CN111675904B - Aromatic sulfone composition, feeding bottle and preparation method and application thereof - Google Patents
Aromatic sulfone composition, feeding bottle and preparation method and application thereof Download PDFInfo
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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
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
Abstract
The invention relates to an aromatic sulfone composition, a feeding bottle, a preparation method and application thereof. The aromatic sulfone composition comprises an aromatic sulfone polymer and a monohalogenated aromatic ring compound; the content of the single halogenated aromatic ring compound in the aromatic sulfone composition is 25-1000 ppm. The aromatic sulfone composition provided by the invention improves the performance of the aromatic sulfone polymer by adding the monohalogenated aromatic ring compound with relatively smaller molecular weight, the monohalogenated aromatic ring compound can reduce the generation of crystal points in the blow molding process of the feeding bottle at a certain content, the light transmittance of the composition can be kept, the monohalogenated aromatic ring compound can perform a certain degree of chemical reaction with the hydroxyl end group of the aromatic sulfone polymer under the high-temperature condition of injection molding processing, the content of the hydroxyl end group of the aromatic sulfone polymer is reduced, the thermal stability of the resin is further improved, and the color grade is improved. In the blow molding process of the feeding bottle, the processing temperature can be reduced, the feeding bottle has light color, less crystal points and low cost, and has greater practical application value.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to an aromatic sulfone composition, a feeding bottle, and a preparation method and application thereof.
Background
After the application of Polycarbonate (PC) in medicines and foods is limited in the European Union, the aromatic sulfone polymer gradually replaces PC to be used for baby bottle products by virtue of the characteristics of high temperature resistance, steam resistance, impact resistance, good dimensional stability, no toxicity, high transparency and the like, and is one of the best high polymer materials in the application of the existing baby bottle market. But the existence of strong polar sulfuryl in the molecular chain leads the intermolecular cohesive energy to be larger, thus leading the hot processing melt to have large viscosity, poor fluidity, high processing temperature, easy generation of yellowing and other product defects. Particularly, in the process of blowing the milk bottle, a certain amount of crystal points appear on the bottle body of the milk bottle, and the appearance of the milk bottle is influenced. The size of the large polycrystalline point of the bottle body of the feeding bottle is between 1 and 100 mu m, and a plurality of small gaps are round or fusiform. Through long-term research by related personnel, more crystal points are caused by that gaps of 1-100 mu m are generated in the blow molding process of the feeding bottle due to poor resin fluidity, so that scattering or refraction to different degrees is formed. At present, the generation of crystal points is mostly reduced by increasing the blow molding processing temperature or increasing the cleaning frequency of an injection molding machine, but the actual improvement effect is not good, and the problem that the color of the feeding bottle is darkened and the like can occur when the processing temperature is increased.
In order to improve the flowability of the aromatic sulfone polymer, the aromatic sulfone polymer is usually blended with other resins or flow modifiers having high flowability physically or chemically copolymerized to obtain a material having high flowability, good heat resistance and mechanical properties. CN109504089 discloses a low-cost polysulfone alloy prepared by blending polysulfone resin, polycarbonate resin and other corresponding additives, which reduces the cost while maintaining the advantages of high temperature resistance and mechanical properties of polysulfone resin, and simultaneously remarkably reduces the processing temperature of polysulfone resin and maintains good melt fluidity at relatively low temperature. CN101743272 discloses a thermoplastic molding composition consisting of polyethersulfone, polysulfone, stearic acid and other additives and auxiliaries, having improved flowability, surface quality and notched impact strength, useful for the manufacture of automotive headlamps. CN104387587 adopts the copolymerization of semi-aromatic dihalogenated diamide, 4,4' -dichlorodiphenyl sulfone and diphenol to prepare the high-fluidity polyether sulfone/amide copolymer, which is suitable for preparing special thin-wall parts.
The flow of aromatic sulfone polymers has been largely worked by researchers in the field, mainly focusing on the improvement of the flow of composite or copolymer molding compositions, and there are few reports on the improvement of the flow and the improvement of the blow molding quality while maintaining the transparency of the body height.
Therefore, the development of an aromatic sulfone polymer material which can improve the flowability and improve the blow molding quality while keeping the transparency of the body height has important research significance and application value.
