CN109705539B - Composition containing polyethylene terephthalate and method for preparing blended plastics - Google Patents
Composition containing polyethylene terephthalate and method for preparing blended plastics Download PDFInfo
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- CN109705539B CN109705539B CN201711009721.9A CN201711009721A CN109705539B CN 109705539 B CN109705539 B CN 109705539B CN 201711009721 A CN201711009721 A CN 201711009721A CN 109705539 B CN109705539 B CN 109705539B
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Abstract
The invention relates to the field of high polymer materials, and discloses a composition containing polyethylene glycol terephthalate and a method for preparing blended plastics. The polyethylene terephthalate-containing composition contains polyethylene terephthalate and a microspherical ionomer with a cross-linked structure, wherein the ionomer has a structural unit A provided by maleic anhydride, a structural unit B provided by a monomer M and a cross-linked structure provided by a cross-linking agent, the monomer M has a structure shown in a formula X, and in the formula X, R is H or methyl. The invention also discloses a method for preparing the polyethylene terephthalate blending plastic, which comprises the steps of carrying out melt extrusion and cooling granulation on the composition. By using the ionomer, the engineering plastic prepared from the composition is not easy to deform, has high dimensional stability, and is particularly beneficial to improving the production efficiency and the product percent of pass.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a composition containing polyethylene terephthalate and a method for preparing blended plastics.
Background
Polyethylene terephthalate (PET) is a multipurpose polymer material, is prepared by polycondensation, has mature technology, wide raw materials and relatively low price, can be used for preparing fibers and hollow packaging bottles, and can also be used for engineering plastics. When used as engineering plastics, the material is required to have high strength, and when processed, especially injection molding, the material is required to complete crystallization relatively quickly so as to prevent warping and maintain the dimensional stability of products. Because PET belongs to semi-crystalline materials due to the structural limitation of PET, the crystallization speed is slow, if the temperature reduction speed is too fast in the forming process, the chain segment is easily frozen when the material system is supercooled and crystallization does not occur or is very little crystallized, and the material can slowly crystallize in the later use process to generate internal stress to cause the warping of the product. The method for solving the problems is that the temperature of the mould is set to be 120 ℃ during injection, the temperature is the temperature for cold crystallization of the material, and the material is polycrystalline as much as possible during the injection molding process; secondly, a substance or an auxiliary agent capable of promoting the crystallization of the material is added into the system. In the former method, the mold is heated to 120 ℃, and there are many disadvantages in the operation process: firstly, energy is consumed, a heating device is required to be equipped to maintain the temperature of the die; secondly, such high temperatures are also a great challenge for equipment and operators, increasing the possibility of personal burns; furthermore, this will increase the production cost and is also environmentally friendly.
In the current method for preparing PET engineering plastics, a method for adding glass fiber (glass fiber) or carbon fiber or other minerals and the like is adopted in the aspect of reinforcement, and a method for adding nucleating agents is adopted in the aspect of promoting crystallization. During the polymerization, the monomer, catalyst and stabilizer are subjected to ester exchange and polycondensation, and the layered silicate material is mixed into suspension and added into a polycondensation system to obtain PET resin, so as to obtain a PET composite material, such as CN1183434A, and the treatment of the layered silicate is complicated. CN1136577A adopts the technical scheme that a nucleating agent nylon is added into PET, epoxy resin is used as a toughening and chain-extending agent, then glass fiber treated by water-soluble epoxy resin is subjected to composite melt extrusion, and the nylon is used as the nucleating agent to cause the viscosity of the blend to be increased and the extrusion to be difficult. CN1238356A is a direct toughening PET by using self-made maleic anhydride grafted POE. CN106366452A is a preparation method of PP/PET microfiber reinforced blend, mainly providing a method for blending polypropylene (PP) and PET; CN106467655A provides a halogen-free flame-retardant long glass fiber reinforced PET composite material and a preparation method thereof.
However, the engineering plastics obtained by the existing method can generate internal stress to deform after being prepared into products, and the dimensional stability is poor.
Disclosure of Invention
The invention aims to overcome the problem of easy deformation in the prior art and provide a composition containing polyethylene terephthalate and a method for preparing blended plastics.
In order to achieve the above object, in one aspect, the present invention provides a polyethylene terephthalate-containing composition, which contains polyethylene terephthalate and a nucleating agent, wherein the nucleating agent is a microspherical ionomer having a cross-linked structure, the ionomer has a structural unit a provided by maleic anhydride, a structural unit B provided by a monomer M, and a cross-linked structure provided by a cross-linking agent, and the monomer M has a structure represented by formula X:
in the formula X, R is H or methyl;
the dissolution of the ionomer in acetone with the weight 5 times that of the ionomer at 50 ℃ for 30min is less than or equal to 10 percent by weight; the molar amount of metal cations in the ionomer is 10-100% of the total molar amount of structural units a provided by maleic anhydride in the ionomer; the ionomer has a crosslinking degree of more than or equal to 60%, is microspherical and has an average particle size of 150-2000 nm.
The invention also provides a method for preparing the polyethylene terephthalate blending plastic, which comprises the steps of carrying out melt extrusion and cooling granulation on the composition.
By using the ionomer, the engineering plastic prepared from the composition is not easy to deform, has high dimensional stability, and is particularly beneficial to improving the production efficiency and the product percent of pass.
