CN114106415A - Liquid titanium dioxide delustering agent for polyester and application thereof - Google Patents
Liquid titanium dioxide delustering agent for polyester and application thereof Download PDFInfo
- Publication number
- CN114106415A CN114106415A CN202110899726.3A CN202110899726A CN114106415A CN 114106415 A CN114106415 A CN 114106415A CN 202110899726 A CN202110899726 A CN 202110899726A CN 114106415 A CN114106415 A CN 114106415A
- Authority
- CN
- China
- Prior art keywords
- titanium dioxide
- tannic acid
- polyester
- phosphate
- matting agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- 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
- 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
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1545—Six-membered rings
-
- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/12—Applications used for fibers
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the field of polyester materials, and discloses a liquid titanium dioxide delustering agent for polyester and application thereof, wherein the delustering agent comprises the following components: tannic acid modified titanium dioxide, free tannic acid, phosphate ester surfactant and solvent. The delustering agent has double functional characteristics, has good dispersibility and obvious delustering effect, and can improve the flame retardant property of polyester. In addition, all the raw materials of the flatting agent are beneficial to the polymer process and the product, so that the flatting agent can be added on line, the operations of separation, purification and the like after modification are not needed, the production process of the titanium dioxide flatting agent can be obviously simplified, and the aims of saving energy and reducing consumption are fulfilled.
Description
Technical Field
The invention relates to the field of polyester materials, in particular to a liquid titanium dioxide delustering agent for polyester and application thereof.
Background
Titanium dioxide (TiO)2) The titanium dioxide is commonly called as rutile, anatase, brookite and other crystal forms. The paint has the advantages of stable physical and chemical properties, no toxicity and harm, opacity, excellent whiteness and glossiness, high covering property, high scattering power, low price and the like. The polyester extinction substance has a refractive index close to 2 times that of polyester, so when the polyester extinction substance is added into the polyester, the purpose of extinction is achieved by utilizing the difference between the refractive indexes of the polyester and the polyester, the light reflectivity of the chemical fiber is reduced, the unsuitable luster is eliminated, and the polyester extinction substance is the most ideal polyester extinction substance.
At present, titanium dioxide manufacturers for terylene at home and abroad mainly adopt wet grinding to modify the surface of titanium dioxide and graft/adsorb an organic treating agent to improve the dispersing performance of the titanium dioxide. The production process mainly comprises the working procedures of pulping, dispersing, grinding, filtering/centrifuging, wet grinding by using a modifier, filter pressing, drying, jet milling and the like. In fact, the existing process still has the problems of longer route, more types of additives, large energy consumption, complex waste liquid components and the like. The produced titanium dioxide is stored, transported and added in the form of slurry in consideration of replacing the traditional delivery form of titanium dioxide powder. Therefore, the processes of filter pressing, drying, crushing and packaging of the slurry after titanium dioxide modification can be reduced, the procedures of preparing and adding titanium dioxide of customers can be simplified, and both the processes can save energy and reduce consumption. Therefore, the ethylene glycol is used as a dispersing solvent of the titanium dioxide, and the modified slurry system can directly enter the polymerization reaction process.
Disclosure of Invention
In order to solve the technical problems, the invention provides a liquid titanium dioxide delustering agent for polyester and application thereof. The delustering agent has double functional characteristics, has good dispersibility and obvious delustering effect, and can improve the flame retardant property of polyester. In addition, all the raw materials of the flatting agent are beneficial to the polymer process and the product, so that the flatting agent can be added on line, the operations of separation, purification and the like after modification are not needed, the production process of the titanium dioxide flatting agent can be obviously simplified, and the aims of saving energy and reducing consumption are fulfilled.
The specific technical scheme of the invention is as follows:
in a first aspect, the invention provides a liquid titanium dioxide flatting agent for polyester, which comprises the following components:
the titanium dioxide is modified by the tannic acid,
the free tannic acid is obtained by the method,
a phosphate ester surfactant, a water-soluble organic acid surfactant,
a solvent.
