CN1353146A - Process for preparing composite nano material and its application in modifying polyester - Google Patents
Process for preparing composite nano material and its application in modifying polyester Download PDFInfo
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- CN1353146A CN1353146A CN 01135271 CN01135271A CN1353146A CN 1353146 A CN1353146 A CN 1353146A CN 01135271 CN01135271 CN 01135271 CN 01135271 A CN01135271 A CN 01135271A CN 1353146 A CN1353146 A CN 1353146A
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Abstract
A composite nanometer material is prepared through reaction between the aqueous solution of zinc sulfate and the aqueous solution of ammonium carbonate (or ammonium hydrogen carbonate) to generate alkaline zinc carbonate, adding the solution of barium hydroxide in diol and homogenizing reaction to obtain the composite nanometer (10-80 nm) material of alkaline zinc carbonate, barium sulfate and zinc hydroxide. The said material after fractionated off water is existent in the state of suspension in diol and can be used for modifying polyester. Before 285 deg.C, the alkaline zinc carbonate is decomposed into zinc oxide, water and CO2 to obtain a multifunctional nanometer material resisting bacteria, X-ray or gamma-ray, ultraviolet ray and static electricity.
Description
(I) technical field
The invention relates to a preparation method of a functional composite nano material applied to polyester engineering and an application of the functional composite nano material in polyester modification.
(II) background of the invention
Dacron is the most widely used synthetic fiber with the largest output in the world at present, and is generally adopted particularly in the clothing industry due to the excellent performances of good dimensional stability, stiffness, no wrinkle, wear resistance, etc. With the improvement of living standard of people, the antibacterial products are necessary trend for aging society. Commonly used antibacterial agents include natural antibacterial agents (such as chitin), organic antibacterial agents and inorganic antibacterial agents. Natural antimicrobial agents have a series of problems in extraction, application and the like, so that the application and popularization of the natural antimicrobial agents are limited, and organic antimicrobial agents are generally not high in temperature resistance, so that the application of the organic antimicrobial agents is also limited. Inorganic antibacterial agents are highly preferred for their high heat resistance and excellent antibacterial and deodorizing functions. The antibacterial polyester can meet the requirements of spinning short fibers and long fibers, and the short fibers can be used for various bedding articles, decorative fabrics, sanitary dressings, medical operating gowns, work clothes, patient clothes, hospital bed sheets, bedding and the like, and special clothes and coating materials in the food industry; the filament can be widely used for underwear, socks, sportswear, shoe linings, filter fabrics, carpets and the like, and the application range of the filament is wider and wider along with the batch production of the antibacterial fiber, so the development of efficient and nontoxic inorganic antibacterial agents and antibacterial polyester is the development trend of the antibacterial fiber.
In the 20 th century and the 80 th century, a great deal of research on inorganic antibacterial agents was conducted in Japan and America, and antibacterial and anticorrosive materials were developed and applied in household appliances, chemical building materials, communication products, food packaging, daily necessities, washing equipment, toys and the like. The development of inorganic antibacterial agents is carried out in China from the beginning of the 90 s of the 20 th century, and the development is rapid in recent years.
The inorganic antibacterial agent can be ① carrier such as zeolite, double phosphate, silica gel, bentonite, soluble glass and tobermorite, etc. as carrier for adsorbing one or more ions of silver, zinc, copper, etc., ② non-carrier such as TiO2Inorganic oxides such as ZnO, ③ composite materials such as organic/inorganic and inorganic/inorganic composite materials.
At present, the inorganic antibacterial agent sold in the market is expensive, the preparation process is complex, the granularity is large, and the requirement on the granularity is strict in the modification and addition of the polyester, so that the grinding treatment is needed, and the auxiliary agent coated on the surface of the antibacterial agent is possibly damaged, so that the antibacterial ions are reduced at high temperature, the effect is influenced in the use process, and the polyester has the problem of color change. Meanwhile, after the external force stops, the opened particles are easy to agglomerate, so that the powder has poor stability, and the agglomerated particles in the polymer are large, thereby influencing the subsequent processing performance of the polymer and the quality of the silk.