Drawings
FIG. 1 is a graph of the infrared spectrum of an ionomer synthesized according to one embodiment of the present invention (preparation example 1);
FIG. 2 is a scanning electron micrograph of an ionomer synthesized according to one embodiment of the present invention (preparation example 1);
FIG. 3 is a scanning electron micrograph of an ionomer synthesized according to one embodiment of the present invention (preparation example 1) after solvent treatment;
FIG. 4 is a scanning electron micrograph of a synthetic ionomer of comparative example 1;
FIG. 5 is a scanning electron micrograph of a solvent-treated ionomer from which comparative example 1 was prepared;
fig. 6 shows the deformation of the samples, wherein fig. 6A-C show the deformation of the samples prepared in example 1, comparative example 5 and comparative example 6, respectively, in which the left side is the sample piece placed at normal temperature and the right side is the sample piece after high temperature treatment.
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 polyethylene terephthalate-containing composition provided by the invention contains polyethylene terephthalate and a nucleating agent, and is characterized in that the nucleating agent is a microspherical ionomer with a cross-linked structure, the ionomer has a structural unit A provided by maleic anhydride, a structural unit B provided by a monomer M and a cross-linked structure provided by the cross-linking agent, and the structure of the monomer M is shown as a formula X:
in the formula X, R is H or methyl;
the dissolution of the ionomer in acetone with the weight 5 times that of the ionomer at 50 ℃ for 30min is less than or equal to 10 percent by weight; the molar amount of metal cations in the ionomer is 10-100% of the total molar amount of structural units a provided by maleic anhydride in the ionomer; the ionomer has a crosslinking degree of more than or equal to 60%, is microspherical and has an average particle size of 150-2000 nm.
The ionomers used in the present invention have less than or equal to 10 wt.% of their solubles in 5 times the weight of acetone at 50 ℃ for 30min (e.g., 1 wt.%, 2 wt.%, 2.5 wt.%, 4 wt.%, 5.5 wt.%, 6.5 wt.%, 7.5 wt.%, 8.5 wt.%)10 wt%, or any value therebetween), solvent resistance is strong. 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%, 85%, 90%, 95%, 100% or any value in between) of the total molar amount of structural units a provided by maleic anhydride in the ionomer. The degree of crosslinking of the ionomer is preferably greater than or equal to 60% (e.g., greater than or equal to 60%, 65%, 70%, 75%, 80%, 85%, 90%, or any value therebetween). The ionomer 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). The ionomer has a shell cross-linked structure, and thus has better solvent resistance and thermal stability. In the present invention, the metal cation may be various common metal ions, for example, Li+、Na+、K+、Ca2+、Mg2+、Ba2+Or Zn2+The molar content is obtained by X-ray fluorescence spectrum 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.
According to a preferred embodiment of the present invention, the method for preparing the microspheroidal ionomer having a crosslinked structure used in the present invention comprises:
(1) in an organic solvent, in the presence of a first part of initiator, maleic anhydride is contacted with a first part of monomer M to react, and then a solution containing a crosslinking agent is introduced to continue the reaction, wherein the solution containing the crosslinking agent contains the crosslinking agent, an optional second part of monomer M and an optional second part of initiator;
(2) in the presence of water, the product obtained in the step (1) is contacted with alkali for salinization (or hydrolysis).
The ratio of the amount of maleic anhydride to the amount of monomer M may be conventionally selected, but in a preferred embodiment of the present invention, the total amount of the first portion of monomer M and the second portion of monomer M is 50 to 150mol, more preferably 75 to 100mol, relative to 100mol of maleic anhydride. It will be appreciated by those skilled in the art that monomer M is alpha-methylstyrene or styrene.
In the step (1), the monomer M may be fed in one step (i.e., the amount of the second portion of the monomer M may be zero), or may be fed in two portions (i.e., the first portion of the monomer M and the second portion of the monomer M). According to a more preferred embodiment of the present invention, the molar ratio between the second portion of monomers M and the first portion of monomers M is between 0 and 100: 100 (e.g.0, 1: 100, 5: 100, 15: 100, 25: 100, 30: 100, 45: 100, 50: 100, 60: 100, 70: 100, 80: 100, 90: 100, 100: 100 or any value between the aforementioned values).
In the method for preparing the ionomer, the amount of the organic solvent may be conventionally selected as long as a medium is provided for the reaction of step (1), and preferably, the amount of the organic solvent is 50 to 150L with respect to 100mol of maleic anhydride.
In the step (1), 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 the method for preparing the ionomer, the amount of the initiator is not particularly limited, and preferably, the total amount of the first portion of the initiator and the second portion of the initiator is 0.05 to 10mol, more preferably 0.8 to 1.5mol, with respect to 100mol of maleic anhydride.
In the step (1), the initiator may be fed in one step (i.e. the amount of the second part of initiator may be zero), or may be fed in two parts (i.e. the first part of initiator and the second part of initiator). According to a more preferred embodiment of the present invention, the molar ratio between the second portion of initiator and the first portion of initiator is between 0 and 100: 100 (e.g.0, 1: 100, 5: 100, 15: 100, 25: 100, 30: 100, 45: 100, 50: 100, 60: 100, 70: 100, 80: 100, 90: 100, 100: 100 or any value in between the above).
In the step (1), 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 the method for preparing the ionomer, the amount of the crosslinking agent is not particularly limited, and preferably, the amount of the crosslinking agent is 1 to 40mol, more preferably 10 to 20mol, with respect to 100mol of maleic anhydride.