Aiming at the problem of poor titanium dioxide dispersibility in the traditional flatting agent dispersion liquid, the invention utilizes the hydrophilic and oleophilic characteristics of the phosphate surfactant to improve the dispersion stability of the titanium dioxide in the solvent; on the other hand, the titanium dioxide is subjected to graft modification by adopting the eco-friendly substance tannic acid, so that the steric effect between titanium dioxide molecules can be further increased, the thermal stability of the titanium dioxide in a polymer (polyester) melt is enhanced, and the titanium dioxide is prevented from agglomerating in the melt.
Unlike conventional modification, all of the agents selected for modification of the present invention are beneficial to the polymer process and product: after the titanium dioxide surface and the free tannic acid and the phosphate ester surfactant are added into the polyester, the tannic acid can produce a carbon layer to isolate oxygen in the polyester combustion process, and the phosphate ester surfactant can also be used as a flame retardant, so that the titanium dioxide surface and the free tannic acid have a flame retardant effect to a certain degree. Therefore, the flatting agent system has the dual functional characteristics of flatting and flame retarding. Therefore, the flatting agent of the invention does not need to be subjected to operations such as separation and purification after modification, can be added on line, remarkably simplifies the production process of the titanium dioxide flatting agent, and achieves the purposes of energy conservation and consumption reduction.
Preferably, the mass fraction of the titanium dioxide with respect to the solvent is 20 to 40 wt%; the mass ratio of the total amount of tannic acid and free tannic acid in the tannic acid modified titanium dioxide to the titanium dioxide is 1: 5-20; the mass ratio of the phosphate ester surfactant to the titanium dioxide is 1-5: 1000.
Preferably, the tannic acid modified titanium dioxide is prepared by wet grinding or airflow grinding modification.
Preferably, the tannic acid modified titanium dioxide is prepared by a wet grinding method.
Preferably, the phosphate ester surfactant is at least one selected from the group consisting of dodecyl phosphate, fatty alcohol ether phosphate, phenol ether phosphate, potassium phosphate, polyoxyethylene ether phosphate, silicone phosphate, alkylolamide phosphate and polyphosphate.
Preferably, the solvent is ethylene glycol.
Preferably, the preparation method of the flatting agent comprises the following steps:
(1) adding tannic acid into solvent to obtain tannic acid solution.
(2) Firstly, mixing titanium dioxide and the tannic acid solution to form a suspension, and mixing a phosphate surfactant solution with the suspension to obtain a mixed dispersion.
(3) Grinding and modifying the mixed dispersion liquid, and centrifuging to obtain an upper suspension.
(4) And (4) supplementing the tannic acid solution to the upper suspension according to the grinding loss so as to maintain the solid content of the titanium dioxide at a set level.
The tannic acid is an eco-friendly substance, contains a large number of phenolic hydroxyl functional groups, and is beneficial to enhancing the compatibility of the delustering agent with ethylene glycol and PTA. In addition, tannin can form a charcoal layer during combustion, so that the charcoal layer can be used as a barrier for blocking external oxygen from flowing in, and the phosphate surfactant can also be used as a flame retardant, so that the phosphate surfactant and the flame retardant can play a flame retardant role.
Compared with a titanium dioxide delustering agent or a mixed delustering agent in the prior art, the method adopts tannic acid as a modifier, the titanium dioxide is subjected to graft modification through simple wet grinding, and the modified dispersion liquid system can be added into a polymerization reaction kettle on line, so that the complex rear-end treatment process of the titanium dioxide is omitted, the energy is effectively saved, and the consumption is reduced.
In addition, in the step (3), the grinding process is a process in which tannic acid molecules collide with titanium dioxide, and tannic acid can sufficiently contact with hydroxyl groups on the surface of titanium dioxide to form stable hydrogen bonds. The centrifugal treatment after grinding is to remove large-particle titanium dioxide, the modification effect of the titanium dioxide is poor, the titanium dioxide is easy to agglomerate, and large particles can block the pores of the polyester melt spinning assembly. The reason for the large-particle titanium dioxide is that the titanium dioxide is not fully ground and can be mixed into the next batch of products to continue grinding.
