CN110885514B - Microwave-assisted synthesized modified nano titanium dioxide and calcium-magnesium-zinc composite stabilizer for PVC and application thereof - Google Patents

Microwave-assisted synthesized modified nano titanium dioxide and calcium-magnesium-zinc composite stabilizer for PVC and application thereof Download PDF

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CN110885514B
CN110885514B CN201911291219.0A CN201911291219A CN110885514B CN 110885514 B CN110885514 B CN 110885514B CN 201911291219 A CN201911291219 A CN 201911291219A CN 110885514 B CN110885514 B CN 110885514B
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titanium dioxide
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CN110885514A (en
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鲁伊恒
陈岩
王兵
马龙娟
李康
薛梦瑶
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Anhui University of Science and Technology
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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 modified nano titanium dioxide and calcium magnesium zinc composite stabilizer for microwave-assisted synthesis of PVC (polyvinyl chloride) and application thereof, wherein the modified nano titanium dioxide and calcium magnesium zinc composite stabilizer is formed by compounding a folic acid modified nano titanium dioxide complex, a stabilizer and an auxiliary stabilizer, and comprises the following components in parts by mass: 1-5 parts of folic acid modified nano titanium dioxide complex, 0.1-0.5 part of stabilizer and 1-10 parts of auxiliary stabilizer. The modified nano titanium dioxide and calcium, magnesium and zinc composite stabilizer for PVC is added into a PVC matrix material, so that the heat resistance of the PVC material can be obviously enhanced.

Description

Microwave-assisted synthesized modified nano titanium dioxide and calcium-magnesium-zinc composite stabilizer for PVC and application thereof
Technical Field
The invention belongs to the field of polymer material processing aids, and particularly relates to a microwave-assisted synthesized modified nano titanium dioxide and calcium, magnesium and zinc composite stabilizer for PVC and application thereof.
Background
In general, calcium-zinc complex metal salts, organotin, rare earth, hydrotalcite, organic compounds, and the like are used as heat stabilizers for polyvinyl chloride to ensure heat stability during processing and use. In the preparation process of the stabilizer, most of the stabilizer has larger molecular weight and contains metal, and belongs to the preparation of metal complexes, while the conventional preparation method has the defects of incomplete complexing reaction, unstable product, incapability of separating and refining the product and the like due to mechanical stirring, mechanical forced stirring and the like, so that the using effect and the using efficiency of the heat stabilizer in PVC are greatly influenced.
The application documents of microwaves in the preparation of PVC heat stabilizers are few, and CN 20161115119 discloses a method for preparing PVC heat stabilizers by taking vermiculite as a raw material; CN2014105766500 discloses a method for preparing a PVC stabilizer by using natural ore as a raw material. The microwave radiation can heat in a chemical reaction system in the preparation of the stabilizer and can also promote and change various chemical reactions, such as exciting the rotation energy level transition of molecules, intensifying the molecular motion, improving the average energy of the molecules, reducing the activation energy of the reaction, further accelerating the chemical reaction speed and promoting the occurrence degree of the chemical reaction. If the formation of metal complex is promoted, the microwave radiation is carried out for 3min, the metal ions Cr (III) and EDTA can be completely complexed, and the reaction takes several hours under the conventional heating condition. The non-thermal effect and the uniform thermal effect of the visible microwave irradiation promote the chemical reaction rate of the complex and have the functions of enhancing and promoting the stability of the complex.
At present, the polyvinyl chloride heat stabilizer is developing towards the direction of no toxicity, high efficiency, excellent cost performance and environmental degradation along with the attention on environmental protection consciousness; and the use of organotin heat stabilizers continues to increase, such as methyltin mercaptide and the like. However, methyl tin mercaptide is expensive, has peculiar smell and cannot meet the requirement on heat stability; therefore, the novel PVC composite stabilizer is synthesized by adopting a novel preparation method, so that the use amount of organic tin is reduced, the use efficiency is improved, the requirement on environmental degradability is met, and the novel PVC composite stabilizer becomes a difficult problem to be solved urgently in the field of PVC stabilizers.
Disclosure of Invention
The invention provides a microwave-assisted synthesized modified nano titanium dioxide and calcium, magnesium and zinc composite stabilizer for PVC and application thereof, aiming at the problems of high price and poor heat resistance of methyl tin mercaptide in the field of heat stabilizers.