In the method for preparing the ionomer, the crosslinking agent may be various common vinyl-containing monomers having two or more functionalities capable of undergoing 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.
In the step (1), the maleic anhydride is contacted with the monomer M to react, namely the maleic anhydride and the monomer M are not completely reacted, and only part of the maleic anhydride and the monomer M are subjected to polymerization reaction in the presence of an initiator. The conditions for the contact reaction of maleic anhydride and the monomer M may be conventional conditions as long as the maleic anhydride and the monomer M are controlled to be polymerized only partially, and preferably, the conditions for the contact reaction of maleic anhydride and the monomer M include: an inert atmosphere at a temperature of 50 to 90 ℃ (more preferably 60 to 70 ℃) for 0.5 to 4 hours (more preferably 0.5 to 2 hours).
In the step (1), after the maleic anhydride is contacted with the monomer M for partial reaction, a solution containing a cross-linking agent is introduced for continuous reaction, so that a shell cross-linked structure is particularly favorably formed. The conditions for continuing the reaction may be conventional conditions as long as each substrate is allowed to participate in the reaction as much as possible, and preferably, the conditions for continuing the reaction include: the temperature is 50-90 ℃ and the time is 2-15 h. According to a more preferred embodiment of the invention, the introduction of the solution containing the crosslinking agent continues the reaction in such a way that: dropwise adding the solution containing the cross-linking agent into the product obtained in the step (1) within 1-3h at 50-90 ℃ (further preferably 60-70 ℃), and continuing the heat preservation reaction for 1-4 h.
In the method for preparing the ionomer, there is no particular requirement on the kind and content of the solvent in the solution containing the crosslinking agent as long as the solute therein is sufficiently dissolved, and generally, the kind of the solvent in the solution containing the crosslinking agent may be selected to be the same as that of the organic solvent (i.e., including the organic acid alkyl ester as described above), and the content of the crosslinking agent in the solution containing the crosslinking agent may be 0.5 to 3 mol/L.
In step (2), the base is used so that the molar amount of metal cations in the ionomer as a percentage of the total molar amount of structural units provided by maleic anhydride in the ionomer is within a certain range, preferably within the above range. The amount of the base may be conventionally selected, and preferably, the base is used in an amount of 10 to 200mol (e.g., 10mol, 50mol, 100mol, 150mol, 190mol, 200mol or any value therebetween) relative to 100mol of maleic anhydride. The base is preferably used in the form of an aqueous solution, the concentration of which is preferably from 1 to 30% by weight.
In the step (2), the base may be a basic substance (a basic substance capable of providing a metal cation (as described above)) conventionally used in the art as long as a part of the carboxyl hydrogen in the polymer obtained in the step (1) after hydrolysis can be replaced with a metal. Preferably, the base is selected from a hydroxide of a metal and/or an acetate of a metal. 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, and zinc acetate.
In step (2), the salination may be carried out under conventional conditions, for example, the salination conditions include: the temperature is 20-100 deg.C (preferably 30-100 deg.C), and the time is 0.5-8h (preferably 0.5-6 h).
In the step (2), the product (suspension) obtained in the step (1) can be subjected to post-treatment (separation, washing and drying) and then reacted with alkali. The washing may employ a conventional washing solvent, for example, at least one of n-hexane, isohexane, cyclohexane, n-heptane, n-octane, isooctane, methanol, ethanol, n-propanol, isopropanol, diethyl ether, isopropyl ether, and methyl tert-butyl ether. The result of this salination is an ionomer-containing dispersion which is subjected to a further separation treatment to give the ionomer product, for example in the following manner: centrifuging, washing with water, washing with an organic solvent (the washing solvent as described above, i.e., at least one of n-hexane, isohexane, cyclohexane, n-heptane, n-octane, isooctane, methanol, ethanol, n-propanol, isopropanol, diethyl ether, isopropyl ether, and methyl tert-butyl ether can be used), centrifuging, and drying (e.g., vacuum drying).
The inventors of the present invention have found in their studies that the ionomer of the present invention can be efficiently obtained by directly reacting the suspension obtained in the step (1) with a base for salinization without performing a step of removing an organic solvent. Thus, according to a preferred embodiment of the invention, in step (2) of the invention, the product obtained in step (1) can be reacted directly with a base (one-pot process), so that after salification a mixed ionomer-containing system is obtained which is subjected to a further separation treatment to obtain the ionomer product, for example in the following manner: standing for layering, recycling the organic phase, centrifuging the heavy phase, washing with water, centrifuging, and drying (such as vacuum drying) to obtain the ionomer. The optimized method adopts a one-pot process, and the product post-treatment only needs one-time liquid-liquid separation, solid-liquid separation, washing and drying, so that the time consumption of a single batch is effectively shortened, the process flow is simplified, unit equipment is reduced, and the energy consumption is effectively reduced; the process only needs one organic solvent as a reaction medium, the solvent can be recycled only through layering and drying operations, a special water distribution device is not needed, layering can be achieved in the reactor, the solvent can be recycled without distillation and purification, energy is saved, consumption is reduced, and pollution of the organic solvent to the environment can be effectively reduced.
In the present invention, the content of the nucleating agent may be conventionally selected, and preferably, the content of the nucleating agent is 0.5 to 4 parts by weight, preferably 0.5 to 3 parts by weight, with respect to 100 parts by weight of polyethylene terephthalate.