The US 2000 patent US 6030627 discloses the preparation of an assembled antibacterial powder, the structure of which is shown in fig. 1. The antibacterial powder is made of TiO2、ZnO、BaSO4、CaSO4Mica, talcum powder,Kaolin, zeolite, silica and the like are taken as carrier cores, a layer of antibacterial material such as Ag, Cu, Zn and the like is coated on the surface of the carrier cores, the second layer is silica, silicate and the like and mainly serves as a barrier of an antibacterial agent and a matrix to avoid the problem of color change after metal ions are contacted with organic matters, the third layer is hydrated metal oxide and the like, the isoelectric point of powder can be changed, the possibility of powder agglomeration is reduced, and the fourth layer is an organic dispersing aid to improve the compatibility of the organic matrix (the structure of the organic dispersing aid is shown in figure 1). Although the powder has good antibacterial performance, the preparation process of the powder is too complicated and too expensive, and the powder is not suitable for industrial production.
Disclosure of the invention
Aiming at the defects of the prior art, the invention provides a method for preparing a high-concentration, good-stability and non-toxic inorganic composite nano material and a method for preparing antibacterial polyester by using the composite nano material.
The general technical scheme of the invention is that firstly, precursor basic zinc carbonate of functional particle zinc oxide is prepared, then a layer of composite layer of zinc hydroxide and barium sulfate is coated outside thebasic zinc carbonate, or a layer of barium sulfate is coated outside the basic zinc carbonate, and the structure of the basic zinc carbonate is shown in figure 2. Then adding the mixture into a polymerization reaction system in the form of suspension, decomposing basic zinc carbonate at the polycondensation temperature to generate nano zinc oxide, carbon dioxide and water, and simultaneously cracking an outer coating layer of the nano zinc oxide, the carbon dioxide and the water to obtain nano barium sulfate to realize in-situ compounding of inorganic microparticles and an organic matrix.
The preparation process of the composite nano material comprises the following steps:
(1) preparing a water solution from zinc sulfate serving as a raw material, wherein the concentration of the zinc sulfate water solution is 0.01-2.0 mol/L, adding an ammonium carbonate or ammonium bicarbonate water solution into the water solution, and preparing basic zinc carbonate crystal nuclei by a uniform precipitation method, wherein the molar ratio of the zinc sulfate to the ammonium carbonate or ammonium bicarbonate is 3: 1; the reaction time is 5 to 60 minutes, preferably 30 minutes.
The concentration of the zinc sulfate aqueous solution is preferably 0.5-1.0 mol/L.
The molar ratio of the zinc sulfate to the ammonium carbonate or ammonium bicarbonate is preferably 15: 2.
(2) In the same reaction system, adding C2-C4The barium hydroxide solution dissolved by the dihydric alcohol is used for obtaining a composite coating layer of zinc hydroxide and barium sulfate by a coprecipitation method;
said C2-C4The dihydric alcohol of (A) is ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol or 1, 4-butanediol.
The concentration of the barium hydroxide glycol solution is 0.01-1.5 mol/L, preferably 0.5-1.0 mol/L, 1/3 is added firstly, the mixture is stirred for 25-35 minutes, and the rest solution is slowly added to avoid generating a cluster.
Adding barium hydroxide in the amount equal to the molar weight of zinc sulfate, or adding excessive barium hydroxide for reaction and neutralizing the excessive barium hydroxide in the system with dilute sulfuric acid to obtain the barium sulfate coating.
(3) Heating and distilling off water in the system, evaporating ammonia in the system along with the water, gradually reducing the pH value of the system to 7-8, and stopping when the temperature of the system reaches 167-.
The application of the composite nano material in polyester synthesis comprises the step of preparing modified polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT) and polybutylene terephthalate (PBT) by using the dihydric alcohol suspension obtained in the step (3).
The composite nano material is added, the dosage is 0.2-3.0% by weight of polyester (calculated by the weight of basic zinc carbonate decomposed into zinc oxide), and the barium sulfate is 0.75-9.0%.
The multifunctional nano polyester composite material is prepared with the said composite nano material, terephthalic acid and glycol as co-polymerizing and co-mixing monomer and through esterification, polycondensation and other steps.
In the preparation of the multifunctional nano polyester composite material, 30ppm (based on the weight of the polyester resin) of cobalt acetate is added before esterification, and the color of polyester is adjusted.