The invention relates to a modified nano titanium dioxide and calcium, magnesium and zinc composite stabilizer for PVC (polyvinyl chloride) synthesized by microwave assistance, which is prepared by compounding a folic acid modified nano titanium dioxide complex, a stabilizer and an auxiliary stabilizer, wherein the components in parts by weight (hereinafter referred to as parts) are as follows:
1-5 parts of folic acid modified nano titanium dioxide complex, 0.1-0.5 part of stabilizer and 1-10 parts of auxiliary stabilizer.
The stabilizer is organic tin, and the organic tin comprises methyl tin mercaptide, octyl tin mercaptide, butyl tin mercaptide, dioctyl tin laurate and the like.
The auxiliary stabilizer is calcium magnesium zinc metal soap, and the calcium magnesium zinc metal soap is calcium stearate, magnesium stearate or zinc stearate.
The addition amount of the auxiliary stabilizer is preferably 5 parts.
The folic acid modified nano titanium dioxide complex is prepared by a method comprising the following steps:
folic acid is used as a modifier, and a microwave radiation process is adopted to modify the nano titanium dioxide.
Further, the microwave power is 200-; the frequency is 2450 MHz.
Furthermore, 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 9 parts.
Further, the modification process comprises the following steps:
firstly, nano TiO is added2Adding the particles into deionized water, stirring and dispersing uniformly to prepare a nano titanium dioxide suspension liquid with the weight percent of 5; then adding folic acid into deionized water, stirring and dissolving to prepare 0.5wt% of FA aqueous solution; adding FA aqueous solution into the nano titanium dioxide suspension, refluxing and stirring for 3h, filtering, washing, and vacuum drying to obtain modified powder, placing the modified powder in a microwave oven, and heating for 15min by microwave to obtain the folic acid modified nano titanium dioxide complex product.
According to the invention, a microwave oven is adopted for heating and reacting in the complex preparation process, the folic acid modified nano titanium dioxide complex is used as a nano particle surface modifier, the surface characteristics of nano particles are changed by changing surface charges and aggregation behaviors, and the molecular structure of the complex is further stabilized through microwave heating reaction, so that the novel PVC heat stabilizer with excellent heat stabilization effect and environmental friendliness is obtained.
The invention relates to an application of a modified nano titanium dioxide and calcium, magnesium and zinc composite stabilizer for PVC, which is to add the modified nano titanium dioxide and calcium, magnesium and zinc composite stabilizer into a PVC matrix material so as to obviously enhance the heat resistance of the PVC material. The folic acid modified nano titanium dioxide complex is used as a synergist, organic tin is used as a stabilizer, calcium magnesium zinc metal soap is used as an auxiliary stabilizer, and the folic acid modified nano titanium dioxide complex has a remarkable synergistic effect on the organic tin and the calcium magnesium zinc metal soap, can remarkably enhance the heat resistance of a PVC material, and is non-toxic and good in environmental compatibility.
The proportion of each component is (by weight portion), 100 portions of PVC resin, 1 to 5 portions of folic acid modified nano titanium dioxide complex, 0.1 to 0.5 portion of stabilizer and 1 to 10 portions of auxiliary stabilizer.
The further preferable mixture ratio is as follows: 100 parts of PVC resin, 3 parts of folic acid modified nano titanium dioxide complex, 0.5 part of stabilizer and 5.0 parts of auxiliary stabilizer.
The modifier adopts natural medicine raw material Folic Acid (FA) which is composed of pteridine, p-aminobenzoic acid and glutamic acid; folic acid is cheap and easily available, and has hydroxyl (OH) and amine (NH)2) A carboxyl group (COOH), an amide group (CONH), and the like. Different actions can be generated 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 is heated.
The method uses folic acid to modify the surface of titanium dioxide nano particles, adopts a microwave radiation process as a green preparation method, and prepares the PVC nano composite film coated by folic acid modified titanium dioxide nano particles with different addition amounts; 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; introducing high-purity nitrogen into PVC powder, heating to 195 ℃, keeping the temperature, and observing the change of the conductivity or the concentration of the hydrogen chloride along with the time of the hydrogen chloride absorbed and released by deionized water. PVC can be rapidly decomposed at the temperature of 180-195 ℃ to release hydrogen chloride gas, and a platinum electrode in a conductivity meter can rapidly sense the conductivity change of hydrogen protons and chloride ions in deionized water. The composite stabilizer is added to inhibit the decomposition of the composite stabilizer, and 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.