The object of the present invention can be achieved by polyethylene terephthalate known in the art, and particularly, the effect of achieving the object of the present invention is more excellent when the intrinsic viscosity of polyethylene terephthalate is 0.6 to 1 dl/g.
According to a preferred embodiment, the composition further comprises at least one of a flame retardant, a lubricant, a toughening agent and other processing aids.
More preferably, the content of the flame retardant is 5 to 22 parts by weight, preferably 6 to 10 parts by weight, relative to 100 parts by weight of polyethylene terephthalate. The purpose of adding the flame retardant is to retard or prevent the combustion of the polyethylene terephthalate-containing composition. Accordingly, various flame retardants known to those skilled in the art to achieve the above objectives are suitable for use in the present invention. The flame retardant may preferably be, for example, tris (2, 3-dichloropropyl) phosphate, triphenyl phosphate, melamine pyrophosphate, decabromodiphenylethane, decabromodiphenyl ether, antimony trioxide, or the like.
More preferably, the lubricant is contained in an amount of 0.03 to 0.3 parts by weight, preferably 0.08 to 0.2 parts by weight, relative to 100 parts by weight of polyethylene terephthalate. The lubricant can improve the lubricity of the composition while maintaining the performance of the composition, and may be a common lubricant such as polyethylene glycol (with a number average molecular weight of 6000-.
More preferably, the content of the toughening agent is 10 to 55 parts by weight, preferably 15 to 35 parts by weight, relative to 100 parts by weight of polyethylene terephthalate. The toughening agent may be a substance conventionally used in the art for improving the mechanical strength of the blended plastic, for example, glass fiber and/or carbon fiber. The toughening agent is glass fiber in view of controlling cost as much as possible.
More preferably, the other processing aid is contained in an amount of 0.1 to 1 part by weight with respect to 100 parts by weight of polyethylene terephthalate. Such other processing aids can impart more varied performance properties to the composition and can be selected by those skilled in the art, for example, such other processing aids can include antioxidants, light stabilizers, acid scavengers, and the like, all of which are conventional in the art. The antioxidant is typically a mixture of a hindered phenol type antioxidant (primary antioxidant) and a phosphite type antioxidant (secondary antioxidant). The hindered phenol antioxidant may be, for example, pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (e.g., antioxidant 1010), octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (e.g., antioxidant 1076), or the like. The phosphite antioxidant may be, for example, tris (2, 4-di-t-butylphenyl) phosphite (e.g., antioxidant 168). In the invention, the antioxidant 1010 and the antioxidant 168 are further preferably mixed to be used as the antioxidant of the invention, and when the antioxidant and the antioxidant are mixed in a ratio of 1-3: 1, the antioxidant effect is better.
The invention also provides a method for preparing the polyethylene terephthalate blending plastic, which is characterized by comprising the steps of carrying out melt extrusion and cooling granulation on the composition. In other words, the method comprises obtaining an ionomer according to the aforementioned method for preparing an ionomer, and then mixing polyethylene terephthalate and the ionomer to perform melt extrusion and cooling granulation. The temperature of the melt extrusion can be 230-260 ℃, for example, the melt extrusion can be carried out at the temperature of 230-245-255-260 ℃ in each section.
The process is typically carried out in a twin screw extruder and the toughening agent (glass fibers) is added during the extrusion process, typically through the extruder glass fiber port. The timing and manner of addition of other ingredients (e.g., lubricants, antioxidants, flame retardants) that may be included in the composition can be made with reference to the prior art. Preferably, the flame retardant is added during extrusion, and more preferably the flame retardant is added laterally during extrusion.
The process may also comprise drying and shaping the product after cooling granulation, generally by injection molding, in order to obtain a blended plastic product. Specific methods of drying and shaping are well known to those skilled in the art and will not be described further herein.
The present invention will be described in detail below by way of examples. In the following examples, PET was purchased from China petrochemical characterized chemical fiber and had an intrinsic viscosity of 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.
In the following preparation examples and preparation comparative examples, the vacuum drying conditions were as follows: the vacuum degree is-0.095 MPa at 100 ℃ and the time is 8 h.
Preparation of example 1
This preparation example is intended to illustrate the use of the inventive microspheroidal ionomers (or ionomer microspheres) having a crosslinked structure and the method of making the same.
(1) Dissolving 1000g of maleic anhydride, 1180g of alpha-methylstyrene and 20g of azobisisobutyronitrile into 8L of isoamyl acetate, and reacting for 1 hour at 70 ℃ in a nitrogen atmosphere;
(2) 260g of divinylbenzene is dissolved in 2L of isoamyl acetate to form a second solution, the second solution is dropwise added into the reaction system in the step (1) for 2 hours, and after the dropwise addition is finished, the reaction system is continuously subjected to heat preservation reaction for 3 hours;
(3) after the reaction, 3500g (14 wt%) of an aqueous sodium hydroxide solution was added thereto, and the mixture was reacted at 80 ℃ for 3 hours. Standing and layering the reacted system, centrifuging and separating the heavy phase for 20 minutes by a centrifuge at 5000rad/min, adding 4L of water into the solid, stirring and washing the solid, centrifuging and separating for 20 minutes by the centrifuge at 5000rad/min, and drying the solid in vacuum to obtain the shell layer crosslinked alpha-methylstyrene/sodium maleate ionomer microsphere (marked as C1), wherein a scanning electron microscope image of the microsphere is shown in figure 2, and C1 can be seen as dispersed microspheres.
