CN110724266A - Ester-terminated sulfone polymer, preparation method and application thereof in wine bottle cap - Google Patents
Ester-terminated sulfone polymer, preparation method and application thereof in wine bottle cap Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Abstract
The invention discloses an ester-terminated sulfone polymer, belonging to the field of special engineering plastics, wherein the sulfone polymer has a repeating unit with a structure shown in formula I:
Description
Technical Field
The invention belongs to the field of special engineering plastics, and relates to an ester-terminated sulfone polymer, a preparation method and application thereof in a wine bottle cap.
Background
The sulfone polymer belongs to special high-temperature-resistant transparent thermoplastic engineering plastic, has outstanding thermal performance, gives the high long-term working temperature to the sulfone polymer, has excellent chemical corrosion resistance and special hot water hydrolysis and superheated steam resistance, can be heated by steam (200 ℃) for more than 10000 times without influencing the performance, has excellent dimensional stability and excellent high-temperature creep resistance, has extremely low smoke and toxic gas emission and good electrical performance, and mainly comprises three types of polysulfone PSU, polyether sulfone PES and polyphenylsulfone PPSU. The development of the last 70 th century has been developed for over 50 years, and with the gradual improvement of the material development, the application range of the material is wider and wider, and the material comprises the fields of food sanitation, medical appliances, small household appliances, aerospace, electronic appliances and the like.
In recent years, in particular, polyphenylsulfone PPSU and polyethersulfone PES have been known for their high mechanical strength, heat resistance and oxidation resistance, hydrolysis resistance, and acid/alkali and solvent corrosion resistance. In the application field of food contact products, because of excellent chemical corrosion resistance, drug water immersion resistance, acid and alkali liquid immersion resistance and cleaning by a cleaning agent, no chemical change is generated; the special characteristics of hot water hydrolysis resistance and superheated steam, the heat resistance temperature is up to 200 ℃, and the repeated high-temperature boiling and steam disinfection can be realized; more importantly, the environment-friendly and environment-friendly composite material does not contain bisphenol A (BPA, environmental hormones and carcinogenic chemical substances disturbing endocrine), conforms to Reach and RoHS rules, is the most ideal and most safe and environment-friendly material which is recommended by the United states, European Union and the like and conforms to infant and food application, has particularly suitable application advantages and prospects, has wide temperature tolerance, can be used in the range of-40-190 ℃, has the retention rate of mechanical performance indexes such as toughness and strength of more than 80 percent, can be used for sterilizing bottles under the condition of high-temperature steam, can be stored for a long time under the condition of extremely low temperature, and can not cause the problems of embrittlement, fracture and the like under the low-temperature environment in winter in the north for a long time; in addition, due to its high transparency and excellent colorability, the prepared products are bright and bright in color, such as baby bottles, coffee machines, cups, non-stick coatings and the like. Therefore, in recent years, the application and development of the water-based paint are more and more extensive in household kitchens and bathrooms.
The wine bottle cap is used as a part of the package of wine commodities, and has two main functions: firstly, the sealing performance is realized, the wine is protected, the bottle cap has the most basic function, and the wine bottle is most easily manufactured by manufacturers; secondly, the appearance is attractive, and the small bottle cap can play a role of drawing dragon dots as an integral part of the package. With the increasing requirement of people on food sanitation, the consideration of plastic on food safety is more and more important, and in the wine drinking industry, the requirement of safety and sanitation must be considered for the selection of the used material of the wine bottle cap. At present, the materials of wine bottle caps used in the market are basically common general plastics, such as PE, PP, TPE, ABS, EVA and the like, although the bottle caps prepared by the materials have various anti-counterfeiting measures, the effect is not good, a large number of counterfeit products still exist in the market, one of the reasons is that the materials are easy to obtain and low in price, the anti-counterfeiting methods are mostly in shape and structure design and are easy to copy, so that the wine bottle caps are easy to copy and counterfeit, certain confusion is brought to the application market, ingredients with unknown food insecurity are probably contained, meanwhile, the general plastics can be used only by adding various modification aids, including toughening agents, plasticizers, lubricants, toner master batches, inorganic and organic fillers and the like, so as to improve the defects of brittleness, fluidity, color and the like of the wine bottle caps, and the like, and the various aids inevitably contain the unknown food insecurity along with the addition of the aids, the risk of food safety and hygiene is also greatly increased.
