CN110885513B - Folic acid modified nano titanium dioxide composite heat stabilizer for PVC and application thereof - Google Patents
Folic acid modified nano titanium dioxide composite heat stabilizer for PVC and application thereof Download PDFInfo
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
- C08K5/57—Organo-tin compounds
- C08K5/58—Organo-tin compounds containing sulfur
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention discloses a folic acid modified nano titanium dioxide composite heat stabilizer for PVC and application thereof, wherein the folic acid modified nano titanium dioxide composite heat stabilizer for PVC comprises the following components in parts by weight: 1.0-5.0 parts of folic acid modified nano titanium dioxide complex, 1.0-10.0 parts of hydrotalcite and 0.1-0.5 part of organic tin. The invention selects organic materials as the surface modifier of the nano particles, namely natural compound-folic acid, and changes the surface characteristics of the titanium dioxide nano particles by changing the surface charge and the aggregation behavior; the natural vitamin-folic acid modified nano titanium dioxide complex, the co-stabilizer hydrotalcite and the organic tin generate strong synergistic action, the thermal stability is obviously improved, and the nano titanium dioxide complex is non-toxic and has good environmental compatibility.
Description
Technical Field
The invention belongs to the field of polymer material processing aids, and particularly relates to a folic acid modified nano titanium dioxide composite heat stabilizer for PVC and application thereof.
Background
Polyvinyl chloride is the third largest plastic with wide application next to polyethylene and polypropylene, and contains polar C-Cl bonds, so that the polyvinyl chloride is easy to modify, and has the characteristics of excellent corrosion resistance, good flame retardance, chemical stability and low price. One of the main problems that limit the practical use of the polymer is the low thermal stability and brittleness of the polymer, the instability of the polymer when exposed to high temperatures during use, and the addition of heat stabilizers such as lead salts, calcium zinc complex metal salts, organotin, rare earth, hydrotalcite (LDHs) and organic compounds is generally required to improve the limitation and obtain high heat resistance. With increasing attention on environmental protection and sustainable development, PVC heat stabilizers are developed towards all-natural, non-toxic, efficient, multifunctional, excellent in cost performance and environment-degradable. At present, bulk commodities with large heat stabilizer use amount mainly comprise calcium zinc, organic tin, rare earth metal soap, hydrotalcite LDHs and the like, wherein the reported documents are CN 201910676040.0 which discloses an organic stannic acid intercalation calcium/zinc aluminum rare earth hydrotalcite composite heat stabilizer for hard PVC and a preparation method thereof, CN 201910476975.4 which discloses a special PVC stabilizer and a preparation method and application thereof, CN 201510929212.2 which discloses a PVC environment-friendly nano heat stabilizer and a preparation method thereof, CN 201710821188. X which discloses an N-hexadecyl maleamic acid-lanthanum (III) -brucite compound, CN 201510821-425.3 which discloses a calcium-based hydrotalcite PVC composite heat stabilizer and the like.
In addition to excellent heat resistance, light resistance and weather resistance, the PVC heat stabilizer has a great trend to develop towards natural, non-toxic and easy environment-oriented degradation, so as to meet the challenges of environment and marine micro-plastics, such as research on amino acid salts, polyhydroxy compounds such as pentaerythritol, allantoin derivatives, barbiturates and calcium-zinc composite stabilizers thereof. With the continuous increase of the usage amount of organic tin heat stabilizers in the processing of polyvinyl chloride products, the substitution of lead salt heat stabilizers is a consensus, but the organic tin is expensive, has peculiar smell and has unsatisfied heat stabilization effect. Therefore, the search for synergistic and synergistic effects as organotin heat stabilizers is urgent. In addition, environmental compatibility and environmental degradability are also one of the main targets of the invention, for example, the long-term thermal stability of the PVC film is realized by adopting the cheap and easily available edible vitamin-folic acid modified nano titanium dioxide, hydrotalcite and tin composite stabilizer, which shows that the composite stabilizer has the advantages of low cost, no toxicity, no harm and excellent heat-resistant effect, and has potential application in the field of medical devices.