In step (4), the solids content is finely adjusted to the desired value by adding solvents in the end process, since grinding and centrifuging lead to a loss of titanium dioxide to varying degrees. The solid content of the final titanium dioxide dispersion liquid is not particularly limited in the present invention, and the concentration suitable for the addition in the polymerization process is defined.
Preferably, the specific process of step (1) is as follows: adding tannic acid into solvent, and stirring at 80-200rpm for 1-3 hr until tannic acid is completely dissolved to obtain tannic acid solution.
Preferably, the specific process of step (2) is as follows: firstly, mixing titanium dioxide and the tannic acid solution to form a suspension, stirring a phosphate surfactant and a solvent at 800-1500rpm for 10-20min to form a phosphate surfactant solution, and mixing the phosphate surfactant solution and the suspension to obtain a mixed dispersion.
Preferably, the specific process of step (3) is as follows: adjusting the temperature of the mixed dispersion liquid to 25-45 ℃, then leading the mixed dispersion liquid to enter a grinder for grinding at the feeding flow rate of 0.5-3m3/h, wherein the rotation speed of the grinder is 30-100rpm, centrifuging at the rotation speed of 1000-1500rpm for 5-15min after grinding, and taking the upper suspension liquid.
The grinding process is a process of collision between tannic acid molecules and titanium dioxide, the collision probability is influenced by temperature, rotating speed and flow rate, and under the optimal condition, tannic acid can fully contact with hydroxyl on the surface of the titanium dioxide to form stable hydrogen bonds.
In a second aspect, the invention provides the use of the above-mentioned liquid titanium dioxide matting agent in polyester synthesis, in particular in polyester chips or polyester chemical fibers, and in particular, suitable for matting of flame-retardant polyester materials.
Compared with the prior art, the invention has the following technical effects:
(1) according to the invention, rich phenolic hydroxyl groups of tannic acid and titanium dioxide hydroxyl groups form hydrogen bond action to be grafted to the surface of titanium dioxide, and tannic acid has high affinity with glycol (polyester synthetic monomer and solvent), so that the affinity of titanium dioxide and glycol can be improved; meanwhile, the phosphate ester surfactant is adsorbed on the surface of the titanium dioxide to improve the hydrophilic and lipophilic properties of the surface of the titanium dioxide, and the dispersion stability of the titanium dioxide in the glycol solvent can be further improved by matching the phosphate ester surfactant and the titanium dioxide.
(2) The matting agents of the invention have dual functional attributes. Usually, the surfactant and the modifier cannot be completely grafted to the surface of a target object, the modifier which is not grafted in the conventional process does not play a role and causes waste, but the flame retardant property of the phosphate and the char formation property of the tannic acid during combustion are fully utilized, the flame retardant property of the polyester can be effectively improved by taking the phosphate as a polyester additive, the limit oxygen index is improved, and thus the dual properties of extinction and flame retardance are endowed to a modified titanium dioxide system.
(3) The matting agent dispersion system can be added into the polymerization process at present, so that the conventional modified titanium dioxide rear-end treatment processes such as washing, centrifuging, filter pressing, crushing and drying processes are omitted, the energy consumption and the waste liquid discharge are obviously reduced, the utilization rate of a modifier and an auxiliary agent is improved, and the cost is saved.
Detailed Description
The present invention will be further described with reference to the following examples. The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
General examples
A liquid titanium dioxide delustering agent for polyester comprises the following components: tannic acid modified titanium dioxide, free tannic acid, a phosphate ester surfactant (the phosphate ester surfactant is at least one selected from dodecyl phosphate, fatty alcohol ether phosphate, phenol ether phosphate, phosphate potassium salt, polyoxyethylene ether phosphate, siloxane phosphate, alkylolamide phosphate and polyphosphate), and a solvent (water, ethanol, ethylene glycol, preferably ethylene glycol).