Disclosure of Invention
Aiming at the defects that the general plastic adopted by the wine bottle cap material in the prior art has food sanitation safety risk, mechanical safety risk and is easy to counterfeit, the invention aims to provide an ester-group-terminated sulfone polymer, a preparation method and application thereof in a wine bottle cap.
In order to achieve the purpose, the invention provides the following technical scheme: an ester-terminated sulfone polymer having a repeating unit of the structure of formula I:
wherein the value range of n is 2-300, and the Ar unit has any one of the following structural formulas:
the sulfone polymer has the transparency of 81-95%, the haze of 0.1-4, the yellowness index of 0.5-5, the melt flow rate of 15-50 g/10min and the content of chlorine end groups of less than 500ppm, and is particularly suitable for preparing food contact products such as wine bottle caps due to high transparency, low haze and solvent resistance.
Preferably, the ester-terminated sulfone polymer is colored with a commercially available high temperature colorant comprising an inorganic pigment or dye, an organic pigment and dye, or a color concentrate thereof, wherein the colorant is required to have a heat resistance temperature of greater than 300 ℃; more preferably, the colorant has a heat resistance temperature of greater than 340 ℃.
Preferably, the colorant comprises a variety of types currently commercially available, such as those available from BASF corporationIn the series of the Chinese patent application,
in the series of the Chinese patent application,
in the series of the Chinese patent application,
in the series of the Chinese patent application,in the series of the Chinese patent application,
series, ARKEMA
And (4) series.
The invention provides a preparation method of the ester group terminated sulfone polymer, which comprises the following steps:
(1) salt forming reaction: under the protection atmosphere, adding a dihydroxy aromatic monomer and a dihalo diphenyl sulfone monomer into a reactor, adding a solvent, stirring and heating until the monomers are dissolved until the solution is transparent, adding a salt-forming agent, then adding a water-carrying agent, continuously stirring and heating until the salt-forming reaction starts, and distilling and discharging the water-carrying agent after the salt-forming reaction is completed;
(2) polymerization reaction: gradually heating to the polymerization temperature to start polymerization reaction, detecting that the viscosity starts to increase, and reducing the polymerization temperature to stop the polymerization reaction after the viscosity increases to a specified range;
(3) end capping reaction: in the later stage of the polymerization reaction, reducing the temperature to 60-90 ℃, adding dimethyl carbonate as a blocking agent, carrying out blocking reaction, continuously reacting for 10-30 min, and stopping stirring and heating;
(4) and (3) post-treatment: slowly pouring the materials into deionized water to cool the materials into white strip-shaped solid, crushing the white strip-shaped solid into powder by a crusher, boiling the powder by the deionized water, filtering the powder, repeatedly boiling and filtering the powder until the filtrate is detected by silver nitrate and does not become turbid, and drying the polymer to constant weight after filtering to obtain the polymer.
In a preferred scheme, in the step (1), the ester group-terminated sulfone polymer comprises PPSU and PES, and is prepared by solution polycondensation;
the dihydroxy aromatic monomer is selected from 4,4 '-dihydroxy diphenyl sulfone or 4,4' -dihydroxy biphenyl;
the dihalodiphenylsulfone monomer is selected from 4,4' -dihalodiphenylsulfone;
the molar ratio of the dihalodiphenyl sulfone monomer to the dihydroxy aromatic monomer is a, a is more than 1 and less than or equal to 1.05, namely the dihalodiphenyl sulfone monomer is excessive.
Preferably, in step (1), the solvent is selected from one or more of diphenyl sulfone, sulfolane, dimethyl sulfone, N-methyl pyrrolidone, dimethyl sulfoxide, N-methyl formamide, N-methyl acetamide and biphenyl benzene sulfinyl.
Preferably, in step (1), the salt forming agent is selected from KOH, NaOH and K2CO3、Na2CO3、KHCO3、NaHCO3One or more of (a).
According to the preferable scheme, in the step (1), xylene is adopted as the water carrying agent, an azeotrope generated by water and xylene generated in the system is blown out to a condensing tube by protective gas and is condensed and dripped to a water separator for layering, xylene on the upper layer reflows to the system, and when the water collection amount is close to a theoretical value, salt formation is proved to be complete, and then the xylene is distilled and discharged.