Compared with the prior art, the invention has the beneficial effects that:
1. the modifier folic acid adopted by the invention belongs to all natural substances, is environment-compatible and is 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, calcium, magnesium and zinc metal soaps and titanium metal oxides and polyvinyl chloride molecules;
4. the folic acid modified nano titanium dioxide complex has obvious synergistic stabilization effect on methyl tin mercaptide and calcium magnesium zinc metal soap, 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 calcium-magnesium-zinc metal soap belong to nontoxic environment-friendly substances, completely meet the development requirements for environmental protection at home and abroad, and have potential application prospects.
6. The microwave radiation process is used as a green preparation method, and has an effect of enhancing the thermal stability of the folic acid modified nano titanium dioxide complex and PVC.
Drawings
FIG. 1 is a graph of conductivity versus time for hydrogen chloride released by PVC films upon microwave and non-microwave heating. The temperature is 195 ℃, and high-purity nitrogen is used; the abscissa: heating time/min, ordinate: conductivity/. mu.Scm-1Wherein C-10 is non-microwave heating, 3 parts of folic acid modified nano titanium dioxide complex, 0.5 part of methyl tin mercaptide and 5 parts of calcium stearate; c-20 is microwave-assisted heating reaction, 3 parts of folic acid modified nano titanium dioxide complex and the balance of folic acid modified nano titanium dioxide complex is C-10; 100 parts of PVC and 50 parts of DOTP were added to each of samples C-10 and C-20.
FIG. 2 shows the release of hydrogen chloride from PVC films during microwave and non-microwave heatingConductivity-time curve of (a). The temperature is 195 ℃, and high-purity nitrogen is used; the abscissa: heating time/min, ordinate: conductivity/. mu.Scm-1Wherein M-10 is non-microwave heating, folic acid modified nano titanium dioxide complex 3 parts, methyl tin mercaptide 0.5 part and magnesium stearate 5 parts; m-20 is microwave-assisted heating reaction, 3 parts of folic acid modified nano titanium dioxide complex and the balance of M-10; 100 parts of PVC and 50 parts of DOTP are added into the samples M-10 and M-20.
FIG. 3 is a graph of conductivity versus time for hydrogen chloride released by PVC films upon microwave and non-microwave heating. The temperature is 195 ℃, and high-purity nitrogen is used; the abscissa: heating time/min, ordinate: conductivity/. mu.Scm-1Wherein Z-10 is non-microwave heating, folic acid modified nano titanium dioxide complex 3 parts, methyl tin mercaptide 0.5 part and magnesium stearate 5 parts; z-20 is microwave-assisted heating reaction, 3 parts of folic acid modified nano titanium dioxide complex and the balance of Z-10; 100 parts of PVC and 50 parts of DOTP were added to both of the samples Z-10 and Z-20.
FIG. 4 is a graph of conductivity versus time for hydrogen chloride evolution from PVC films without microwave heating. The temperature is 195 ℃, and high-purity nitrogen is used; the abscissa: heating time/min, ordinate: conductivity/. mu.Scm-1Wherein S0 is not added with any auxiliary agent; s1 adding only 1 part of methyl tin mercaptide; c-1 is prepared by adding 1 part of folic acid modified nano titanium dioxide complex, 0.5 part of methyl tin mercaptide and 5 parts of calcium stearate; c-3 is the same as C-1 except that 3 parts of folic acid modified nano titanium dioxide complex is added; c-5 is the same as C-1 except that 5 parts of folic acid modified nano titanium dioxide complex is added. 100 parts of PVC and 50 parts of DOTP were added to each of samples S0, S1, C-1, C-3 and C-5.