Disclosure of Invention
The invention aims to overcome the defects or shortcomings of large melt viscosity, poor flowability, high processing temperature, easy generation of yellowing and other product defects (such as crystal points) of hot processing of aromatic sulfone polymers in the prior art, and provides an aromatic sulfone composition. The aromatic sulfone composition provided by the invention improves the performance of the aromatic sulfone polymer by adding the monohalogenated aromatic ring compound with relatively small molecular weight, the monohalogenated aromatic ring compound can reduce the generation of crystal points in the blow molding process of the feeding bottle at a certain content, the light transmittance of the composition can be maintained, and the monohalogenated aromatic ring compound can perform a certain degree of chemical reaction with the terminal hydroxyl of the aromatic sulfone polymer under the high-temperature condition of injection molding processing, so that the content of the terminal hydroxyl of the aromatic sulfone polymer is reduced, the thermal stability of the resin is further improved, and the color grade is improved. In the blow molding process of the feeding bottle, the processing temperature can be reduced, the feeding bottle has light color, less crystal points and low cost, and has greater practical application value.
Another object of the present invention is to provide a method for preparing the above aromatic sulfone composition.
Another object of the present invention is to provide the use of the above aromatic sulfone composition for the preparation of a baby bottle.
Another object of the present invention is to provide a nursing bottle.
The invention also aims to provide a preparation method of the milk bottle.
In order to achieve the purpose, the invention adopts the following technical scheme:
an aromatic sulfone composition comprising an aromatic sulfone polymer and a monohalogenated aromatic ring-type compound; the content of the single halogenated aromatic ring compound in the aromatic sulfone composition is 25-1000 ppm.
The size of the large polycrystalline point of the bottle body of the feeding bottle is between 1 and 100 mu m, and a plurality of small gaps are round or fusiform. Through long-term research by the relevant personnel, more crystal points are caused by that gaps of 1-100 mu m are generated in the blow molding process of the feeding bottle due to poor resin flowability, so that light is scattered or refracted to different degrees.
The molecular weight and the molecular weight distribution of the aromatic sulfone polymer melt glue are closely related to the flowability of the aromatic sulfone polymer melt glue, tiny gaps are inevitably generated due to tiny differences of the flowability in the processing process of the milk bottle, the tiny gaps can cause light scattering or refraction, and then the shining tiny bright points (namely crystal points) can be seen through direct observation, so that the appearance of the bottle body of the milk bottle is adversely affected.
Through multiple researches, the inventor of the invention finds that the monohalogenated aromatic ring compound with relatively small molecular weight can obviously improve the fluidity of the aromatic sulfone polymer and greatly reduce the generation of crystal points in the blow molding process of the feeding bottle. In addition, the monohalogenated aromatic ring compound can perform a certain degree of chemical reaction with the terminal hydroxyl of the aromatic sulfone polymer under the high-temperature condition of injection molding processing, so that the content of the terminal hydroxyl of the aromatic sulfone polymer can be reduced, the thermal stability of the resin is further improved, and the color grade is improved.
The aromatic sulfone composition provided by the invention can reduce the processing temperature in the blow molding process of the feeding bottle, and the feeding bottle has the advantages of light color, less crystal points, low cost and larger practical application value.
The dosage of the monohalogenated aromatic ring compound has great influence on the performance of the composition. If the dosage is too small, the improvement effect on the performance (crystal point and color grade) is not good; if the amount of the aromatic sulfone is too large, the light transmittance of the aromatic sulfone composition is possibly reduced, and in the processing process of the feeding bottle, if the volatile amount is large and the aromatic sulfone cannot be timely discharged from a mold, a small amount of micron-sized bubbles appear on the bottle body of the feeding bottle, crystal points are formed, and the appearance of the bottle body of the feeding bottle is adversely affected.
Preferably, the content of the single halogenated aromatic ring compound in the aromatic sulfone compound is 45-830 ppm.
More preferably, the content of the single halogenated aromatic ring compound in the aromatic sulfone compound is 550-770 ppm.
Preferably, the molecular weight of the monohalogenated aromatic ring compound is 100-500 g/mol.