Wherein, relative to the solvent, the mass fraction of the titanium dioxide is 20-40 wt%; the mass ratio of the total amount of tannic acid and free tannic acid in the tannic acid modified titanium dioxide to the titanium dioxide is 1: 5-20; the mass ratio of the phosphate surfactant to the titanium dioxide is 1-5: 1000.
The tannic acid modified titanium dioxide is prepared by wet grinding or airflow grinding modification. Preferably by a wet milling process.
The preparation method of the liquid titanium dioxide delustering agent for the polyester comprises the following steps:
(1) adding tannic acid into solvent, and stirring at 80-200rpm for 1-3 hr until tannic acid is completely dissolved to obtain tannic acid solution.
(2) Firstly, mixing titanium dioxide and the tannic acid solution to form a suspension, stirring a phosphate surfactant and a solvent at 800-1500rpm for 10-20min to form a phosphate surfactant solution, and mixing the phosphate surfactant solution and the suspension to obtain a mixed dispersion.
(3) Adjusting the temperature of the mixed dispersion to 25-45 deg.C, and then feeding at a flow rate of 0.5-3m3And/h, grinding the mixed dispersion in a grinder at the rotation speed of 30-100rpm, and centrifuging at the rotation speed of 1000-1500rpm for 5-15min after grinding to obtain an upper suspension.
(4) And (4) supplementing the tannic acid solution to the upper suspension according to the grinding loss so as to maintain the solid content of the titanium dioxide at a set level.
The present invention will be described in detail below by way of specific examples. In the following examples, the raw materials were all commercially available except for the others, and a laboratory single screw extruder model BL-6176-B was used for the filtration performance test, Bao Tao Rou precision testing apparatus Co., Ltd. YZS-8A model full-automatic limit oxygen index tester, Beijing Xinshengtuorui science and technology Limited.
Example 1
(1) Preparing a glycol solution of tannic acid: 40Kg of tannic acid was added to 560Kg of ethylene glycol and stirred continuously at 100rpm for 1 hour until the tannic acid was completely dissolved.
(2) Pulping and dispersing titanium dioxide: adding 400Kg of titanium dioxide into the solution in the step (1), stirring at 100rpm to form a titanium dioxide suspension, mixing siloxane phosphate with ethylene glycol to form a dispersion solution with the concentration of 20 wt%, adding 5L of the dispersion solution into the titanium dioxide suspension, and continuously stirring at 200rpm for 2h to obtain a titanium dioxide dispersion with the titanium dioxide concentration of 40 wt%.
(3) Grinding modification and centrifugation: the temperature of the dispersion was adjusted to 45 ℃ by heat exchange, and then the dispersion was fed at a flow rate of 2m3And/h, grinding twice in a grinder, wherein the rotation speed of the grinder is 80 rpm. And (4) feeding the ground dispersion liquid into a centrifugal machine, and centrifuging for 10min at the rotating speed of 1500 rpm. Pumping the centrifuged upper suspension into titanium dioxide finished productIn the tank, the titanium dioxide dispersion had a solid content of 31%, and 478Kg of the above-mentioned ethylene glycol solution of tannic acid was added to adjust the solid content to 20%.
The obtained matting agents were subjected to filtration performance and limiting oxygen index combustion tests, and the results are shown in table 1.
Examples 2 to 7
The matting agents of examples 2 to 7 were prepared according to the method of example 1. Except that the corresponding parameters in table 1 below were used instead of the preparation parameters of example 1, where examples 4-6 used polyphosphate as phosphate ester surfactant. The titanium dioxide solids content of the dispersion was maintained at 20% for all of examples 1-7. The flatting agent is used for preparing full-dull polyester (the content of titanium dioxide is 2 weight percent) according to the conventional process. The filtration performance and the limiting oxygen index combustion test were performed on the polyester, respectively, and the results are shown in table 2.