The preparation of the multifunctional nano polyester composite material is carried out by two stages of esterification and polycondensation, and is characterized in that the esterification stage is carried out; controlling the pressure to be 3-3.6 kg/cm2Raising the temperature to 268 +/-2 ℃, reaching the theoretical water yield, reacting for 2-3 hours, and in a pre-polycondensation stage, controlling the temperature to slowly rise to 285 +/-5 ℃, wherein the time is 1-1.5 hours, and gradually reducing the pressure from 2600Pa to 260 Pa; and in the polycondensation stage, the temperature is controlled to be 285-290 ℃, the pressure is 10-100 Pa, and the reaction time is 1-1.5 hours.
The multifunctional nano polyester composite material has the functions of resisting bacteria and deodorizing, resisting ultraviolet rays, preventing rays, strengthening and toughening and resisting static electricity.
In a polymerization reaction system, the added inorganic nano composite material begins to decompose along with the rise of temperature to generate carbon dioxide and water, so that the barium sulfate coating layer is cracked to obtain functional particles of zinc oxide, and the nano material and the inorganic particles are compounded in situ to prepare the modified polyester chip.
The stabilizers, toners, catalysts and other technical features related to esterification and polycondensation required in the preparation of the modified polyester are the same as those of the known art.
The invention is characterized in that zinc sulfate and ammonium carbonate (or ammonium bicarbonate) are selected as raw materials to prepare basic zinc carbonate, then sulfate radicals in the basic zinc carbonate are precipitated by using a dihydric alcohol solution of barium hydroxide, ammonia gas can be simultaneously distilled out in subsequent fractional distillation water to obtain a dihydric alcohol suspension with the pH value close to 7, and thus the system does not contain other impurity ions. The reaction equation is as follows:
of course, the barium hydroxide solution used may also be used in a molar excess and then neutralized by adding the same amount of dilute sulfuric acid. The dihydric alcohol as used herein means C2-C4The dihydric alcohol of (1). The process flow is shown in figure 3.
Another important feature of the present invention is that the precursor of the antibacterial agent is C2-C4Form of the dihydric alcohol suspensionThe preparation method is directly applied to polyester modification without separation, the prepared concentration is 35 percent at most, and preferably 10 to 20 percent (the mass percentage of the solid is), so that the agglomeration among particles caused by the separation of powder can be greatly reduced. The relationship between the particle size and the concentration of the precursor of the antibacterial agent is shown in table 1.
TABLE 1 relationship of particle size to concentration of antimicrobial agent precursor
| Organic solvent | Concentration (%) | pH value | Water content (%) | Particle size (nm) |
| Ethylene glycol | 5 | 6.5-7.0 | ≤6.0 | 10-40 |
| Ethylene glycol | 10 | 6.5-7.0 | ≤6.0 | 10-65 |
| Ethylene glycol | 15 | 6.5-7.0 | ≤6.0 | 38-75 |
| Ethylene glycol | 20 | 6.5-7.0 | ≤6.0 | 80-120 |
| Ethylene glycol | 30 | 6.5-7.0 | ≤6.0 | 150-300 |
| 1, 4-butanediol | 15 | 6.5-7.0 | ≤6.0 | 20-95 |
The invention has another important characteristic that the antibacterial agent is added into a polymerization reaction system in the form of a precursor, the particle size of the antibacterial agent is mostly between 40 nm and 80nm, the stability is good, the distribution is uniform, the aggregation is not easy, and the storage is convenient.
The invention has the further important characteristic that the decomposition rate of the prepared antibacterial agent precursor reaches at least more than 97 percent before the polymerization temperature of 285-290 ℃, so that the outer coating layer falls off and cracks simultaneously to obtain particles with smaller particle size while generating the functional particle zinc oxide, and the agglomeration among the particles is greatly hindered due to the increased viscosity of the organic matrix in the polymerization kettle, thereby realizing the in-situ compounding of the functional particle zinc oxide and the barium sulfate with the organic matrix. The composition of the precursor of the antibacterial agent mainly changes along with the length of the reaction time of the adding amount of ammonium carbonate, so that the molar ratio of zinc sulfate to ammonium carbonate selected in the experiment is 3: 1, the reaction time is 5-60 minutes, the preferred scheme is that the molar ratio is 15: 2, and the reaction time is 30 minutes. Tables 2 and 3 show the comparison of decomposition temperature and thermogravimetric analysis of the antibacterial agent precursor powder prepared in different concentration ratios and different reaction times, respectively.