Disclosure of Invention
The invention provides a folic acid modified nano titanium dioxide composite heat stabilizer for PVC and application thereof, aiming at solving the problems of environmental compatibility, degradability and synergistic effect with organic tin.
The Folic Acid (FA) used in the invention is also called antianemic vitamin,the molecular formula is (C)19H19N7O6) Consisting of pteridine, p-aminobenzoic acid and glutamic acid; folic acid becomes a new health vitamin product in the international market after vitamin C and vitamin E, and the market prospect is very wide; the pure folic acid is light yellow crystal, is slightly soluble in water and is insoluble in organic solvent; the nano titanium dioxide is an anatase industrial qualified product and white loose powder in appearance, and has good compatibility, uniform particle size, large specific surface area and good dispersibility; folic acid is a biologically safe natural synthetic molecule, and has hydroxyl (OH) and amine (NH) along with nicotinic acid to prevent damage of free radicals to chromosomes2) Functional groups such as Carboxyl (COOH), amide (CONH) and the like and hydroxyl on the surface of the nano titanium dioxide are easy to be heated and dehydrated to generate stable functional groups such as ether and ester; after 195 ℃ heat storage, the complex structure is stable through reflection infrared and X-ray diffraction analysis; several interactions can occur between the PVC substrate and the folic acid modified nano titanium dioxide complex, and the generation of chlorine free radicals is prevented when the PVC substrate and the folic acid modified nano titanium dioxide complex are heated, so that the folic acid and the folic acid modified nano titanium dioxide complex are suitable accelerators for improving the thermal stability of PVC.
The folic acid modified nano titanium dioxide composite heat stabilizer for PVC comprises the following components in parts by mass:
1.0-5.0 parts of folic acid modified nano titanium dioxide complex, 1.0-10.0 parts of hydrotalcite and 0.1-0.5 part of organic tin.
More preferably: 3.0 parts of folic acid modified nano titanium dioxide complex, 5.0 parts of hydrotalcite and 0.5 part of organic tin.
The folic acid modified nano titanium dioxide complex takes natural organic matter-folic acid as a nano titanium dioxide particle surface modifier, and changes the surface characteristics of nano particles by changing surface charges and aggregation behaviors to obtain a novel PVC heat stabilizer which has excellent heat stabilization effect and potential environmental photodegradation.
The folic acid modified nano titanium dioxide complex takes folic acid as a modifier and adopts a high-speed stirring process to modify nano titanium dioxide. Wherein the addition amount of the nano titanium dioxide is 100 parts, the addition amount of the modifier folic acid is 1-15 parts, and the preferred addition amount is 5 parts. The modification process comprises the following steps:
firstly, adding titanium dioxide nanoparticles into deionized water, stirring for 30min, and uniformly dispersing to obtain a 5% titanium dioxide suspension; then adding folic acid into deionized water, stirring and dissolving for 30min to obtain 0.5% folic acid solution; adding the folic acid solution into the titanium dioxide suspension, stirring at 80 ℃ for 60 minutes, dehydrating, and drying in vacuum to obtain folic acid modified nano titanium dioxide complex powder.
The organotin includes methyltin mercaptide, octyltin mercaptide, butyltin mercaptide, or dioctyltin laurate.
The application of the folic acid modified nano titanium dioxide and hydrotalcite composite heat stabilizer is to add the composite heat stabilizer to a PVC matrix material to improve the thermal stability of PVC. Specifically, PVC is used as a matrix material, the folic acid modified nano titanium dioxide complex is used as a component I, hydrotalcite is used as a component II, and organic tin is used as a supplementary additive. PVC processing parameters: the screw rotation speed is 40 r/min, the set torque is 45 N.m, and the actual torque is less than 35 N.m. Experiments show that the folic acid modified nano titanium dioxide complex has obvious synergistic effect on organic tin and hydrotalcite, and can effectively improve the heat resistance of PVC products.
Wherein the mass ratio of each component is as follows: 100 parts of PVC resin, 1-5 parts of folic acid modified nano titanium dioxide complex, 1-10 parts of hydrotalcite and 0.1-0.5 part of organic tin.
The preferable mass ratio is as follows: 100 parts of PVC resin, 3 parts of folic acid modified nano titanium dioxide complex, 5 parts of hydrotalcite and 0.5 part of organic tin.
