CN108864602B - Eutectic nano composite heat stabilizer applied to PVC (polyvinyl chloride) material and preparation method thereof - Google Patents
Eutectic nano composite heat stabilizer applied to PVC (polyvinyl chloride) material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a eutectic nano composite heat stabilizer applied to PVC materials and a preparation method thereof. During preparation, the inorganic compound, the dispersant and the absolute ethyl alcohol are ground to prepare inorganic compound suspension with the particle size of below 120 nanometers; uniformly mixing the medical intermediate and polyhydric alcohol, heating, adding calcium stearate and zinc stearate, grinding, adding an inorganic compound suspension, and carrying out ultrasonic treatment for 1-2 hours to prepare a crystalline product containing a large amount of eutectic crystals; adding a processing aid to the prepared crystalline product; kneading treatment was performed on a high-speed kneader to obtain a mixture: and mixing, extruding and granulating the prepared mixture to obtain a product. The eutectic nanometer composite heat stabilizer is environment-friendly, nontoxic, efficient and excellent in heat stability, not only improves the initial colorability of PVC and prolongs the heat stability in the later period, but also effectively solves the phenomenon of 'zinc burning' in the later period of the heat stabilizer, and applies the mechanical property of materials.
Description
Technical Field
The invention relates to the technical field of polyvinyl chloride (PVC) processing aids, in particular to a PVC eutectic nano composite heat stabilizer and a preparation method thereof.
Background
Polyvinyl chloride (PVC) is one of five general-purpose plastics, and is widely used as general-purpose plastics in the fields of buildings, light industry, chemical industry, electronics, aerospace, automobiles, agriculture and the like due to the advantages of nonflammability, bright color, corrosion resistance, good performance, low price and the like, rich raw material sources, mature synthesis process and the like. PVC also has some defects which are difficult to overcome, and due to the defect structure of the PVC molecular chain, the PVC is easy to degrade in the heating process, so that the surface of the PVC material is seriously colored and degraded in mechanical property, the processing process is easy to decompose, and great difficulty is brought to the processing technology, so that the thermal degradation of the PVC is inhibited by adding a proper heat stabilizer. PVC heat stabilizers are various in variety, and currently commercialized varieties mainly include lead salt heat stabilizers, organic tin heat stabilizers, composite metal salt heat stabilizers (metal soap heat stabilizers) and rare earth heat stabilizers.
Although the lead salt heat stabilizer has excellent performance, under the condition that the current environmental protection requirement is increasingly improved, the toxic lead salt heat stabilizer is not advocated to be used.
The organic tin heat stabilizer has good performance, has multiple important heat stabilizing functions of absorbing HCl, replacing unstable chlorine atoms, adding conjugated polyene chain segments and the like, and has no catalytic action on PVC with products of stable reaction of PV C, so that the stabilizer has excellent capability of inhibiting initial coloring of PV C and long-term heat stabilizing effect, and is a variety with the best heat stabilizing effect in all heat stabilizers. However, free mercaptan or mercaptan vinegar generated by the organotin heat stabilizer after PVC hot processing has unpleasant odor, no lubricity, poor weather resistance and high price.
The rare earth elements of the rare earth heat stabilizer have the function of absorbing 230-320nm ultraviolet light, and can improve the weather resistance of PVC. The rare earth heat stabilizer is non-toxic, efficient, highly transparent, excellent in weather resistance and high in cost performance, but the initial heat stability is not high, and the initial colorability is relatively poor.
The composite metal salt heat stabilizer mainly comprises C8-C12The fatty acid is compounded with metal salt of cadmium, zinc, barium, calcium, magnesium, etc. and synergist, and the compounded salt is solid, liquid, paste, etc. Wherein the metal soap formed by cadmium, zinc, etc. can inhibit the initial coloring of PVC, has good thermal stability, but the generated chloride has catalytic action on removing HCl from PVC, especially ZnCI2The catalytic action of the catalyst is more obvious, so that the long-term burning resistance of the catalyst is poor, the color is severely changed, and the phenomenon of 'zinc burning' occurs. The initial coloration cannot be suppressed by the metallic soaps formed by barium, calcium, magnesium, etc., but the chlorides formed do not contribute to the HCl elimination of PVC. The two types of stabilizers have long respective lengths and are often used in combination to prepare the composite metal salt heat stabilizer. Because of the requirements of environmental regulations, cadmium metal salts face the same forbidden situation as lead salts, so that calcium/zinc and barium/zinc are the development directions of the prior metal salt stabilizers. The composite metal salt heat stabilizer can not be used alone generally, and auxiliary heat stabilizers (such as phosphorous acid, epoxy compounds, polyols, hydrotalcite, zeolite and the like) are required to be matched.