TABLE 1
| Numbering | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 |
| Titanium dioxide dosage/Kg | 400 | 400 | 400 | 300 | 300 | 100 | 400 |
| Phosphate dosage/Kg | 1 | 0.4 | 0.6 | 0.8 | 0.6 | 0.6 | 0.8 |
| dosage/Kg of ethylene glycol | 560 | 580 | 570 | 560 | 420 | 880 | 390 |
| The dosage of tannic acid per Kg | 40 | 20 | 30 | 40 | 30 | 20 | 10 |
| Reaction temperature/. degree.C | 45 | 25 | 35 | 35 | 35 | 25 | 45 |
| Feed flow/m3/h | 2 | 2 | 3 | 1 | 2 | 2 | 2 |
| Grinder speed/rpm | 80 | 80 | 60 | 100 | 80 | 80 | 80 |
Comparative example 1 (addition of siloxane phosphate only, no grinding)
Adding 400Kg of titanium dioxide raw powder into 1600Kg of ethylene glycol under the stirring of 100rpm to form a titanium dioxide suspension, contacting siloxane phosphate with the ethylene glycol to form a dispersion solution with the concentration of 20 wt%, adding 5L of the dispersion solution into the titanium dioxide suspension, and continuously stirring at 200rpm for 2 hours to prepare a 20 wt% titanium dioxide raw powder dispersion solution. Full-dull polyester chips (titanium dioxide content: 2 wt%) were produced by a conventional process, and experimental studies on filtration performance and flame retardant properties were carried out.
Comparative example 2 (No grinding treatment)
40Kg of tannic acid was added to 560Kg of ethylene glycol and stirred continuously at a stirring speed of 100rpm for 1 hour until the tannic acid was completely dissolved. Adding 400Kg of titanium dioxide into the solution, stirring at 100rpm to form a titanium dioxide suspension, contacting polyphosphate with ethylene glycol to form a dispersion solution with the concentration of 20 wt%, adding 5L of the dispersion solution into the titanium dioxide suspension, and continuously stirring at 200rpm for 2h to obtain a titanium dioxide dispersion with the titanium dioxide concentration of 40 wt%. Then adding more than 1200Kg of glycol solution of tannic acid to prepare 20 wt% titanium dioxide dispersion. Full-dull polyester chips (titanium dioxide content: 2 wt%) were produced by a conventional process, and experimental studies on filtration performance and flame retardant properties were carried out.
Comparative example 3 (no phosphate surfactant added and no grinding treatment)
40Kg of tannic acid was added to 560Kg of ethylene glycol and stirred continuously at a stirring speed of 100rpm for 1 hour until the tannic acid was completely dissolved. 400Kg of titanium dioxide was added to the above solution to form a titanium dioxide suspension with stirring at 100rpm, and the suspension was continuously stirred at 200rpm for 2 hours to obtain a titanium dioxide dispersion having a titanium dioxide concentration of 40% by weight. Then adding more than 1200Kg of glycol solution of tannic acid to prepare 20 wt% titanium dioxide dispersion. Full-dull polyester chips (titanium dioxide content: 2 wt%) were produced by a conventional process, and experimental studies on filtration performance and flame retardant properties were carried out.
To test the dispersibility of the matting agent of the invention and its flame retardant properties for polyesters, the following application examples were made:
application example 1
This application example serves to illustrate the dispersibility of the matting agent systems of examples 1-7 and comparative examples 1-3 in polyesters.
The titanium dioxide matting agent systems of examples 1 to 7 were each prepared by a conventional polymerization method to give polyester chips having a titanium dioxide content of 2% by weight, and the corresponding chips were each designated by the names P1 to P7. The full dull polyester chips prepared in comparative examples 1 to 3 were designated D1 to D3, respectively. The number of agglomerated particles is the number of particles > 10 μm in the polyester chip, and the agglomeration phenomenon in the chip can be visually observed. And a single-screw extruder is adopted to test the filtering performance of each slice, and the pressure rise is caused by the blockage of the pore channel of the filter by large particles, so the dispersion stability of the flatting agent in the molten polyester is represented by the pressure change of the filter.
