CN109705250B - Microspherical ionomer with cross-linked structure and preparation method and application thereof - Google Patents
Microspherical ionomer with cross-linked structure and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the field of high polymer materials, and discloses a microspherical ionomer with a cross-linked structure, a preparation method and application thereof. The ionomer contains a structural unit A represented by formula (1), a structural unit B represented by formula (2), and a crosslinked structure provided by a crosslinking agent, wherein M is1And M2Each independently is a metal cation or C1‑C20R is H or methyl. Also disclosed are methods of making ionomers and ionomers made by the methods, the methods comprising: the method comprises the following steps of (1) contacting maleic anhydride, a monomer B providing a structural unit B shown in a formula (2) and a crosslinking agent for reaction; the resulting product is reacted by mixing with a base and a saturated monohydric alcohol. In addition, the invention also discloses application of the ionomer as a nucleating agent in modification of PET. The ionomer obtained by the invention has good nucleation effect on PET, and the preparation process is simple, green and environment-friendly.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a microspherical ionomer with a cross-linked structure and a preparation method and application thereof.
Background
The ionic polymer is ionomer or ionomer, and is a polymer material with a small amount of ionic groups on a high molecular chain, wherein the molar content of the ionic groups is not more than 15%. The ionomer is a perfect combination of inorganic ions and organic molecules, and due to the introduction of ionic groups, the molecules in the ionomer have special interaction which is not existed in general polymers, such as ion-ion interaction; ion pairs interact with ion pairs; the ion interacts with the dipole; hydrogen bonding interactions, and the like. These specific interactions give ionomers many unique properties and have important applications in polymer modification, functional materials, etc.
In addition, the research on the preparation and application of the polymer microspheres is a hotspot in the field of functional polymer materials, and the polymer microspheres from nano-scale to micron-scale have the special properties of large specific surface area, strong adsorbability, large coacervation effect and strong surface reaction capability, and can be widely applied to many high and new technical fields.
Yan philosophy, Qiang xi Huai, et al, in the text of "preparation of fatty alcohol monoester sodium salt of styrene/maleic anhydride copolymer and its surface activity" ((daily chemical industry, 2012, 42 (2): 97-100)), the higher fatty alcohol monoester sodium salt of styrene/maleic anhydride copolymer was prepared using 1, 4-dioxane as solvent and p-toluenesulfonic acid as catalyst.
According to the research on the synthesis and pH sensitivity of SMA ethylation products in Leirin, Sunwei and the like (applied chemical engineering, 2008, 37 (5): 498-501), ethyl ester of styrene/maleic anhydride copolymer is prepared by using butanone as a solvent and triethylamine as a catalyst, and a reaction mixture is precipitated in petroleum ether, filtered, dried, dissolved again in tetrahydrofuran, precipitated in the petroleum ether again, filtered and dried to obtain a product.
However, the nucleation effect of the polymer prepared by the above method on PET still has room for improvement.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a microspherical ionomer with a cross-linked structure and a preparation method and application thereof.
In order to achieve the above object, according to one aspect of the present invention, there is provided a microspheroidal ionomer having a crosslinked structure, the ionomer comprising a structural unit A represented by formula (1), a structural unit B represented by formula (2), and a crosslinked structure provided by a crosslinking agent,
wherein M is1And M2Each independently is a metal cation or C1-C20R is H or methyl.
In a second aspect, the present invention provides a method of making an ionomer, the method comprising:
(1) in an organic solvent, in the presence of an initiator, contacting maleic anhydride, a monomer B providing a structural unit B shown in a formula (2) and a crosslinking agent for reaction;
(2) mixing the product obtained in the step (1) with alkali and saturated monohydric alcohol for reaction.
In a third aspect, the invention provides an ionomer prepared by the method of the second aspect.
In a fourth aspect, the present invention provides the use of the ionomer as a nucleating agent for the modification of polyethylene terephthalate.
The ionomer (or ionomer microsphere) obtained by the method has a cross-linking and microsphere structure, a good nucleation effect on PET, a simple preparation process, and green and environment-friendly effects, and the ionomer microsphere can be obtained by simple separation operation (without using a precipitant) after the reaction is finished.
Drawings
FIG. 1 is a graph of the infrared spectrum of an ionomer synthesized according to one embodiment of the present invention (example 1);
FIG. 2 is a scanning electron micrograph of an ionomer synthesized according to one embodiment of the present invention (example 1);
FIG. 3 is an infrared spectrum of the styrene/maleic acid sodium salt ionomer synthesized in comparative example 1;
FIG. 4 is a scanning electron micrograph of the styrene/maleic acid sodium salt ionomer synthesized in comparative example 1.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The microspherical ionomer having a crosslinked structure provided by the present invention comprises a structural unit A represented by formula (1), a structural unit B represented by formula (2), and a crosslinked structure provided by a crosslinking agent,
wherein M is1And M2Each independently is a metal cation or C1-C20(e.g. C)1、C2、C4、C6、 C8、C10、C12、C15、C20Or any value therebetween), R is H or methyl (metal cations are introduced into at least a part of the structural units a in the ionomer).
