CN115746472B - PVC composite heat stabilizer containing dibenzoylmethane - Google Patents
PVC composite heat stabilizer containing dibenzoylmethane Download PDFInfo
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- CN115746472B CN115746472B CN202211295782.7A CN202211295782A CN115746472B CN 115746472 B CN115746472 B CN 115746472B CN 202211295782 A CN202211295782 A CN 202211295782A CN 115746472 B CN115746472 B CN 115746472B
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Abstract
The invention discloses a composite heat stabilizer for PVC containing dibenzoylmethane, which relates to the technical field of functional auxiliary agents, wherein the composite heat stabilizer is prepared by taking calcium stearate and/or zinc stearate as main stabilizers and taking dibenzoylmethane and zinc ethylphenyl dithiocarbamate as auxiliary stabilizers, and the heat stability of PVC is improved by adjusting the proportion relation of the components, and meanwhile, the addition amount of the heat stabilizer is controlled, so that the input cost of the heat stabilizer is reduced; the composite heat stabilizer prepared by the invention is nontoxic, and can not influence the safety of PVC products and the transparency of the PVC products.
Description
Technical field:
the invention relates to the technical field of functional auxiliary agents, in particular to a composite heat stabilizer for PVC containing dibenzoylmethane.
The background technology is as follows:
polyvinyl chloride (PVC) is the most widely used thermoplastic resin, and has excellent mechanical properties, corrosion resistance, insulation properties and chemical resistance, and also has good flame retardancy and high transparency. PVC has a glass transition temperature of 77-90 deg.C, a decomposition start at about 170 deg.C, poor stability to light and heat, decomposition to generate hydrogen chloride after exposure to sunlight at over 100 deg.C or for a long time, further autocatalysis to cause discoloration, and rapid decrease in physical and mechanical properties, and in practical application, a stabilizer must be added to improve its stability to heat and light.
At present, the commonly used PVC heat stabilizer mainly comprises lead salts, metal soaps, organic tin, organic stibium, rare earth and organic auxiliary heat stabilizer, and the heat stabilizer has the defects of toxicity, high price, poor transparency, poor stabilizing effect and the like although the heat stabilizer has the advantages. In order to make PVC better applied to the field of plastic products, composite heat stabilizer has been developed, and the heat stability of PVC is improved efficiently by compounding two or more heat stabilizers, the cost is controlled, and the non-toxicity and environmental protection are ensured.
The invention comprises the following steps:
the invention aims to solve the technical problem of providing the composite heat stabilizer for PVC containing dibenzoylmethane, which achieves a good synergistic effect by adopting calcium stearate and/or zinc stearate as main stabilizers and zinc dibenzoylmethane and ethylphenyl dithiocarbamate as auxiliary stabilizers, thereby remarkably improving the heat stability of PVC, reducing the input cost of the heat stabilizer and ensuring the non-toxicity and environmental protection of the heat stabilizer.
The technical problems to be solved by the invention are realized by adopting the following technical scheme:
the invention aims at providing a composite heat stabilizer which is formed by compounding calcium stearate and/or zinc stearate, dibenzoylmethane and zinc ethylphenyl dithiocarbamate.
Preferably, the mass ratio of the calcium stearate to the zinc dibenzoyl methane to the zinc ethylphenyl dithiocarbamate is (30-50): 5-20.
It is further preferable that the mass ratio of the calcium stearate and/or zinc stearate, dibenzoylmethane and zinc ethylphenyl dithiocarbamate is (35-45): 10-20): 5-15.
Preferably, the mass ratio of the calcium stearate to the zinc stearate is (1-5): 1.
Further preferably, the mass ratio of the calcium stearate to the zinc stearate is (2-3): 1.
Calcium stearate, white powder, molecular formula C 36 H 70 CaO 4 Can be used as PVC resin heat stabilizer, and can also be used as lubricant, mold release agent and the like for processing various plastics.
Zinc stearate, white powder, molecular formula C 36 H 70 ZnO 4 Can be used as PVC resin heat stabilizer, and can also be used as lubricant, accelerator, thickener, etc. for processing various plastics.
Dibenzoylmethane, colorless knotCrystal, molecular formula C 15 H 12 O 2 Typically as co-stabilizer for calcium/zinc hydroxy acid salt stabilization systems.
Zinc ethylphenyl dithiocarbamate, white powder, molecular formula C 9 H 11 NS 2 Zn is usually used as a rubber vulcanization accelerator, shortens the vulcanization time, reduces the vulcanization temperature, reduces the consumption of vulcanizing agent, improves the physical and mechanical properties of rubber and the like,
according to the PVC heat stabilizer, calcium stearate and/or zinc stearate are/is used as the main stabilizer, dibenzoylmethane and zinc ethylphenyl dithiocarbamic acid are used as the auxiliary stabilizers, the PVC heat stabilizer is nontoxic, low in price and good in transparency, and the optimal synergistic effect can be achieved by adjusting the composition ratio, so that the heat stability of the PVC is effectively improved. Among them, calcium stearate, zinc stearate and dibenzoylmethane belong to heat stabilizers commonly used in the art, but zinc ethylphenyl dithiocarbamate does not belong to heat stabilizers known in the art. The zinc ethylphenyl dithiocarbamate has an atmospheric boiling point of 269.9 ℃, and can be used as an auxiliary stabilizer as long as the processing temperature of the PVC plastic product does not exceed its boiling point.