TABLE 2 analysis and comparison of decomposition temperature and decomposition rate of the precursor of the antibacterial agent prepared in different concentration ratios
Weight loss before injection of 1.100 deg.CPossibly moisture in the sample; note 2. the decomposition temperature range refers to the major weight loss temperature region.
| ZnSO4∶(NH4)CO3 (molar ratio) | Reaction time (minutes) | Range of decomposition temperature (℃)1，2 | Thermal weight loss ratio (%) (before 290 ℃ C.) | Theoretical weight loss rate (％) | Decomposition rate (％) |
| 3∶1 | 30 | 257-290 | 7.418 | 7.828 | 94.76 |
| 15∶4 | 30 | 230-290 | 7.097 | 7.356 | 96.48 |
| 15∶3 | 30 | 245-290 | 6.689 | 6.880 | 97.23 |
| 15∶2 | 30 | 215-290 | 6.270 | 6.399 | 97.98 |
| 15∶1 | 30 | 150-235 | 5.892 | 5.913 | 99.64 |
TABLE 3 analysis and comparison of decomposition temperature and decomposition rate of precursor of antibacterial agent prepared at different reaction time
| ZnSO4∶(NH4)CO3 (molar ratio) | Reaction time (minutes) | Particle size distribution (nm) | Decomposition temperature (℃) | Decomposition rate (％) |
| 15∶2 | 0 | 20-70 | 270 | 95.78 |
| 15∶2 | 10 | 25-82 | 255 | 96.12 |
| 15∶2 | 30 | 40-90 | 215 | 97.98 |
| 15∶2 | 45 | 20-140 | 195 | 97.84 |
| 15∶2 | 60 | 70-230 | 155 | 98.02 |
As can be seen from table 2, as the amount of ammonium carbonate added to the system decreases, the decomposition temperature of the powder obtained gradually decreases and the decomposition rate gradually increases at a constant reaction time, but if the powder is decomposed in the esterification stage, the system still passes through a high-temperature polymerization stage for a long time and the viscosity of the system does not increase, so that the possibility of agglomeration of the decomposed functional particles is greatly increased, and the preferred embodiment is selected in order to avoid the decomposition of the powder in the low-temperature stage of the polymerization reaction and to obtain a good decomposition rate.
In addition, as can be seen from table 3, when the amount of ammonium carbonate added was constant, the particle size of the powder obtained increased with the increase of the uniform precipitation time, and the decomposition temperature decreased, but the decomposition rate increased. The two competing reactions exist in the uniform precipitation system, wherein one is the combination of zinc ions and carbonate ions to generate zinc carbonate precipitates, and the other is the double hydrolysis promoting reaction of the zinc ions and the carbonate ions to generate zinc hydroxide precipitates, and the reaction equation is expressed as follows,
Yet another aspect of the inventionThe polyester chip synthesized by the preparation method has the important characteristics of antibacterial function, ultraviolet resistance, ray resistance, reinforcement and toughening and certain antistatic function. The zinc oxide as functional particle decomposes negative electron capable of moving freely under ultraviolet ray or illumination while leaving positive hole, and the hole can activate oxygen in air to become active oxygen negative ion, and has strong oxidizing property to produce antibacterial effect, so that it can absorb ultraviolet ray and has antistatic capacity owing to its unique antibacterial mechanism. Through the detection of the polyester film containing 1.93 percent of zinc oxide, the shielding rate of ultraviolet rays in the UVA and UVB wave bands of 280-400nm, which are harmful to human bodies, reaches over 96 percent, the antibacterial detection of the fiber is carried out, the antibacterial rate of escherichia coli reaches 96 percent, the antibacterial rate of staphylococcus aureus reaches 65 percent, and the specific resistance of the polyester fiber with the content of 1-2 percent is 2.4-5.9 multiplied by 1013Omega cm. Meanwhile, the existence of the functional particle barium sulfate enables the functional particle barium sulfate to have the function of preventing X and gamma rays
And (4) performing functions. Due to the ultramicro size and the surface activity effect of the nano inorganic particles, the defects in the polymer material can be excellently modified, and meanwhile, the inorganic/organic interface is increased, so that the strength and the toughness of the polymer material are improved.