Chinese patent CN101717526A discloses a preparation method of a low-melting-point eutectic PVC heat stabilizer, which comprises the following steps: 1) heating pentaerythritol, dipentaerythritol and dicarboxylic acid at 190-220 ℃ for melting, mixing uniformly, and then sequentially adding a catalyst and a water-carrying agent for reaction at 180-200 ℃ for 0.5-2 hours; 2) and cooling the system to 160-180 ℃, adding zinc stearate, calcium stearate and hindered phenol antioxidant, melting, uniformly mixing, keeping the temperature at 150-180 ℃, heating for 0.5-2 hours, cooling, crushing and grinding to obtain the low-melting-point eutectic PVC heat stabilizer. The eutectic melting point is lower than the melting point of the main component zinc stearate, so that the plasticization and oxidation resistance of PVC are better promoted in the processing process, and the thermal stability effect on PVC is increased. However, the PVC heat stabilizer prepared by the method adopts a solvent eutectic method to realize eutectic, and a large amount of organic reagents with strong toxicity are used in the preparation process, thereby causing serious pollution to the environment. And a large amount of polyhydric alcohol compound stabilizers such as pentaerythritol, dipentaerythritol and the like are added, although the early discoloration and the color fastness of the PV C product can be improved by adding the polyhydric alcohol stabilizers, and the 'zinc burning' can be eliminated by adding high content of polyhydric alcohols, the polyhydric alcohol stabilizers are easy to dissolve in water, so that the stability in the later period is poor, and the improvement range of the thermal stability of PVC is small. In addition, the high melting point of pentaerythritol leads to poor compatibility with PVC and difficult dispersion, resulting in formation of mottling on the articles.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a eutectic nano composite heat stabilizer applied to PVC materials and a preparation method thereof, the eutectic nano composite heat stabilizer is environment-friendly, nontoxic, efficient and excellent in heat stability, can obviously improve the heat stability of PVC, improves the initial colorability of PVC, prolongs the heat stability of PVC at the later stage, effectively solves the phenomenon of 'zinc burning' at the later stage of the heat stabilizer, obviously reduces the balance torque in the PVC production process, reduces the production energy consumption, and improves the compatibility and the dispersibility of the heat stabilizer and PVC.
In order to realize the purpose, the invention adopts the technical scheme that:
a eutectic nanometer composite heat stabilizer applied to PVC materials comprises the following components in percentage by mass:
the processing aids comprise lubricants, impact modifiers, antioxidants and light stabilizers;
the catalyst is one or more of p-toluenesulfonic acid, sulfamic acid, strong acid cation exchange resin and crystalline ferric trichloride;
the inorganic compound is one or two of hydrotalcite and zeolite;
the medical intermediate organic matter comprises one or more of urea derivatives, pyridine compounds, 4-methylimidazole and pyrimidine compounds;
during preparation, the inorganic compound, the dispersant and the absolute ethyl alcohol are ground to prepare inorganic compound suspension with the particle size of below 120 nanometers;
uniformly mixing the medical intermediate organic matter and polyhydric alcohol, heating to 120-180 ℃, adding calcium stearate and zinc stearate, grinding until the particle size is below 120 nanometers, adding an inorganic compound suspension, grinding and dispersing uniformly, and performing ultrasonic treatment for 1-2 hours to prepare a crystalline product containing a large amount of eutectic crystals; the method comprises the following steps of adopting a liquid eutectic grinding method on a nano grinder, utilizing a mechanism that a mechanical acting force inducing substance forms eutectic in a non-covalent bond mode, adopting an ultrasonic eutectic method to accelerate the synthesis of the eutectic, promoting the formation of the eutectic, and enhancing the intermolecular interaction force after ultrasonic treatment to obtain a large amount of eutectic products.
Adding a processing aid to the prepared crystalline product; kneading the mixture on a high-speed kneader to obtain a mixture;
and mixing, extruding and granulating the prepared mixture to obtain a product.
To further achieve the object of the present invention, preferably, the polyhydric alcohol is one or more of pentaerythritol, Ethylene Glycol (EG), 1, 2-propanediol (MPD), 1, 4-Butanediol (BDO), 1, 6-Hexanediol (HD), neopentyl glycol (NPG), diethylene glycol (EG), dipropylene glycol (PG), Trimethylolpropane (TMP) and glycerol.