Wherein the metal cation may be various common metal ions, for example, Li+、Na+、 K+、Ca2+、Mg2+、Ba2+Or Zn2+。
In a preferred embodiment of the present invention, the molar ratio between the structural unit A and the structural unit B is 100: 100-.
In a further preferred embodiment of the present invention, the molar ratio of structural units A to crosslinked structures is 100: 1-40, more preferably 100: 10-30.
In the present invention, according to a preferred embodiment, the molar amount of metal cations in the ionomer is 10-100% (e.g. 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 100% or any value in between) of the total molar amount of structural units a in the ionomer. The degree of crosslinking of the ionomer is preferably greater than or equal to 65% (e.g., 65%, 70%, 75%, 80%, 85%, 90%, or any value therebetween). The ionomer is microspherical and has an average particle size of 150-2000nm (e.g., 150nm, 250nm, 350nm, 450nm, 550nm, 650nm, 750nm, 850nm, 950nm, 1050nm, 1150nm, 1250nm, 1350nm, 1450nm, 1550nm, 1650nm, 1750nm, 1850nm, 2000nm, or any value therebetween). In the present invention, the molar content of the metal cation is obtained by X-ray fluorescence spectroscopic analysis. The degree of crosslinking is indicative of the gel content, as measured by the solvent extraction method. The average particle size is characterized by a number average particle size and is determined by means of a scanning electron microscope.
In the present invention, the crosslinking agent may be any of various conventional vinyl-containing monomers having two or more functionalities and capable of radical polymerization. Preferably, the crosslinking agent is divinylbenzene and/or an acrylate crosslinking agent containing at least two acrylate groups of the formula: -O-C (O) -C (R') ═ CH2R' is H or C1-C4Alkyl (e.g., methyl).
More preferably, the crosslinking agent is selected from divinylbenzene, propylene glycol-based di (meth) acrylates (such as 1, 3-propylene glycol dimethacrylate, 1, 2-propylene glycol dimethacrylate, 1, 3-propylene glycol diacrylate, 1, 2-propylene glycol diacrylate), ethylene glycol-based di (meth) acrylates (ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate), trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, ethylene glycol dimethacrylate, propylene glycol-based di (meth) acrylates, ethylene glycol-based di (meth) acrylates, propylene glycol-based di (meth) acrylates, ethylene, At least one of diethylene glycol diacrylate phthalate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and ethoxylated multifunctional acrylate.
The present invention provides a method of making an ionomer comprising:
(1) in an organic solvent, in the presence of an initiator, contacting maleic anhydride, a monomer B providing a structural unit B shown in a formula (2) and a crosslinking agent for reaction;
(2) mixing the product obtained in the step (1) with alkali and saturated monohydric alcohol for reaction.
In the step (1) of the present invention, the amount of each raw material used is not particularly limited, and preferably, the amount of the monomer B used is 50 to 150mol, more preferably 75 to 100mol, relative to 100mol of maleic anhydride. As can be appreciated by those skilled in the art, maleic anhydride is a substance that provides the structural unit A represented by the formula (1). The monomer B is a substance which provides the structural unit B represented by the formula (2), and may be alpha-methylstyrene or styrene.
Preferably, the crosslinking agent is used in an amount of 1 to 40mol, more preferably 10 to 20mol, and further preferably 15 to 20mol, relative to 100mol of maleic anhydride.
Preferably, the organic solvent is used in an amount of 50 to 150L, more preferably 75 to 100L, relative to 100mol of maleic anhydride.
Preferably, the initiator is used in an amount of 0.05 to 10mol, more preferably 1 to 1.5mol, relative to 100mol of maleic anhydride.
In step (1) of the present invention, the organic solvent may be any solvent commonly used in solution polymerization, for example, the organic solvent includes organic acid alkyl ester, that is, organic acid alkyl ester, or a mixture of organic acid alkyl ester and alkane, or a mixture of organic acid alkyl ester and aromatic hydrocarbon. Wherein the organic acid alkyl esters include, but are not limited to: at least one of methyl formate, ethyl formate, propyl formate, butyl formate, isobutyl formate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, pentyl acetate, isopentyl acetate, benzyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, isobutyl butyrate, isoamyl isovalerate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isoamyl benzoate, methyl phenylacetate, and ethyl phenylacetate. Such alkanes include, but are not limited to: n-hexane and/or n-heptane. The aromatic hydrocarbons include, but are not limited to: at least one of benzene, toluene and xylene.
In step (1) of the present invention, the initiator may be a reagent commonly used in the art for initiating the polymerization reaction of maleic anhydride and α -methylstyrene (or styrene), and may be a thermal decomposition type initiator. Preferably, the initiator is at least one selected from the group consisting of dibenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, lauroyl peroxide, t-butyl peroxybenzoate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, azobisisobutyronitrile, and azobisisoheptonitrile.
In step (1) of the present invention, the specific type of the crosslinking agent is as described above, and is not described herein again.
In step (1) of the present invention, the reaction conditions are not particularly limited, but preferably such that the degree of crosslinking of the ionomer is 65% or more. More preferably, in step (1), the reaction conditions include: an inert atmosphere at a temperature of 50 to 90 ℃ (more preferably 60 to 70 ℃) for 3 to 15 hours (more preferably 5 to 12 hours).
According to the process of the invention, in step (2), the base is used in such a way that the molar amount of metal cations in the ionomer is in a certain range, preferably in the above range, as a percentage of the total molar amount of structural units provided by the maleic anhydride in the ionomer. The amount of the base may be conventionally selected, and preferably, the base is used in an amount of 5 to 100mol (e.g., 5mol, 10mol, 20mol, 50mol, 80mol, 100mol or any value therebetween) relative to 100mol of maleic anhydride.
In step (2) of the present invention, the base may be a basic substance (a basic substance capable of providing a metal cation (as described above)) conventionally used in the art. Preferably, the base is selected from the group consisting of metal hydroxides, metal acetates and metal alkoxides (in particular C)1-C10Alkoxide of (a). The metal may be a monovalent metal or a divalent metal, such as a group IA, IIA and/or IIB metal (particularly lithium, sodium, potassium, calcium, barium, zinc and/or magnesium). More preferably, the base is selected from at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, zinc hydroxide, magnesium hydroxide, lithium acetate, sodium acetate, potassium acetate, calcium acetate, barium acetate, zinc acetate, sodium methoxide, sodium ethoxide, sodium propoxide, sodium isopropoxide, sodium tert-butoxide, sodium tert-pentoxide, sodium isooctanolate, potassium methoxide, lithium methoxide, zinc methoxide, magnesium methoxide, calcium methoxide, sodium ethoxide, potassium ethoxide, barium ethoxide, calcium ethoxide, lithium ethoxide and potassium tert-butoxide.
According to the process of the invention, in step (2), the use of said saturated monoalcohol allows the introduction of ester groups into the ionomer. The amount of the saturated monohydric alcohol is not particularly limited, but the amount of the saturated monohydric alcohol is preferably 100-20000mol with respect to 100mol of the maleic anhydride.
According to the present invention, the saturated monohydric alcohol may be selected conventionally in the art, as long as it can undergo an esterification reaction with the polymer, and may be a straight-chain alkanol, a branched-chain alkanol, or a cycloalkane alcohol. Preferably, the saturated monohydric alcohol is C1-C20(e.g. C)1、C2、C4、C6、C8、C10、C12、 C15、C20Or any value therebetween) of a saturated monohydric alcohol. More preferably, the saturated monoalcohol is selected from at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, 2-methylbutanol, 3-methylbutanol, n-hexanol, cyclohexanol, n-heptanol, n-octanol, n-nonanol, isononanol, n-decanol, 2-propylheptanol, n-dodecanol, n-tetradecanol, n-hexadecanol, and n-octadecanol.
In step (2) of the present invention, the reaction may be carried out under conventional conditions, for example, the conditions of the reaction include: the temperature is 20-150 deg.C (preferably 30-100 deg.C), and the time is 0.5-8h (preferably 0.5-6 h).
In the invention, the ionomer can be obtained from the product obtained in the step (2) through a simple solid-liquid separation step without introducing other reagents (or solvents). The liquid phase obtained by the solid-liquid separation can be reused in the step (2). The solid-liquid separation method may be a solid-liquid separation method such as filtration or centrifugation. The resulting solid phase may be further dried to obtain an ionomer product.
The invention also provides an ionomer prepared by the method. The ionomer prepared by the invention has a cross-linked structure and is microspherical, and the metal cation content, the molar ratio among all structural units, the cross-linking degree, the average particle diameter and the like of the ionomer are as described above, and are not described again.
In addition, the invention also provides application of the ionomer as a nucleating agent in modification of PET. In actual use, the ionomers of the present invention can be melt blended with PET. The ionomer may be used in an amount of 0.5 to 5g with respect to 100g of PET. The temperature of the melt blending may be 250-300 ℃. The melt blending time may be 5-8 min. And extruding and granulating the product after melt blending to obtain the modified PET product.
The present invention will be described in detail below by way of examples. In the following examples and comparative examples, the vacuum drying conditions were: the vacuum degree is-0.095 MPa at 100 ℃ and the time is 8 h.