The invention selects organic materials as the surface modifier of the nano particles, namely organic natural compound-folic acid, and changes the surface characteristics of the titanium dioxide nano particles by changing the surface charge and the aggregation behavior; the natural vitamin-folic acid modified nano titanium dioxide complex, the co-stabilizer hydrotalcite and the organic tin generate strong synergistic action, the thermal stability is obviously improved, and the nano titanium dioxide complex is non-toxic and has good environmental compatibility.
The method uses folic acid to modify the surface of titanium dioxide nano particles, and adopts a high-speed stirring preparation method to prepare different quantities of PVC nano composite films coated by folic acid modified titanium dioxide nano particles; and the release rates of hydrogen chloride of different composite membranes are measured by adopting a 195 ℃ conductivity method.
The method for evaluating the thermal stability of PVC is conductivity or hydrogen chloride release rate, and the test device refers to ENIS 0182-3: 2000 standard; weighing 2 g of PVC film particles (the size is 2.0 multiplied by 1.0mm), filling the PVC film particles into a test tube, introducing high-purity nitrogen with the flow rate of 100ml/min, placing the test tube in 195 ℃ silicone oil for constant temperature, taking out hydrogen chloride generated in the test tube by the nitrogen, dissolving the hydrogen chloride in deionized water absorption liquid, and observing and recording the change of the conductivity of the hydrogen chloride or the concentration of the hydrogen chloride along with time, wherein the hydrogen chloride is absorbed and released by the deionized water on line. The PVC film product can be rapidly decomposed to release hydrogen chloride gas at the temperature of 180-195 ℃, and a platinum electrode in a conductivity meter can rapidly sense the conductivity change of hydrogen protons and chloride ions in deionized water. After the composite stabilizer is added, the decomposition of a film sample is inhibited, the quality of the effect of the composite heat stabilizer can be judged by measuring the induction period and the stabilization time through a conductivity curve, and the method avoids human vision errors possibly existing in Congo red and whiteness methods due to the adoption of instrumental analysis.
Compared with the prior art, the invention has the beneficial effects that:
1. the folic acid modifier belongs to a pure natural compound, is environment-friendly and easy to degrade;
2. the folic acid modified nano titanium dioxide complex is used as a potential photodecomposition promoter, and can promote the photodegradation of polyvinyl chloride in the environment when the service life of the polyvinyl chloride is terminated;
3. the folic acid modified nano titanium dioxide complex can promote the generation of electrostatic attraction and chemical bond force between tin, hydrotalcite and titanium metal oxide and polyvinyl chloride molecules;
4. the folic acid modified nano titanium dioxide complex has obvious synergistic stabilization effect on methyl tin mercaptide and hydrotalcite, can reduce the using amount of the methyl tin mercaptide, has better effect than that of singly using a methyl tin mercaptide stabilizer, and effectively improves the heat resistance of PVC;
5. the folic acid modified nano titanium dioxide complex, the methyl tin mercaptide and the hydrotalcite belong to nontoxic environment-friendly substances, completely meet the development requirements for environmental protection at home and abroad, and have potential application prospects.
Drawings
FIG. 1 is a graph of conductivity versus time for hydrogen chloride evolution from various PVC films.
The abscissa represents heating time/min, and the ordinate represents conductivity/. mu.S cm-1Wherein curve S0 is without any adjuvant added; curve S1 with the addition of only 1.0 part of methyltin mercaptide; curve H-1 is the addition of 1 part of folic acid modified nano titanium dioxide complex, 0.5 part of methyl tin mercaptide and 5 parts of hydrotalcite; curve H-3 is the addition of folic acid modified nano titanium dioxide complex 3 parts, the remainder being H-1; the curve H-5 is the addition of 5 parts of folic acid modified nano titanium dioxide complex, the remainder being H-1. Samples S0, S1, H-1, H-3, and H-5 were all added with 100 parts PVC and 50 parts DOTP.