More preferably, the monohalogenated aromatic ring compound is one or more of 4-chlorobenzenesulfone, 4-fluorobenzenesulfone, 4-bromobenzenesulfone, 4-chlorobenzophenone, 4-fluorobenzophenone or 4-bromobenzophenone.
Aromatic sulfone polymers conventional in the art can be used in the present invention.
Preferably, the aromatic sulfone polymer is one or more of polyphenylsulfone, polyethersulfone, polysulfone, polyether ether sulfone, polyether sulfone ketone or polyphenylene sulfide sulfone.
The aromatic sulfone polymer can be obtained by a conventional polymerization reaction.
More preferably, the aromatic sulfone polymer is obtained by polymerization of an aromatic sulfone monomer; the monomer can be one or more of 4,4 '-dichlorodiphenyl sulfone, 4,4' -biphenol, 2,2 '-bis (4-hydroxyphenyl) propane or 4,4' -dihydroxydiphenyl sulfone.
Specifically, the aromatic sulfone polymers of the present application can be obtained by the following solution polycondensation process:
(1) Salt forming reaction: quantitatively adding a solvent (such as sulfolane, N-methyl pyrrolidone and the like), a reaction monomer, a salt forming agent (such as sodium carbonate, potassium carbonate and the like) and an entrainer (such as toluene, xylene, trimethylbenzene and the like) into a reaction kettle, reacting at 180-220 ℃ by adopting a solution polycondensation method, azeotropically and continuously removing reaction water by the entrainer in the reaction process until no water is removed, finishing the salt forming reaction, and distilling out the entrainer;
(2) Polymerization reaction: after the entrainer is evaporated, further heating, stabilizing the reaction system to 230-240 ℃, keeping the temperature for 2-3 h, and continuing the reaction until the polymerization reaction is finished;
(3) And (3) post-polymerization treatment: stopping stirring and heating, precipitating the polymer material in water into strips, crushing by a crusher to obtain powdery material, boiling with deionized water, centrifuging, filtering, repeating for several times until byproduct salt is removed, and removing water from the purified polymer under vacuum drying to obtain the aromatic sulfone polymer.
The preparation method of the aromatic sulfone composition comprises the following steps: and uniformly mixing the aromatic sulfone polymer and the monohalogenated aromatic ring compound, melting and mixing, extruding and granulating to obtain the aromatic sulfone composition.
Preferably, the temperature of the melt kneading is 280 to 350 ℃.
Specifically, the aromatic sulfone composition is prepared by the following process: and (3) uniformly mixing the aromatic sulfone polymer and the monohalogenated aromatic ring compound, adding the mixture into a double-screw extruder, carrying out melt mixing at the extrusion temperature of 280-350 ℃, and carrying out extrusion granulation to obtain the aromatic sulfone composition.
The application of the aromatic sulfone composition in preparing the milk bottle is also within the protection scope of the invention.
The invention also provides a feeding bottle, which is prepared from the aromatic sulfone composition through dehumidification drying, melt glue injection molding and stretch blow molding.
Preferably, the number of crystal points with the size of 1-100 mu m on the body of the feeding bottle is not higher than 10/10 g.
The thickness and the quality of the body of the feeding bottle are both conventional.
Preferably, the thickness of the body of the feeding bottle is 0.5-2 mm; the mass of the milk bottle is 30-60 g.
The preparation method of the milk bottle comprises the following steps:
s1, dehumidifying and drying, and baking the granular aromatic sulfone composition for 5-7 hours at the temperature of 150-170 ℃;
s2, molten glue injection molding: melting the dehumidified and dried aromatic sulfone composition at 350-380 ℃, then injecting the melted aromatic sulfone composition into a bottle blank mold of the feeding bottle, and maintaining the pressure to obtain a bottle blank;
s3: and transferring the bottle blank into a feeding bottle mold, and blowing high-pressure air for molding to obtain the feeding bottle.
Compared with the prior art, the invention has the following beneficial effects:
the aromatic sulfone composition provided by the invention improves the performance of the aromatic sulfone polymer by adding the monohalogenated aromatic ring compound with relatively smaller molecular weight, the monohalogenated aromatic ring compound can reduce the generation of crystal points in the blow molding process of the feeding bottle at a certain content, the light transmittance of the composition can be kept, the monohalogenated aromatic ring compound can perform a certain degree of chemical reaction with the terminal hydroxyl of the aromatic sulfone polymer under the high-temperature condition of injection molding processing, the content of the terminal hydroxyl of the aromatic sulfone polymer is reduced, the thermal stability of the resin is further improved, and the color grade is improved. In the blow molding process of the feeding bottle, the processing temperature can be reduced, the feeding bottle has light color, few crystal points and low cost, and has larger practical application value.