Example 1
This example illustrates the crosslinked microsphere ionomer and the preparation method thereof.
(1) 100g of maleic anhydride, 118g of alpha-methylstyrene, 26g of divinylbenzene, and 2g of azobisisobutyronitrile were dissolved in 1000mL of isoamyl acetate and reacted at 70 ℃ for 5 hours under a nitrogen atmosphere. And centrifuging the reacted system for 30 minutes by a centrifuge under the condition of 5000rad/min to obtain the crosslinked alpha-methylstyrene/maleic anhydride polymer microspheres, washing and purifying by normal hexane, and drying in vacuum.
Meanwhile, the supernatant after centrifugation was analyzed by LC-MC to measure the amount of the remaining monomer therein, and the amount of the monomer (or the amount of the crosslinking agent) actually involved in the reaction was subtracted from the amount of the monomer (or the amount of the crosslinking agent) charged, thereby obtaining the molar ratio among the structural unit a, the structural unit B and the crosslinked structure, as specifically shown in table 1 below (the same applies hereinafter).
(2) 50g of crosslinked alpha-methylstyrene/maleic anhydride polymer microspheres and 4.4g of sodium hydroxide (0.55 mol of base per mol of maleic anhydride) were added to 200mL of methanol, and reacted at 64.7 ℃ for 5 hours. And centrifuging the reacted system for 30 minutes by a centrifuge under the condition of 5000rad/min, adding 300mL of methanol into the solid, stirring and washing the solid, centrifuging the solid for 30 minutes by the centrifuge under the condition of 5000rad/min, and drying the solid in vacuum to obtain the crosslinked alpha-methylstyrene/sodium methyl maleate ionomer microsphere (marked as C1).
Example 2
This example illustrates the ionomeric microspheres of the present invention and methods of making the same.
(1) 100g of maleic anhydride, 118g of alpha-methylstyrene, 26g of divinylbenzene, and 2g of azobisisobutyronitrile were dissolved in 1000mL of isoamyl acetate and reacted at 70 ℃ for 5 hours under a nitrogen atmosphere. Centrifuging the reacted system for 30 minutes by a centrifuge under the condition of 5000rad/min to obtain crosslinked alpha-methylstyrene/maleic anhydride polymer microspheres, washing and purifying by methanol, and drying in vacuum;
(2) 50g of crosslinked alpha-methylstyrene/maleic anhydride polymer microspheres and 2.2g of sodium hydroxide (0.28 mol of base per mol of maleic anhydride) were added to 200mL of ethanol, and reacted at 78 ℃ for 4 hours. And centrifuging the reacted system for 30 minutes by a centrifuge under the condition of 5000rad/min, adding 300mL of ethanol into the solid, stirring and washing the solid, centrifuging the solid for 30 minutes by the centrifuge under the condition of 5000rad/min, and drying the solid in vacuum to obtain the crosslinked alpha-methylstyrene/maleic acid ethyl ester sodium salt ionomer microsphere (marked as C2).
Example 3
This example illustrates the ionomeric microspheres of the present invention and methods of making the same.
(1) 100g of maleic anhydride, 118g of alpha-methylstyrene, 26g of divinylbenzene, and 2g of azobisisobutyronitrile were dissolved in 1000mL of isoamyl acetate and reacted at 70 ℃ for 5 hours under a nitrogen atmosphere. Centrifuging the reacted system for 30 minutes by a centrifuge under the condition of 5000rad/min to obtain crosslinked alpha-methylstyrene/maleic anhydride polymer microspheres, washing and purifying by methanol, and drying in vacuum;
(2) 50g of crosslinked alpha-methylstyrene/maleic anhydride polymer microspheres and 6.2g of potassium hydroxide (0.55 mol of base per mol of maleic anhydride) were added to 300mL of isopropanol and reacted at 80 ℃ for 4 hours. And centrifuging the reacted system for 30 minutes by a centrifuge under the condition of 5000rad/min, adding 300mL of isopropanol into the solid, stirring and washing the solid, centrifuging the solid for 30 minutes by the centrifuge under the condition of 5000rad/min, and drying the solid in vacuum to obtain the crosslinked alpha-methylstyrene/isopropyl maleate potassium salt ionomer microsphere (marked as C3).
Example 4
This example illustrates the ionomeric microspheres of the present invention and methods of making the same.
(1) 130g of maleic anhydride, 118g of alpha-methylstyrene, 26g of divinylbenzene and 2.5g of azobisisobutyronitrile were dissolved in 1000mL of isoamyl acetate and reacted at 60 ℃ for 12 hours under a nitrogen atmosphere. Centrifuging the reacted system for 30 minutes by a centrifuge under the condition of 5000rad/min to obtain crosslinked alpha-methylstyrene/maleic anhydride polymer microspheres, washing and purifying by methanol, and drying in vacuum;
(2) 50g of crosslinked alpha-methylstyrene/maleic anhydride polymer microspheres and 6.6g of sodium hydroxide (0.83 mol of base per mol of maleic anhydride) were added to 300mL of 2-propylheptanol, and reacted at 90 ℃ for 4 hours. Centrifuging the reacted system by a centrifuge under the condition of 5000rad/min for 30 minutes, adding 300mL of ethanol into the solid, stirring and washing the solid, centrifuging the solid by the centrifuge under the condition of 5000rad/min for 30 minutes, adding 500mL of ethanol into the solid, stirring and washing the solid, centrifuging the solid by the centrifuge under the condition of 5000rad/min for 30 minutes, and drying the solid in vacuum to obtain the crosslinked alpha-methylstyrene/maleic acid C10Alcohol ester sodium salt ionomer microspheres (denoted as C4).
Example 5
This example illustrates the ionomeric microspheres of the present invention and methods of making the same.
(1) 130g of maleic anhydride, 104g of styrene, 26g of divinylbenzene and 2.5g of azobisisobutyronitrile were dissolved in 1000mL of isoamyl acetate and reacted at 60 ℃ for 10 hours under a nitrogen atmosphere. Centrifuging the reacted system for 30 minutes by a centrifuge under the condition of 5000rad/min to obtain crosslinked alpha-methylstyrene/maleic anhydride polymer microspheres, washing and purifying by methanol, and drying in vacuum;
(2) 50g of crosslinked alpha-methylstyrene/maleic anhydride polymer microspheres and 14.3g of sodium ethoxide (0.98 mol of base per mol of maleic anhydride) were added to 200mL of ethanol, and reacted at 78 ℃ for 4 hours. And centrifuging the reacted system for 30 minutes by a centrifuge under the condition of 5000rad/min, adding 400mL of ethanol into the solid, stirring and washing the solid, centrifuging the solid for 30 minutes by the centrifuge under the condition of 5000rad/min, adding 500mL of ethanol into the solid, stirring and washing the solid, centrifuging the solid for 30 minutes by the centrifuge under the condition of 5000rad/min, and drying the solid in vacuum to obtain the crosslinked alpha-methylstyrene/maleic acid ethyl ester sodium salt ionomer microsphere (marked as C5).
Example 6
Ionomeric microspheres were prepared according to the method of example 1, except that divinylbenzene was used in an amount of 10g, giving ionomeric microspheres C6.
Comparative example 1
(1) 100g of maleic anhydride, 118g of alpha-methylstyrene, 26g of divinylbenzene, and 2g of azobisisobutyronitrile were dissolved in 1000mL of isoamyl acetate and reacted at 70 ℃ for 5 hours under a nitrogen atmosphere. Centrifuging the reacted system for 30 minutes by a centrifuge under the condition of 5000rad/min to obtain crosslinked alpha-methylstyrene/maleic anhydride polymer microspheres, washing and purifying by normal hexane, and drying in vacuum;
(2) 15.2g of sodium hydroxide was dissolved in 350mL of water, and 50g of crosslinked α -methylstyrene/maleic anhydride polymer microspheres were added to an aqueous sodium hydroxide solution (1.9 mol of a base per mol of maleic anhydride) and reacted at 100 ℃ for 3 hours. And centrifuging the reacted system for 30 minutes by a centrifuge under the condition of 5000rad/min, adding 400mL of water into the solid, stirring and washing the solid, centrifuging and separating for 30 minutes by the centrifuge under the condition of 5000rad/min, adding 500mL of methanol into the solid, stirring and washing the solid, centrifuging and separating for 30 minutes by the centrifuge under the condition of 5000rad/min, and drying the solid in vacuum to obtain the crosslinked alpha-methylstyrene/sodium maleate ionomer microsphere (marked as C-D1).
Comparative example 2
(1) 98g of maleic anhydride and 118g of alpha-methylstyrene are weighed and placed in a three-neck flask, 2g of azobisisobutyronitrile is added as an initiator, a proper amount of toluene is added as a reaction solvent, and the mixture is reacted for 5 hours at 70 ℃ under the atmosphere of nitrogen. After the reaction, carrying out suction filtration on the polymer, washing a filter cake for 3 times by using methylbenzene, and carrying out vacuum drying to obtain an alpha-methylstyrene/maleic anhydride polymer;
(2) 20.2g of an α -methylstyrene/maleic anhydride polymer was dissolved in 200mL of 1, 4-dioxane, and 4g of a saturated aqueous solution of sodium hydroxide was added to the solution to react at room temperature for 3 hours. After the reaction, the ionomer solid was obtained by filtration. The solids were dried under vacuum to give an alpha-methylstyrene/maleic acid sodium salt ionomer (designated as polymer C-D2).
Test example 1
(1) The polymers obtained in example 1 and comparative example 1 were subjected to IR spectroscopy, as shown in FIGS. 1 and 3, respectively, and the successful synthesis of ionomers was observed from the IR spectroscopy, and ionomers were successfully obtained in examples 2 to 6, which were similar to those of example 1.
(2) The ionomer microspheres prepared in the above examples and comparative examples were subjected to X-ray fluorescence spectroscopy to determine the metal cation content in the ionomer, i.e., the percentage of the total molar amount of the structural units a in the ionomer.
(3) The ionomers prepared in the above examples and comparative examples were subjected to scanning electron microscopy, wherein the scanning electron microscopy images of the ionomers obtained in example 1 and comparative example 1 are shown in fig. 2 and 4, respectively, and it can be seen that the ionomers of the present invention are microspherical; whereas the ionomer obtained in comparative example 2 does not have a microsphere structure. The average particle size and the degree of crosslinking of the ionomer microspheres (particle size test method: 500 microspheres were selected from an electron micrograph, the diameters thereof were measured, and the average particle size of the microspheres was calculated by a mathematical average method; degree of crosslinking test method: 2-3 g of polymer microspheres (w1) were weighed, wrapped with medium-speed qualitative filter paper, put into a soxhlet extractor, extracted with tetrahydrofuran for 24 hours, dried and weighed w2, and the degree of crosslinking was calculated by w2/w 1) were measured as shown in table 1 below, and the like.
TABLE 1
(4) The ionomer microspheres prepared in the above examples and comparative examples were respectively and uniformly mixed with PET, the addition amount of the ionomer microspheres was 1 wt% of the mass of PET, and then melt-blended at 280 ℃ for 8 minutes, and extruded and pelletized to obtain modified polyethylene terephthalate. The modified PET was subjected to Differential Scanning Calorimetry (DSC) tests and the results are shown in table 2 using unmodified PET as a control.
TABLE 2
| Item | Cold crystallization Peak/deg.C | Melting crystallization Peak/deg.C | Half peak width/deg.C | ΔH/J·g-1 |
| PET | - | 151.7 | 23.3 | -11.3 |
| C1 modified PET | 116.7 | 214.1 | 7.2 | -39.4 |
| C2 modified PET | 117.5 | 212.4 | 6.5 | -38.7 |
| C3 modified PET | 119.2 | 210.5 | 7.1 | -38.1 |
| C4 modified PET | 118.4 | 213.7 | 6.2 | -39.8 |
| C5 modified PET | 116.0 | 214.7 | 6.0 | -39.7 |
| C6 modified PET | 130.0 | 197.0 | 8.9 | -35.5 |
| C-D1 modified PET | 127.3 | 204.8 | 5.3 | -36.7 |
| C-D2 modified PET | 134.7 | 195.2 | 10.2 | -35.0 |
As can be seen from the results in Table 2, the ionomer prepared by the method of the present invention has a significantly better nucleation effect on PET than the comparative example, and can significantly increase the crystallization temperature of PET and accelerate the crystallization rate; in addition, compared with the non-crosslinked alpha-methylstyrene/maleic acid sodium salt ionomer without a microsphere structure, the polyethylene terephthalate/polyethylene terephthalate copolymer has a better nucleating effect on PET. Moreover, due to the introduction of the ester group, the compatibility of the crosslinked ionomer microsphere and PET is increased, and compared with the ionomer microsphere without the ester group, the crosslinked ionomer microsphere has a better nucleating effect on PET.
Further, as can be seen from comparison of example 1 with example 6, controlling the amount of the crosslinking agent in the preferred range enables to obtain a more excellent nucleating effect.
Test example 2
In the test example, PET was purchased from China petrochemical certified chemical fiber, and the intrinsic viscosity was 0.7 dl/g; the nitrogen-phosphorus type halogen-free flame retardant (HT202A) is purchased from Jinan Taxing Fine chemical Co., Ltd; lubricant (PET100) was purchased from bluegrass inc; glass fibers (or fiberglass or GF) were purchased from zhejiang ganglite group ltd; the processing aid antioxidant was purchased from Ciba specialty Chemicals. The method comprises the following specific steps:
weighing 100 parts by weight of PET, 1.5 parts by weight of ionomer microspheres, 0.2 part by weight of processing aid (antioxidant 1010 and antioxidant 168 with the weight ratio of 1: 1), 8 parts by weight of flame retardant and 0.04 part by weight of lubricant, putting into a high-speed stirrer, uniformly stirring, and extruding at the temperature of 230-segment temperature, 245-segment temperature, 255-segment temperature, 260-segment temperature, by using WP ZSK25 double screws; adding glass fiber into a double-screw feeding port; adding the nitrogen-phosphorus type halogen-free flame retardant (HT202A) through lateral feeding, extruding, cooling, granulating, drying (100 ℃, 8h), and injecting into a standard sample wafer (the mold temperature is 60 ℃) by a Haitian 125 injection machine at the temperature of 230-:
a standard sample strip with the size of 250 mm (length) multiplied by 25 mm (width) multiplied by 10 mm (thickness) is obtained by injection of a 300 g injection machine (manufactured by Ningbo Haitian company) and the tensile strength and the elongation at break of the standard sample strip are measured by a GB/T1040-1992 plastic tensile property test method;
a standard sample strip with the size of 80 mm (length) multiplied by 10 mm (width) multiplied by 4 mm (thickness) is obtained by injection of a 300 g injection machine (manufactured by Ningbo Haitian company), and the bending strength and the bending modulus of the standard sample strip are measured by a GB/T9341-2008 plastic bending performance test method;
injecting by a 300 g injection machine (manufactured by Ningbo Haitian company) to obtain a standard sample strip with the size of 80 mm (length) multiplied by 10 mm (width) multiplied by 4 mm (thickness) and the gap of 2mm, and measuring the impact strength of the simply supported beam gap of the standard sample strip by using a measuring method of GB/T1043-93 plastic cantilever beam impact strength;
deformation conditions are as follows: two injection-molded sample squares (60 mm. times.60 mm. times.2 mm) were taken, one of them was placed in an oven at 120 ℃ for 3 hours, and the other was placed at normal temperature, and the deformation of the sample was observed.
The results show that the ionomer of the invention can ensure that the obtained plastic product has the tensile strength within the range of 120-145MPa, the elongation at break of about 2 percent, the bending strength within the range of 140-180MPa, the bending modulus within the range of 6-10GPa and the notch impact strength of a simple beam within the range of 5-10kJ/m2Within this range, no significant deformation was observed after 3 hours in an oven at 120 ℃.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (23)
1. A microspheroidal ionomer having a crosslinked structure, which comprises a structural unit A represented by the formula (1), a structural unit B represented by the formula (2) and a crosslinked structure provided by a crosslinking agent,
wherein M is1And M2Each independently is a metal cation or C1-C20R is H or methyl; the crosslinking degree of the ionomer is more than or equal to 65 percent;
the method for testing the crosslinking degree comprises the following steps: weighing 2-3 g of ionomer microspheres, recording the weight as w1, wrapping the microspheres by using medium-speed qualitative filter paper, putting the microspheres into a Soxhlet extractor, extracting the microspheres for 24 hours by using tetrahydrofuran, drying and weighing w2 on the ionomer, and calculating the crosslinking degree according to w2/w 1.
2. The ionomer of claim 1, wherein the molar ratio between structural unit a, structural unit B, and crosslinked structure is 100: 100-120: 1-40.
3. The ionomer of claim 2, wherein the molar ratio between structural unit a, structural unit B, and the crosslinked structure is 100: 100-105: 10-30.
4. The ionomer of claim 1, wherein the molar amount of metal cations in the ionomer is from 10 to 100% of the total molar amount of structural units a in the ionomer; the average particle size of the ionomer is 150-2000 nm.
5. The ionomer of claim 1, wherein the crosslinker is divinylbenzene and/or an acrylate crosslinker comprising at least two acrylate groups of the formula: -O-C (O) -C (R') ═ CH2R' is H or C1-C4Alkyl group of (1).
6. The ionomer of claim 1, wherein the crosslinker is selected from at least one of divinylbenzene, propylene glycol diacrylate, propylene glycol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, diethylene glycol diacrylate phthalate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and ethoxylated multifunctional acrylates.
7. The ionomer of claim 6, wherein the crosslinker is polyethylene glycol diacrylate and/or polyethylene glycol dimethacrylate.
8. A method of making a microspheroidal ionomer, comprising:
(1) in an organic solvent, in the presence of an initiator, contacting maleic anhydride, a monomer B providing a structural unit B shown in a formula (2) and a crosslinking agent for reaction;
(2) mixing the product obtained in the step (1) with alkali and saturated monohydric alcohol for reaction;
in the step (1), the reaction condition ensures that the crosslinking degree of the ionomer is more than or equal to 65 percent;
the method for testing the crosslinking degree comprises the following steps: weighing 2-3 g of ionomer microspheres, recording the weight as w1, wrapping the microspheres by using medium-speed qualitative filter paper, putting the microspheres into a Soxhlet extractor, extracting the microspheres for 24 hours by using tetrahydrofuran, drying and weighing w2 on the ionomer, and calculating the crosslinking degree according to w2/w 1.
9. The process according to claim 8, wherein the monomer B is used in an amount of 50 to 150mol with respect to 100mol of maleic anhydride; the dosage of the cross-linking agent is 1-40 mol; the dosage of the organic solvent is 50-150L; the dosage of the initiator is 0.05-10 mol; the dosage of the alkali is 5-100 mol; the amount of the saturated monohydric alcohol is 100-.