Preferably, in the step (3), a sulfolane solution of dimethyl carbonate is added as an end-capping agent, and the mass concentration is 5-25%.
Preferably, in step (3), the addition amount of the dimethyl carbonate is greater than or equal to the molar difference between the two monomers.
Preferably, in the step (4), deionized water is used for boiling for 0.5-2 h, water is filtered, and the boiling and filtering operations are repeated for 5-20 times.
The invention also provides the use of said ester-terminated sulfone polymer for the preparation of food-contact hygiene articles, for example comprising wine bottle caps, particularly suitable as wine bottle caps with high alcohol content, such as wine bottle caps, or wine bottle caps with low alcohol content, such as beer bottle caps, wine bottle caps; the sulfone polymer with the ester-terminated end has high transparency, is convenient to realize the function of adding laser etching anti-counterfeiting marks and the like in the material, and plays a role in anti-counterfeiting.
Further, the wine bottle cap made of the ester-group-terminated sulfone polymer comprises the parts of all parts of the wine bottle mouth made of plastics, such as the outer cap of the bottle cap, the upper wine mouth, the lower wine mouth, a check valve, an upper top cap, a connecting cap, an upper cap and a lower cap, a limiting ring, a wine distribution plate, a wine inlet, a threaded connecting cap, a vent hole, a hoop, a circular ring clamping plug and the like. The wine bottle cap prepared from the sulfone polymer has the advantages of delicate and atmospheric appearance, high-efficiency anti-counterfeiting, production by a general injection molding machine and the like, is convenient for users to use and easy to distinguish, can be matched according to needs, and has delicate appearance.
Preferably, the ester-terminated sulfone polymer is used for manufacturing wine bottle caps, and the injection molding process comprises the following steps:
the temperature of the machine table is as follows: 320-390 ℃; temperature of the die: 120E180 ℃; injection molding pressure: 90-120 MPa; injection speed: 5-20 cm3S; cooling time: 5-30 seconds.
The chemical reaction formula involved in the invention is as follows:
(1) salt forming reaction:
HO-Ar-OH+M2CO3→MO-Ar-OM+CO2+H2O
(2) polymerization reaction:
(3) end capping reaction:
wherein M is an alkali metal, including Na and/or K.
The principle of the invention is as follows: when the end group of the polymer molecular chain contains a salt end group (such as-ONa, nucleophilic reagent), methylation reaction can be carried out with added dimethyl carbonate (electrophilic reagent) to form a methyl end group, so that the molecular chain is more stable, the heat resistance is better, the end capping effect is improved, and the purpose of improving the material stability is achieved.
DMC as electrophilic reagent can be methylated with nucleophilic reagent (formula 1) or methoxycarbonylated (formula 2), the reaction mechanism is as follows:
wherein, Nu-Represents a nucleophile.
As can be seen from the above two reaction formulas, the reaction mechanism is as follows: when the reaction temperature is higher than 120 ℃, alkoxy bond breakage occurs, the reaction is a bimolecular process, DMC participates in methylation reaction, and the reaction equation is shown as the formula (1); when the reaction temperature is lower than 90 ℃, acyl-oxygen bond breakage occurs, bimolecular process occurs, DMC participates in methoxycarbonylation reaction, and the reaction equation is shown as the above formula (2). According to the theory of soft and hard acids and bases: the methoxycarbonylation reaction is a hard-hard nucleophilic substitution reaction, and the methylation reaction is a soft-soft nucleophilic substitution reaction, and the two reactions are competitive reactions as can be seen from the above analysis. By varying the reaction conditions (e.g., temperature), the structural nature of the reactants can greatly enhance the selectivity propensity of the methoxycarbonylation reaction or the methylation reaction. The core of the invention is to control the end-capping temperature to be 60-90 ℃, so that the methoxycarbonylation reaction is carried out to obtain the ester-terminated sulfone polymer material.
Compared with the prior art, the invention has the advantages that:
(1) according to the invention, dimethyl carbonate is used as a blocking agent to prepare an ester-group-blocked sulfone polymer, the transparency of the sulfone polymer is 81-95%, the haze is 0.1-4, the yellowness index is 0.5-5, the melt flow rate is 15-50 g/10min, the content of chlorine end groups is less than 500ppm, and the ester-group-blocked sulfone polymer has high transparency, low haze and solvent resistance.