TABLE 2
As shown in Table 2, the smaller the number of aggregated particles, the better the dispersion of titanium dioxide, the smaller the number of large particles in the polyester, and the better the dispersion of the matting agent in the polyester by examples 1 to 7 of the present invention, from the viewpoint of the number of aggregated particles and the pressure difference of the filter after 4 hours; especially, the matting agents obtained in examples 1 to 5 in the preferable ranges of the amounts of titanium dioxide and tannic acid used in the present invention and in the preferable ranges of the reaction temperature and the milling conditions described in the present invention have more excellent effects. The higher number of agglomerated particles for comparative examples 1-3 indicates that grinding, tannic acid, and phosphate all have a beneficial effect on the dispersion of titanium dioxide. The number of agglomerated particles is greatly affected by the selected area, so melt filtration performance can be used to feed back the overall dispersion. The polyester chip P1 with the addition of the matting agent of example 1 had a lower filter pressure in the single-screw extruder than in comparative examples 1 to 3, indicating that the matting agent of example 1 had fewer large particles in the polyester and good dispersion stability in the molten polymer.
Application example 2
This application example illustrates the limiting oxygen index burn test in polyester for the gloss reducing agents of examples 1-7 and the gloss reducing agent systems of comparative examples 1-4.
The limiting oxygen index combustion test was carried out in the manner named in application example 1 and corresponding polyester chip. The limiting oxygen index method is that under the specified experimental conditions, in the mixed gas of oxygen and nitrogen, the material just can keep the minimum oxygen concentration required by the combustion state, and is expressed by LOI, wherein LOI is the volume percentage of oxygen in the mixed gas, and a common detecting instrument is an oxygen index determinator. Respectively taking 10g of polyester slices, putting the polyester slices into a 135 +/-5 ℃ oven for baking for 2 hours, putting the slices into a strip making machine, and making sample strips with the diameter of about 1.3mm and the length of 75mm, wherein each group of samples has not less than 15 samples. The industry standard HX/T50003-2011 was performed for oxygen index testing. The sample is clamped on the sample clamp and is vertical to the combustion cylinder, the upper end of the sample is ignited in the upward flowing oxygen-nitrogen gas flow, the combustion characteristic is observed, and the continuous combustion time or the damage length is compared with the specified limit value. The lowest oxygen concentration value, expressed as a percentage of oxygen, at which combustion is maintained, is determined by testing a series of samples at different oxygen concentrations.
The test results are shown in Table 2, and it can be seen from Table 2 that the limiting oxygen index of the P1-7 and D3-4 samples is higher than that of the D1 and D2 samples, especially the sample of the polyester prepared in example 4 shows higher limiting oxygen index which reaches 29.2%, and is 31.5% higher than that of the sample of the polyester prepared by the commercial delustering agent. The above data indicate that tannic acid is effective in improving the burning characteristics of polyesters. This is because the matting agents contain tannic acid and can provide flame retardancy.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (11)
1. A liquid titanium dioxide delustering agent for polyester is characterized in that: comprises the following components:
the titanium dioxide is modified by the tannic acid,
the free tannic acid is obtained by the method,
a phosphate ester surfactant, a water-soluble organic acid surfactant,
a solvent.
2. A matting agent according to claim 1, characterized in that:
the mass fraction of the titanium dioxide is 20 to 40wt% relative to the solvent;
the mass ratio of the total amount of tannic acid and free tannic acid in the tannic acid modified titanium dioxide to the titanium dioxide is 1: 5-20;
the mass ratio of the phosphate ester surfactant to the titanium dioxide is 1-5: 1000.
3. A matting agent according to claim 1, characterized in that: the tannic acid modified titanium dioxide is prepared by wet grinding or airflow grinding modification.
4. A matting agent according to claim 3, characterized in that: the tannic acid modified titanium dioxide is prepared by a wet grinding method.