10. The process according to claim 9, wherein the monomer B is used in an amount of 75 to 100mol with respect to 100mol of maleic anhydride.
11. The method according to claim 9 or 10, wherein the crosslinking agent is used in an amount of 10 to 20mol with respect to 100mol of maleic anhydride.
12. The method according to claim 9 or 10, wherein the organic solvent is used in an amount of 75 to 100L with respect to 100mol of maleic anhydride.
13. The process according to claim 9 or 10, wherein the initiator is used in an amount of 1 to 1.5mol with respect to 100mol of maleic anhydride.
14. The method according to claim 9, wherein the monomer B is used in an amount of 75 to 100mol, the crosslinking agent is used in an amount of 10 to 20mol, the organic solvent is used in an amount of 75 to 100L, and the initiator is used in an amount of 1 to 1.5mol, relative to 100mol of maleic anhydride.
15. The method of any of claims 8-10 and 14, wherein the organic solvent comprises an organic acid alkyl ester;
and/or the initiator is selected from at least one of dibenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, azobisisobutyronitrile and azobisisoheptonitrile;
and/or the crosslinking agent is divinyl benzene and/or an acrylate crosslinking agent containing at least two acrylate groups, and the acrylate groups have the structural formula: -O-C (O) -C (R') ═ CH2R' is H or C1-C4Alkyl groups of (a);
and/or, the alkali is selected from at least one of metal hydroxide, metal acetate and metal alkoxide;
and/or, the saturated monohydric alcohol is selected from C1-C20A saturated monohydric alcohol of (1).
16. The method according to claim 15, wherein the crosslinking agent is selected from at least one of divinylbenzene, propylene glycol diacrylate, propylene glycol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, diethylene glycol diacrylate phthalate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and ethoxylated multifunctional acrylates.
17. The method of claim 16, wherein the crosslinking agent is polyethylene glycol diacrylate and/or polyethylene glycol dimethacrylate.
18. The process according to claim 15, wherein the base is selected from at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, zinc hydroxide, magnesium hydroxide, lithium acetate, sodium acetate, potassium acetate, calcium acetate, barium acetate, zinc acetate, sodium methoxide, sodium ethoxide, sodium propoxide, sodium isopropoxide, sodium tert-butoxide, sodium tert-pentoxide, sodium isooctanolate, potassium methoxide, lithium methoxide, zinc methoxide, magnesium methoxide, calcium methoxide, potassium ethoxide, barium ethoxide, calcium ethoxide, lithium ethoxide, and potassium tert-butoxide.
19. The method of claim 15, wherein the saturated monoalcohol is selected from at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, 2-methylbutanol, 3-methylbutanol, n-hexanol, cyclohexanol, n-heptanol, n-octanol, n-nonanol, isononanol, n-decanol, 2-propylheptanol, n-dodecanol, n-tetradecanol, n-hexadecanol, and n-octadecanol.
20. The method of claim 8, wherein in step (1), the reaction conditions comprise: inert atmosphere at 50-90 deg.C for 3-15 h.
21. The method of claim 8 or 20, wherein in step (2), the reaction conditions comprise: the temperature is 20-150 ℃ and the time is 0.5-8 h.
22. An ionomer produced by the process of any one of claims 8-21.
23. Use of the ionomer of any one of claims 1-7 and 22 as a nucleating agent for the modification of polyethylene terephthalate.
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| CN201711016388.4A CN109705250B (en) | 2017-10-25 | 2017-10-25 | Microspherical ionomer with cross-linked structure and preparation method and application thereof |
| JP2020523424A JP7154291B2 (en) | 2017-10-25 | 2018-10-25 | Microspherical ionomer having crosslinked structure, its production method, its use, and its production system |
| US16/758,839 US11965089B2 (en) | 2017-10-25 | 2018-10-25 | Microspheric ionomer having cross-linked structure, preparation method therefor, applications thereof, and preparation system thereof |
| TW107137774A TWI785136B (en) | 2017-10-25 | 2018-10-25 | Microspherical ionomer with crosslinked structure, preparation method, application and preparation system thereof |
| PCT/CN2018/111825 WO2019080891A1 (en) | 2017-10-25 | 2018-10-25 | Microspheric ionomer having cross-linking structure, preparation method therefor, applications thereof, and preparation system thereof |
| EP18871366.3A EP3702384A4 (en) | 2017-10-25 | 2018-10-25 | Microspheric ionomer having cross-linking structure, preparation method therefor, applications thereof, and preparation system thereof |
| KR1020207014615A KR102522818B1 (en) | 2017-10-25 | 2018-10-25 | Microspherical ionomer with a cross-linked structure, its preparation method, its use and production system |
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