Preferably, the dispersant is Solsperse 24000SC/GR dispersant, BYK-2008 wetting dispersant, Sago-9006 wetting dispersant or EFKA 4510 polymeric dispersant.
Preferably, the urea derivative is barbituric acid or cyanuric acid, and the barbituric acid is Cinnamaldehyde Barbituric Acid (CBA), p-hydroxybenzaldehyde barbituric acid or p-dimethylaminobenzaldehyde barbituric acid; the pyridine compound is 3-n-propyl-5-hydroxy-1-methylimidazole, 3-picolinic acid or 3-methylpyridine; the pyrimidine compound is 4-amino-2, 6-dimethyl pyrimidine, 2, 4-diamino-6-hydroxypyrimidine, 2-mercapto-4-methyl-6-hydroxypyrimidine or 2-chloro-4-methyl-6-methoxypyrimidine.
Preferably, the lubricant is one or more of stearic acid, butyl stearate, oleamide, ethylene bis stearamide, natural paraffin, liquid paraffin and polyethylene wax.
Preferably, the impact modifier is one or more of acrylate copolymer, chlorinated polyethylene, methyl methacrylate, butadiene and styrene terpolymer.
Preferably, the antioxidant is one or more of thiobisphenol type antioxidant, phosphite, antioxidant CA, antioxidant 264, antioxidant 2246 and antioxidant 1076; the light stabilizer is light stabilizer 622, light stabilizer 770, light stabilizer 944 or light stabilizer 783.
The preparation method of the eutectic nanometer composite heat stabilizer applied to the PVC material comprises the following steps:
1) putting an inorganic compound, a dispersing agent and absolute ethyl alcohol into a nano grinder to grind for 4-5 hours, so that the inorganic compound is fully dispersed, refined and suspended to prepare an inorganic compound suspension with the particle size of below 120 nanometers;
2) uniformly mixing a medical intermediate organic substance and polyhydric alcohol, heating to 120-180 ℃, adding calcium stearate and zinc stearate, grinding for 5-6 hours on a nano grinder by adopting a liquid eutectic grinding method until the particle size is below 120 nanometers, adding an inorganic compound suspension, grinding and dispersing uniformly, and performing ultrasonic treatment for 1-2 hours to prepare a crystallization product containing a large amount of eutectic;
3) adding a processing aid into the crystallized product prepared in the step 2); kneading treatment was performed on a high-speed kneader to obtain a mixture:
4) and mixing, extruding and granulating the prepared mixture to obtain a product.
Preferably, the grinding and dispersing are carried out in a nano grinder for mixing and grinding for 2 to 3 hours; the ultrasonic treatment is ultrasonic treatment by using a full-automatic ultrasonic oscillator.
Preferably, the mixing, extruding and granulating of the prepared mixture is to add the prepared mixture into a double-screw granulating extruder for mixing, extruding and granulating.
The eutectic nano composite heat stabilizer applied to PVC materials takes a medical intermediate organic matter as a main heat stabilizer, and is compounded with a calcium-zinc heat stabilizer, an inorganic compound heat stabilizer and a polyalcohol heat stabilizer; however, in the invention, the medical intermediate organic matter, the calcium-zinc heat stabilizer, the inorganic compound heat stabilizer and the polyol heat stabilizer are not simply mixed, but a liquid eutectic grinding method and an ultrasonic eutectic method are adopted to organically combine the four substances, and the synergistic cooperation effect is found when the different types of heat stabilizers are mixed. In the prior art, the different types of heat stabilizers have different mechanisms of action, so that the different types of heat stabilizers do not need to be mixed, and the heat stabilizers are considered to have adverse effects on the mechanical properties of PVC materials, and the more the heat stabilizers are added, the greater the adverse effects are; and even when mixed, cannot exert a synergistic effect between different heat stabilizers.
The inventor finds that the medical intermediate organic matters have high biological activity, can replace active chlorine atoms, capture free radicals and the like, are converted into enol forms from ketone forms in the reaction process, and then replace the active chlorine atoms in a PVC chain by utilizing hydroxyl groups in molecules to block the generation capacity of conjugated polyene sequences, so that the thermal stability effect of PVC is improved, and the long-term thermal stability of a compound system is improved; and active molecules (API) of the medical intermediate organic matters usually contain various functional groups and have different biological activities, and the functional groups can generate compound eutectic with other organic molecules through intermolecular recognition by utilizing hydrogen bond or other non-covalent bond actions, so that the crystallization performance and the physicochemical property of the heat stabilizer are effectively improved, and the heat stability of the composite heat stabilizer is effectively improved.
