CN112175312A - Environment-friendly stabilizer applied to transparent PVC (polyvinyl chloride) hard product - Google Patents
Environment-friendly stabilizer applied to transparent PVC (polyvinyl chloride) hard product Download PDFInfo
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Abstract
The application discloses an environment-friendly stabilizer applied to a transparent PVC hard product, which comprises the following raw material components in parts by weight: 25-37 parts of modified magnesium aluminum hydrotalcite, 20-28 parts of zinc dodecanethiolate, 8-13 parts of dibenzoyl methane, 28-36 parts of trihydroxy methyl propane and 0.3-0.7 part of water. The calcium-zinc stabilizer system which takes zinc dodecanethiolate as a main stabilizer and takes modified magnesium-aluminum hydrotalcite/dibenzoylmethane/trihydroxy methyl propane as an auxiliary stabilizer is screened out. The selected main stabilizer and the selected auxiliary stabilizer both have good transparency (the light refractive index is close to that of PVC resin), and the three auxiliary stabilizers, namely modified magnesium aluminum hydrotalcite/dibenzoylmethane/trihydroxy methyl propane, are added into the formula in a compounding manner, so that the later-stage stability performance of the stabilizer is enhanced through the synergistic effect of the three stabilizers.
Description
Technical Field
The invention relates to an environment-friendly stabilizer applied to a transparent PVC hard product.
Background
PVC (namely polyvinyl chloride) is one of five major synthetic resins with the largest usage in the world, and is widely applied in practical use because PVC has the advantages of high strength, low price, strong chemical stability resistance and the like, and in addition, PVC has the advantages of better insulativity, difficult combustion and the like.
PVC is prepared by a suspension method in industrial production to obtain polyvinyl chloride resin as a main method, and an initiator is added as an auxiliary agent in the preparation process in the process of preparing the polyvinyl chloride resin from a vinyl chloride monomer, so that the processing difficulty of the PVC is increased in the later use process. PVC releases chlorine radicals (i.e., Cl) to some extent during processing, and thus decomposes to release hydrogen chloride (i.e., HCl) at processing temperatures up to 140 ℃. The released HCl and Cl radicals can not be treated, can be accumulated in materials, and can aggravate the decomposition of PVC, so that the color of the product is sharply deepened, the physical property is sharply reduced, and even a more serious carbonization and blackening phenomenon can occur, thereby losing the use value. Therefore, during the processing of PVC articles, heat stabilizers must be used to improve processing stability.
Commonly used stabilizers are lead salt stabilizers (lead-based complexes formed with lead ions as the central body and organic groups as the ligands) and organotin stabilizers. The lead salt stabilizer has good stability, but has certain environmental pollution because of containing heavy metal element lead, and is difficult to be continuously used in the existing processing system. The organic tin stabilizer has good stability, organic tin is generally used as a processing stabilizer in CPVC and transparent products, but tin is also a heavy metal element, and the organic tin stabilizer is expensive, so that the organic tin stabilizer is applied to PVC processing and has a narrow processing range.
The calcium zinc stabilizer mainly comprises a main stabilizer and an auxiliary stabilizer. The calcium zinc stabilizer has the advantages of environmental protection, wide processing range and the like. In the prior art, the calcium zinc stabilizer is mainly applied to the processing systems of common PVC and transparent soft PVC, and the calcium zinc stabilizer of a transparent PVC hard product has few application cases. The hard PVC is more difficult to process than common PVC hard products (containing inorganic filler) and transparent soft products, and has the characteristics of high viscosity of the hard transparent PVC, high mold pressure in the processing process, quick decomposition of raw materials in the production and processing process and the like. Therefore, in the prior art, the hard PVC transparent pipe is difficult to produce by taking calcium and zinc as the stabilizer under the condition of not adding a plasticizer.
Disclosure of Invention
Aiming at the technical problems in the prior art, the application aims to provide an environment-friendly stabilizer applied to a transparent PVC hard product.
The environment-friendly stabilizer applied to the transparent PVC hard product is characterized by comprising the following raw material components in parts by weight: 25-37 parts of modified magnesium aluminum hydrotalcite, 20-28 parts of zinc dodecanethiolate, 8-13 parts of dibenzoyl methane, 28-36 parts of trihydroxy methyl propane and 0.3-0.7 part of water.
The environment-friendly stabilizer applied to the transparent PVC hard product is characterized by comprising the following raw material components in parts by weight: 31-33 parts of modified magnesium aluminum hydrotalcite, 22-24 parts of zinc dodecanethiolate, 10-11 parts of dibenzoyl methane, 33-34 parts of trihydroxymethyl propane and 0.4-0.5 part of water.
The environment-friendly stabilizer applied to the transparent PVC hard product is characterized in that the preparation method of the zinc dodecyl sulfate comprises the following steps:
s1 preparation of zinc-based complex: uniformly mixing zinc oxide powder with deionized water to obtain zinc oxide slurry; slowly injecting the zinc oxide slurry into ammonia water drop by drop, and stirring until the slurry is completely dissolved to form a uniform and transparent zinc-based complex solution;
preparation of S2 zinc decamercaptide: adding dodecyl mercaptan and an ethanol solvent into a flask, uniformly stirring, dropwise adding the zinc-based complex solution obtained in the step S1, stirring at the temperature of 65-85 ℃ for 3-4 hours to obtain a colloid, standing for layering, removing an upper water layer to obtain a white pasty substance, and drying to obtain white solid powder zinc dodecyl sulfate.
The environment-friendly stabilizer applied to the transparent PVC hard product is characterized in that in the step S1, the molar concentration of ammonia water is 25-28%; the mass ratio of the zinc oxide to the ammonia water is 1: 2.5-4; the mass ratio of the zinc oxide in the step S1 to the dodecyl mercaptan in the step S2 is 1: 1.5-1: 4.
The environment-friendly stabilizer applied to the transparent PVC hard product is characterized in that the preparation method of the modified magnesium aluminum hydrotalcite comprises the following steps:
1) dissolving sodium hydroxide and sodium carbonate in deionized water to prepare an alkali solution (the prepared alkali solution has a certain slow-release agent effect and can control and adjust the pH value of the solution); dissolving magnesium salt and aluminum salt in deionized water to prepare a magnesium-aluminum salt solution; uniformly mixing the obtained alkali solution and the magnesium-aluminum salt solution drop by drop in a water bath at the temperature of 70-80 ℃ to finally obtain a white suspension;
2) adding phthalate ester compounds into the suspension obtained in the step 1), fully dispersing, crystallizing at normal temperature to obtain a solid, crystallizing for 8-24 h (the size of the finally prepared modified magnesium-aluminum hydrotalcite can be controlled by crystallization), and drying the solid obtained by crystallization to obtain the modified magnesium-aluminum hydrotalcite.
The environment-friendly stabilizer applied to the transparent PVC hard product is characterized in that the feeding mass ratio of sodium hydroxide, sodium carbonate, magnesium salt and aluminum salt is 1: 1.2-1.8: 1.0-1.5, and preferably 1:1.6:1.2: 1.2.
The environment-friendly stabilizer applied to the transparent PVC hard product is characterized in that the phthalate ester compound is tetrabutyl titanate, and the feeding mass ratio of the phthalate ester compound to the magnesium salt is 1: 0.5-0.8.
Compared with the prior art, the beneficial effect that this application was got is:
1. the calcium zinc stabilizer can be mainly divided into two parts: a primary stabilizer and a secondary stabilizer. In order to provide better thermal stability, a calcium zinc stabilizer system which takes zinc dodecanethiolate as a main stabilizer and takes modified magnesium aluminum hydrotalcite/dibenzoyl methane/trihydroxy methyl propane as an auxiliary stabilizer is screened out. The selected main stabilizer and the auxiliary stabilizer both have good transparency (the optical refractive index is close to that of PVC resin).
In the prior art, the stability of the calcium zinc stabilizer is insufficient, mainly because the later stability of the calcium zinc stabilizer is obviously insufficient compared with that of an organic tin stabilizer, the production difficulty in hard transparent PVC is very high. Therefore, three auxiliary stabilizers, namely modified magnesium aluminum hydrotalcite/dibenzoylmethane/trihydroxy methyl propane, are added in the formula in a composite manner, and the later-stage stability of the stabilizer is enhanced through the synergistic effect of the three stabilizers. The modified magnesium-aluminum hydrotalcite is used as the main component of the auxiliary stabilizer, can absorb decomposed Cl radicals and HCl to a certain extent, and increases the later stability of the product, and has the characteristics of small pore diameter and better adsorption performance.
2. In the calcium-zinc stabilizer, the zinc-based stabilizer has a great effect on the early-stage stability in the processing process under the action of the main stabilizer, so that the zinc content in the zinc dodecyl sulfate is adjusted to prepare the zinc dodecyl sulfate with different zinc contents, and the early-stage stabilizing effect of the product in the processing process is guaranteed.
The environment-friendly stabilizer provided by the invention is applied to preparation of transparent PVC hard products, has both early-stage stability and later-stage stability of the hard products, and integrally enables the finally prepared transparent PVC hard products to have good stability.
Drawings
FIG. 1 is a comparative graph of the rheological effects of high light transmittance PVC pipes respectively prepared from the organotin stabilizer and the environment-friendly stabilizer of example 1.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example 1:
an environment-friendly stabilizer applied to transparent PVC hard products comprises the following raw material components in parts by weight: 32.16 parts of magnesium aluminum hydrotalcite, 23.35 parts of zinc dodecanethiolate, 10.23 parts of dibenzoyl methane, 33.76 parts of trihydroxymethyl propane and 0.5 part of water.
The preparation method of the zinc decadithiolate comprises the following steps:
s1 preparation of zinc-based complex: uniformly mixing 5g of zinc oxide powder with 30 g of deionized water to obtain zinc oxide slurry; slowly injecting the zinc oxide slurry into 15 g of ammonia water (the molar concentration of the ammonia water is 25%) drop by drop, and stirring until the slurry is completely dissolved to form a uniform and transparent zinc-based complex solution;
preparation of S2 zinc decamercaptide: adding 10 g of dodecyl mercaptan and 25 g of ethanol into a flask, uniformly stirring, then dropwise adding the zinc-based complex solution obtained in the step S1, stirring at the temperature of 23 ℃ for 12 hours to obtain colloid, standing for layering, removing an upper water layer to obtain a white pasty substance, and drying to obtain white solid powder zinc dodecyl sulfate.
The preparation method of the modified magnesium-aluminum hydrotalcite comprises the following steps:
1) 5g of sodium hydroxide and 8 g of sodium carbonate are dissolved in 30 g of deionized water to prepare an alkali solution; 6 g of magnesium nitrate and 8 g of aluminum nitrate are dissolved in 30 g of deionized water together to prepare a magnesium-aluminum salt solution; uniformly mixing the obtained alkali solution and the magnesium-aluminum salt solution drop by drop in a water bath at 75 ℃ to finally obtain a white suspension;
2) adding 10 g of tetrabutyl titanate into the suspension obtained in the step 1), fully dispersing, crystallizing at 23 ℃ to obtain a solid, wherein the crystallization time is 20 h (the size can be controlled during crystallization, and the adsorption capacity of hydrotalcite can be improved to a certain extent in the later use process), and drying the solid obtained by crystallization to obtain the modified magnesium-aluminum hydrotalcite.
Through detection of a nanometer particle size analyzer, the size of the modified magnesium-aluminum hydrotalcite prepared in the embodiment 1 is nanometer, and the specific surface area can reach 99 square meters per gram by BET specific surface area analysis, and the apparent performance can show better adsorption capacity.
In the embodiment, the environment-friendly stabilizer is obtained by simply and physically blending the prepared modified magnesium aluminum hydrotalcite and zinc dodecyl sulfate, dibenzoyl methane, trihydroxymethyl propane and a small amount of water according to the raw material ratio.
Example 2:
an environment-friendly stabilizer applied to transparent PVC hard products comprises the following raw material components in parts by weight: 28 parts of modified magnesium aluminum hydrotalcite, 25 parts of zinc dodecyl sulfate, 12 parts of dibenzoyl methane, 30 parts of trihydroxy methyl propane and 0.4 part of water.
Wherein the preparation method of the zinc decamercaptide and the modified magnesium aluminum hydrotalcite is repeated with the embodiment 1.
In the embodiment, the environment-friendly stabilizer is obtained by simply and physically blending the prepared modified magnesium aluminum hydrotalcite and zinc dodecyl sulfate, dibenzoyl methane, trihydroxymethyl propane and a small amount of water according to the raw material ratio.
Example 3:
an environment-friendly stabilizer applied to transparent PVC hard products comprises the following raw material components in parts by weight: 35 parts of modified magnesium aluminum hydrotalcite, 26 parts of zinc dodecanethiolate, 11 parts of dibenzoyl methane, 28 parts of trihydroxymethyl propane and 0.7 part of water.
Wherein the preparation method of the zinc decamercaptide and the modified magnesium aluminum hydrotalcite is repeated with the embodiment 1.
In the embodiment, the environment-friendly stabilizer is obtained by simply and physically blending the prepared modified magnesium aluminum hydrotalcite and zinc dodecyl sulfate, dibenzoyl methane, trihydroxymethyl propane and a small amount of water according to the raw material ratio.
Comparative example 1:
an environment-friendly stabilizer applied to transparent PVC hard products, which is prepared by repeating the raw material ratio of the environment-friendly stabilizer in example 1, and is different from the following raw materials in that: the magnesium aluminum hydrotalcite starting material of comparative example 1 was commercially available from Jiangsu Kanggao plastics science and technology Limited.
Application example 1:
both an organic tin stabilizer purchased from Yunnan tin industries GmbH and the environment-friendly stabilizer of example 1 are used for preparing the high-light-transmission PVC pipeline, and the prepared high-light-transmission PVC pipeline consists of the following components in parts by weight:
50 portions of PVC resin (model SG-5)
50 portions of PVC resin (model SG-8)
8 portions of nano calcium carbonate powder (the grain diameter is less than 100 nm)
3.6 parts of stabilizer
6 parts of acrylate lubricating toughening modifier
Reactive siloxane 0.4 part
PE wax 0.3 part
0.5 part of glycerol partial fatty acid composite ester
0.6 part of pentaerythritol ester modifier;
among them, acrylate lubricating toughening modifiers (available from Dow, usa), reactive siloxanes (available from danyang crystallinity optical materials, ltd), pentaerythritol ester modifiers (available from jincheng auxiliaries, ltd, hangzhou). The stabilizer in the raw material formula of the high-light-transmission PVC pipeline is an organic tin stabilizer purchased from Yunnan tin industry or the environment-friendly stabilizer of the embodiment 1.
The preparation method of the high-light-transmission PVC pipeline comprises the following steps: mixing the components in parts by weight, putting the components into a high-speed mixer together, stirring and mixing, wherein the stirring temperature of the high-speed mixer is lower than 80 ℃, stirring at the rotating speed of 700-800 rpm for 3-6 minutes, then stirring at the rotating speed of 1300-1500 rpm for 5-8 minutes to obtain a PVC mixture, transferring the PVC mixture into a double-screw extruder once, controlling the temperature of a first zone to be 170 ℃, the temperature of a second zone to be 170 ℃, the temperature of a third zone to be 170 ℃, and performing extrusion molding under the conditions that the rotating speed of a screw is 25 rpm and the feeding rotating speed is 20 rpm to obtain the high-light-transmittance PVC pipeline product.
According to the method, the high-light-transmission PVC pipeline prepared by taking the organic tin stabilizer purchased from Yunnan tin industries, Ltd and the environment-friendly stabilizer of the embodiment 1 as raw materials is respectively subjected to rheological property test, and the method for the rheological property test comprises the following steps: the feeding amount is 65 g; the temperature of the first zone is 170 ℃; the temperature of the second zone is 170 ℃; the temperature of three zones is 170 ℃; the rotor speed was 35.0 rpm. The results are shown in fig. 1 as curve a and curve b, respectively. From the comparison of the rheology in fig. 1, in the case of adding the same quality of stabilizer, the rheology of the high light transmittance PVC pipe prepared from the environment-friendly stabilizer of example 1 is better, and the prepared PVC pipe has strong stability and high transparency. This is probably because the processing torque of the eco-friendly stabilizer of example 1 is significantly lower than that of the organotin stabilizer due to the addition of dibenzoylmethane/trihydroxymethylpropane, which shows that dibenzoylmethane/trihydroxymethylpropane also has a significant lubricant effect, which also provides some support for the long-term stability of the calcium zinc stabilizer.
The environmentally friendly stabilizer of example 1 is more environmentally friendly and has a wider processing window than commercially available organotin stabilizers, and product applications have been achieved. In addition, the balance torque is significantly lower than that of organotin formulations due to the relatively significant lubrication contained therein. Therefore, in the processing process, the current is small, and the conditions of energy conservation and environmental protection are realized.
As can be seen from the comparison of the pressed sheets of the PVC pipeline sample strips after the rheological test, the transparency of the PVC pipeline sample prepared by using the environment-friendly stabilizer in the embodiment 1 as the raw material is higher than that of the commercial organotin stabilizer. The PVC pipe sample prepared by using the environment-friendly stabilizer in the embodiment 1 as a raw material cannot be seen to be yellow or black, which shows that the stability of the environment-friendly stabilizer in the embodiment 1 is not obviously different from that of an organic tin stabilizer.
Application example 2:
the environment-friendly stabilizers of examples 1 to 3 and comparative example 1 were used for preparing the high-transmittance PVC pipe, and the formulation of the raw material and the preparation method of the high-transmittance PVC pipe were repeated as in example 1 except that the stabilizers were different.
The PVC products prepared by the environment-friendly stabilizer of the embodiments 1-3 and the comparative example 1 are subjected to performance test, and the test results are shown in Table 1;
detecting the transparency and the haze according to the GB/T2410 'determination of the light transmittance and the haze of the transparent plastic';
detecting the flame retardant property and the electrical property according to the standard of JG 3050 'insulating electrical casing and accessories for buildings';
the detection of weather resistance (retention rate of impact strength and chromatic aberration) is carried out according to the method A of GB/T16422.2 method for exposing light source in plastic laboratory-part 2-xenon arc lamp;
the bending performance is detected according to the standard of JG 3050 'insulating electrical casing and fittings for buildings';
detecting the environmental protection performance according to the European Union REACH standard;
TABLE 1 Performance test results for PVC products
As can be seen from the test results in Table 1, the samples of PVC pipes prepared from the environmentally friendly stabilizer of example 1 have no significant differences in transparency (appearance), handling properties (bending properties) and processing stability compared to organotin stabilizer; in addition, the PVC pipeline sample prepared by using the environment-friendly stabilizer in the embodiment 1 as a raw material has significant advantages in transparency and usability.
The statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.
Claims (7)
1. An environment-friendly stabilizer applied to transparent PVC hard products is characterized by comprising the following raw material components in parts by weight: 25-37 parts of modified magnesium aluminum hydrotalcite, 20-28 parts of zinc dodecanethiolate, 8-13 parts of dibenzoyl methane, 28-36 parts of trihydroxy methyl propane and 0.3-0.7 part of water.
2. The environment-friendly stabilizer applied to the transparent PVC hard product as recited in claim 1, characterized by comprising the following raw material components in parts by weight: 31-33 parts of modified magnesium aluminum hydrotalcite, 22-24 parts of zinc dodecanethiolate, 10-11 parts of dibenzoyl methane, 33-34 parts of trihydroxymethyl propane and 0.4-0.5 part of water.
3. The environmentally friendly stabilizer for transparent PVC rigid products as claimed in claim 1, wherein the preparation method of the zinc dodecyl sulfate comprises the following steps:
s1 preparation of zinc-based complex: uniformly mixing zinc oxide powder with deionized water to obtain zinc oxide slurry; slowly injecting the zinc oxide slurry into ammonia water drop by drop, and stirring until the slurry is completely dissolved to form a uniform and transparent zinc-based complex solution;
preparation of S2 zinc decamercaptide: adding dodecyl mercaptan and an ethanol solvent into a flask, uniformly stirring, dropwise adding the zinc-based complex solution obtained in the step S1, stirring at the temperature of 65-85 ℃ for 3-4 hours to obtain a colloid, standing for layering, removing an upper water layer to obtain a white pasty substance, and drying to obtain white solid powder zinc dodecyl sulfate.
4. The environment-friendly stabilizer applied to the rigid transparent PVC product as claimed in claim 3, wherein in the step S1, the molar concentration of ammonia water is 25% -28%; the mass ratio of the zinc oxide to the ammonia water is 1: 2.5-4; the mass ratio of the zinc oxide in the step S1 to the dodecyl mercaptan in the step S2 is 1: 1.5-1: 4.
5. The environment-friendly stabilizer applied to the rigid transparent PVC products in claim 1, wherein the preparation method of the modified magnesium aluminum hydrotalcite comprises the following steps:
1) dissolving sodium hydroxide and sodium carbonate in deionized water to prepare an alkali solution; dissolving magnesium salt and aluminum salt in deionized water to prepare a magnesium-aluminum salt solution; uniformly mixing the obtained alkali solution and the magnesium-aluminum salt solution drop by drop in a water bath at the temperature of 70-80 ℃ to finally obtain a white suspension;
2) adding phthalate ester compounds into the suspension obtained in the step 1), fully dispersing, crystallizing at normal temperature to obtain a solid, wherein the crystallization time is 8-24 h, and drying the solid obtained by crystallization to obtain the modified magnesium-aluminum hydrotalcite.
6. The environment-friendly stabilizer applied to transparent PVC hard products as claimed in claim 5, wherein the mass ratio of the sodium hydroxide, the sodium carbonate, the magnesium salt and the aluminum salt is 1: 1.2-1.8: 1.0-1.5, preferably 1:1.6:1.2: 1.2.
7. The environment-friendly stabilizer applied to transparent PVC hard products as claimed in claim 5, wherein the phthalate ester compound is tetrabutyl titanate, and the feeding mass ratio of the phthalate ester compound to the magnesium salt is 1: 0.5-0.8.
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| CN102604271A (en) * | 2012-04-09 | 2012-07-25 | 浙江嘉澳环保科技股份有限公司 | Magnesium-zinc composite thermal stabilizer for polyvinyl chloride products and preparation method thereof |
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| CN108912021A (en) * | 2018-08-08 | 2018-11-30 | 美轲（广州）化学股份有限公司 | The preparation method of alkyl hydrosulfide zinc |
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| CN102604271A (en) * | 2012-04-09 | 2012-07-25 | 浙江嘉澳环保科技股份有限公司 | Magnesium-zinc composite thermal stabilizer for polyvinyl chloride products and preparation method thereof |
| WO2018072263A1 (en) * | 2016-10-17 | 2018-04-26 | 美轲（淮安）化学有限公司 | Aqueous pvc composite heat stabilizer and preparation method thereof |
| CN108912021A (en) * | 2018-08-08 | 2018-11-30 | 美轲（广州）化学股份有限公司 | The preparation method of alkyl hydrosulfide zinc |
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Cited By (2)
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| CN115109353A (en) * | 2022-07-20 | 2022-09-27 | 巢湖市金鸿电缆有限公司 | Processing method of fluorescent flame-retardant cable |
| CN115109353B (en) * | 2022-07-20 | 2023-12-15 | 巢湖市金鸿电缆有限公司 | Processing method of fluorescent flame-retardant cable |
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