(4) And (3) centrifuging the system reacted in the step (2) 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 methanol, and drying in vacuum. 3500g (10 wt%) of an aqueous sodium hydroxide solution was further added thereto, and the reaction was carried out at 80 ℃ 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 shell-crosslinked alpha-methylstyrene/sodium maleate ionomer microsphere (marked as C1-1).
(5) 10.00g of shell crosslinked alpha-methylstyrene/sodium maleate ionomer microsphere C1 was weighed into 50g of acetone and stirred at 50 ℃ for 30 min. The system was centrifuged at 5000rad/min for 30 minutes in a centrifuge, dried under vacuum and weighed to give 9.38g polymer and 0.62g eluate. Fig. 3 shows a scanning electron micrograph of ionomer microspheres after solvent treatment. As can be seen by comparing fig. 2 and 3, the morphology of the ionomeric microspheres was less altered by the solvent treatment.
Preparation of example 2
This preparation example is intended to illustrate the ionomeric microspheres useful in the present invention and the method of making the same.
(1) Dissolving 1000g of maleic anhydride, 900g of alpha-methylstyrene and 20g of azobisisobutyronitrile into 7L of isoamyl acetate, and reacting for 2 hours at 70 ℃ in a nitrogen atmosphere;
(2) dissolving 200g of alpha-methyl styrene and 260g of divinylbenzene in 3L of isoamyl acetate to obtain a second solution, dropwise adding the second solution into the reaction system obtained in the step (1) for 3 hours, and after dropwise adding is finished, keeping the temperature of the reaction system for reaction for 3 hours;
(3) after the reaction, 4000g (20 wt%) of an aqueous sodium acetate solution was added thereto, and the reaction was carried out at 100 ℃ for 4 hours. Standing and layering the reacted system, centrifuging and separating the heavy phase for 20 minutes by a centrifuge under the condition of 5000rad/min, adding 4L of water into the solid, stirring and washing the solid, centrifuging and separating for 20 minutes by the centrifuge under the condition of 5000rad/min, and drying the solid in vacuum to obtain shell crosslinked alpha-methylstyrene/sodium maleate ionomer microspheres (marked as C2);
(4) 10.00g of shell crosslinked alpha-methylstyrene/sodium maleate ionomer microspheres were weighed into 50g of acetone and stirred at 50 ℃ for 30 min. The system was centrifuged at 5000rad/min for 30 minutes in a centrifuge, dried under vacuum and weighed to give 9.44g of polymer and 0.56g of eluate. Similar to C1, the morphology of the microspheres changed less before and after solvent treatment.
Preparation of example 3
This preparation example is intended to illustrate the ionomeric microspheres useful in the present invention and the method of making the same.
(1) Dissolving 1000g of maleic anhydride, 1020g of alpha-methylstyrene and 15g of azobisisobutyronitrile into 8L of isoamyl acetate, and reacting at 70 ℃ for 0.5 hour in a nitrogen atmosphere;
(2) 260g of divinylbenzene and 5g of azobisisobutyronitrile are dissolved in 2L of isoamyl acetate to form a second solution, the second solution is dropwise added into the reaction system in the step (1) for 2 hours, and after the dropwise addition is finished, the reaction system is continuously subjected to heat preservation reaction for 4 hours;
(3) after the reaction, 9000g (20 wt%) of an aqueous solution of zinc acetate was added and the mixture was reacted at 100 ℃ for 7 hours. Standing and layering the reacted system, centrifuging and separating a heavy phase for 20 minutes by a centrifuge under the condition of 5000rad/min, adding 4L of water into the solid, stirring and washing the solid, centrifuging and separating for 20 minutes by the centrifuge under the condition of 5000rad/min, and drying the solid in vacuum to obtain shell crosslinked alpha-methylstyrene/zinc maleate ionomer microspheres (marked as C3);
(4) 10.00g of shell crosslinked alpha-methylstyrene/zinc maleate salt ionomer microspheres were weighed into 50g of acetone and stirred at 50 ℃ for 30 min. The system was centrifuged at 5000rad/min for 30 minutes in a centrifuge, dried under vacuum and weighed to give 9.74g of polymer and 0.26g of eluate. Similar to C1, the morphology of the microspheres changed less before and after solvent treatment.
Preparation of example 4
This preparation example is intended to illustrate the ionomeric microspheres useful in the present invention and the method of making the same.
(1) Dissolving 1000g of maleic anhydride, 910g of alpha-methylstyrene and 20g of azobisisobutyronitrile into 7L of isoamyl acetate, and reacting for 1 hour at 70 ℃ in a nitrogen atmosphere;
(2) dissolving 200g of alpha-methyl styrene and 260g of divinylbenzene in 3L of isoamyl acetate to obtain a second solution, dropwise adding the second solution into the reaction system obtained in the step (1) for 3 hours, and after dropwise adding is finished, keeping the temperature of the reaction system for reaction for 3 hours;
(3) after the reaction, 2000g (10 wt%) of an aqueous lithium hydroxide solution was added and the reaction was carried out at 100 ℃ for 5 hours. Standing and layering the reacted system, centrifuging and separating a heavy phase for 20 minutes by a centrifuge under the condition of 5000rad/min, adding 4L of water into the solid, stirring and washing the solid, centrifuging and separating for 20 minutes by the centrifuge under the condition of 5000rad/min, and drying the solid in vacuum to obtain shell layer crosslinked alpha-methylstyrene/lithium maleate ionomer microspheres (marked as C4);
(4) 10.00g of shell crosslinked alpha-methylstyrene/lithium maleate ionomer microspheres were weighed into 50g of acetone and stirred at 50 ℃ for 30 min. The system was centrifuged at 5000rad/min for 30 minutes in a centrifuge, dried under vacuum and weighed to give 9.29g of polymer and 0.71g of eluate. Similar to C1, the morphology of the microspheres changed less before and after solvent treatment.
