CN115850925B - High-strength heat-resistant polyethylene terephthalate and preparation method thereof - Google Patents

High-strength heat-resistant polyethylene terephthalate and preparation method thereof Download PDF

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CN115850925B
CN115850925B CN202211581144.1A CN202211581144A CN115850925B CN 115850925 B CN115850925 B CN 115850925B CN 202211581144 A CN202211581144 A CN 202211581144A CN 115850925 B CN115850925 B CN 115850925B
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polyethylene terephthalate
agent
parts
antioxidant
decoupling
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CN115850925A (en
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董大鹏
陶慷
臧义文
洪江
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Nanjing Xuzhi Material Technology Co ltd
Jiangsu Jitri Advanced Polymer Materials Research Institute Co Ltd
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Nanjing Xuzhi Material Technology Co ltd
Jiangsu Jitri Advanced Polymer Materials Research Institute Co Ltd
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Abstract

The invention discloses high-strength heat-resistant polyethylene glycol terephthalate which is prepared from the following components in parts by weight: 90-95 parts of polyethylene terephthalate matrix, 2-5 parts of cross-linking agent, 2-5 parts of decoupling agent, 0.07-0.5 part of decoupling auxiliary agent and 0.5-2 parts of antioxidant. The cross-linking agent can cross-link linear PET molecular chains to form a bulk phase network structure, so that the thermal deformation temperature and mechanical strength of PET are remarkably improved, the decoupling agent can form a dynamic exchangeable covalent bond network, and the fluidity of the reinforced PET material at high temperature is ensured, so that the traditional extrusion, injection molding and other processing and forming processes can be adopted, additional equipment is not required to be changed, and the method is suitable for all processing factories.