Detailed Description
The PVC resin is S-65, and 100 parts of PVC and 50 parts of DOTP are taken, wherein:
the composite stabilizer I contains: 1 part of folic acid modified nano titanium dioxide complex; 0.5 part of methyl tin mercaptide and 5 parts of hydrotalcite;
the composite stabilizer II comprises: 3 parts of folic acid modified nano titanium dioxide complex; 0.5 part of methyl tin mercaptide and 5 parts of hydrotalcite;
the composite stabilizer III contains: 5 parts of folic acid modified nano titanium dioxide complex; 0.5 part of methyl tin mercaptide and 5 parts of hydrotalcite;
the control sample is:
s1, taking 1 part of methyl tin mercaptide;
s0 blank additive.
Example 1:
weighing 2.0 g of titanium dioxide nanoparticles, dispersing in deionized water to prepare a 5% titanium dioxide suspension, stirring for 30min, then dissolving 0.1 g of folic acid in deionized water to prepare a 0.5% folic acid aqueous solution, and stirring for dissolving for 30min to obtain a uniform solution. And adding a folic acid solution into the titanium dioxide suspension, carrying out high-speed stirring treatment at 80 ℃ for 60min, grafting folic acid on the surfaces of the nano particles, heating for dehydration, and carrying out vacuum drying to obtain folic acid modified nano titanium dioxide complex powder.
Example 2:
firstly, adding 1 part of folic acid modified titanium dioxide nano particles (with folic acid content of 5 percent), 5 parts of hydrotalcite and 0.5 part of methyl tin mercaptide into DOTP (50 parts) to be mixed, mechanically stirring for 60min at 80 ℃ to dissolve, then adding the mixture into PVC resin (100 parts), continuously mixing at 80 ℃ and stirring for 30min to obtain a uniform premix; and (2) banburying the obtained premix in a small internal mixer at the melt temperature of 170 ℃ and 178 ℃ at the rotating speed of 40 r/min, rising after the shearing force is reduced firstly, carrying out banburying for 2-3min, discharging after the banburying is finished, and tabletting at 100 ℃ by using a flat vulcanizing machine until the thickness is 1mm to obtain the PVC film containing the composite stabilizer I.
Example 3:
the same procedure as in example 2 was repeated except for taking 3 parts (folic acid content: 5%) of folic acid-modified titanium dioxide nanoparticles to obtain a PVC film containing a composite stabilizer II.
Example 4:
the same procedure as in example 2 was repeated except for taking 5 parts (folic acid content: 5%) of folic acid-modified titanium dioxide nanoparticles to obtain a PVC film containing the composite stabilizer III.
Comparative example 1:
mixing and dissolving PVC resin (100 parts) and DOTP (50 parts), and heating and mechanically stirring at 80 ℃ for 30min to obtain a uniform premix; and (3) banburying the obtained premix in a small-sized banbury mixer at the melting temperature of 170 ℃ and the rotating speed of 40 r/min, rising after the shearing force is reduced firstly, and banburying for 2-3min, discharging after the mixing is finished, and tabletting at 100 ℃ by using a flat vulcanizing machine until the thickness is 1mm to obtain the pure PVC film (blank sample).
Comparative example 2:
firstly, adding 1 part of methyl tin mercaptide into 50 parts of DOTP (dimethyl disulfide terephthalate), heating, mixing and dissolving, then adding 100 parts of PVC resin, stirring and mixing, and mechanically stirring for 30min at 80 ℃ to obtain a uniform premix; and (3) banburying the obtained premix in a small-sized banbury mixer at the melting temperature of 170 ℃ and 175 ℃ at the rotating speed of 40 r/min, rising after the shearing force is reduced, and banburying for 2-3min, discharging after the mixing is finished, and tabletting at 100 ℃ by using a flat-plate vulcanizing machine until the thickness is 1mm to obtain the single-component organotin-containing PVC film (a comparison sample).
TABLE 1 Effect of different PVC films on the conductivity of the liberated Hydrogen chloride
Note: example 1 is TiO only2-FA (5%) -folate-modified nano-titanium dioxide complex (folate 5%); FA-folic acid; HT-hydrotalcite; OT-methyl tin mercaptide; examples 2-4 and comparative examples 1-2 are PVC films containing 100 parts of PVC and 50 parts of DOTP, respectively, and the other components are charged as shown in Table 1, and the oil bath temperature is 195 ℃.