The inventor also finds that the inorganic compound stabilizer can be nanocrystallized only by adopting a liquid eutectic grinding method and an ultrasonic eutectic method, and a medical intermediate organic heat stabilizer, a calcium-zinc heat stabilizer and a polyol heat stabilizer are organically combined through eutectic, so that the interface effect is enhanced by utilizing the quantum size effect, the high specific surface area effect and the like of nanoparticles, the compatibility between the nano inorganic compound stabilizer, the organic stabilizer and other composite components and a PVC material matrix is improved, and the purposes of reducing the using amount of the composite stabilizer in the PVC matrix material and improving the thermal stability of the PVC material are achieved. The embodiment proves that the compounding of the medical intermediate organic stabilizer, the zinc heat stabilizer, the polyalcohol and the nano inorganic compound eutectic nano stabilizer has the application performance of high energy and high activity.
Thirdly, with the reduction of the particle size of the nano inorganic compound material and the reduction of the addition amount of the organic composite stabilizer, the adverse effect of the eutectic nano composite heat stabilizer containing the nano inorganic compound stabilizer and the medical intermediate organic stabilizer on the performance of the PVC material is remarkably reduced compared with a non-nano common heat stabilizer;
fourthly, the interaction between the composite stabilizer and the PVC material matrix interface is enhanced by the nano-dispersion of the inorganic compound material, so that the nano-composite heat stabilizer can be more uniformly dispersed in the PVC material matrix, and the nano-inorganic compound rigid particles can play a role in plasticizing and enhancing the PVC material matrix, thereby greatly improving the processing performance of the PVC material and the mechanical performance of the final PVC product.
Compared with the prior art, the invention has the following advantages:
1) the invention adopts a method of combining a liquid eutectic grinding method and an ultrasonic eutectic method to prepare the eutectic nano composite heat stabilizer applied to PVC materials, solves the three problems of insufficient long-term heat stability, poor weather resistance, easy color reddening and the like of the traditional PVC heat stabilizer, reduces the initial coloring of PVC and prolongs the stability of the later period, has long-term anti-tarnishing capability, can convert hard PVC products from products with numerous problems into products friendly to the environment, and greatly improves the application field of the PVC products. Meanwhile, the balance torque in the PVC production process is obviously reduced, the fluidity of the molten material is good, the production energy consumption is reduced, and the compatibility and the dispersibility of the heat stabilizer and PVC are improved. Meanwhile, a compounding system can generate a synergistic effect, and the thermal stability of the PVC eutectic nano composite heat stabilizer is improved.
2) The eutectic nano composite heat stabilizer prepared by the invention is added with multiple synergistic stabilizer composite components of nano inorganic stabilizer and calcium-zinc heat stabilizer on the basis of taking medical intermediate organic matter as a main stabilizer, so that the thermal stability of the composite heat stabilizer is effectively improved, the stability of PVC material to light and heat can be obviously improved only by adding a small amount of the eutectic nano composite heat stabilizer into PVC material matrix, and the compatibility and dispersion uniformity of the eutectic nano composite heat stabilizer and PVC are improved, so that the processability and mechanical property of the PVC material are obviously improved, therefore, the application of the eutectic nano composite stabilizer technology in the traditional PVC material stabilizer opens up a new field for the stabilizer technology.
3) The traditional PVC heat stabilizer is powdery, various processing aids are fully dispersed and mixed by adopting an efficient hyper-dispersant, and an antioxidant, a light stabilizer, an impact modifier and other processing aids are added to be subjected to mixing extrusion granulation on a double-screw granulation extruder, so that the final product is prepared into granules, and the problem of serious dust pollution in various links of production, transportation, use and the like of the heat stabilizer for the PVC material is effectively solved;
4) the eutectic nano composite stabilizer prepared by the invention has a good thermal stability effect, also has composite functions of oxidation decomposition resistance, illumination decomposition resistance and the like, is a full-effect one-coating auxiliary agent (alinone), is particularly suitable for small and medium-sized enterprises lacking in professional technicians, can simplify the production process and production technology debugging steps of PVC products, improves and stabilizes the performance of PVC products, and greatly saves the production cost.
5) The eutectic nano composite stabilizer prepared by the invention not only has good thermal stability effect on PVC materials, but also has composite functions of oxidation resistance, light stability and the like, and can be used for producing PVC-U extruded pipes for water supply, PVC-U extruded pipes for building drainage, PVC-U extruded pipes for insulating electrical casing pipes for buildings and matched injection pipe fittings of the pipes.
Detailed Description
For better understanding of the present invention, the present invention is further illustrated by the following examples, but the embodiments of the present invention are not limited thereto.