5. A matting agent according to claim 1, characterized in that: the phosphate ester surfactant is at least one selected from dodecyl phosphate ester, fatty alcohol ether phosphate ester, phenol ether phosphate ester, phosphate potassium salt, polyoxyethylene ether phosphate ester, siloxane phosphate ester, alkylolamide phosphate ester and polyphosphate ester.
6. A matting agent according to claim 1, characterized in that: the solvent is ethylene glycol.
7. A matting agent according to claim 1, 2, 4, 5 or 6, characterized in that: the preparation method comprises the following steps:
(1) adding tannic acid into a solvent to prepare a tannic acid solution;
(2) mixing titanium dioxide and the tannic acid solution to form a suspension, and mixing a phosphate surfactant solution with the suspension to obtain a mixed dispersion;
(3) grinding and modifying the mixed dispersion liquid, centrifuging and taking an upper suspension;
(4) and (4) supplementing the tannic acid solution to the upper suspension according to the grinding loss so as to maintain the solid content of the titanium dioxide at a set level.
8. A matting agent according to claim 7, characterized in that: the specific process of the step (1) is as follows: adding tannic acid into solvent, and stirring at 80-200rpm for 1-3 hr until tannic acid is completely dissolved to obtain tannic acid solution.
9. A matting agent according to claim 7, characterized in that: the specific process of the step (2) is as follows: firstly, mixing titanium dioxide and the tannic acid solution to form a suspension, stirring a phosphate surfactant and a solvent at 800-1500rpm for 10-20min to form a phosphate surfactant solution, and mixing the phosphate surfactant solution and the suspension to obtain a mixed dispersion.
10. A matting agent according to claim 7, characterized in that: the specific process of the step (3) is as follows: adjusting the temperature of the mixed dispersion to 25-45 deg.C, and then feeding at a flow rate of 0.5-3m3And/h, grinding the mixed dispersion in a grinder at the rotation speed of 30-100rpm, and centrifuging at the rotation speed of 1000-1500rpm for 5-15min after grinding to obtain an upper suspension.
11. Use of a matting agent according to any one of claims 1 to 10 in polyester synthesis.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110899726.3A CN114106415B (en) | 2021-08-05 | 2021-08-05 | Liquid titanium dioxide delustrant for polyester and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110899726.3A CN114106415B (en) | 2021-08-05 | 2021-08-05 | Liquid titanium dioxide delustrant for polyester and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114106415A true CN114106415A (en) | 2022-03-01 |
| CN114106415B CN114106415B (en) | 2023-06-13 |
Family
ID=80440768
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110899726.3A Active CN114106415B (en) | 2021-08-05 | 2021-08-05 | Liquid titanium dioxide delustrant for polyester and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114106415B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB483694A (en) * | 1936-11-05 | 1938-04-25 | British Titan Products | Improvements in and relating to the preparation of suspensions of titanium pigments |
| US4183843A (en) * | 1978-09-20 | 1980-01-15 | Aluminum Company Of America | Phosphate ester coating on inorganic fillers for polyester resins |
| US5318625A (en) * | 1991-01-25 | 1994-06-07 | Kerr-Mcgee Chemical Corporation | Pigments for improved dispersibility in thermoplastic resins |
| US6437088B1 (en) * | 2001-08-14 | 2002-08-20 | E. I. Du Pont De Nemours And Company | Process for producing polyester with coated titanium dioxide |
| CN103113782A (en) * | 2013-02-05 | 2013-05-22 | 陕西科技大学 | Preparation process of titanium dioxide containing double-wavelength light absorption water-based anti-forgery ink additive |
| CN107109040A (en) * | 2015-01-19 | 2017-08-29 | 帝人株式会社 | Polytrimethylene terephthalate composition, polyester fiber and its manufacture method |
-
2021