(2) The invention discloses a wine bottle cap made of PPSU or PES, which is not added with a modifier, is almost made of pure resin, overcomes the use defects of the existing material, such as food sanitation safety risk, mechanical safety risk and the like, and accords with the low-carbon, environment-friendly, healthy, sanitary and green life concept and life style which are more and more emphasized and advocated by people.
(3) The invention provides a production process of the wine bottle cap, which is suitable for industrial production, and the wine bottle cap produced by the invention can be recycled after being used as an engineering material to produce engineering parts such as gears, valve plates and the like, becomes a new high-performance material which can be recycled, and avoids the problem of pollution caused by waste or garbage.
Detailed Description
The following examples are further illustrative of the present invention and are not intended to be limiting thereof.
Test criteria or methods for each property:
melt mass flow rate: the detection method according to ISO 1133, wherein the detection conditions are that PPSU adopts 365 ℃/5kg, PES adopts 360 ℃/10kg, and the test unit is g/10 min.
Transparency: according to ASTM D1003-07, plaques having a thickness of 2mm were first injection-molded with a resin and then tested (%) with a transparency tester.
End group chlorine content: the chlorine content was determined by means of ion chromatography.
In the examples of the present invention, unless otherwise specified, the means employed are those conventional in the art, and the reagents employed are commercially available in a conventional manner.
The present invention will be described in detail with reference to the following specific examples:
example 1
This example is a method of preparing an ester-terminated sulfone polymer, comprising the steps of:
(1) salt forming reaction: 93.10g (0.5mol) of 4,4 '-dihydroxybiphenyl and 147.17g (0.5125mol) of 4,4' -dichlorodiphenyl sulfone are sequentially added into a three-neck flask provided with a thermometer, a nitrogen pipe, a condensation water separator and a stirrer according to the mixture ratio in the table 1, 426g of sulfolane solvent is added, the mixture is stirred and heated to 80 ℃ to dissolve the monomers until the solution is transparent, 55.65g of sodium carbonate is added, 80mL of dimethylbenzene is added subsequently, the mixture is heated to 140 ℃ under continuous stirring to start salt forming reaction, azeotrope generated by water and the dimethylbenzene produced in the system is blown out by protective gas into a condensation pipe to be condensed and dripped into the water separator for layering, and the dimethylbenzene on the upper layer reflows into the system again; maintaining the temperature within the range of 200-210 ℃, continuously refluxing for 20 minutes when the collected water amount is close to a theoretical value (9g), observing that water drops fall, proving that the salt formation is complete, and distilling and discharging dimethylbenzene;
(2) polymerization reaction: gradually heating to 230 ℃ to start polymerization reaction, and keeping the temperature for 3 hours until the torque of a stirring motor is unchanged, which indicates that the viscosity of the system is basically constant;
(3) end capping reaction: cooling to 85 ℃, adding a mixed solution of 1.17g (0.013mol) of dimethyl carbonate and 10g of sulfolane, continuously reacting for 30min, and stopping stirring and heating;
(4) and (3) post-treatment: slowly pouring the materials into deionized water to be cooled into white strip-shaped solid, crushing the white strip-shaped solid into powder by using a crusher, boiling the powder for 1 hour by using the deionized water, filtering the water, repeating the process for 10 times until the filtrate is detected by silver nitrate and does not become turbid, so that the byproduct salt in the powder is washed clean, and drying the polymer to constant weight by using a vacuum oven at 120 ℃ after filtering to obtain the PPSU material.
The PPSU was found to have a transparency of 85%, a haze of 0.3, a yellowness index of 0.6, a melt flow rate of 30g/10min and a chlorine end group content of 386 ppm.
The wine bottle cap mold is used for injection molding, and the specific process of a 90-ton machine table is as follows:
the outer cover of the wine bottle is mixed with PPSU granules which are 0.3 percent of titanium pigment 2233 and 0.05 percent
Red K2915, 16 cavities in the mold 1, barrel temperature: 330-340-350-360 ℃; temperature of the die: 120 ℃; injection molding pressure: 110 MPa; injection speed: 80cm3S; cooling time: 10 seconds; the wine bottle cap is formed into a red outer bottle cap by injection molding, and superfluous materials such as flash, pouring gates, edges and corners are cut off or ground off, so that the wine bottle cap is smooth and flat.
Feeding a wine nozzle: using PPSU pure resin transparent particles, 1 mould 8 holes, screw cylinder temperature: 330-340-350-360 ℃; temperature of the die: 140 ℃; injection molding pressure: 115 MPa; injection speed: 60cm3S; cooling time: 18 seconds; the connecting cover is molded into a light yellow transparent threaded connecting cover by injection molding, and redundant materials such as flash, a pouring gate, edges and corners are cut off or ground off, so that the threaded connecting cover is smooth and flat, and the thread has no broken filaments.
Check valve: using PPSU pure resin transparent particles, 1 mould of a mould with 16 holes, and the temperature of a screw cylinder: 330-340-350-360 ℃; temperature of the die: 150 ℃; injection molding pressure: 120 MPa; injection speed: 40cm3S; cooling time: 12 seconds; the connecting cover is molded into a light yellow transparent threaded connecting cover by injection molding, and redundant materials such as flash, a pouring gate, edges and corners are cut off or ground off, so that the threaded connecting cover is smooth and flat, and the thread has no broken filaments.
A wine nozzle is arranged, PPSU pure resin transparent particles are used, 10 holes are formed in a die 1, and the temperature of a screw cylinder is as follows: 330-340-350-360 ℃;temperature of the die: 130 ℃; injection molding pressure: 95 MPa; injection speed: 50cm3S; cooling time: 12 seconds; and (3) performing injection molding to obtain a light yellow transparent wine distribution plate, and cutting or grinding excessive materials such as flash, pouring gates, edges and corners and the like to make the wine distribution plate smooth and flat.
Outer hoop: mixing 0.5% titanium pigment 2233, 0.08% with PPSU granules
Red K2915, mold 1 mold 6 cavity, barrel temperature: 330-340-350-360 ℃; temperature of the die: 150 ℃; injection molding pressure: 115 MPa; injection speed: 90cm3S; cooling time: 15 seconds; the wine bottle cap is formed into a red outer hoop through injection molding, and redundant materials such as flash, pouring gates, edges and corners are cut off or ground off, so that the wine bottle cap is smooth and flat. The clamp is used for fixing the threaded chain connecting cover on the glass wine bottle mouth or the ceramic wine bottle mouth and has a sealing effect.
Taking 100 sets of bottle cap products, sterilizing the bottle cap products for 10min by high-temperature steam at 174 ℃, then packaging the bottle cap products with a glass wine bottle, sealing and storing the bottle cap products for 24 hours in a refrigerator at the temperature of minus 20 ℃, taking out the bottle cap products and placing the bottle cap products to normal temperature without cracking.
Example 2
The method is basically the same as the example 1, 125.135g (0.5mol) of 4,4 '-dihydroxy diphenyl sulfone and 145.877g (0.508mol) of 4,4' -dichloro diphenyl sulfone are sequentially added into a three-neck flask provided with a thermometer, a nitrogen pipe, a condensation water separator and a stirrer according to the mixture ratio in the table 1, 520mL of N-methylpyrrolidone solvent is added, the mixture is stirred and heated to 80 ℃ to dissolve the monomers until the solution is transparent, 55.65g of sodium carbonate is added, then 80mL of xylene is added, the mixture is continuously stirred and heated to 140 ℃ to start salt forming reaction, azeotrope generated by water and xylene produced in the system is blown out to a condensation pipe by protective gas to be condensed and dripped into the water separator to be layered, and xylene on the upper layer reflows to the system again; maintaining the temperature at about 190 ℃, continuously refluxing for 20 minutes when the collected water amount is close to a theoretical value (9g), observing that water drops do not fall, proving that the salt formation is complete, distilling and discharging dimethylbenzene, gradually heating to 195 ℃ to start a polymerization reaction, keeping the temperature for 4-5 hours until the torque of a stirring motor is unchanged, indicating that the viscosity of the system is basically constant, cooling to 80 ℃, adding a mixed solution of 0.72g (0.008mol) of dimethyl carbonate and 5g N-methyl pyrrolidone, and continuously reacting for 30 minutes; stopping stirring and heating, slowly pouring the materials into deionized water to cool the materials into white strip-shaped solid, crushing the white strip-shaped solid into powder by using a crusher, boiling the powder for 1 hour by using the deionized water, filtering the water, repeating the process for 10 times until the filtrate does not become turbid by using silver nitrate detection, washing the by-product salt in the powder to be clean, and drying the polymer to constant weight by using a vacuum oven at 120 ℃ after filtering to obtain the PES material.
PES has a transparency of 85%, a haze of 0.3, a yellowness index of 0.6, a melt flow rate of 30g/10min and a chlorine end group content of 465 ppm.
The wine bottle cap mold is used for injection molding, and the specific process of a 90-ton machine table is as follows:
an outer bottle cap, which is prepared by mixing PES granules with 0.3 percent of titanium pigment 2233 and 0.05 percent of titanium pigment
Blue K7104 LW, die 1, 16 holes, barrel temperature: 330-340-350-360 ℃; temperature of the die: 120 ℃; injection molding pressure: 110 MPa; injection speed: 80cm3S; cooling time: 10 seconds; the wine bottle cap is molded into a blue outer bottle cap by injection molding, and superfluous materials such as flash, pouring gates, edges and corners are cut off or ground off, so that the wine bottle cap is smooth and flat.
The screw thread is connected with the cover: PES pure resin transparent particles, 1 die of a die, 8 holes, a screw cylinder temperature: 330-340-350-360 ℃; temperature of the die: 140 ℃; injection molding pressure: 115 MPa; injection speed: 60cm3S; cooling time: 18 seconds; after injection molding, excess materials such as flash, pouring gates, edges and corners are cut off or ground off, so that the threaded connecting cover is smooth and flat, and the threads have no broken filaments.
Wine distribution plate, PES pure resin transparent particles, die 1, 10 holes, barrel temperature: 330-340-350-360 ℃; temperature of the die: 130 ℃; injection molding pressure: 95 MPa; injection speed: 50cm3S; cooling time: 5 seconds; after injection molding, excess materials such as flash, pouring gate, edges and corners are cut off or ground off, so that the wine distribution plate is smooth and flat。
Outer hoop: PES granules are mixed with 0.5 percent of titanium pigment 2233 and 0.08 percent of titanium pigment
Brown K2711, die 1, 6 holes, barrel temperature: 330-340-350-360 ℃; temperature of the die: 150 ℃; injection molding pressure: 115 MPa; injection speed: 90cm3S; cooling time: 15 seconds; the wine bottle cap is formed into a brown outer hoop through injection molding, and redundant materials such as flash, pouring gates, edges and corners are cut off or ground off, so that the wine bottle cap is smooth and flat. The clamp is used for fixing the threaded chain connecting cover on the glass wine bottle mouth or the ceramic wine bottle mouth and has a sealing effect.
Taking 100 sets of bottle cap products, sterilizing the bottle cap products for 10min by high-temperature steam at 174 ℃, then packaging the bottle cap products with a glass wine bottle, sealing and storing the bottle cap products for 24 hours in a refrigerator at the temperature of minus 20 ℃, taking out the bottle cap products and placing the bottle cap products to normal temperature without cracking.
Example 3
The implementation method is similar to that of the embodiment 2, the used solvent is sulfolane, the polymerization temperature is 230 ℃, the constant temperature time of polymerization is 3 hours, then the temperature is reduced to 85 ℃, the mixed solution of 0.72g (0.008mol) of dimethyl carbonate and 5g of sulfolane is added, and the reaction is continued for 60min, so that the PES material is obtained.
PES had a transparency of 83%, a haze of 0.8, a yellowness index of 0.9, a melt flow rate of 38g/10min and a chlorine end group content of 405 ppm.
The wine bottle cap mold is used for injection molding, and the specific process of a 90-ton machine table is as follows:
the screw thread is connected with the cover: PES pure resin transparent particles, 1 die of a die, 8 holes, a screw cylinder temperature: 330-340-350-360 ℃; temperature of the die: 140 ℃; injection molding pressure: 115 MPa; injection speed: 60cm3S; cooling time: 18 seconds; after injection molding, excess materials such as flash, pouring gates, edges and corners are cut off or ground off, so that the threaded connecting cover is smooth and flat, and the threads have no broken filaments. Finally, the prepared threaded connecting cover and the glass plug are heated to 250 ℃, and the threaded connecting cover and the glass plug can be nested together, and the whole bottle cap can be tightly held after cooling.
Example 4
The method is basically the same as that of the example 1, and before the injection molding of the wine bottle cap, the obtained PPSU material is mixed with 2.3 percent of titanium white R2233 and 0.05 percent of BASF inorganic pigment
Carrying out melt extrusion granulation on Blue K7104 LW by using a double-screw extruder to obtain Blue plastic particles; then carrying out injection molding; a blue cap of wine bottle was obtained.
The above-mentioned embodiments only express the centralized implementation mode of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. An ester-terminated sulfone polymer, comprising a repeating unit having a structure according to formula I:
wherein the value range of n is 2-300, and the Ar unit has any one of the following structural formulas:
the sulfone polymer has the transparency of 81-95%, the haze of 0.1-4, the yellowness index of 0.5-5, the melt flow rate of 15-50 g/10min and the content of chlorine end groups of less than 500ppm, and is particularly suitable for preparing food contact products such as wine bottle caps due to high transparency, low haze and solvent resistance.
2. The ester-terminated sulfone polymer of claim 1, wherein the ester-terminated sulfone polymer is colored with a commercially available high temperature colorant comprising an inorganic pigment or dye, an organic pigment and dye, or a color concentrate thereof, wherein the colorant has a heat resistance temperature of greater than 300 ℃.
3. The method of preparing an ester group terminated sulfone polymer according to claim 1 or 2, characterized by comprising the steps of:
(1) salt forming reaction: under the protection atmosphere, adding a dihydroxy aromatic monomer and a dihalo diphenyl sulfone monomer into a reactor, adding a solvent, stirring and heating until the monomers are dissolved until the solution is transparent, adding a salt-forming agent, then adding a water-carrying agent, continuously stirring and heating until the salt-forming reaction starts, and distilling and discharging the water-carrying agent after the salt-forming reaction is completed;
the reaction process of the salt forming reaction is as follows:
HO-Ar-OH+M2CO3→MO-Ar-OM+CO2+H2O
(2) polymerization reaction: gradually heating to the polymerization temperature to start polymerization reaction, detecting that the viscosity starts to increase, and reducing the polymerization temperature to stop the polymerization reaction after the viscosity increases to a specified range;
the reaction process of the polymerization reaction:
(3) end capping reaction: in the later stage of the polymerization reaction, reducing the temperature to 60-90 ℃, adding dimethyl carbonate as a blocking agent, carrying out blocking reaction, continuously reacting for 10-30 min, and stopping stirring and heating;
the reaction process of the end capping reaction:
(4) and (3) post-treatment: slowly pouring the materials into deionized water to cool the materials into white strip-shaped solid, crushing the white strip-shaped solid into powder by a crusher, boiling the powder by the deionized water, filtering the powder, repeatedly boiling and filtering the powder until the filtrate is detected by silver nitrate and does not become turbid, and drying the polymer to constant weight after filtering to obtain the polymer.
4. The method for preparing an ester group-terminated sulfone polymer according to claim 3, wherein in the step (1), the ester group-terminated sulfone polymer comprises PPSU and PES, which is prepared by solution polycondensation;
the dihydroxy aromatic monomer is selected from 4,4 '-dihydroxy diphenyl sulfone or 4,4' -dihydroxy biphenyl;
the dihalodiphenylsulfone monomer is selected from 4,4' -dihalodiphenylsulfone;
the molar ratio of the dihalodiphenyl sulfone monomer to the dihydroxy aromatic monomer is a, a is more than 1 and less than or equal to 1.05, namely the dihalodiphenyl sulfone monomer is excessive.
5. The method for preparing an ester group-terminated sulfone polymer according to claim 3, wherein in the step (1), the salt-forming agent is selected from KOH, NaOH, K2CO3、Na2CO3、KHCO3、NaHCO3One or more of (a).
6. The method for producing an ester-terminated sulfone polymer according to claim 3, wherein in the step (3), a sulfolane solution of dimethyl carbonate is added as an end-capping agent at a mass concentration of 5 to 25%.