Description

High-strength heat-resistant polyethylene terephthalate and preparation method thereof
Technical Field
The invention relates to the field of high polymer materials, in particular to high-strength heat-resistant polyethylene terephthalate and a preparation method thereof.
Background
Polyethylene terephthalate (PET) is one of five engineering plastics, and has good processing fluidity, excellent chemical reagent resistance, low price and degradability, and is currently applied to various industries such as electronics, household appliances, automobiles and the like. However, in practical processing and molding processes (such as extrusion and injection), pure PET is slow to crystallize, semi-crystalline products are obtained, the dimensional stability is poor, the heat distortion temperature is generally only 60-75 ℃, and once the temperature is exceeded, the original mechanical properties of the PET are lost, so that the practical application of the PET is greatly limited.
At present, PET is subjected to enhanced heat resistance modification mainly in terms of improving crystallinity, blending modification enhancement and the like. The surface free energy barrier required by PET nucleation is reduced by adding the nucleating agent, so that the crystallinity of PET can be effectively improved, and the heat resistance of PET is enhanced. However, the nucleating agent needs to be matched with a higher injection molding temperature, has a long period and cannot completely solve the problem of heat resistance of PET. The blending modification reinforcement is mainly realized by two modes of alloying and glass fiber reinforcement, wherein the alloying is to introduce PBT, PC, PPS and other high-performance resins into a PET matrix to form an alloy structure, the performance is hard to be expected due to the compatibility problem of the two resin matrixes in the prior PET alloying, and the high-performance resins used in the alloying are high in price and raise the cost of materials undoubtedly. The glass fiber reinforced PET is adopted to reform the equipment, and the side feeding is adopted to avoid the glass fiber from being cut off or even ground under the shearing of the screw rod, so that the reinforcing effect is lost, the glass fiber reinforced PET also can cause the surface roughness of PET products, the glossiness is reduced, and the application range of PET materials is limited.
In view of the foregoing, in order to enhance the overall performance of PET and expand the application range of PET, it is highly desirable to design an efficient and economical PET heat resistance enhancement scheme.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide the high-strength heat-resistant polyethylene terephthalate and the preparation method thereof, wherein the linear polyethylene terephthalate chain segments are crosslinked to form a three-dimensional bulk phase structure through the crosslinking agent, so that the chain segment slip is inhibited, and the thermal mechanical strength of PET is improved.
In order to achieve the above object, the present invention adopts the following technical scheme:
the high-strength heat-resistant polyethylene terephthalate is prepared from the following components in parts by weight: 90-95 parts of polyethylene terephthalate matrix, 2-5 parts of cross-linking agent, 2-5 parts of decoupling agent, 0.07-0.5 part of decoupling auxiliary agent and 0.5-2 parts of antioxidant.
Preferably, the intrinsic viscosity of the polyethylene terephthalate matrix is 0.5-1 dl/g, and the carboxyl end group content is less than 0.05mmol/g.
Preferably, the polyethylene terephthalate matrix is one of CZ-5011, BG80, or TH 103.
Preferably, the structure of the cross-linking agent is Y-R n (n is more than or equal to 2), Y is a main chain, and R is one or more of hydroxyl, carboxyl and epoxy groups.
Preferably, the aforementioned crosslinking agent is one of glycidyl methacrylate, bisphenol a diglycidyl ether, 2-hydroxypropane-1, 2, 3-tricarboxylic acid, or triglycidyl isocyanurate.
Preferably, the disintegating agent is polyfunctional aromatic acid with a boiling point of more than 260 ℃ and adopts one of pyromellitic acid, 4' -diphenyl ether dicarboxylic acid or 2-hydroxy-3-naphthoic acid.
Preferably, the antioxidant is one of antioxidant-1010, antioxidant-1076 or antioxidant-3114.
Preferably, the above-mentioned decoupling auxiliary is nano aluminium chloride, and its preparation method specifically includes the following steps:
S1, adding aluminum ammonium sulfate and a surfactant into deionized water, and stirring until the aluminum ammonium sulfate and the surfactant are completely dissolved to obtain mother liquor A;
s2, stirring the mother solution A, and simultaneously dropwise adding an ammonium hydroxide solution into the mother solution A to react to obtain an intermediate suspension B;
S3, placing a cell breaker amplitude transformer in the suspension B, placing the suspension B in an ice-water bath, starting an ultrasonic probe, dropwise adding hydrochloric acid, and reacting to obtain a nano aluminum chloride dispersion;
And S4, carrying out vacuum suction filtration, cleaning and vacuum drying on the nano aluminum chloride dispersion liquid to obtain the nano aluminum chloride.
Preferably, the surfactant is one of OP-10, sodium dodecyl benzene sulfonate or Tween-20.
The preparation method of the high-strength heat-resistant polyethylene glycol terephthalate comprises the following specific steps: uniformly mixing a polyethylene terephthalate matrix, a cross-linking agent, a decoupling auxiliary agent and an antioxidant in a high-speed mixer according to a certain proportion, adding the obtained mixture into a screw extruder for blending extrusion, and granulating to obtain the polyethylene terephthalate, wherein the length-diameter ratio of the screw in the screw extruder is L/D=40/1-44/1.
The invention has the advantages that:
(1) According to the invention, the linear polyethylene terephthalate chain segments are crosslinked by the crosslinking agent to form a three-dimensional bulk phase structure, so that chain segment slip is inhibited, and the thermal deformation temperature and mechanical strength of PET are obviously improved; the decoupling agent carries out transesterification reaction under the catalysis of the decoupling auxiliary agent to form a dynamic covalent cross-linked network, so that the mobility of the reinforced PET material at high temperature can be ensured;
(2) The invention adopts a crosslinking enhancement mechanism, the consumption of a crosslinking agent is small, the performance is improved, and the invention is different from alloying and has good economy; the second-phase resin matrix or inorganic reinforcing material is not introduced, so that the purity of the resin in the service life is ensured, and the recycling is facilitated; the dynamic cross-linking network is adopted, so that the problem that the traditional thermosetting cross-linking resin can be molded only once and cannot be reused is solved.
Drawings
FIG. 1 is a schematic diagram of the principle of the crosslinking agent of the present invention to crosslink linear PET segments into a three-dimensional bulk structure;
FIG. 2 is a schematic diagram of the transesterification reaction of a debonding agent according to the present invention;
FIG. 3 is an electron micrograph of the decoupling agent of example 1;