Preparation of example 5
This preparation example is intended to illustrate the ionomeric microspheres useful in the present invention and the method of making the same.
(1) Dissolving 100g of maleic anhydride, 58g of alpha-methylstyrene and 2g of azobisisobutyronitrile into 700mL of isoamyl acetate, and reacting at 80 ℃ for 0.5 hour under a nitrogen atmosphere;
(2) 38g of divinylbenzene is dissolved in 100mL of isoprene acetate to form a second solution, the second solution is dropwise added into the reaction system in the step (1) for 2 hours, and after the dropwise addition is finished, the reaction system is continuously subjected to heat preservation reaction for 3 hours; 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 methanol, and drying in vacuum.
(3) 14g 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 (1.8 mol of a base per mol of maleic anhydride) and reacted at 100 ℃ for 3 hours. 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 the solid 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 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 maleate ionomer microsphere (marked as C5);
(4) 10.00g of shell crosslinked alpha-methylstyrene/sodium maleate ionomer microspheres were weighed into 50g of acetone and stirred at 50 ℃ for 30 min. The system was centrifuged at 5000rad/min for 30 minutes in a centrifuge, dried under vacuum and weighed to give 9.35g polymer and 0.65g eluate. Similar to C1, the morphology of the microspheres changed less before and after solvent treatment.
Preparation of example 6
Ionomer microspheres were prepared according to the method of preparation example 1 except that divinylbenzene was used in an amount of 100g to obtain ionomer microspheres C6.
10.00g of shell crosslinked alpha-methylstyrene/sodium maleate ionomer microspheres were weighed into 50g of acetone and stirred at 50 ℃ for 30 min. The system was centrifuged at 5000rad/min for 30 minutes in a centrifuge, dried under vacuum and weighed, with 9g of polymer and 1g of eluate.
Preparation of comparative example 1
(1) Dissolving 1000g of maleic anhydride, 1180g of alpha-methyl styrene, 260g of divinylbenzene and 20g of azobisisobutyronitrile into 10L of isoamyl acetate, and reacting at 70 ℃ for 5 hours under the atmosphere of nitrogen;
(2) after the reaction, 3500g (14 wt%) of an aqueous sodium hydroxide solution was added thereto, and the mixture was reacted at 80 ℃ for 3 hours. Standing and layering the reacted system, centrifuging and separating the heavy phase for 20 minutes by a centrifuge at 5000rad/min, adding 4L of water into the solid, stirring and washing the solid, centrifuging and separating for 20 minutes by the centrifuge at 5000rad/min, and drying the solid in vacuum to obtain the crosslinked alpha-methylstyrene/sodium maleate ionomer microsphere (marked as C-D1), wherein a scanning electron microscope image of the ionomer microsphere is shown in figure 4;
10.00g of crosslinked alpha-methylstyrene/sodium maleate ionomer microspheres were weighed into 50g of acetone and stirred at 50 ℃ for 30 min. The system was centrifuged at 5000rad/min for 30 minutes in a centrifuge, dried under vacuum and weighed to give 8.51g of polymer and 1.49g of eluate. Fig. 5 shows ionomer microspheres after solvent treatment, and it can be seen that the polymer prepared in comparative example 1 has no shell cross-linked structure and the morphology of the microspheres is greatly changed compared to that before solvent treatment.
Preparation of 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).
10.00g of alpha-methylstyrene/sodium maleate ionomer microspheres are weighed into 50g of acetone and stirred at 50 ℃ for 30 min. The system was centrifuged at 5000rad/min for 30 minutes in a centrifuge, vacuum dried and weighed to give 1.04g polymer and 8.96g eluate.
Preparation of comparative example 3
Ionomer microspheres were prepared according to the method of preparation example 1 except that 260g of the crosslinking agent was introduced into the reaction system in two portions, wherein 130g of the crosslinking agent was dissolved in isoamyl acetate together with maleic anhydride in step (1) to react, and further 130g of the crosslinking agent was introduced into the reaction system in step (2) to obtain ionomer microspheres C-D3.
10.00g of alpha-methylstyrene/sodium maleate ionomer microspheres are weighed into 50g of acetone and stirred at 50 ℃ for 30 min. The system was centrifuged at 5000rad/min for 30 minutes in a centrifuge, vacuum dried and weighed to give 8.92g polymer and 1.08g eluate.
Test example 1
(1) The result of infrared spectroscopic analysis of the ionomer microspheres obtained in preparation example 1 is shown in fig. 1, and from the results of infrared spectroscopic analysis, it can be seen that the ionomers were successfully synthesized, and the results of infrared spectroscopic analysis of preparation examples 2 to 6 were similar to those of preparation example 1, and all of the crosslinked ionomers were successfully obtained.