The evaluation method of the PVC thermal stability comprises the following steps: the conductivity of the aqueous hydrogen chloride solution released was determined, with reference to ENIS 0182-3: 2000 standard; introducing high-purity nitrogen into a PVC particle heating test tube, using silicone oil as an oil bath, heating at 195 ℃, and observing a change curve of the electrical conductivity of the deionized water absorbing and releasing hydrogen chloride along with time; table 1 shows the effect of different PVC films on the conductivity of the released hydrogen chloride.
The PVC sample can be decomposed to release hydrogen chloride gas at the temperature of 180-195 ℃, and a platinum electrode in the conductivity meter can quickly sense the conductivity change of hydrogen protons and chloride ions in deionized water. The composite stabilizer is added to inhibit the decomposition of the heat stabilizer, and the quality of the effect of the heat stabilizer can be judged by measuring the induction period and the stabilization time through a conductivity curve.
As can be seen from Table 1 and FIG. 1, S0 was not heat resistant at 195 deg.C, S1 was substantially stable until 28min, and the amount of hydrogen chloride released increased dramatically over 28min, indicating that the sample began to decompose. The conductivity of the PVC film added with the composite stabilizer for releasing the hydrogen chloride is relatively slow, which shows that the release of the hydrogen chloride is inhibited; however, with the increase of the complex dosage, the induction period and the stability of H-1(1 part of complex) are similar to those of H-3(3 parts of complex) and H-5(5 parts of complex), and are all more than 210 min; the thermal stability time is that the samples H-1 ═ H-3 ═ H-5> S1> S0 from large to small.
Therefore, 1-5 parts of folic acid modified titanium dioxide complex (folic acid content is 5%), 5 parts of hydrotalcite and 0.5 part of OT composite stabilizer have excellent thermal stability on PVC, hydrogen chloride is not released at constant temperature of 195 ℃ for 210min, and the stabilizing effect is far better than that of 1 part of single-component OT.
Claims (6)
1. The application of the folic acid modified nano titanium dioxide and hydrotalcite composite heat stabilizer is characterized in that:
adding the composite heat stabilizer into a PVC base material to improve the heat stability of PVC; the mass ratio of each component is as follows: 100 parts of PVC resin, 1-5 parts of folic acid modified nano titanium dioxide complex, 1-10 parts of hydrotalcite and 0.1-0.5 part of organic tin;
the folic acid modified nano titanium dioxide complex takes folic acid as a modifier and adopts a high-speed stirring process to modify nano titanium dioxide; wherein when the addition amount of the nano titanium dioxide is 99-85 parts, the addition amount of the modifier folic acid is 1-15 parts.
2. Use according to claim 1, characterized in that:
the addition amount of modifier folic acid is 5 parts.
3. Use according to claim 1 or 2, characterized in that the modification process comprises the following steps:
firstly, adding titanium dioxide nanoparticles into deionized water, stirring for 30min, and uniformly dispersing to obtain a 5% titanium dioxide suspension; then adding folic acid into deionized water, stirring and dissolving for 30min to obtain 0.5% folic acid aqueous solution; adding the folic acid solution into the titanium dioxide suspension, stirring at 60-80 ℃ for 60 minutes, dehydrating, and drying in vacuum to obtain folic acid modified nano titanium dioxide complex powder.
4. Use according to claim 1, characterized in that:
the mass ratio of each component is as follows: 100 parts of PVC resin, 3 parts of folic acid modified nano titanium dioxide complex, 5 parts of hydrotalcite and 0.5 part of organic tin.
5. Use according to claim 1, characterized in that:
the organotin includes methyltin mercaptide, octyltin mercaptide, butyltin mercaptide, or dioctyltin laurate.
6. Use according to claim 1, characterized in that:
PVC processing parameters: the screw rotation speed is 40 r/min, the torque is set to be 45 N.m, and the actual value is less than 35 N.m.
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| CN105367954B (en) * | 2015-12-15 | 2018-06-26 | 常州大学 | A kind of PVC environment-protection nanos heat stabilizer and preparation method thereof |
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