In order to show the advancement of the present invention, the intrinsic viscosity, diethylene glycol content, melting point, agglomerated particles, heat resistance, spinnability, specific resistance, and ultraviolet shielding rate of the polyester prepared by the addition method of the present invention were measured and compared with those of the polyester to which zinc oxide and barium sulfate were added, and the results are shown in Table 4.
Measuring the intrinsic viscosity, the content of diethylene glycol, the melting point and the agglomerated particles of the polyester chip according to the GB/T14190-93 fiber-grade polyester chip analysis method; heat resistance according to the thermal oxidation stability coefficient (melting peak area under air atmosphere/melting peak area under nitrogen atmosphere) proposed by Enster Wesener when studying crystallization and melting of polyester, the apparatus used was a CDR-3 differential momentum thermal analyzer; the spinnability is mainly inspected from the replacement period of a filter and a component during spinning and the full-winding rate of the polyester pre-oriented yarn (POY).
(IV) description of the drawings
Fig. 1 is a schematic structure of an assembled antibacterial powder disclosed in US 2000 patent US, 6030627.
FIG. 2 is a structural schematicof the composite nanomaterial of the present invention, wherein 1 is a basic zinc carbonate matrix core, 2 is a coating layer of zinc hydroxide and barium sulfate, and 3 is an outer coating layer of barium sulfate.
Fig. 3 is a flow chart of the preparation of the composite nanomaterial ethylene glycol suspension.
FIG. 4 is a schematic of a polyester synthesis process flow.
The synthesis of the antibacterial polyester is further described below with reference to the schematic flow diagram of the polyester synthesis process of FIG. 4. The first step in the figure is the esterification reaction of terephthalic acid and ethylene glycol, and as the number of added functional particles increases, the esterification reaction time, pressure and temperature increase accordingly, because the fine particles are coated on the surface of terephthalic acid, and the esterification reaction with ethylene glycol is hindered. The second step is polycondensation reaction to obtain functional polyester chip, but with the increase of added functional particles, the polycondensation time is correspondingly reduced, because zinc oxide has a certain catalytic action on polycondensation reaction.
TABLE 4 inventive composition and method containing ZnO and BaSO powders4Comparison of polyester Properties
Note 1: the particle size before addition is the detection result of a projection electron microscope, the particle size in the polyester is the detection result of a scanning electron microscope, and the particle size ranges of the two are more than 95%.
| Coefficient of thermal oxidation stability | 0.901 | 0.934 | 0.976 | 0.985 | 0.992 | 0.994 | 0.987 | |
| Spinnability | Good taste | Difference (D) | Good taste | Good taste | Good taste | Good taste | Is preferably used | |
| Rate of inhibition of bacteria (％) | Staphylococcus aureus | 0 | 20 | 40 | 55 | 75 | 80 | 65 |
| Escherichia coli | 0 | 35 | 54 | 75 | 86 | 78 | 72 | |
| Ultraviolet ray shielding Rate (%) | 30 | 65 | 70 | 85 | 90 | 96 | 97 | |
| Specific resistance (. times.10)13Ωcm) | 11.3 | 9.8 | 5.9 | 3.4 | 3.2 | |||
(V) detailed description of the preferred embodiments
Example 1.
(1) Preparation of antibacterial agent precursor ethylene glycol suspension
201.29g of zinc sulfate (heptahydrate) is weighed, 700mL of water is added and stirred to dissolve, 8.54g of ammonium carbonate dissolved by 50mL of water is added under stirring, stirring is carried out for 30 minutes, 220.83g of barium hydroxide (octahydrate) solution dissolved by 1000mL of ethylene glycol is slowly added, one third of the barium hydroxide solution is added firstly, the rest of the ethylene glycol solution is added after stirring for 30 minutes, and after stirring for 5 minutes, the water is fractionated to 185 ℃ to prepare suspension.
(2) Synthesis of antibacterial polyester
Adding 2500g of terephthalic acid, 250mL of ethylene glycol, 1.00g of antimony trioxide catalyst, 0.15g of cobalt acetate hue modifier, 0.4g of trimethyl phosphate stabilizer and the suspension prepared in the step 1 into a 10L reaction kettle, and adding nitrogen to 2.0kg/cm2Heating to about 210 deg.C, and maintaining the pressure at 3.5kg/cm2And (2) beginning to fractionate water, increasing the temperature to 268 ℃ after the theoretical water yield is reached, reducing the pressure to the normal pressure for 2.5 hours, then beginning the pre-polycondensation reaction, controlling the temperature rise speed, increasing the temperature to 285 ℃ within 1.5 hours, gradually reducing the pressure from 2600Pa to 260Pa, and finally conducting the polycondensation reaction, wherein the temperature is controlled to 285 ℃, the pressure is 80Pa, and the reaction time is 1.5 hours, so that the antibacterial polyester is prepared.