(2) The ionomer microspheres prepared in the above preparation examples were subjected to X-ray fluorescence spectroscopy to determine the metal cation content in the ionomer.
(3) The average particle diameter and the crosslinking degree of the polymers prepared in the above preparation examples and preparation comparative examples were measured (particle diameter test method: 500 microspheres were selected from an electron micrograph, the diameters thereof were measured, and the average particle diameter of the microspheres was calculated by a mathematical average method; crosslinking degree measurement method: 2 to 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, the polymer was dried and weighed w2, and the crosslinking degree was calculated by w2/w 1), and the results are shown in table 1 below.
TABLE 1
(4) The ionomer microspheres prepared in the preparation examples and the preparation comparative examples are respectively and uniformly mixed with PET, the addition amount of the ionomer microspheres is 1 wt% of the mass of the PET, and then the mixture is melted and blended for 8 minutes at 280 ℃, and is extruded and granulated to obtain the 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 | 123.3 | 208.8 | 6.2 | -35.8 |
| C1-1 modified PET | 122.5 | 207.9 | 6.5 | -36.0 |
| C2 modified PET | 124.5 | 205.8 | 6.8 | -35.2 |
| C3 modified PET | 122.9 | 206.1 | 7.2 | -35.0 |
| C4 modified PET | 125.4 | 205.1 | 7.1 | -35.8 |
| C5 modified PET | 127.0 | 202.8 | 7.2 | -33.9 |
| C6 modified PET | 132.1 | 197.3 | 9.0 | -32.8 |
| C-D1 modified PET | 129.5 | 202.2 | 6.4 | -36.8 |
| C-D2 modified PET | 134.7 | 195.2 | 10.2 | -35.0 |
| C-D3 modified PET | 126.5 | 203.9 | 7.9 | -35.7 |
As can be seen from the results in table 2, the ionomer prepared in the preparation example has a significantly better nucleation effect on PET than that prepared in the comparative example, and can significantly increase the crystallization temperature of PET and accelerate the crystallization rate; compared with the preparation comparative example 1 in which a cross-linking agent is added at the beginning of the reaction, the polymer has a microsphere structure with a highly cross-linked shell layer, better solvent resistance and thermal stability are shown, and the microsphere surface is smoother in the salinized modified ionomer, so that the ionomer obtained by the invention has better dispersibility, solvent resistance and thermal stability in PET modification application. The nucleating effect of the ionomers of preparation examples 1-5 was superior to that of the nucleating agent of the ionomer of the comparative example; 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.
Further, as can be seen by comparing production example 1 with production example 6, controlling the amount of the crosslinking agent in the preferred range enables to obtain a more excellent nucleating effect.
Examples 1 to 4
Weighing 100 parts by weight of PET, ionomer microspheres (C1-C4), processing aids (antioxidant 1010 and antioxidant 168 with the weight ratio of 1: 1) and a lubricant according to the formula (in parts by weight) shown in Table 3, putting the materials into a high-speed stirrer, uniformly stirring, and extruding by using WP ZSK25 twin-screw at the temperature of 230-; 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 which was placed in an oven at 120 ℃ for 3 hours and the other was placed at normal temperature, and deformation of the samples was observed, and the symbol ". smallcircle" indicates that no deformation was observed as compared with the samples placed at normal temperature, and the symbol "x" indicates that significant deformation was observed as compared with the samples placed at normal temperature.
The results of the performance tests are shown in table 4. Fig. 6A shows a modification of the sample obtained in example 1.
Examples 5 to 6
An experiment was conducted in the same manner as in example 1 except that the ionomer microsphere C1 was replaced with C5 and C6 prepared in preparation examples 5 and 6, and the results of the performance test were shown in table 4.
Example 7
An experiment was performed in the same manner as in example 1, except that the ionomer microsphere C1 was used in an amount of 5 parts by weight and GF was used in an amount of 10.5 parts by weight, and the results of the performance test were as shown in table 4.
Comparative examples 1 to 4
An experiment was conducted in the same manner as in example 1 except that no ionomeric microspheres were used, the specific formulation is shown in Table 3, and the results of the performance test are shown in Table 4. Further, fig. 6B shows a deformation of the sample obtained in comparative example 1.
Comparative examples 5 to 7
An experiment was conducted in the same manner as in example 1 except that the ionomer microsphere C1 was replaced with C-D1 to C-D3 prepared in comparative examples 1-3, and the results of the performance test were shown in table 4. Further, fig. 6C shows a deformation of the sample obtained in comparative example 5.
TABLE 3
| GF | Ionomer microspheres | Flame retardant | Lubricant agent | Processing aid | |
| Comparative example 1 | 15 | 0 | 8 | 0.04 | 0.2 |
| Comparative example 2 | 25 | 0 | 11 | 0.04 | 0.2 |
| Comparative example 3 | 35 | 0 | 15 | 0.04 | 0.2 |
| Comparative example 4 | 40 | 0 | 18 | 0.04 | 0.2 |
| Example 1 | 15 | 0.5 | 6 | 0.08 | 0.1 |
| Example 2 | 25 | 1.0 | 6 | 0.08 | 0.1 |
| Example 3 | 35 | 2.0 | 10 | 0.1 | 0.2 |
| Example 4 | 25 | 3.0 | 10 | 0.16 | 0.1 |
TABLE 4
From the above results, it can be seen that the addition of the ionomer microspheres allows rapid injection molding at a mold temperature of only 65 ± 5 ℃ when processing the injection molded article. The product after injection molding is not easy to deform, has high dimensional stability, and improves the production efficiency and the product percent of pass.