Example 1
The eutectic nanometer composite heat stabilizer applied to PVC materials comprises the following raw material components in parts by weight:
a preparation method of a eutectic nanometer composite heat stabilizer applied to PVC materials comprises the following steps:
1) and (3) putting the hydrotalcite, the Solsperse 24000SC/GR dispersant and absolute ethyl alcohol on a nano grinder to grind for 5 hours, so that the hydrotalcite is fully dispersed, refined and suspended, and the inorganic compound suspension with the particle size of less than 120 nanometers is prepared.
2) Uniformly mixing p-hydroxybenzaldehyde barbituric acid and pentaerythritol, heating to 140 ℃, respectively adding calcium stearate and zinc stearate, and grinding for 5 hours on a nano grinder; then adding the inorganic compound suspension prepared in the step 1) into a nano grinder for mixing and grinding for 2 hours, and then carrying out ultrasonic treatment for 2 hours by using a full-automatic ultrasonic oscillator to prepare a crystallization product containing a large amount of eutectic crystals.
The method comprises the following steps of (1) adopting a liquid eutectic grinding method on a nano grinder, utilizing a mechanism that a mechanical acting force inducing substance forms eutectic in a non-covalent bond mode, then adopting an ultrasonic eutectic method to accelerate the synthesis of the eutectic and promote the formation of the eutectic, enhancing the interaction force among molecules after ultrasonic treatment to obtain a large amount of eutectic products, and preparing a stabilizer product containing a large amount of eutectic;
3) adding a processing aid into the crystalline product prepared in the step 2), and kneading the crystalline product on a high-speed kneader to obtain a mixture:
the lubricant, impact modifier, light stabilizer and antioxidant constitute the processing aid of this example. The processing aid comprises the following components in parts by mass:
4) adding the mixture prepared in the step 3) into a double-screw granulation extruder for mixing, extruding and granulating to prepare the eutectic nano composite heat stabilizer applied to the PVC material.
Example 2
The eutectic nanometer composite heat stabilizer applied to PVC materials comprises the following raw material components in parts by weight:
a preparation method of a eutectic nanometer composite heat stabilizer applied to PVC materials comprises the following steps:
1) and (3) putting the hydrotalcite, the BYK-2008 wetting dispersant and absolute ethyl alcohol into a nano grinder to grind for 5 hours, so that the hydrotalcite is fully dispersed, refined and suspended, and the inorganic compound suspension with the particle size of less than 120 nanometers is prepared.
2) Uniformly mixing 3-methylpyridine and 1, 2-propylene glycol (MPD), heating to 150 ℃, adding calcium stearate and zinc stearate, and grinding for 5 hours on a nano grinder; then adding the inorganic compound suspension prepared in the step 1) into a nano grinder for mixing and grinding for 2 hours, and then carrying out ultrasonic treatment for 2 hours by using a full-automatic ultrasonic oscillator to prepare a crystallization product containing a large amount of eutectic crystals. The method comprises the following steps of (1) adopting a liquid eutectic grinding method on a nano grinder, utilizing a mechanism that a mechanical acting force inducing substance forms eutectic in a non-covalent bond mode, then adopting an ultrasonic eutectic method to accelerate the synthesis of the eutectic and promote the formation of the eutectic, enhancing the interaction force among molecules after ultrasonic treatment to obtain a large amount of eutectic products, and preparing a stabilizer product containing a large amount of eutectic;
3) adding a processing aid into the crystalline product prepared in the step 2), and kneading the crystalline product on a high-speed kneader to obtain a mixture:
the lubricant, impact modifier, light stabilizer and antioxidant constitute the processing aid of this example. The processing aid comprises the following components in parts by mass:
4) adding the mixture prepared in the step 3) into a double-screw granulation extruder for mixing, extruding and granulating to prepare the eutectic nano composite heat stabilizer applied to the PVC material.
Example 3
The eutectic nanometer composite heat stabilizer applied to PVC materials comprises the following raw material components in parts by weight:
a preparation method of a eutectic nanometer composite heat stabilizer applied to PVC materials comprises the following steps:
1) zeolite, EFKA 4510 polymeric dispersant and absolute ethyl alcohol are put into a nano grinder to be ground for 5 hours, so that the zeolite is fully dispersed, refined and suspended, and inorganic compound suspension with the particle size of less than 100 nanometers is prepared.