FIG. 5 is a graph of conductivity versus time for hydrogen chloride evolution from PVC films without microwave heating. The temperature is 195 ℃, and high-purity nitrogen is used; the abscissa: heating time/min, ordinate: conductivity/. mu.Scm-1S0 and S1 are the same as in FIG. 4; m-1 is the mixture added with 1 part of folic acid modified nano titanium dioxide complex, 0.5 part of methyl tin mercaptide and 5 parts of magnesium stearate; m-3 is the same as M-1 except that 3 parts of folic acid modified nano titanium dioxide complex is added; m-5 is 5 parts of folic acid modified nano titanium dioxide complex, and the rest is M-1. 100 parts of PVC and 50 parts of DOTP were added to each of samples M-1, M-3 and M-5.
FIG. 6 is a graph of conductivity versus time for hydrogen chloride evolution from PVC films without microwave heating. The temperature is 195 ℃, and high-purity nitrogen is used; the abscissa: heating time/min, ordinate: conductivity/. mu.Scm-1S0 and S1 are the same as in FIG. 4; z-1 is the mixture added with 1 part of folic acid modified nano titanium dioxide complex, 0.5 part of methyl tin mercaptide and 5 parts of zinc stearate; z-3 is the same as Z-1 except that 3 parts of folic acid modified nano titanium dioxide complex is added; and 5 parts of folic acid modified nano titanium dioxide complex and the balance of Z-1 are added into the Z-5. 100 parts of PVC and 50 parts of DOTP were added to each of samples Z-1, Z-3 and Z-5.
Detailed Description
The microwave-assisted modified nano titanium dioxide and calcium-magnesium-zinc composite stabilizer is adopted, the using amount is that per 100 parts of PVC, 1-15 parts of folic acid is added, 85-99 parts of modified nano titanium dioxide are added, and 3 parts of 100 parts of PVC addition complex are preferred;
the folic acid modified nanometer titanium dioxide has folic acid content of 9 percent.
Calcium stearate is used as a co-stabilizer, and the use amount of the calcium stearate is 1-10 parts per 100 parts of PVC, preferably 5 parts.
Taking 100 parts of PVC resin model S-65, 50 parts of DOTP, wherein:
1 part of folic acid modified nano titanium dioxide complex; 0.5 part of methyl tin mercaptide and 5 parts of calcium stearate;
3 parts of folic acid modified nano titanium dioxide complex; 0.5 part of methyl tin mercaptide and 5 parts of calcium stearate;
5 parts of folic acid modified nano titanium dioxide complex; 0.5 part of methyl tin mercaptide and 5 parts of calcium stearate;
the control sample is:
s1 is 1 part of methyl tin mercaptide;
s0 is blank;
example 1:
1.820 g of TiO are taken2Adding deionized water into the nano particles to prepare 5 percent TiO2Stirring the aqueous solution for 30min, then adding 0.180 g of folic acid into deionized water to prepare 0.5% FA aqueous solution, and stirring and dissolving for 30min to obtain a uniform solution. The folic acid solution was added to the titanium dioxide suspension and stirred for 60 minutes to graft FAFiltering, washing and vacuum drying the titanium dioxide particles on the surface, placing the obtained product in a microwave oven, and heating and reacting for 15min by soft fire to obtain a complex powder product.
Comparative example 1:
1.820 g of TiO are taken2Adding deionized water into the nano particles to prepare 5 percent TiO2Stirring the aqueous solution for 30min, then adding 0.180 g of folic acid into deionized water to prepare 0.5% FA aqueous solution, and stirring and dissolving for 30min to obtain a uniform solution. And adding the folic acid solution into the titanium dioxide suspension, stirring for 60 minutes to graft FA onto the surfaces of the nano titanium dioxide particles, filtering, washing and vacuum drying to obtain complex powder.
Example 2:
heating 100 parts of PVC and 50 parts of DOTP by microwave to prepare folic acid modified TiO prepared in example 123 parts of nano particles (9 percent of FA content), 5 parts of calcium metal soap and 0.5 part of organic tin stabilizer are mixed and dissolved, and the mixture is forcibly stirred for 1 hour at 40 ℃ to obtain a uniform premix; and (3) banburying the obtained premix in a small banbury mixer at the melting temperature of 170 ℃ and 175 ℃ for 2-3min, rising after the shearing force is reduced, and tabletting to 1mm at 100 ℃ by using a flat vulcanizing machine after the shearing force is finished to obtain the PVC nano-particle sheet C-20.
