adsorption process.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE59611265D1 (en) * | 1995-10-13 | 2005-09-29 | Crompton Vinyl Additives Gmbh | Stabilizer combinations for chlorine-containing polymers |
| DE102008005339A1 (en) * | 2008-01-21 | 2009-07-23 | Chemson Polymer-Additive Ag | Stabilizer composition for halogen-containing polymers |
| CN109897308A (en) * | 2019-03-18 | 2019-06-18 | 浙江东阳君邦科技有限公司 | A kind of sheet calcium zinc stabilizer |
| CN109942984A (en) * | 2019-03-18 | 2019-06-28 | 浙江东阳君邦科技有限公司 | A kind of preparation method of sheet calcium zinc stabilizer |
-
2020
- 2020-10-15 CN CN202011104221.5A patent/CN112143040A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE59611265D1 (en) * | 1995-10-13 | 2005-09-29 | Crompton Vinyl Additives Gmbh | Stabilizer combinations for chlorine-containing polymers |
| DE102008005339A1 (en) * | 2008-01-21 | 2009-07-23 | Chemson Polymer-Additive Ag | Stabilizer composition for halogen-containing polymers |
| CN109897308A (en) * | 2019-03-18 | 2019-06-18 | 浙江东阳君邦科技有限公司 | A kind of sheet calcium zinc stabilizer |
| CN109942984A (en) * | 2019-03-18 | 2019-06-28 | 浙江东阳君邦科技有限公司 | A kind of preparation method of sheet calcium zinc stabilizer |
Non-Patent Citations (1)
| Title |
|---|
| 张立德 编著: "《纳米材料》", 30 November 2000, 化学工业出版社 * |
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