Detailed Description
The invention is further illustrated by the following examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. Experimental procedures without specific conditions noted in the examples below, generally according to conditions conventional in the art or as suggested by the manufacturer; the raw materials, reagents and the like used are, unless otherwise specified, those commercially available from the conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art based on the present invention are intended to be covered by the claims.
Some reagents selected in the examples and comparative examples of the present invention are described below:
sulfolane: solvent with purity of 99.8%, liaoyang Guanghua chemical Co., ltd;
4,4' -dichlorodiphenyl sulfone: reaction monomers with the purity of more than 99.5 percent, taiwan and chemical engineering Co., ltd;
4,4' -biphenol: reaction monomers with purity of more than 99.5%, taiwan and chemical industry Co., ltd;
4,4' -dihydroxydiphenyl sulfone: reaction monomers with the purity of 99.5 percent, jiangsu Aolanda scientific and technical practical company, inc.;
xylene: entrainer, isomerization grade, petrochemical company, ltd, china.
The aromatic sulfone compositions of the examples and comparative examples of the present invention were injection molded in an injection molding machine at 360 ℃ to give a standard color plate having a thickness of 2mm, and the L, a, b values of the color plate were measured by a color difference meter according to the standard ASTM E1164, and the color shades were compared with the b value, the smaller the b value, the lighter the color and the higher the color grade. Meanwhile, the light transmittance of the color palette sample is tested by a light transmittance haze tester according to the GB/T2410 standard.
The size and the number of the crystal points of the feeding bottles of the examples and the comparative examples of the invention are obtained by directly observing the plastic of the bottle body of the feeding bottle under a high-power optical microscope.
The content of the single halogenated aromatic ring compound in the aromatic sulfone composition is determined by GC-MS test after the composition is extracted, and the specific process is as follows:
1. sample preparation: taking 100 plus or minus 0.5g of sample, placing the sample in a Soxhlet extractor for extraction, selecting acetone as an extraction solvent, performing reflux extraction at the temperature of 80 plus or minus 5 ℃ for 7 days to obtain acetone extract, performing rotary evaporation and concentration at low temperature, and weighing.
2. GC-MS test: testing by adopting GC-MS testing equipment of an Agilent company 7890B-5977A MSD model; chromatographic conditions are as follows: the capillary column is HP-5MS, 30mmy 250 mu m,0.25m; the temperature rise program is heated to 200 ℃ at a speed of 15 ℃/min, then the temperature is kept, the carrier gas is He gas, and the split ratio is 50.
And establishing a standard working curve of the monohalogenated aromatic ring compound in the gas chromatography by using ethyl acetate as an internal standard substance by adopting an internal standard method. Quantitatively adding ethyl acetate internal standard substance solution with known concentration into an acetone extraction liquid sample to be detected, determining the peak area of the monohalogenated aromatic ring compound in the sample, calculating the content of the monohalogenated aromatic ring compound in the sample to be detected according to a standard working curve, and reversely deducing the content of the monohalogenated aromatic ring compound in the composition.
Examples 1 to 7 and comparative examples 1 to 4
The present example and comparative examples provide a series of polyphenylsulfone compositions. The preparation process comprises the following steps:
(1) Preparation of polyphenylsulfone polymers
Quantitatively adding 36kg of sulfolane, 8.79kg of 4,4 '-dichlorodiphenyl sulfone and 5.59kg of 4,4' -biphenol into a 100L reaction kettle protected by high-purity nitrogen, stirring and heating, adding 33kg of sodium carbonate and 3kg of dimethylbenzene, keeping for 5 hours at 180-220 ℃ by adopting a solution polycondensation method, continuously discharging reaction water by azeotropic distillation of the dimethylbenzene in the reaction process until no water is discharged, finishing the salt-forming reaction, and distilling out the dimethylbenzene. Then, the reaction system was heated to 235 ℃ and maintained for 3 hours. Stopping stirring and heating, precipitating the polymer material into strips in water, crushing by a crusher to obtain powdery material, boiling for 1 hour by deionized water, centrifugally filtering, and repeating for 8-10 times until the filtrate is detected by silver nitrate and does not become turbid, namely the byproduct salt is washed out completely. And (3) removing water from the purified polymer under vacuum drying to obtain the polyphenylsulfone polymer.
(2) Preparation of polyphenylsulfone composition
And (2) uniformly mixing the polyphenylsulfone polymer obtained in the step (1) and 4-chlorobenzenesulfone, adding the mixture into a double-screw extruder, carrying out melt mixing at the extrusion temperature of 280-350 ℃, and carrying out extrusion granulation to obtain the polyphenylsulfone composition.
The ratio of the 4-chloro-diphenyl sulfone added in the step (2) to the total mass of the polyether sulfone polymer and the 4-chloro-diphenyl sulfone is changed within the range of 0-3000 ppm (0-0.3%).
Specifically, as shown in Table 1, the ratio of the mass of 4-tert-butylphenol added in step (2) to the sum of the mass of polyethersulfone polymer and 4-tert-butylphenol was 0 (comparative example 1), 15ppm (comparative example 2), 30ppm (example 5), 50ppm (example 4), 0.03% (300 ppm, example 3), 0.06% (600 ppm, example 2), 0.08% (800 ppm, example 1), 0.09% (900 ppm, example 6) 0.11% (1100 ppm, example 7), 0.2% (2000 ppm, comparative example 3), and 0.3% (3000 ppm, comparative example 4), respectively.
Examples 8 to 14 and comparative examples 5 to 8
The present examples and comparative examples provide a range of polyethersulfone compositions. The preparation process comprises the following steps:
(1) Preparation of polyether sulfone polymers
Quantitatively adding 36kg of sulfolane, 8.79kg of 4,4 '-dichlorodiphenyl sulfone and 7.51kg of 4,4' -dihydroxydiphenyl sulfone into a 100L reaction kettle protected by high-purity nitrogen, stirring and heating, adding 33kg of sodium carbonate and 3kg of dimethylbenzene, adopting a solution polycondensation method, keeping the temperature at 180-220 ℃ for 5 hours, continuously discharging reaction water by azeotropic distillation of the dimethylbenzene in the reaction process until no water is discharged, finishing the salt-forming reaction, and distilling out the dimethylbenzene. Then, the reaction system was heated to 235 ℃ and maintained for 3 hours. Stopping stirring and heating, precipitating the polymer material into strips in water, crushing the strips by a crusher to obtain a powdery material, boiling the powdery material for 1 hour by using deionized water, centrifugally filtering the powdery material, and repeating the centrifugal filtering for 8 to 10 times until the filtrate is detected by silver nitrate to be not turbid, namely the byproduct salt is washed out completely. And (3) removing water from the purified polymer under vacuum drying to obtain the polyether sulfone polymer. (2) Preparation of polyethersulfone compositions
And (2) uniformly mixing the polyether sulfone polymer obtained in the step (1) and 4-chlorobenzenesulfone, adding the mixture into a double-screw extruder, carrying out melt mixing at the extrusion temperature of 280-350 ℃, and carrying out extrusion granulation to obtain the polyether sulfone composition.
The ratio of the mass of the 4-chloro-diphenyl sulfone added in the step (2) to the total mass of the polyether sulfone polymer and the 4-chloro-diphenyl sulfone is changed within 0-3000 ppm (0-0.3%).
Specifically, as shown in Table 2, the ratios of the mass of 4-chlorobenzenesulfone added in step (2) to the sum of the mass of polyethersulfone polymer and 4-tert-butylphenol were 0 (comparative example 5), 18ppm (comparative example 6), 35ppm (example 12), 50ppm (example 11), 0.03% (300 ppm, example 10), 0.06% (600 ppm, example 9), 0.08% (800 ppm, example 8), 0.09% (900 ppm, example 13), 0.112% (1120 ppm, example 14), 0.2% (2000 ppm, comparative example 7), and 0.3% (3000 ppm, comparative example 8), respectively.