2) Mixing 4-amino-2, 6-dimethylpyrimidine and 1, 6-Hexanediol (HD) uniformly, heating to 150 ℃, adding calcium stearate and zinc stearate, and grinding for 5 hours on a nano grinder; then adding the inorganic compound suspension prepared in the step 1) into a nano grinder for mixing and grinding for 2 hours, and then carrying out ultrasonic treatment for 2 hours by using a full-automatic ultrasonic oscillator to prepare a crystallization product containing a large amount of eutectic crystals. The method comprises the following steps of (1) adopting a liquid eutectic grinding method on a nano grinder, utilizing a mechanism that a mechanical acting force inducing substance forms eutectic in a non-covalent bond mode, then adopting an ultrasonic eutectic method to accelerate the synthesis of the eutectic and promote the formation of the eutectic, enhancing the interaction force among molecules after ultrasonic treatment to obtain a large amount of eutectic products, and preparing a stabilizer product containing a large amount of eutectic;
3) adding a processing aid into the crystalline product prepared in the step 2), and kneading the crystalline product on a high-speed kneader to obtain a mixture:
the lubricant, impact modifier, light stabilizer and antioxidant constitute the processing aid of this example. The processing aid comprises the following components in parts by mass:
4) adding the mixture prepared in the step 3) into a double-screw granulation extruder for mixing, extruding and granulating to prepare the eutectic nano composite heat stabilizer applied to the PVC material.
Comparative example
The formula of the comparative example is as follows:
in the experimental comparison process of the examples, the contents of the resin and the auxiliary agent in the formula are unchanged, and only the content of the heat stabilizer is changed.
The test method and the basis are as follows:
GB.T2917.1-2002, Congo red color changing method for performance test;
tensile strength GB 1040-2006;
impact strength of the simply supported beam notch: GB 1843-
And (4) performance testing, namely testing the thermal stability time of the sample by adopting a Congo red discoloration method.
The performance test Congo red color changing method is that according to GB.T2917.1-2002, a prepared PVC sample is cut into a granular sample with the size of 2mmX 2mm X1 mm, and the granular sample is placed into a test tube, and the height of the sample is 50 mm. The test tube is sealed by a plug and fixed with Congo red test paper, and the sealed test tube is placed in an oil bath pan at 180 ℃ to start timing. And (4) observing the color change of the Congo red test paper, and finishing timing when the Congo red test paper begins to turn blue, wherein the period of time is the thermal stability time of the PVC.
The performance comparison ratio of the eutectic nano composite heat stabilizer prepared in 3 examples and the comparative example PVC rare earth composite heat stabilizer XT-1 is shown in Table 1. Table 1 shows the static thermal stability, tensile strength, simple beam notched impact strength and equilibrium torque comparisons of examples and comparative examples.
TABLE 1 comparison of PVC composite Heat stabilizer comparative example and example Properties
As is apparent from the Congo red discoloration method measurement tables of comparative examples and examples 1 to 3 in Table 1, the Congo red discoloration times of the comparative examples were 75.3min, respectively. In examples 1-3, the eutectic nano composite heat stabilizer was added, and the Congo red discoloration times of the PVC sample sheets were 90.6min, 89.8min, and 91.2min, respectively. The examples compare with comparative examples, and the addition of the eutectic nanocomposite heat stabilizer can improve the static heat stabilization time of PVC.
The congo red color change time of the PVC sample sheet in the embodiment 3 is longest, and the thermal stability effect is relatively good, and as can be seen from table 1, when the eutectic nano composite heat stabilizer of the embodiment of the invention is added, compared with the PVC rare earth composite heat stabilizer XT-1, the PVC prepared by the embodiment of the invention has the advantages that the addition amount of the stabilizer is less, the thermal decomposition time of the PVC is obviously longer than that of the rare earth composite heat stabilizer, the thermal stability is better, and the PVC sample sheet has long-term anti-tarnishing capability; the better heat stability is obtained under the condition of lower total heat stabilizer adding amount, which shows that four heat stabilizers of a medical intermediate compound, a calcium/zinc stabilizer, a polyol stabilizer and a nano inorganic stabilizer generate synergistic action. Meanwhile, as can be seen from table 1, the heat stabilizer in the embodiment of the invention obviously reduces the equilibrium torque in the PVC production process, and proves that the fluidity of the molten material is good, and the production energy consumption is reduced. Table 1 also clearly shows that the tensile strength and impact strength tested in the examples of the present invention are significantly improved, which indicates that the compatibility and dispersion uniformity of the eutectic nanocomposite heat stabilizer with PVC are improved, and the mechanical properties of the material are improved, rather than the mechanical properties of the material are adversely affected.
Table 2 shows the discoloration of the samples with aging time by static thermal aging method, which comprises cutting the mixed PVC samples into 4cm X2 cm pieces, placing in an oven at 180 deg.C, taking out one piece at intervals of 5min, taking pictures, recording and comparing the discoloration of the PVC samples with aging time.
TABLE 2 static thermal aging method for testing discoloration of samples with aging time
As can be seen from the results of the static heat aging tests of examples 1-3 and comparative examples in Table 2, the PVC plaques continued to darken in color from white, light yellow, brownish yellow, light brownish, brown, brownish red, dark brownish, brownish black to eventually black as the PVC plaques progressively deepened in degradation upon heating.
As can be seen from Table 2, the color of the PVC sample sheet of example 1 remained white before 25min and changed to brown at 65min, which indicates that the eutectic nanocomposite heat stabilizer can inhibit the initial degradation of PVC and improve the initial coloration, and the PVC sample sheet has good long-term thermal stability. The PVC sample in the embodiment 2 is changed into light yellow before 20min, the initial degradation color of the PVC is relatively common, the capability of absorbing HCl gas is not strong, the color of the PVC sample is gradually deepened, but the color is slowly changed, the long-term thermal stability of the PVC sample is relatively good, the PVC sample in the embodiment 3 is kept in slight yellow all the time in 25-60min, and the color change rate is relatively slow, so that the initial coloring of the PVC can be improved by the eutectic nano composite heat stabilizer, the initial degradation capability of the PVC is large, the color of the PVC sample is slowly deepened, the color change is slow, the phenomenon of zinc burning can be eliminated, the long-term thermal stability of the PVC is improved, and the thermal stability effect of the compound system is relatively better in the embodiment. The PVC sample sheet of the heat stabilizer of the comparative example has poor thermal stability, the color of the PVC sample sheet is kept white before 10min and quickly turns yellow after 15min, which shows that the composite heat stabilizer inhibits the initial degradation color of PVC and is brownish red after 50min, then the color of the PVC sample sheet is gradually deepened, the PVC sample sheet quickly turns black due to the phenomenon of 'zinc burning' at 75min, and the delaying effect on the phenomenon of 'zinc burning' is not obvious. The thermal stability of the inventive examples was significantly increased over the comparative examples.
In addition to the requirement of a stabilizer to satisfy thermal stability, the actual PVC formulation is often required to have excellent processability, weather resistance, initial colorability, light stability, and strict requirements for odor and viscosity. Also, PVC articles are widely varied (including pipes, sheets, blow-molded parts, injection molded parts, foamed articles, paste resins, etc.). However, the performance of the prior art of single variety of heat stabilizer has disadvantages, the comprehensive performance is not good, and the requirement of high comprehensive performance in the prior art is difficult to meet. According to the invention, multiple heat stabilizers are scientifically compounded, and the development of an environment-friendly composite heat stabilizer which is non-toxic, efficient and excellent in cost performance becomes a research hotspot of PVC processing aids. As can be seen from tables 1 and 2, the eutectic nano composite heat stabilizer is environment-friendly, non-toxic, efficient and excellent in thermal stability, can obviously improve the thermal stability of PVC, not only improves the initial colorability of PVC and prolongs the thermal stability in the later period, but also effectively solves the phenomenon of 'zinc burning' in the later period of the heat stabilizer; the heat stabilizer also obviously reduces the balance torque in the PVC production process, reduces the production energy consumption, improves the compatibility and the dispersibility of the heat stabilizer and PVC, not only does not reduce the mechanical property of an application material, but also improves the mechanical property of the application material, and obviously improves the tensile strength and the impact strength.
The above embodiments are merely examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Variations or modifications in different forms may occur to those skilled in the art upon reading the foregoing description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention are included in the protection scope of the claims of the present invention.
Claims (10)
1. The eutectic nanometer composite heat stabilizer applied to PVC materials is characterized by comprising the following raw materials in parts by mass:
10-20 parts of calcium stearate
10-20 parts of zinc stearate
30-50 parts of medical intermediate organic matter
10-20 parts of polyol
1-5 parts of catalyst
5-10 parts of inorganic compound
5-10 parts of dispersant
15-25 parts of absolute ethyl alcohol
5.5-16 parts of processing aid
The processing aids comprise lubricants, impact modifiers, antioxidants and light stabilizers;
the catalyst is one or more of p-toluenesulfonic acid, sulfamic acid, strong acid cation exchange resin and crystalline ferric trichloride;
the inorganic compound is one or two of hydrotalcite and zeolite;
the medical intermediate organic matter comprises one or more of urea derivatives, pyridine compounds, 4-methylimidazole and pyrimidine compounds;
during preparation, the inorganic compound, the dispersant and the absolute ethyl alcohol are ground to prepare inorganic compound suspension with the particle size of below 120 nanometers;
uniformly mixing the medical intermediate organic matter and polyhydric alcohol, heating to 120-180 ℃, adding calcium stearate and zinc stearate, grinding until the particle size is below 120 nanometers, adding an inorganic compound suspension, grinding and dispersing uniformly, and performing ultrasonic treatment for 1-2 hours to prepare a crystalline product containing a large amount of eutectic crystals;
adding a processing aid to the prepared crystalline product; kneading the mixture on a high-speed kneader to obtain a mixture;
and mixing, extruding and granulating the prepared mixture to obtain a eutectic nano composite heat stabilizer particle product.
2. The eutectic nanocomposite heat stabilizer applied to PVC materials according to claim 1, wherein the dispersant is Solsperse 24000SC/GR dispersant, BYK-2008 wetting dispersant, Sago-9006 wetting dispersant or EFKA 4510 polymeric dispersant.
3. The eutectic nanocomposite heat stabilizer applied to PVC materials according to claim 1, wherein the polyhydric alcohol is one or more of pentaerythritol, ethylene glycol, 1, 2-propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, trimethylolpropane and glycerol.
4. The eutectic nanocomposite heat stabilizer applied to PVC materials as claimed in claim 1, wherein the urea derivative is barbituric acid or cyanuric acid, and the barbituric acid is cinnamic aldehyde barbituric acid, p-hydroxybenzaldehyde barbituric acid or p-dimethylaminobenzaldehyde barbituric acid; the pyridine compound is 3-picolinic acid or 3-methylpyridine; the pyrimidine compound is 4-amino-2, 6-dimethyl pyrimidine, 2, 4-diamino-6-hydroxypyrimidine, 2-mercapto-4-methyl-6-hydroxypyrimidine or 2-chloro-4-methyl-6-methoxypyrimidine.
5. The eutectic nanocomposite heat stabilizer applied to PVC materials according to claim 1, wherein the lubricant is one or more of stearic acid, butyl stearate, oleamide, ethylene bis stearamide, natural paraffin, liquid paraffin and polyethylene wax.
6. The eutectic nanocomposite heat stabilizer applied to PVC materials according to claim 1, wherein the impact modifier is one or more of acrylate copolymer, chlorinated polyethylene, methyl methacrylate, butadiene and styrene terpolymer.
7. The eutectic nanocomposite heat stabilizer for PVC materials according to claim 1, wherein the antioxidant is one or more of thiobisphenol type antioxidant, phosphite, antioxidant CA, antioxidant 264, antioxidant 2246 and antioxidant 1076; the light stabilizer is light stabilizer 622, light stabilizer 770, light stabilizer 944 or light stabilizer 783.
8. The preparation method of the eutectic nanocomposite heat stabilizer for PVC materials according to any one of claims 1 to 7, comprising the following steps:
1) putting an inorganic compound, a dispersing agent and absolute ethyl alcohol into a nano grinder to grind for 4-5 hours, so that the inorganic compound is fully dispersed, refined and suspended to prepare an inorganic compound suspension with the particle size of below 120 nanometers;
2) uniformly mixing a medical intermediate organic substance and polyhydric alcohol, heating to 120-180 ℃, adding calcium stearate and zinc stearate, grinding for 5-6 hours on a nano grinder by adopting a liquid eutectic grinding method until the particle size is below 120 nm, adding an inorganic compound suspension, grinding and dispersing uniformly, and performing ultrasonic treatment for 1-2 hours by utilizing an ultrasonic eutectic method to prepare a crystallization product containing a large amount of eutectic;
3) adding a processing aid into the crystallized product prepared in the step 2); kneading treatment was performed on a high-speed kneader to obtain a mixture:
4) and mixing, extruding and granulating the prepared mixture to obtain a eutectic nano composite heat stabilizer particle product.
9. The method for preparing eutectic nanocomposite heat stabilizer for PVC materials according to claim 8, wherein the grinding dispersion is carried out by mixing and grinding in a nano grinder for 2-3 hours; the ultrasonic treatment is ultrasonic treatment by using a full-automatic ultrasonic oscillator.
10. The method for preparing a eutectic nanocomposite heat stabilizer for PVC materials according to claim 8, wherein the mixing, extruding and granulating the prepared mixture comprises adding the prepared mixture into a twin-screw granulating extruder for mixing, extruding and granulating.
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