The product meets Q/01WJHX15-2001, and the indexes are as follows:
intrinsic viscosity (dl/g) 0.660. + -. 0.015
Melting Point (. degree.C.) 264
Diethylene glycol (%) 2.7
Aggregate particles (per mg) 0
Compared with the prior art, the invention has the following characteristics:
1. the preparation process of the inorganic antibacterial agent precursor is simple, the preparation can be completed in two steps in the same reaction device, the concentration is high, the particle size distribution is uniform, the use is simple and convenient, the investment of grinding equipment is reduced, the energy consumption is reduced, the raw materials are cheap and easy to obtain, and the inorganic antibacterial agent precursor can be obtained in various chemical markets.
2. By adopting a unique adding process, the antibacterial agent is added into a polymerization reaction system in the form of a precursor of certain basic zinc carbonate, and is heated and decomposed to obtain functional particles, so that the agglomeration is reduced. When the total concentration is less than 6%, the particle diameter is below 100nm when detected by scanning electron microscope, and no agglomerated particles exist. Compared with the technique of adding powder, the particle diameter is 0.5-2.0 mu, and the coagulated particles exist, so compared with the technique, the spinnability and fiber performance of the polyester chip of the invention are obviously better than the technique.
The present invention will be further illustrated by the following examples, which are not intended to limit the scope of the invention.
Example 2. as in example 1, except that 1, 4-butanediol was used in place of ethylene glycol to dissolve barium hydroxide (octahydrate).
Example 3.
(1) Preparation of antibacterial agent precursor ethylene glycol suspension
Weighing 86.27g of zinc sulfate (heptahydrate), adding 600mL of water, stirring for dissolving, adding 5.28g of ammonium carbonate dissolved by 50mL of water understirring, stirring for 30 minutes, slowly adding 94.64g of barium hydroxide (octahydrate) solution dissolved by 600mL of ethylene glycol, adding one third of the barium hydroxide solution, stirring for 30 minutes, then adding the rest of the ethylene glycol solution, stirring for 5 minutes, and fractioning to remove water to 185 ℃ to obtain a suspension.
(2) Synthesis of antibacterial polyester
Adding 2500g of terephthalic acid, 600mL of ethylene glycol, 1.00g of antimony trioxide catalyst, 0.06g of cobalt acetate hue modifier and 0.4g of trimethyl phosphate stabilizer into the suspension prepared in the step 1, adding nitrogen into a 10L reaction kettle, and adding nitrogen to 2.0kg/cm2Heating to 210 deg.C, and maintaining the pressure at 3.0kg/cm2And (2) beginning to fractionate water, increasing the temperature to 268 ℃ after the theoretical water yield is reached, reducing the pressure to the normal pressure for 2 hours, then beginning the pre-polycondensation reaction, controlling the temperature rise speed to 285 ℃ within 1.5 hours, gradually reducing the pressure from 2600Pa to 260Pa, and finally conducting the polycondensation reaction, wherein the temperature is controlled to 285 ℃, the pressure is 70Pa, and the reaction time is 1.5 hours, so that the antibacterial polyester is prepared.
Example 4 barium hydroxide was dissolved as described in example 3, replacing ethylene glycol with 1, 2-propanediol.
Example 5.
(1) Preparation of antibacterial agent precursor ethylene glycol suspension
115.02g of zinc sulfate (heptahydrate) is weighed, 600mL of water is added and stirred to dissolve, 4.69g of ammonium carbonate dissolved by 50mL of water is added under stirring, the mixture is stirred for 30 minutes, 126.19g of barium hydroxide (octahydrate) solution dissolved by 1000mL of ethylene glycol is slowly added, one third of the barium hydroxide solution is added firstly, the rest of the ethylene glycol solution is added after stirring for 30 minutes, and after stirring for 5 minutes, the water is fractionated to 185 ℃ to prepare suspension.