Example 15
This example provides an aromatic sulfone composition. In the preparation process, the rest is the same as the example 1 except that the selected monohalogenated aromatic ring compound is 4-fluoro diphenyl sulfone.
Example 16
This example provides an aromatic sulfone composition. In the preparation process, the rest is the same as the example 1 except that the selected monohalogenated aromatic ring compound is 4-bromodiphenyl sulfone.
The content of the monohalogenated aromatic ring compound in the obtained aromatic sulfone composition was measured according to the above-mentioned method to obtain the content of the monohalogenated aromatic ring compound in the polyethersulfone composition provided in each example and comparative example, as shown in tables 1 to 3.
TABLE 1 compounding ratio conditions and test results for examples 1 to 7 and comparative examples 1 to 4
TABLE 2 compounding ratio conditions and test results for examples 8 to 14 and comparative examples 5 to 8
TABLE 3 compounding ratio conditions and test results of examples 1, 15 to 16
From table 1, the addition of the monohalogenated aromatic ring compound is beneficial to reducing the generation of crystal points of the aromatic sulfone composition in the blow molding process of the feeding bottle and improving the color grade, and the larger the addition of the monohalogenated aromatic ring compound is, the more obvious the improvement of the crystal points is, and the higher the color grade is; however, when the amount of the additive is too large, the volatile amount of the additive is large in the processing process of the feeding bottle, so that the additive cannot be discharged from the mold in time, and further a small amount of micron-sized bubbles appear on the body of the feeding bottle, crystal points are formed, and the appearance of the body of the feeding bottle is adversely affected. Meanwhile, as the addition amount of the monohalogenated aromatic ring compound is increased, the light transmittance is reduced. Specifically, the polyphenylsulfone compositions of examples 1 to 7 contained 25 to 1000ppm of 4-chlorobenzenesulfone, compared with comparative example 1, and the b value was reduced by 2 to 3, the color was remarkably lightened, the number of crystal points was reduced, and the change in light transmittance was small. Meanwhile, when the content in comparative example 2 is 10ppm, the appearance is closer to that of the milk bottle without the liquid, and when the content in comparative examples 3 and 4 is larger, although the color grade is greatly improved, the light transmittance is reduced, the number of crystal points of the bottle body of the milk bottle is obviously larger, and the appearance performance is poor. Therefore, it is most advantageous to maintain a certain range of 4-chlorobenzenesulfone in the minor component of the polyphenylsulfone composition.
Similarly, it can be seen from Table 2 that the polyethersulfone compositions of examples 8-14 containing 25-1000 ppm of 4-chlorobenzenesulfone had a b value reduced by 2-3, a significantly lighter color, a reduced number of crystal grains, and a smaller change in light transmittance compared to comparative example 5. Meanwhile, when the content in comparative example 6 is 10ppm, the appearance is closer to that of the milk bottle, and when the contents in comparative examples 7 and 8 are larger, the light transmittance is reduced although the color grade is greatly improved, the number of crystal points of the bottle body of the milk bottle is obviously larger, and the appearance performance is poor. Therefore, it is most advantageous to maintain a range of 4-chlorobenzenesulfone levels in the polyethersulfone composition.
From the above, it is more favorable that the content of the single halogenated aromatic ring compound in the aromatic sulfone composition is kept in a certain range, and when the content is 45-830 ppm, the comprehensive performances such as crystal point, color grade, light transmittance and the like are better; when the content is 550-770 ppm, the comprehensive properties such as crystal point, color grade, light transmittance and the like are more excellent.
In addition, as can be seen from Table 3, the compositions obtained by adding 800ppm of 4-fluorodiphenyl sulfone or 4-bromodiphenyl sulfone respectively during blending and extrusion-granulating (the contents of the monohalogenated aromatic ring compounds in the compositions of examples 15 and 16 are 738ppm and 762ppm respectively) can achieve the same effects as those of the 4-chlorodiphenyl sulfone added in example 1, namely, the color becomes lighter, the number of crystal points is reduced, and the light transmittance is maintained.
It will be appreciated by those of ordinary skill in the art that the examples provided herein are intended to assist the reader in understanding the principles of the invention and are to be construed as being without limitation to such specifically recited examples and embodiments. Those skilled in the art, having the benefit of this disclosure, may effect numerous modifications thereto and changes may be made without departing from the scope of the invention in its aspects.
Claims (9)
1. An aromatic sulfone composition for blow molding of a baby bottle, comprising an aromatic sulfone polymer and a monohalogenated aromatic ring-type compound; the content of the single halogenated aromatic ring compound in the aromatic sulfone composition is 25 to 1000 ppm;
the preparation method of the aromatic sulfone composition for blow molding of the feeding bottle comprises the following steps: uniformly mixing an aromatic sulfone polymer and a monohalogenated aromatic ring compound, then melting and mixing at 280-350 ℃, and extruding and granulating to obtain the aromatic sulfone composition;
the monohalogenated aromatic ring compound is one or more of 4-chlorobenzenesulfone, 4-fluorobenzenesulfone, 4-bromobenzenesulfone, 4-chlorobenzophenone, 4-fluorobenzophenone or 4-bromobenzophenone;
the aromatic sulfone polymer is one or more of polyphenylsulfone, polyethersulfone, polyether ether sulfone, polyether sulfone ketone or polyphenylene sulfide sulfone;
in the preparation method of the aromatic sulfone composition for blow molding of the feeding bottle, the ratio of the added monohalogenated aromatic ring compound to the total mass of the aromatic sulfone polymer and the monohalogenated aromatic ring compound is changed within 30-1120 ppm.
2. The aromatic sulfone composition for blow molding of baby bottles of claim 1, wherein the content of the monohalogenated aromatic ring compound in the aromatic sulfone composition is from 45 to 830ppm.
3. The aromatic sulfone composition for blow molding of baby bottles of claim 2, wherein the content of the monohalogenated aromatic ring compound in the aromatic sulfone composition is from 550 to 770 ppm.
4. The aromatic sulfone composition for blow molding of baby bottles of claim 1, wherein the aromatic sulfone polymer is obtained by polymerization of aromatic sulfone monomers.
5. The aromatic sulfone composition for blow molding of baby bottles of claim 4, wherein the aromatic sulfone monomer is one or more of 4,4 '-dichlorodiphenyl sulfone, 4,4' -biphenyl diphenol, 2,2 '-bis (4-hydroxyphenyl) propane, or 4,4' -dihydroxydiphenyl sulfone.
6. Use of the aromatic sulfone composition of any of claims 1~5 for bottle blow molding in the manufacture of a bottle.
7. A baby bottle prepared from the aromatic sulfone composition for blow molding of a baby bottle of any one of claims 1~5 by dehumidification, drying, melt-blown injection molding and stretch blow molding.
8. The feeding bottle as claimed in claim 7, wherein the number of the crystal points with the size of 1-100 μm is not higher than 10/10 g on the bottle body of the feeding bottle.
9. A method of making the baby bottle of any of claims 7~8 comprising the steps of:
s1, dehumidifying and drying, and baking the granular aromatic sulfone composition at 150-170 ℃ for 5-7 h;
s2, molten gel injection molding: melting the dehumidified and dried aromatic sulfone composition at 350-380 ℃, then injecting the molten aromatic sulfone composition into a bottle blank mold of the feeding bottle, and maintaining the pressure to prepare a bottle blank;
s3: and transferring the bottle blank into a milk bottle mold, and blowing high-pressure air for molding to obtain the milk bottle.
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| CN115028837B (en) * | 2022-02-21 | 2023-09-19 | 金发科技股份有限公司 | Polymerization method of aromatic sulfone polymer, aromatic sulfone polymer obtained by polymerization method and application of aromatic sulfone polymer |
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| CN102174199A (en) * | 2011-01-24 | 2011-09-07 | 吉林大学 | Polyether sulfone containing side group as well as preparation method and application thereof in gas separation membrane |
| CN109354686A (en) * | 2018-11-22 | 2019-02-19 | 山东浩然特塑股份有限公司 | A kind of preparation method of polysulfones resinoid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102174199A (en) * | 2011-01-24 | 2011-09-07 | 吉林大学 | Polyether sulfone containing side group as well as preparation method and application thereof in gas separation membrane |
| CN109354686A (en) * | 2018-11-22 | 2019-02-19 | 山东浩然特塑股份有限公司 | A kind of preparation method of polysulfones resinoid |
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