7. The method for preparing an ester group-terminated sulfone polymer according to claim 3, wherein the dimethyl carbonate is added in an amount of more than or equal to the molar difference between the two monomers in the step (3).
8. The method for preparing an ester group-terminated sulfone polymer according to claim 3, wherein in the step (4), the mixture is boiled with deionized water for 0.5 to 2 hours, filtered to remove water, and the boiling and filtering operations are repeated for 5 to 20 times.
9. Use of the ester-terminated sulfone polymer according to claim 1 or 2 for the preparation of food contact hygiene articles, such as wine bottle caps, particularly suitable for high alcohol content wine bottle caps such as wine bottle caps, or low alcohol content wine bottle caps such as beer bottle caps and red wine bottle caps, wherein the ester-terminated sulfone polymer has high transparency, facilitates the realization of functions such as laser engraving anti-counterfeiting marks and the like added in the material, and achieves the anti-counterfeiting purpose.
10. Use of an ester terminated sulfone polymer according to claim 9, wherein the ester terminated sulfone polymer is used for making wine bottle caps by injection molding process comprising:
the temperature of the machine table is as follows: 320-390 ℃; temperature of the die: 120-180 ℃; injection molding pressure: 90-120 MPa; injection speed: 5-20 cm3S; cooling time: 5-30 seconds.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4200728A (en) * | 1977-07-14 | 1980-04-29 | Basf Aktiengesellschaft | Manufacture of polyethers from bis-(4-hydroxyphenyl)-sulfone and bis-(4-chlorophenyl)-sulfone in N-methylpyrrolidone using an alkali metal carbonate as catalysts |
| US4721771A (en) * | 1983-03-31 | 1988-01-26 | Raychem Corporation | Preparation of aromatic polymers |
| US20130072629A1 (en) * | 2011-09-20 | 2013-03-21 | Ticona Llc | Low Halogen Content Disulfide Washed Polyarylene Sulfide |
| CN103626992A (en) * | 2013-11-27 | 2014-03-12 | 江门市优巨新材料有限公司 | Industrialized synthesis method of high-heat-stability blocked polyether sulfone resin |
| CN107371367A (en) * | 2015-01-23 | 2017-11-21 | 巴斯夫欧洲公司 | The desalination of polyaryl ether from melt polymerization process |
| CN109734913A (en) * | 2019-01-21 | 2019-05-10 | 江西金海新能源科技有限公司 | Bromoalkane blocks sulfone polymer and preparation method thereof |
| CN110128656A (en) * | 2019-05-27 | 2019-08-16 | 江西金海新能源科技有限公司 | A kind of low chlorine content sealing end sulfone polymer and its preparation method and application |
-
2019
- 2019-11-05 CN CN201911071161.9A patent/CN110724266A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4200728A (en) * | 1977-07-14 | 1980-04-29 | Basf Aktiengesellschaft | Manufacture of polyethers from bis-(4-hydroxyphenyl)-sulfone and bis-(4-chlorophenyl)-sulfone in N-methylpyrrolidone using an alkali metal carbonate as catalysts |
| US4721771A (en) * | 1983-03-31 | 1988-01-26 | Raychem Corporation | Preparation of aromatic polymers |
| US20130072629A1 (en) * | 2011-09-20 | 2013-03-21 | Ticona Llc | Low Halogen Content Disulfide Washed Polyarylene Sulfide |
| CN103626992A (en) * | 2013-11-27 | 2014-03-12 | 江门市优巨新材料有限公司 | Industrialized synthesis method of high-heat-stability blocked polyether sulfone resin |
| CN107371367A (en) * | 2015-01-23 | 2017-11-21 | 巴斯夫欧洲公司 | The desalination of polyaryl ether from melt polymerization process |
| CN109734913A (en) * | 2019-01-21 | 2019-05-10 | 江西金海新能源科技有限公司 | Bromoalkane blocks sulfone polymer and preparation method thereof |
| CN110128656A (en) * | 2019-05-27 | 2019-08-16 | 江西金海新能源科技有限公司 | A kind of low chlorine content sealing end sulfone polymer and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| 沈玉龙，曹文华编著: "《绿色化学》", 31 May 2009, 中国环境科学出版社 * |
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