- 2021-08-05 CN CN202110899726.3A patent/CN114106415B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB483694A (en) * | 1936-11-05 | 1938-04-25 | British Titan Products | Improvements in and relating to the preparation of suspensions of titanium pigments |
| US4183843A (en) * | 1978-09-20 | 1980-01-15 | Aluminum Company Of America | Phosphate ester coating on inorganic fillers for polyester resins |
| US5318625A (en) * | 1991-01-25 | 1994-06-07 | Kerr-Mcgee Chemical Corporation | Pigments for improved dispersibility in thermoplastic resins |
| US6437088B1 (en) * | 2001-08-14 | 2002-08-20 | E. I. Du Pont De Nemours And Company | Process for producing polyester with coated titanium dioxide |
| CN103113782A (en) * | 2013-02-05 | 2013-05-22 | 陕西科技大学 | Preparation process of titanium dioxide containing double-wavelength light absorption water-based anti-forgery ink additive |
| CN107109040A (en) * | 2015-01-19 | 2017-08-29 | 帝人株式会社 | Polytrimethylene terephthalate composition, polyester fiber and its manufacture method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114106415B (en) | 2023-06-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111269408B (en) | In-situ polymerization-based flame-retardant anti-dripping negative ion health-care polyester and preparation method thereof | |
| CN104404647B (en) | Hydrophilic polyesters fiber that a kind of Cellulose nanocrystal is modified and preparation method thereof | |
| CN109589653B (en) | Defoaming agent and preparation method and application thereof | |
| CA2230667A1 (en) | Titanium oxide and resin composition | |
| CN107641196A (en) | Delustering polyester and low-glossiness elastic composite fiber | |
| CN113896818A (en) | Emulsifier and PVB resin production method using same | |
| CN114106415A (en) | Liquid titanium dioxide delustering agent for polyester and application thereof | |
| CN112457691B (en) | Low-photocatalytic-activity delustering agent and preparation method and application thereof | |
| CN101077946A (en) | Preparing method of silicon dioxide abrasive material | |
| CN107723833B (en) | Preparation method of α -nano-alumina modified polyester fiber | |
| Lin | A New Lignosulfonate Dispersant for Dyes. | |
| CN113845647B (en) | Preparation method of special material for producing in-situ polymerized antibacterial polyester flat filaments | |
| CN114806225B (en) | Preparation method of liquid titanium dioxide | |
| CN116333173A (en) | Cellulose acetate and preparation method thereof | |
| CN114687057A (en) | Flash evaporation sheet and application thereof | |
| CA1155774A (en) | Filtering aid for the filtration of beverages | |
| WO2022194284A1 (en) | Activated carbon, preparation method therefor, and use thereof in grease | |
| CN115124721B (en) | Modified gelatin for coating printing and dyeing adhesive as well as preparation method and application thereof | |
| CN112898942B (en) | Special heavy calcium carbonate for endowing single-component dealcoholized silicone sealant with good flame retardant property and preparation method thereof | |
| CN111349981B (en) | Low-toxicity low-smoke flame-retardant polyester fiber and preparation method thereof | |
| CN101525420B (en) | Fire retardant polyethylene terephthalate | |
| CN110467562B (en) | Light stabilizer, and preparation method and application thereof | |
| CN111573683A (en) | Preparation method of silica with high specific surface area and low oil absorption value and product thereof | |
| CN112604325A (en) | Organic silicon modified unsaturated higher fatty alcohol ester defoaming agent and preparation method thereof | |
| CN115138106B (en) | High-temperature general high-carbon alcohol defoamer for papermaking white water and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: 311200 29 Chenghu Road, Yaqian Town, Xiaoshan District, Hangzhou City, Zhejiang Province Applicant after: Zhejiang Hengyi Petrochemical Research Institute Co.,Ltd. Applicant after: Haining Lanti New Material Co.,Ltd. Address before: 311200 29 Chenghu Road, Yaqian Town, Xiaoshan District, Hangzhou City, Zhejiang Province Applicant before: ZHEJIANG HENGLAN TECHNOLOGY Co.,Ltd. Applicant before: Haining Lanti New Material Co.,Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |