CN114106415B - Liquid titanium dioxide delustrant for polyester and application - Google Patents

Liquid titanium dioxide delustrant for polyester and application Download PDF

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CN114106415B
CN114106415B CN202110899726.3A CN202110899726A CN114106415B CN 114106415 B CN114106415 B CN 114106415B CN 202110899726 A CN202110899726 A CN 202110899726A CN 114106415 B CN114106415 B CN 114106415B
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titanium dioxide
tannic acid
phosphate
polyester
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CN114106415A (en
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刘明明
王松林
杜玮辰
朱晓东
孙妍妍
陈爽
刘雨
易凡丰
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Haining Lanti New Material Co ltd
Zhejiang Hengyi Petrochemical Research Institute Co Ltd
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Haining Lanti New Material Co ltd
Zhejiang Hengyi Petrochemical Research Institute Co Ltd
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    • 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

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  • Polymers & Plastics (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
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Abstract

The invention relates to the field of polyester materials, and discloses a liquid titanium dioxide matting agent for polyester and application thereof, wherein the matting agent comprises the following components: tannic acid modified titanium dioxide, free tannic acid, phosphate ester surfactant and solvent. The matting agent has dual functional characteristics, not only has good dispersibility and remarkable matting effect, but also can improve the flame retardant property of polyester. In addition, because all raw materials of the matting agent are beneficial to the polymer process and the product, the online addition can be realized, the operations such as separation and purification after modification are not needed, the production process of the titanium dioxide matting agent can be obviously simplified, and the purposes of energy conservation and consumption reduction are achieved.

Description

Liquid titanium dioxide delustrant for polyester and application
Technical Field
The invention relates to the field of polyester materials, in particular to a liquid titanium dioxide delustrant for polyester and application thereof.
Background
Titanium dioxide (TiO) 2 ) Commonly known as titanium dioxide, mainly comprises crystal forms of rutile, anatase, brookite and the like. The product has stable physical and chemical properties, no toxicity or harm, high whiteness and glossiness, high covering power, high scattering power, low cost, etc. The polyester extinction material has a refractive index close to 2 times that of polyester, and when the polyester extinction material is added into the polyester, the extinction purpose is achieved by utilizing the difference of 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 material is the most ideal polyester extinction material.
At present, manufacturers of titanium dioxide for terylene at home and abroad mainly adopt wet grinding to modify the surface of the titanium dioxide, and graft/adsorb an organic treating agent to improve the dispersion performance of the titanium dioxide. The production process mainly comprises the procedures of beating dispersion, grinding, filtering/centrifuging, wet grinding of modifying agent, press filtration, drying, jet milling and the like. In fact, the existing technology still has the problems of long route, more additive types, high 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 conventional titanium dioxide powder delivery form. Thus, the processes of pressure filtration, drying, crushing and packaging of the slurry after the titanium dioxide modification can be reduced, the process steps of preparing and adding titanium dioxide for customers can be simplified, and both sides can save energy and reduce consumption. Therefore, glycol is used as a dispersing solvent of 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 delustrant for polyester and application thereof. The matting agent has dual functional characteristics, not only has good dispersibility and remarkable matting effect, but also can improve the flame retardant property of polyester. In addition, because all raw materials of the matting agent are beneficial to the polymer process and the product, the online addition can be realized, the operations such as separation and purification after modification are not needed, the production process of the titanium dioxide matting agent can be obviously simplified, and the purposes of energy conservation and consumption reduction are achieved.
The specific technical scheme of the invention is as follows:
in a first aspect, the present invention provides a liquid titanium dioxide matting agent for polyesters comprising the following components:
the tannic acid modified titanium dioxide is prepared from tannic acid,
free tannic acid is used for preparing the water-soluble oil,
a phosphate ester surfactant, and a surfactant-containing compound,
and (3) a solvent.
Aiming at the problem of poor titanium dioxide dispersibility in the traditional flatting agent dispersion liquid, on one hand, the invention utilizes the hydrophilic and lipophilic characteristics of the phosphate surfactant to improve the dispersion stability of the titanium dioxide in the solvent; on the other hand, the ecological friendly substance tannic acid is adopted to carry out grafting modification on the titanium dioxide, so that the steric effect among titanium dioxide molecules can be further increased, the thermal stability of the titanium dioxide in a polymer (polyester) melt is enhanced, and the agglomeration of the titanium dioxide in the melt is avoided.
Unlike conventional modification modes, all reagents selected for modification of the invention are beneficial to the polymer process and the product: after the titanium dioxide surface, free tannic acid and phosphate ester surfactant are added into polyester, the tannic acid can produce a carbon layer to isolate oxygen in the combustion process of the polyester, and the phosphate ester surfactant can be used as a flame retardant, so that the two components have a flame retardant effect to a certain extent. Therefore, the matting agent system has dual functional characteristics of matting and flame retardance. Therefore, the matting 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 matting agent, and achieves the aims of energy conservation and consumption reduction.
Preferably, the mass fraction of the titanium dioxide is 20-40wt% 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 surfactant to the titanium dioxide is 1-5:1000.
Preferably, the tannic acid-modified titanium dioxide is prepared by wet milling or air-jet milling modification.
Preferably, the tannic acid modified titanium dioxide is produced by a wet milling method.
Preferably, the phosphate surfactant is at least one selected from dodecyl phosphate, fatty alcohol ether phosphate, phenol ether phosphate, phosphate potassium salt, polyoxyethylene ether phosphate, siloxane phosphate, alkyl alcohol amide phosphate and polyphosphate.
Preferably, the solvent is ethylene glycol.
Preferably, the preparation method of the matting agent comprises the following steps:
(1) Adding tannic acid into solvent to obtain tannic acid solution.
(2) Firstly mixing titanium dioxide with the tannic acid solution to form a suspension, and mixing the 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 liquid.
(4) The upper suspension was replenished with tannic acid solution according to the amount of grinding loss to maintain the solids content of titania at a set level.
Tannic acid is an eco-friendly substance, contains a large number of phenolic hydroxyl functional groups, is beneficial to enhancing the compatibility of the matting agent with ethylene glycol and PTA, and is grafted onto the surface of titanium dioxide through the action of phenolic hydroxyl of tannic acid and hydroxyl on the surface of titanium dioxide to achieve the aim of improving the dispersibility of the titanium dioxide under the coordination of phosphate surfactant. In addition, tannic acid can form a charcoal layer upon combustion, thereby functioning as a barrier against the inflow of external oxygen, and the phosphate surfactant itself can also function as a flame retardant, so that both can play a role in flame retardance.
Compared with the titanium dioxide delustrant or mixed delustrant in the prior art, the invention adopts tannic acid as the modifier, and the titanium dioxide is grafted and modified by simple wet grinding, so that the modified dispersion liquid system can be added into a polymerization reaction kettle on line, thereby omitting the complex rear-end treatment process of the titanium dioxide, and effectively saving energy and reducing consumption.
In addition, in the step (3), the grinding process is a process in which tannic acid molecules collide with titanium oxide, and tannic acid can sufficiently contact with hydroxyl groups on the surface of titanium oxide to form stable hydrogen bonds. The centrifugal treatment is carried out after grinding to remove large-particle titanium dioxide, the modification effect of the part of titanium dioxide is not good, the titanium dioxide is easy to agglomerate, and the large particles can block the holes of the polyester melt spinning component. The reason why large-particle titanium dioxide is caused is that it is insufficiently ground and can be mixed into the next batch of products to continue grinding.