Comparative example 2:
folic acid-modified TiO prepared in control example 1 was used23 parts of nanoparticles (FA content 9%) of the complex, and the remainder of the same procedure as in example 2, PVC nanoparticle sheet C-10(C-3) was obtained.
Example 3:
folic acid modified TiO prepared in example 1 with microwave heating 23 parts of nanoparticles (FA content: 9%) complex, 5 parts of magnesium metal soap, and the remainder of the same procedure as in example 2, to obtain PVC nanoparticle sheet M-20.
Comparative example 3:
folic acid-modified TiO prepared in control example 1 was used23 parts of nanoparticle (9% of FA content) complex, 5 parts of magnesium metal soap, and the rest of the same procedure as in example 2, to obtain PVC nanoparticle sheet M-10 (M-3).
Example 4:
folic acid modified TiO prepared in example 1 with microwave heating 23 parts of nanoparticles (FA content: 9%) complex and 5 parts of zinc metal soap (example 2) were repeated to obtain PVC nanoparticle sheet Z-20.
Comparative example 4:
folic acid-modified TiO prepared in control example 1 was used23 parts of nanoparticle (9% of FA content) complex, 5 parts of zinc metal soap, and the rest of the same procedure as in example 2, to obtain a PVC nanoparticle sheet Z-10 (Z-3).
TABLE 1 conductivity of hydrogen chloride released by PVC films upon microwave and non-microwave heating
Figure BDA0002319166010000061
(Note: TiO)2-FA (9%) -folate-modified nano-titanium dioxide complex (folate 9%); cast2-calcium stearate; MgSt2-magnesium stearate; ZnSt2-zinc stearate; OT-methyl tin mercaptide; c-20, M-20 and Z-20 are respectively microwave heated and reacted samples, and all the samples comprise 100 parts of PVC and 50 parts of DOTP
Example 5:
100 parts of PVC and 50 parts of DOTP are taken, and the folic acid modified TiO prepared in the comparative example 2 is heated by non-microwaves2Mixing and dissolving a nanoparticle (1 part) (9% of FA content) complex, calcium metal soap (5 parts) and organic tin stabilizer (0.5 part), and forcibly stirring at 40 ℃ for 1 hour to obtain a uniform premix; and (3) banburying the obtained premix in a small banbury mixer at the melting temperature of 170 ℃ and 175 ℃ for 2-3min, rising after the shearing force is reduced, and tabletting to 1mm at 100 ℃ by using a flat vulcanizing machine after the shearing force is finished to obtain the PVC nano-particle sheet C-1.
Example 6:
folic acid modified TiO prepared in control example 2 was heated by non-microwave2Nanoparticle (3 parts) (9% FA content) complex, as in example 5, to give PVC nanoparticle sheet C-3.
Example 7:
folic acid modified TiO prepared in control example 2 was heated by non-microwave25 parts of nanoparticles (FA content: 9%) of the complex, and the remainder of the same procedure as in example 5, PVC nanoparticle sheet C-5 was obtained.
TABLE 2 conductivity of hydrogen chloride released by PVC film upon non-microwave heating
Figure BDA0002319166010000071
(Note: TiO)2-FA (9%) -folate-modified nano-titanium dioxide complex (folate 9%); cast2-calcium stearate; MgSt2-magnesium stearate; ZnSt2-zinc stearate; OT-methyl tin mercaptide; all samples contained PVC-100 parts, DOTP-50 parts)
Taking PVC resin model S-65100 parts and DOTP50 parts, wherein:
1 part of folic acid modified nano titanium dioxide complex; 0.5 part of methyl tin mercaptide and 5 parts of magnesium stearate;
3 parts of folic acid modified nano titanium dioxide complex; 0.5 part of methyl tin mercaptide and 5 parts of magnesium stearate;
5 parts of folic acid modified nano titanium dioxide complex; 0.5 part of methyl tin mercaptide and 5 parts of magnesium stearate;
example 8:
folic acid modified TiO prepared in control example 2 was heated by non-microwave21 part of nanoparticle (9% of FA content) complex and 5 parts of magnesium metal soap, and the remainder was the same as in example 5 to obtain PVC nanoparticle sheet M-1.
Example 9:
folic acid modified TiO prepared in control example 2 was heated by non-microwave23 parts of nanoparticles (FA content: 9%) complex, 5 parts of magnesium metal soap, and the remainder as in example 5 to obtain PVC nanoparticle sheet M-3.
Example 10:
folic acid modified TiO prepared in control example 2 was heated by non-microwave25 parts of nanoparticles (FA content: 9%) complex, 5 parts of magnesium metal soap, and the remainder as in example 5 to obtain PVC nanoparticle sheet M-5.
Taking 100 parts of PVC resin model S-65, 50 parts of DOTP, wherein:
1 part of folic acid modified nano titanium dioxide complex; 0.5 part of methyl tin mercaptide and 5 parts of zinc stearate;
3 parts of folic acid modified nano titanium dioxide complex; 0.5 part of methyl tin mercaptide and 5 parts of zinc stearate;
5 parts of folic acid modified nano titanium dioxide complex; 0.5 part of methyl tin mercaptide and 5 parts of zinc stearate;
example 11:
folic acid modified TiO prepared in control example 2 was heated by non-microwave21 part of nanoparticle (9% of FA content) complex and 5 parts of zinc metal soap, and the remainder was the same as in example 5 to obtain PVC nanoparticle sheet Z-1.
Example 12:
folic acid modified TiO prepared in control example 2 was heated by non-microwave23 parts of nanoparticles (FA content: 9%) complex and 5 parts of zinc metal soap, and the remainder was the same as in example 5 to obtain PVC nanoparticle sheet Z-3.
Example 13:
folic acid modified TiO prepared in control example 2 was heated by non-microwave25 parts of nanoparticles (FA content: 9%) complex and 5 parts of zinc metal soap, and the remainder was the same as in example 5 to obtain PVC nanoparticle sheet Z-5.
Comparative example 5:
mixing and dissolving 100 parts of PVC and 50 parts of DOTP, and stirring for 1 hour at 40 ℃ to obtain a uniform premix; and (3) placing the obtained premix into a small internal mixer for internal mixing, wherein the melting temperature is 170-.
Comparative example 6:
100 parts of PVC, 50 parts of DOTP and 1 part of methyl tin mercaptide were mixed and dissolved, and the rest was the same as in comparative example 5 to obtain a PVC film S1.
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 powder heating test tube, using silicone oil as an oil bath, heating at 195 ℃, and observing the change curve of the conductivity of the deionized water absorbing and releasing hydrogen chloride along with time.
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, the conductivity of hydrogen chloride released by the PVC sample C-20 heated and reacted by microwave is slower than that of the PVC sample C-10 without microwave, and the induction period is prolonged by 10min, namely, the thermal stability of the microwave-heated folic acid modified titanium dioxide complex (folic acid 9%) 3 parts, calcium stearate 5 parts and OT 0.5 part to PVC is better than that of the sample which is not heated by microwave and has the same composition; the release of hydrogen chloride is inhibited, indicating that the microwave has an enhancing effect on the heat resistance of the PVC sample.
As can be seen from Table 1 and FIG. 2, the conductivity of hydrogen chloride released by the PVC sample M-20 heated and reacted by microwave is almost the same as that of M-10 without microwave, and the induction period is unchanged, i.e. the thermal stability of 3 parts of folic acid modified titanium dioxide complex (folic acid 9%) and 5 parts of magnesium stearate and 0.5 part of OT to PVC by microwave heating are the same as that of the sample which is not heated by microwave with unchanged composition; the release of hydrogen chloride was not inhibited and the microwave had no effect on the improvement of the heat resistance of the PVC sample, indicating that microwave heating was selective for the sample.
As can be seen from Table 1 and FIG. 3, the conductivity of hydrogen chloride released by the PVC sample Z-20 heated and reacted by microwave is slower than that of the PVC sample Z-10 without microwave, and the induction period is prolonged by 7min, i.e. the thermal stability of 3 parts of folic acid modified titanium dioxide complex (folic acid 9%) and 5 parts of zinc stearate and 0.5 part of OT to PVC by microwave heating is better than that of the sample which is not heated by microwave and has the same composition, and the release of hydrogen chloride is inhibited, which indicates that the heat resistance of the PVC sample is enhanced by microwave.