The second purpose of the invention is to provide the application of the composite heat stabilizer in PVC plastic product processing.
Preferably, the addition amount of the composite heat stabilizer is 100 parts of PVC and 3-5 parts of the composite heat stabilizer.
In order to improve the blending compatibility of the composite heat stabilizer and PVC, promote the uniform dispersion of the composite heat stabilizer in the PVC, and proper compatilizer is also needed to be added, so that the composite heat stabilizer can better exert the heat stability.
Preferably, the composite heat stabilizer is used in combination with a compatilizer, and the compatilizer is zinc methacrylate.
Preferably, the addition amount of the compatilizer is 100 parts of PVC and 3-5 parts of compatilizer.
Zinc methacrylate, white powder, molecular formula C 8 H 10 O 4 Zn, which is usually used as a rubber vulcanization aid and a heat-resistant additive, has acid resistance, alkali resistance, oil resistance, corrosion resistance and high temperature resistance, and can improve the vulcanized rubberStrength, elasticity and tear resistance. The invention can effectively improve the blending compatibility of PVC and the composite heat stabilizer by taking the PVC as the compatilizer of the PVC and the composite heat stabilizer.
The beneficial effects of the invention are as follows: according to the composite heat stabilizer, calcium stearate and/or zinc stearate are used as main stabilizers, dibenzoylmethane and zinc ethylphenyl dithiocarbamate are used as auxiliary stabilizers, the heat stability of PVC is improved by adjusting the component proportion relation, the addition amount of the heat stabilizer is controlled, and the input cost of the heat stabilizer is reduced; the composite heat stabilizer prepared by the invention is nontoxic, and can not influence the safety of PVC products and the transparency of the PVC products.
The specific embodiment is as follows:
the invention is further described in connection with the following embodiments in order to make the technical means, the creation features, the achievement of the purpose and the effect of the invention easy to understand.
Example 1
Adding calcium stearate, dibenzoylmethane and zinc ethylphenyl dithiocarbamate with the mass ratio of 40:15:5 into a high-speed mixer, and mixing for 5min at the rotating speed of 1000r/min to obtain the composite heat stabilizer A.
Example 2
Adding zinc stearate, dibenzoylmethane and zinc ethylphenyl dithiocarbamate with the mass ratio of 35:12:5 into a high-speed mixer, and mixing for 5min at the rotating speed of 1000r/min to obtain the composite heat stabilizer B.
Example 3
Adding calcium stearate and zinc stearate with the mass ratio of 45:10:5, dibenzoylmethane and zinc ethylphenyl dithiocarbamate into a high-speed mixer, wherein the mass ratio of the calcium stearate to the zinc stearate is 2:1, and mixing for 5min at the rotating speed of 1000r/min to obtain the composite heat stabilizer C.
Example 4
Adding calcium stearate and zinc stearate with the mass ratio of 45:10:10, dibenzoylmethane and zinc ethylphenyl dithiocarbamate into a high-speed mixer, wherein the mass ratio of the calcium stearate to the zinc stearate is 3:1, and mixing for 5min at the rotating speed of 1000r/min to obtain the composite heat stabilizer D.
Example 5
Adding calcium stearate and zinc stearate with the mass ratio of 35:15:10, dibenzoylmethane and zinc ethylphenyl dithiocarbamate into a high-speed mixer, wherein the mass ratio of the calcium stearate to the zinc stearate is 4:1, and mixing for 5min at the rotating speed of 1000r/min to obtain the composite heat stabilizer E.
Comparative example 1
The zinc ethylphenyl dithiocarbamate of example 4 was deleted to give comparative example 1.
Adding calcium stearate and zinc stearate with the mass ratio of 40:10 and dibenzoylmethane into a high-speed mixer, wherein the mass ratio of the calcium stearate to the zinc stearate is 3:1, and mixing for 5min at the rotating speed of 1000r/min to obtain the composite heat stabilizer F.
Comparative example 2
The zinc ethylphenyl dithiocarbamate in example 4 was replaced with zinc acetylacetonate to give comparative example 2.
Adding calcium stearate, zinc stearate, dibenzoylmethane and zinc acetylacetonate with the mass ratio of 40:10:10 into a high-speed mixer, wherein the mass ratio of the calcium stearate to the zinc stearate is 3:1, and mixing for 5min at the rotating speed of 1000r/min to obtain the composite heat stabilizer G.
3 to 5 parts of the composite heat stabilizer prepared in the examples 1 to 6 and the comparative examples 1 to 2 were mixed with 30 parts of plasticizer DOP and 100 parts of PVC-SG5 at a rotation speed of 1000r/min for 10min, respectively, and then plasticated into pieces on a twin-roll rubber mixing mill with a roll temperature of 170 ℃ and a roll gap of 1.5mm, and granulated to obtain particles with a particle size of 0.4 to 0.6 mm. The thermal stability was measured at 180℃according to the standard GB/T2917.1-2002 and the results are shown in Table 1.
TABLE 1
Note that: the maleic anhydride grafted polyethylene was dupont E100.
As can be seen from table 1, the heat stability of PVC is changed with the adjustment of the proportions of the components in the composite heat stabilizer; the effect of the zinc ethylphenyl dithiocarbamate serving as a heat stabilizer is better than that of zinc acetylacetonate; compared with maleic anhydride grafted polyethylene, the zinc methacrylate is used as a compatilizer, so that the thermal stability of PVC can be further improved.
The foregoing has shown and described the basic principles and main features of the present invention and the advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (7)
1. A composite heat stabilizer is characterized in that: is compounded by calcium stearate and/or zinc stearate, dibenzoylmethane and ethyl phenyl zinc dithiocarbamate;
the mass ratio of the calcium stearate to the zinc dibenzoylmethane to the zinc ethylphenyl dithiocarbamate is (30-50): 5-20;
the mass ratio of the calcium stearate to the zinc stearate is (1-5): 1.
2. The composite heat stabilizer according to claim 1, wherein: the mass ratio of the calcium stearate to the zinc dibenzoyl methane to the zinc ethylphenyl dithiocarbamic acid is (35-45)/(10-20)/(5-15).
3. The composite heat stabilizer according to claim 1, wherein: the mass ratio of the calcium stearate to the zinc stearate is (2-3): 1.
4. Use of the composite heat stabilizer according to any one of claims 1 to 3 in the processing of PVC plastic products.
5. The use according to claim 4, characterized in that: the addition amount of the composite heat stabilizer is 100 parts of PVC and 3-5 parts of the composite heat stabilizer.
6. The use according to claim 4, characterized in that: the composite heat stabilizer is matched with a compatilizer, and the compatilizer is zinc methacrylate.
7. The use according to claim 6, characterized in that: the addition amount of the compatilizer is 100 parts of PVC and 3-5 parts of compatilizer.
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Citations (8)
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| JPH08311350A (en) * | 1995-05-23 | 1996-11-26 | Yokohama Rubber Co Ltd:The | Thermoplastic elastomer composition and its production |
| CN1176268A (en) * | 1993-04-16 | 1998-03-18 | 希巴特殊化学控股公司 | Stabilized polyvinyl chloride |
| CN1366536A (en) * | 2000-04-07 | 2002-08-28 | 三井化学株式会社 | Thermoplastic elastomer composition with high resistance to thermal deterioration |
| CN101268140A (en) * | 2005-08-11 | 2008-09-17 | Lg化学株式会社 | Highly elastic polyvinyl chloride composition and products prepared using the same |
| CN102166404A (en) * | 2009-12-02 | 2011-08-31 | 阿库施耐特公司 | Multilayer core golf ball |
| CN104893184A (en) * | 2015-06-27 | 2015-09-09 | 邵阳学院 | Zinc-containing hydroxyl apatite-based PVC composite heat stabilizer and application |
| CN107001742A (en) * | 2014-12-05 | 2017-08-01 | 阿朗新科荷兰有限公司 | Compositions of vulcanize rubbers |
| CN111423637A (en) * | 2019-01-10 | 2020-07-17 | 中国石油化工股份有限公司 | Nitrile rubber/lignin composition, nitrile rubber/lignin composite material, and preparation method and application thereof |
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- 2022-10-21 CN CN202211295782.7A patent/CN115746472B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1176268A (en) * | 1993-04-16 | 1998-03-18 | 希巴特殊化学控股公司 | Stabilized polyvinyl chloride |
| JPH08311350A (en) * | 1995-05-23 | 1996-11-26 | Yokohama Rubber Co Ltd:The | Thermoplastic elastomer composition and its production |
| CN1366536A (en) * | 2000-04-07 | 2002-08-28 | 三井化学株式会社 | Thermoplastic elastomer composition with high resistance to thermal deterioration |
| CN101268140A (en) * | 2005-08-11 | 2008-09-17 | Lg化学株式会社 | Highly elastic polyvinyl chloride composition and products prepared using the same |
| CN102166404A (en) * | 2009-12-02 | 2011-08-31 | 阿库施耐特公司 | Multilayer core golf ball |
| CN107001742A (en) * | 2014-12-05 | 2017-08-01 | 阿朗新科荷兰有限公司 | Compositions of vulcanize rubbers |
| CN104893184A (en) * | 2015-06-27 | 2015-09-09 | 邵阳学院 | Zinc-containing hydroxyl apatite-based PVC composite heat stabilizer and application |
| CN111423637A (en) * | 2019-01-10 | 2020-07-17 | 中国石油化工股份有限公司 | Nitrile rubber/lignin composition, nitrile rubber/lignin composite material, and preparation method and application thereof |
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