In step (4), the solids content is fine-tuned to the desired value by adding solvent in the end process, since various losses of titanium dioxide are caused during grinding, centrifugation. The present invention is not particularly limited in terms of the solid content of the final titania dispersed liquid, and is based on the concentration suitable for addition in the polymerization process.
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 with 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 with the suspension to obtain a mixed dispersion.
Preferably, the specific process of step (3) is as follows: the temperature of the mixed dispersion liquid is adjusted to 25-45 ℃, then the mixed dispersion liquid is put into a grinding machine for grinding at the feeding flow rate of 0.5-3m3/h, the rotating speed of the grinding machine is 30-100rpm, and the upper suspension liquid is taken after the grinding is centrifugally treated for 5-15min at the rotating speed of 1000-1500 rpm.
The grinding process is a process of collision of tannic acid molecules and titanium dioxide, the collision probability is influenced by temperature, rotating speed and flow speed, and under the preferable condition, tannic acid can be fully contacted with hydroxyl on the surface of the titanium dioxide to form stable hydrogen bonds.
In a second aspect, the present invention provides the use of a liquid titanium dioxide matting agent as described above in polyester synthesis, in particular in polyester chips or polyester fibres, in particular for matting applications of flame retardant polyester materials.
Compared with the prior art, the invention has the following technical effects:
(1) The invention grafts on the surface of titanium dioxide through the hydrogen bond action of the phenolic hydroxyl group rich in tannic acid and the titanium dioxide hydroxyl group, and the tannic acid has very high affinity with ethylene glycol (polyester synthetic monomer and solvent), thereby improving the affinity of the titanium dioxide and the ethylene glycol; meanwhile, the phosphate surfactant is adsorbed on the surface of the titanium dioxide to improve the hydrophilic and oleophylic properties of the surface of the titanium dioxide, and the dispersion stability of the titanium dioxide in the glycol solvent can be further improved under the cooperation of the phosphate surfactant and the titanium dioxide.
(2) The matting agent of the present invention has dual functional properties. The surface active agent and the modifier are not completely grafted to the surface of a target object, the ungrafted modifier does not play a role in the conventional process to cause waste, and the flame retardant property of the phosphate and the char formation property of the tannic acid during combustion are fully utilized as polyester additives, so that the combustion property of the polyester can be effectively improved, the limiting oxygen index is improved, and the dual characteristics of extinction and flame retardance are endowed to a modified titanium dioxide system.
(3) The matting agent dispersion liquid system can be added to the polymerization process at present, the conventional modified titanium dioxide back-end treatment process such as washing, centrifuging, pressure filtering, crushing and drying processes are omitted, the energy consumption and the waste liquid discharge are obviously reduced, the utilization rate of the modifying agent and the auxiliary agent is improved, and the cost is saved.
Detailed Description
The invention is further described below with reference to examples. The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
General examples
A liquid titanium dioxide matting agent for polyesters, comprising the following components: tannic acid modified titanium dioxide, free tannic acid, a phosphate surfactant (the phosphate surfactant is at least one selected from dodecyl phosphate, fatty alcohol ether phosphate, phenol ether phosphate, phosphate potassium salt, polyoxyethylene ether phosphate, siloxane phosphate, alkyl alcohol amide phosphate and polyphosphate), and a solvent (water, ethanol, ethylene glycol, preferably ethylene glycol).
Wherein the mass fraction of titanium dioxide relative to the solvent is 20-40wt%; 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 air flow grinding modification. Preferably by a wet milling process.
The preparation method of the liquid titanium dioxide delustrant for 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 with 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 with the suspension to obtain a mixed dispersion.
(3) The temperature of the mixed dispersion is adjusted to 25-45 ℃, and then the feeding flow rate is 0.5-3m 3 Grinding the mixed dispersion liquid in a grinder at 30-100rpm, centrifuging at 1000-1500rpm for 5-15min, and collecting the upper suspension.
(4) The upper suspension was replenished with tannic acid solution according to the amount of grinding loss to maintain the solids content of titania at a set level.
The present invention will be described in detail by way of specific examples. In the following examples, all materials were commercially available except as otherwise noted, and the filtration performance test was performed using a BL-6176-B laboratory single screw extruder, toguan Bao round precision detection instruments, inc. YZS-8A full-automatic limiting oxygen index determinator, beijing Xinsheng Zhuo Rui technology Co.
Example 1
(1) Preparing ethylene glycol solution of tannic acid: 40Kg of tannic acid was added to 560Kg of ethylene glycol and stirring was continued at a stirring speed of 100rpm for 1h until tannic acid was completely dissolved.
(2) Beating and dispersing titanium dioxide: 400Kg of titanium dioxide was added to the solution of step (1) and stirred at 100rpm to form a titanium dioxide suspension, siloxane phosphate was mixed with ethylene glycol to form a dispersion solution having a concentration of 20wt%, and 5L of the dispersion solution was added to the titanium dioxide suspension and stirred continuously at a stirring speed of 200rpm for 2 hours to obtain a titanium dioxide dispersion having a titanium dioxide concentration of 40 wt%.
(3) Grinding modification and centrifugation: the temperature of the dispersion was adjusted to 45℃by heat exchange, and the flow rate of the dispersion was 2m 3 And/h, grinding the mixture twice in a grinder, wherein the rotating speed of the grinder is selected to be 80rpm. The milled dispersion was then fed into a centrifuge and centrifuged at 1500rpm for 10min. Pumping the centrifuged upper suspension into a titanium dioxide finished product tank by a pump, wherein the solid content of the titanium dioxide dispersion is 31%, and adding 478Kg of the ethylene glycol solution of tannic acid to adjust the solid content to 20%.
The obtained matting agents were subjected to filtration performance and limiting oxygen index combustion test, and the results are shown in table 1.
Examples 2 to 7
Matting agents of examples 2 to 7 were prepared as in example 1. Except that the corresponding parameters in table 1 below were used instead of the preparation parameters of example 1, wherein examples 4-6 used polyphosphates as phosphate surfactants. The titanium dioxide solids content of the dispersion was finally maintained at 20% in each of examples 1 to 7. The matting agent was used to prepare a full-matted polyester (titanium dioxide content 2 wt%) by conventional procedure. The polyester was subjected to filtration performance and limiting oxygen index combustion test, and the results are shown in Table 2.
TABLE 1
Numbering device Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7
Titanium dioxide usage/Kg 400 400 400 300 300 100 400
Phosphate ester dosage/Kg 1 0.4 0.6 0.8 0.6 0.6 0.8
Ethylene glycol amount/Kg 560 580 570 560 420 880 390
Tannic acid dosage/Kg 40 20 30 40 30 20 10
Reaction temperature/. Degree.C 45 25 35 35 35 25 45
Feed flow/m 3 /h 2 2 3 1 2 2 2
Grinding machine rotation speed/rpm 80 80 60 100 80 80 80
Comparative example 1 (addition of Silicone phosphate alone, no milling)
The preparation method comprises the steps of adding 400Kg of titanium dioxide raw powder into 1600Kg of ethylene glycol, stirring at 100rpm to form a titanium dioxide suspension, contacting siloxane phosphate with the ethylene glycol to form a dispersion solution with the concentration of 20wt%, adding 5L of the dispersion solution into the titanium dioxide suspension, and continuously stirring at the stirring speed of 200rpm for 2 hours to prepare the 20wt% titanium dioxide raw powder 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 conducted.
Comparative example 2 (no grinding treatment)
40Kg of tannic acid was added to 560Kg of ethylene glycol and stirring was continued for 1 hour at a stirring speed of 100rpm until the tannic acid was completely dissolved. 400Kg of titanium dioxide was added to the above solution, stirred at 100rpm to form a titanium dioxide suspension, polyphosphoester was brought into contact with ethylene glycol to form a dispersion solution having a concentration of 20% by weight, 5L of the dispersion solution was added to the titanium dioxide suspension, and stirring was continued at a stirring speed of 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 ethylene glycol solution of tannic acid to prepare a 20wt% 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 conducted.
Comparative example 3 (no phosphate surfactant added and no grinding treatment)
40Kg of tannic acid was added to 560Kg of ethylene glycol and stirring was continued for 1 hour at a stirring speed of 100rpm until the tannic acid was completely dissolved. 400Kg of titanium dioxide was added to the above solution, and stirred at 100rpm to form a titanium dioxide suspension, and stirred continuously at a stirring speed of 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 ethylene glycol solution of tannic acid to prepare a 20wt% 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 conducted.
To test the dispersibility of the matting agent according to the invention and its flame-retardant properties for polyesters, the following application examples were now made:
application example 1
This application example is intended to illustrate the dispersibility of the matting agent systems of examples 1 to 7 in polyesters and comparative examples 1 to 3.
Polyester chips with a titanium dioxide content of 2wt% were prepared by a general polymerization method from the titanium dioxide matting agent systems of examples 1 to 7, respectively, and the corresponding chips were named as P1 to P7, respectively. The full-dull polyester chips prepared in comparative examples 1 to 3 were designated as D1 to D3, respectively. The agglomerated particle number refers to the number of particles of > 10 μm in the polyester chip, and the agglomeration phenomenon in the chip can be visually observed. The filter performance of each slice is tested by adopting a single screw extruder, and the dispersion stability of the matting agent in molten polyester is characterized by adopting the change of the filter pressure because large particles can block the pore canal of the filter to cause the pressure to rise.
TABLE 2
Figure BDA0003198534470000061
As shown in Table 2, the smaller the number of agglomerated particles, the smaller the number of large particles in the polyester, the better the dispersion of titanium dioxide, and the matting agent of examples 1 to 7 of the present invention was well dispersed in the polyester in terms of the number of agglomerated particles and the pressure difference of the filter after 4 hours of continuation; in particular, the matting agents produced in examples 1 to 5, which are in the preferred ranges of the amounts of titanium oxide and tannic acid according to the present invention and in the preferred ranges of the reaction temperature and the milling conditions according to the present invention, have more excellent effects. The higher number of agglomerated particles in comparative examples 1-3 indicates that grinding, tannic acid, and phosphate all have beneficial effects on the dispersion of titanium dioxide. The agglomerated particle number is greatly affected by the selected region, so melt filtration properties can be used to feed back the bulk dispersion. The polyester chip P1 to which the matting agent of example 1 was added had a lower filter pressure in the single screw extruder than comparative examples 1 to 3, indicating that the matting agent of example 1 had fewer large particles in the polyester and had good dispersion stability in the molten polymer.
Application example 2
This application is intended to illustrate the limiting oxygen index burn test of the matting agent of examples 1 to 7 and the matting agent systems of comparative examples 1 to 4 in polyesters.
Limiting oxygen index burn tests were performed on the corresponding polyester chips in the manner of nomenclature used in application example 1. The oxygen limiting index method is characterized in 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 the minimum oxygen concentration is expressed by LOI (Low-oxygen index) which is the volume percentage of oxygen in the mixed gas, and a common detection instrument is an oxygen index tester. Respectively taking 10g of polyester chips, putting the polyester chips into a baking oven at 135+/-5 ℃ for 2 hours, putting the chips into a strip making machine, and making into test strips with the diameter of about 1.3mm and the length of 75mm, wherein each group of test strips is not less than 15. Industry standard HX/T50003-2011 was performed for oxygen index testing. The sample is clamped on the sample clamp and is perpendicular to the combustion cylinder, the upper end of the sample is ignited in the upward flowing oxygen-nitrogen flow, the combustion characteristic is observed, and the continuous combustion time or the damage length is compared with a specified limit value. The lowest oxygen concentration value, expressed as percent oxygen at the time of sustaining combustion, can be measured by testing a series of samples in different oxygen concentrations.
The test results are shown in Table 2, and it is clear 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, and especially the polyester spline prepared in example 4 shows a higher limiting oxygen index, reaching 29.2%, which is 31.5% higher than that of the polyester spline prepared by the commercially available matting agent. The above data indicate that tannic acid is effective in improving the burn characteristics of polyesters. This is because these matting agents contain tannic acid and act as flame retardants.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent transformation of the above embodiment according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.

Claims (9)

1. The application of the liquid titanium dioxide matting agent for the polyester in improving the matting property and the flame retardance of the polyester is characterized in that: the liquid titanium dioxide delustrant for polyester comprises the following components:
the tannic acid modified titanium dioxide is prepared from tannic acid,
free tannic acid is used for preparing the water-soluble oil,
a phosphate ester surfactant, and a surfactant-containing compound,
the mass fraction of the titanium dioxide relative to the solvent is 20-40wt%;
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.
2. The use according to claim 1, wherein: the tannic acid modified titanium dioxide is prepared by wet grinding or air flow grinding modification.
3. The use according to claim 2, wherein: the tannic acid modified titanium dioxide is prepared by a wet grinding method.
4. The use according to claim 1, wherein: the phosphate surfactant is at least one selected from dodecyl phosphate, fatty alcohol ether phosphate, phenol ether phosphate, potassium phosphate, polyoxyethylene ether phosphate, siloxane phosphate, alkyl alcohol amide phosphate and polyphosphate.
5. The use according to claim 1, wherein: the solvent is ethylene glycol.
6. The use according to claim 1 or 3 or 4 or 5, characterized in that: the preparation method of the liquid titanium dioxide delustrant for polyester comprises the following steps:
(1) Adding tannic acid into solvent to obtain tannic acid solution;
(2) Firstly mixing titanium dioxide with 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 liquid;
(4) The upper suspension was replenished with tannic acid solution according to the amount of grinding loss to maintain the solids content of titania at a set level.
7. The use according to claim 6, wherein: 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.
8. The use according to claim 6, wherein: the specific process of the step (2) is as follows: firstly mixing titanium dioxide with 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 with the suspension to obtain a mixed dispersion.
9. The use according to claim 6, wherein: the specific process of the step (3) is as follows: the temperature of the mixed dispersion was adjusted to 25-45℃and then at a feed flow rate of 0.5-3m 3 Grinding the mixed dispersion liquid in a grinder at 30-100rpm, centrifuging at 1000-1500rpm for 5-15min, and collecting the upper suspension.
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GB482980A (en) * 1936-11-05 1938-04-08 Titan Co Inc Improvements in or relating to the preparation of the 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
CN103113782B (en) * 2013-02-05 2014-10-01 陕西科技大学 Preparation process of titanium dioxide containing double-wavelength light absorption water-based anti-forgery ink additive
CN107109040B (en) * 2015-01-19 2019-06-28 帝人富瑞特株式会社 Polytrimethylene terephthalate composition, polyester fiber and its manufacturing method

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