(2) Synthesis of antibacterial polyester
Adding 2500g of terephthalic acid, 250mL of ethylene glycol, 1.00g of antimony trioxide catalyst, 0.08g of cobalt acetate hue modifier and 0.4g of trimethyl phosphate stabilizer into the suspension prepared in the step 1, adding nitrogen into a 10L reaction kettle, and adding nitrogen to 2.0kg/cm2Heating to 210 deg.C, and maintaining the pressure at 3.0kg/cm2The water begins to be fractionated, the temperature is increased to about 268 ℃ after the theoretical water yield is reached, the pressure is reduced to the normal pressure for 1.5 hours, then the pre-polycondensation reaction is started, the temperature is increased to 284 ℃ within 1 hour, and the pressure is increased from 2600PaGradually reducing the pressure to 260Pa, finally carrying out polycondensation reaction, controlling the temperature at 284 ℃, the pressure at 60Pa and the reaction time at 1 hour to obtain the antibacterial polyester.
Example 6.
(1) Preparation of antibacterial agent precursor ethylene glycol suspension
172.53g of zinc sulfate (heptahydrate) is weighed, 600mL of water is added and stirred to dissolve, 7.16g of ammonium carbonate dissolved by 50mL of water is added under stirring, 30 minutes of stirring is carried out, 189.28g of barium hydroxide (octahydrate) solution dissolved by 1000mL of ethylene glycol is slowly added, about one third of the barium hydroxide solution is added firstly, the rest of the ethylene glycol solution is added after 30 minutes of stirring, 5 minutes of stirring is carried out, thewater is fractionated to 185 ℃, and suspension is prepared.
(2) Synthesis of antibacterial polyester
2500g of terephthalic acid, 250mL of ethylene glycol, 1.00g of antimony trioxide catalyst, 0.06g of cobalt acetate color modifier and 0.4g of trimethyl phosphate stabilizer are prepared in step 1The suspension was charged into a 10L reactor, and nitrogen was added to 2.0kg/cm2Heating to about 210 deg.C, and maintaining the pressure at 3.2kg/cm2And (2) about, beginning to fractionate water, increasing the temperature to about 268 ℃ after the theoretical water yield is reached, reducing the pressure to the normal pressure for about 1.5-2.0 hours, then beginning to perform pre-polycondensation reaction, controlling the temperature rise speed, increasing the temperature to about 285 ℃ within 1-1.5 hours, gradually reducing the pressure from 2600Pa to 260Pa, and finally performing polycondensation reaction, controlling the temperature to about 285 ℃ and the pressure to 40Pa, wherein the reaction time is 1.5 hours, so that the antibacterial polyester is prepared.
Claims (10)
1. The preparation method of the composite nano material is characterized by comprising the following steps of:
(1) preparing a water solution from zinc sulfate serving as a raw material, wherein the concentration of the zinc sulfate water solution is 0.01-2.0 mol/L, adding an ammonium carbonate or ammonium bicarbonate water solution into the water solution, and preparing basic zinc carbonate crystal nuclei by a uniform precipitation method, wherein the molar ratio of the zinc sulfate to the ammonium carbonate or ammonium bicarbonate is 3: 1; the reaction time is 10-60 minutes;
(2) in the same reaction system, adding C2～C4The barium hydroxide solution dissolved by the dihydric alcohol is used for obtaining a composite coating layer of zinc hydroxide and barium sulfate by a coprecipitation method;
the concentration of the barium hydroxide dihydric alcohol solution is 0.01-1.5 mol/L, 1/3 parts of the barium hydroxide dihydric alcohol solution is added firstly, the mixture is stirred for 25-35 minutes, and the rest solution is slowly added;
adding barium hydroxide in the amount equal to the molar weight of zinc sulfate, or adding excessive barium hydroxide for reaction and neutralizing the excessive barium hydroxide in the system with dilute sulfuric acid to obtain a barium sulfate coating layer;
(3) heating and distilling off water in the system, evaporating ammonia in the system along with the water, gradually reducing the pH value of the system to 7-8, and stopping when the temperature of the system reaches 167-; and obtaining the composite nano material of the basic zinc carbonate and the barium sulfate.
2. The method for preparing the composite nanomaterial of claim 1, wherein the concentration of the zinc sulfate aqueous solution is 0.5-1.0 mol \ L.
3. The method of claim 1, wherein C is selected from the group consisting of2-C4The diol of (a) is ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol or 1, 4-butylene glycol.