Further, as can be seen from comparison of example 1, example 6 and comparative examples 5 to 7 or comparison of example 1 and example 7, the preparation of ionomers according to the preferred embodiment of the present invention or the control of the contents of the respective components within the preferred ranges can further improve the properties of plastic articles.
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 (21)
1. A polyethylene terephthalate-containing composition, which contains polyethylene terephthalate and a nucleating agent, wherein the nucleating agent is a microspherical ionomer having a cross-linked structure, the ionomer has a structural unit A provided by maleic anhydride, a structural unit B provided by a monomer M and a cross-linked structure provided by the cross-linking agent, and the monomer M has a structure represented by the formula X:
in the formula X, R is H or methyl;
the dissolution of the ionomer in acetone with the weight 5 times that of the ionomer at 50 ℃ for 30min is less than or equal to 10 percent by weight; the molar amount of metal cations in the ionomer is 10-100% of the total molar amount of structural units a provided by maleic anhydride in the ionomer; the crosslinking degree of the ionomer is more than or equal to 60 percent, the ionomer is microspherical and has the average particle size of 150-2000 nm;
the method for measuring the crosslinking degree of the ionomer 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 composition of claim 1, wherein the ionomer is made by a process comprising:
(1) in an organic solvent, in the presence of a first part of initiator, maleic anhydride is contacted with a first part of monomer M to react, and then a solution containing a crosslinking agent is introduced to continue the reaction, wherein the solution containing the crosslinking agent contains the crosslinking agent, an optional second part of monomer M and an optional second part of initiator;
(2) in the presence of water, the product obtained in the step (1) is contacted with alkali for salinization.
3. The composition according to claim 2, wherein the total amount of monomers M of the first fraction and of monomers M of the second fraction is between 50 and 150mol with respect to 100mol of maleic anhydride; the dosage of the organic solvent is 50-150L; the total dosage of the first part of the initiator and the second part of the initiator is 0.05-10 mol; the dosage of the cross-linking agent is 1-40 mol; the amount of the alkali is 10-200 mol.
4. The composition according to claim 3, wherein the total amount of the first portion of monomers M and the second portion of monomers M is 75 to 100mol with respect to 100mol of maleic anhydride.
5. The composition according to claim 3 or 4, wherein the total amount of the first portion of initiator and the second portion of initiator is 0.8 to 1.5mol with respect to 100mol of maleic anhydride.
6. The composition according to claim 3 or 4, wherein the crosslinking agent is used in an amount of 10 to 20mol with respect to 100mol of maleic anhydride.
7. The composition of claim 2, wherein the molar ratio between the second portion of monomers M and the first portion of monomers M is from 0 to 100: 100;
and/or the molar ratio between the second portion of initiator and the first portion of initiator is 0-100: 100.
8. The composition of claim 2, 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 base is selected from a hydroxide of a metal and/or an acetate of a metal.
9. The composition according to claim 8, 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 acrylate.
10. The composition of claim 9, wherein the crosslinker is polyethylene glycol diacrylate and/or polyethylene glycol dimethacrylate.
11. The composition of any one of claims 2 and 8-10, 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, and zinc acetate.
12. The composition according to any one of claims 2 to 4 and 7 to 10, wherein in the step (1), the conditions for contacting the maleic anhydride and the monomer M to react comprise: inert atmosphere at 50-90 deg.C for 0.5-4 h;
and/or, in the step (1), the conditions for introducing the solution containing the cross-linking agent to continue the reaction comprise: the temperature is 50-90 ℃ and the time is 2-15 h.
13. The composition of any of claims 2-4 and 7-10, wherein the introduction of the solution containing the crosslinking agent continues the reaction by: dropwise adding the solution containing the cross-linking agent into the reaction system within 1-3h at 50-90 ℃, and continuing to perform heat preservation reaction for 1-4 h.
14. The composition of any one of claims 2-4 and 7-10, wherein the salinated conditions in step (2) comprise: the temperature is 20-100 ℃ and the time is 0.5-8 h.
15. The composition according to claim 1, wherein the nucleating agent is contained in an amount of 0.5 to 4 parts by weight, relative to 100 parts by weight of polyethylene terephthalate.
16. The composition of claim 1, wherein the composition further comprises at least one of a flame retardant, a lubricant, a toughener, and other processing aids.
17. The composition as set forth in claim 16, wherein the flame retardant is contained in an amount of 5 to 22 parts by weight with respect to 100 parts by weight of the polyethylene terephthalate.
18. The composition according to claim 16 or 17, wherein the lubricant is contained in an amount of 0.03 to 0.3 parts by weight with respect to 100 parts by weight of the polyethylene terephthalate.
19. The composition of claim 16 or 17, wherein the toughening agent is present in an amount of 10 to 55 parts by weight, relative to 100 parts by weight of polyethylene terephthalate.
20. The composition according to claim 16 or 17, wherein the other processing aid is contained in an amount of 0.1 to 1 part by weight with respect to 100 parts by weight of polyethylene terephthalate.
21. A process for the preparation of a polyethylene terephthalate blended plastic, characterized in that the process comprises melt extrusion and cooling granulation of a composition according to any of claims 1 to 20.
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