As can be seen from Table 2 and FIG. 4, S0 was not heat resistant when microwave heating was not used 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 three-component compound for releasing the hydrogen chloride is relatively slow, which shows that the release of the hydrogen chloride is inhibited; but with the increase of the dosage of the complex, the induction period of C-3 is longest, the stability is best, C-1 is poorer, and C-5 is better than C-1; the thermal stability time of the sample is C-3> C-5> S1> C1> S0 from large to small. Thus, 3 parts of the folate-modified titanium dioxide complex (9% folate) and 5 parts of calcium stearate and 0.5 part of OT have better thermal stability to PVC than 1 part of the single component OT.
As can be seen from table 2 and fig. 5, the conductivity of the PVC film with the three-component compound added thereto released hydrogen chloride relatively slowly when microwave heating was not used at 195 ℃, indicating that the release of hydrogen chloride was inhibited; however, with the increase of the complex dosage, the induction period of M-3 is longest and the stability is best, M-1 is less than M-1, and M-1 and M-5 are similar; the thermal stability time is that the sample M-3 is more than M-5, M-1 is more than S1 and S0 from large to small. Thus, the thermal stability of 3 parts folic acid modified titanium dioxide complex (folic acid 9%) and 5 parts magnesium stearate and 0.5 part OT to PVC is better than 1 part OT alone.
As can be seen from table 2 and fig. 6, the conductivity of the PVC film with the three-component compound added thereto released hydrogen chloride relatively slowly when microwave heating was not used at 195 ℃, indicating that the release of hydrogen chloride was inhibited; however, with the increase of the dosage of the complex, the induction period of Z-3 is longest and the stability is best, Z-1 is less than Z-5, and Z-5 is similar to S1; the thermal stability time is that the sample Z-3 is larger than the sample Z-1, the sample Z-5 is S1 and the sample S0 sequentially from large to small. Therefore, the thermal stability of 3 parts of folic acid modified titanium dioxide complex (folic acid 9%) and 5 parts of zinc stearate and 0.5 part of OT to PVC is better than that of 1 part of single-component OT.

Claims (4)

1. The application of the modified nano titanium dioxide and calcium, magnesium and zinc composite stabilizer for PVC is characterized in that:
the modified nano titanium dioxide and the calcium-magnesium-zinc composite stabilizer are added into a PVC base material to obviously enhance the heat resistance of the PVC material;
the mixture ratio of each component is as follows according to the mass portion: 100 parts of PVC resin, 1-5 parts of folic acid modified nano titanium dioxide complex, 0.1-0.5 part of stabilizer and 1-10 parts of auxiliary stabilizer;
the stabilizer is organic tin, and the organic tin comprises methyl tin mercaptide, octyl tin mercaptide, butyl tin mercaptide or dioctyl tin laurate;
the auxiliary stabilizer is calcium magnesium zinc metal soap, and the calcium magnesium zinc metal soap is calcium stearate or zinc stearate;
the folic acid modified nano titanium dioxide complex is obtained by modifying nano titanium dioxide by using folic acid as a modifier through a microwave radiation process, and the modification process comprises the following steps:
firstly, nano TiO is added2Adding the particles into deionized water, stirring and dispersing uniformly to prepare a nano titanium dioxide suspension liquid with the weight percent of 5; then adding folic acid into deionized water, stirring and dissolving to prepare 0.5wt% of FA aqueous solution; adding FA aqueous solution into the nano titanium dioxide suspension, refluxing and stirring for 3h, filtering, washing, and vacuum drying to obtain modified powder, placing the modified powder in a microwave oven, and heating for 15min by microwave to obtain the folic acid modified nano titanium dioxide complex product.
2. Use according to claim 1, characterized in that:
in the preparation process of the folic acid modified nano titanium dioxide complex, the microwave power is 200-2000W, and the frequency is 2450 MHz.
3. Use according to claim 1, characterized in that:
in the preparation process of the folic acid modified nano titanium dioxide complex, the addition amount of nano titanium dioxide is 100 parts, and the addition amount of modifier folic acid is 1-15 parts.
4. Use according to claim 1, characterized in that:
100 parts of PVC resin, 3 parts of folic acid modified nano titanium dioxide complex, 0.5 part of stabilizer and 5.0 parts of auxiliary stabilizer.
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