4. The method of claim 1, wherein the concentration of the barium hydroxide glycol solution is 0.5 to 1.0 mol/L.
5. The method of preparing a composite nanomaterial of claim 1, wherein the molar ratio of the zinc sulfate to the ammonium carbonate or bicarbonate is 15: 2.
6. Use of the composite nanomaterial of claim 1 in polyester synthesis to prepare modified polyethylene terephthalate, polytrimethylene terephthalate and polybutylene terephthalate using the suspension of basic zinc carbonate and barium sulfate glycol of step (3).
7. Use of a composite nanomaterial in polyester synthesis according to claim 6 wherein the composite nanomaterial of basic zinc carbonate and barium sulphate is added in an amount of 0.2 to 3.0% by weight of the polyester based on the weight of zinc oxide decomposed from basic zinc carbonate and barium sulphate is 0.75 to 9.0%.
8. The use of the composite nanomaterial of claim 6 in polyester synthesis, wherein the composite nanomaterial of zinc carbonate hydroxide and barium sulfate is prepared by using terephthalic acid and ethylene glycol as copolymerization and blending monomers through esterification and polycondensation processes, and the composite nanomaterial of zinc carbonate hydroxide and barium sulfate is added before esterification or added after esterification and before polycondensation.
9. The use of the composite nanomaterial in polyester synthesis of claim 6, wherein 30ppm of cobalt acetate is added before esterification, based on the weight of the polyester resin.
10. The use of the composite nanomaterial of claim 6 in polyester synthesis, wherein the pressure during the esterification stage is controlled to be 3-3.6 kg/cm2Raising the temperature to 268 +/-2 ℃, reaching the theoretical water yield, reacting for 2-3 hours, and in a pre-polycondensation stage, controlling the temperature to slowly rise to 285 +/-5 ℃, wherein the time is 1-1.5 hours, and gradually reducing the pressure from 2600Pa to 260 Pa; and in the polycondensation stage, the temperature is controlled to be 285-290 ℃, the pressure is controlled to be 20-100 Pa, and the time is 1-1.5 hours.
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| CNB01135271XA CN1137222C (en) | 2001-12-10 | 2001-12-10 | Process for preparing composite nano material and its application in modifying polyester |
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| CNB01135271XA CN1137222C (en) | 2001-12-10 | 2001-12-10 | Process for preparing composite nano material and its application in modifying polyester |
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|---|---|---|---|
| CNB01135271XA Expired - Fee Related CN1137222C (en) | 2001-12-10 | 2001-12-10 | Process for preparing composite nano material and its application in modifying polyester |
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| Country | Link |
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| CN (1) | CN1137222C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111436675A (en) * | 2020-05-08 | 2020-07-24 | 江苏斑竹科技有限公司 | High-breathability antibacterial deodorant sock and preparation method thereof |
| CN114592342A (en) * | 2021-04-30 | 2022-06-07 | 江苏锵尼玛新材料股份有限公司 | Multifunctional textile softening composition and preparation method thereof |
| CN114747592A (en) * | 2021-05-28 | 2022-07-15 | 江苏锵尼玛新材料股份有限公司 | Stable and efficient antibacterial composition and preparation method thereof |
| CN115305707A (en) * | 2021-05-06 | 2022-11-08 | 江苏锵尼玛新材料股份有限公司 | Long-acting broad-spectrum antibacterial and antiviral composition and preparation method thereof |
-
2001
- 2001-12-10 CN CNB01135271XA patent/CN1137222C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111436675A (en) * | 2020-05-08 | 2020-07-24 | 江苏斑竹科技有限公司 | High-breathability antibacterial deodorant sock and preparation method thereof |
| CN114592342A (en) * | 2021-04-30 | 2022-06-07 | 江苏锵尼玛新材料股份有限公司 | Multifunctional textile softening composition and preparation method thereof |
| CN115305707A (en) * | 2021-05-06 | 2022-11-08 | 江苏锵尼玛新材料股份有限公司 | Long-acting broad-spectrum antibacterial and antiviral composition and preparation method thereof |
| CN114747592A (en) * | 2021-05-28 | 2022-07-15 | 江苏锵尼玛新材料股份有限公司 | Stable and efficient antibacterial composition and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1137222C (en) | 2004-02-04 |
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