FIG. 4 is an XRD diffraction pattern of the decoupling aid of example 1;
FIG. 5 is a photograph of PET splines in example 3 and comparative example 3 after heating at 500 ℃.
Detailed Description
The invention is described in detail below with reference to the drawings and the specific embodiments.
The invention relates to high-strength heat-resistant polyethylene terephthalate which is prepared from the following components in parts by weight: 90-95 parts of polyethylene terephthalate matrix, 2-5 parts of cross-linking agent, 2-5 parts of decoupling agent, 0.07-0.5 part of decoupling auxiliary agent and 0.5-2 parts of antioxidant.
Wherein, the intrinsic viscosity of the polyethylene terephthalate matrix is 0.5-1 dl/g, the carboxyl end group content is less than 0.05mmol/g, and the polyethylene terephthalate matrix is one of CZ-5011, BG80 or TH 103. The cross-linking agent has the structure of Y-R n (n is more than or equal to 2), Y is a main chain, and R is one or more of hydroxyl, carboxyl and epoxy groups. The cross-linking agent is one of glycidyl methacrylate, bisphenol A diglycidyl ether, 2-hydroxy propane-1, 2, 3-tricarboxylic acid or triglycidyl isocyanurate. The disintegating agent is polyfunctional aromatic acid with the boiling point of more than 260 ℃ and adopts one of pyromellitic acid, 4' -diphenyl ether dicarboxylic acid or 2-hydroxy-3-naphthoic acid. The antioxidant is one of antioxidant-1010, antioxidant-1076 or antioxidant-3114.
The decoupling auxiliary agent is nano aluminum chloride, and the preparation steps are as follows:
S1, adding aluminum ammonium sulfate and a surfactant into deionized water, and stirring until the aluminum ammonium sulfate and the surfactant are completely dissolved to obtain mother liquor A;
s2, stirring the mother solution A, and simultaneously dropwise adding an ammonium hydroxide solution into the mother solution A to react to obtain an intermediate suspension B;
S3, placing a cell breaker amplitude transformer in the suspension B, placing the suspension B in an ice-water bath, starting an ultrasonic probe, dropwise adding hydrochloric acid, and reacting to obtain a nano aluminum chloride dispersion;
And S4, carrying out vacuum suction filtration, cleaning and vacuum drying on the nano aluminum chloride dispersion liquid to obtain the nano aluminum chloride.
Preferably, the surfactant is one of OP-10, sodium dodecyl benzene sulfonate or Tween-20.
The preparation method of the high-strength heat-resistant polyethylene glycol terephthalate comprises the following specific steps: uniformly mixing a polyethylene terephthalate matrix, a cross-linking agent, a decoupling auxiliary agent and an antioxidant in a high-speed mixer according to a certain proportion, adding the obtained mixture into a screw extruder for blending extrusion, and granulating to obtain the polyethylene terephthalate, wherein the length-diameter ratio of the screw in the screw extruder is L/D=40/1-44/1.
The reinforcing mechanism of the high-strength PET is that a linear PET chain segment is crosslinked to form a three-dimensional bulk phase structure through a crosslinking agent, chain segment slip is restrained, the thermal deformation temperature and mechanical strength of the PET can be remarkably improved, and a schematic diagram is shown in figure 1. The decoupling agent is subjected to transesterification reaction under the catalysis of the decoupling auxiliary agent to form a dynamic covalent cross-linking network, so that the fluidity of the reinforced PET material at high temperature can be ensured, and a polymer conventional molding processing technology can be adopted, and the principle schematic diagram is shown in figure 2.
The matrix resin used in the examples was CZ-5011 of three-lane or TH103 of Lanshan Tun river. The cross-linking agent is bisphenol A diglycidyl ester or triglycidyl isocyanurate. The disintegating agent is pyromellitic acid or 4,4' -diphenyl ether dicarboxylic acid. The surfactant is OP-10 or Tween-20. The glass fiber used in comparative example 1 is alkali-free glass fiber HCR-5019, the coupling agent is KH-550, and the compatilizer is maleic anhydride grafted polypropylene of Shanghai good easy-to-use company. The catalyst used in comparative example 3 was polyethylene polyamine of Tosoh, japan.
Example 1
Preparation of a decoupling auxiliary agent nano aluminum chloride:
s1, adding 10g of aluminum ammonium sulfate and 0.1gOP-10 g of deionized water into 100ml of deionized water at the temperature of 30 ℃, and stirring until the aluminum ammonium sulfate and the deionized water are completely dissolved to obtain mother liquor A;
S2, stirring the mother liquor A at a speed of 20rpm, adding 450ml of ammonium hydroxide solution with a pH value of 12-13 into the mother liquor A at a speed of 3-6 drops per second, and reacting to obtain an intermediate suspension B;
S3, placing a 100W and 20KHz cell breaker amplitude transformer in the suspension B, simultaneously placing the suspension B in an ice-water bath, starting an ultrasonic probe, simultaneously dropwise adding 1M hydrochloric acid at a rate of 1-3 drops per second for 50ml, and completing the reaction to obtain a nano aluminum chloride dispersion;
S4, vacuum-filtering the nano aluminum chloride dispersion liquid, cleaning the nano aluminum chloride dispersion liquid with deionized water for 4-5 times, and vacuum-drying the nano aluminum chloride dispersion liquid at 60 ℃ to obtain the nano aluminum chloride.
Uniformly mixing a polyethylene terephthalate matrix, a cross-linking agent, a decoupling auxiliary agent nano aluminum chloride and an antioxidant in a high-speed mixer according to a certain proportion, adding the obtained mixture into a screw extruder, blending and extruding, wherein the length-diameter ratio of the screw in the screw extruder is L/D=44/1, and granulating to obtain the polyethylene terephthalate, wherein the proportion of each component is shown in table 1.
Table 1 the proportions of the components for preparing polyethylene terephthalate
Component (A) Matrix body Crosslinking agent Disintegating agent Decoupling auxiliary agent Antioxidant
Raw materials CZ-5011 Bisphenol A diglycidyl esters Pyromellitic acid Nanometer aluminum chloride Antioxidant-1010
Proportion (parts by mass) 94.9 2 2 0.1 1
Example 2
The preparation steps of the decoupling auxiliary nano aluminum chloride in the embodiment are the same as those in the embodiment 1, and the specific differences are that: the surfactant is Tween-20, and the specific component proportions for preparing polyethylene terephthalate are shown in Table 2.
Table 2 proportions of the components for preparing polyethylene terephthalate
Component (A) Matrix body Crosslinking agent Disintegating agent Decoupling auxiliary agent Antioxidant
Raw materials CZ-5011 Bisphenol A diglycidyl esters Pyromellitic acid Nanometer aluminum chloride Antioxidant-1010
Proportion (parts by mass) 90.7 5 3 0.3 1
Example 3
The preparation steps of the decoupling auxiliary nano aluminum chloride in the embodiment are the same as those in the embodiment 1, and the specific differences are that: the specific components and proportions of the preparation of polyethylene terephthalate are different, and the proportions of the components are shown in Table 3.
TABLE 3 proportions of the components for the preparation of polyethylene terephthalate
Component (A) Matrix body Crosslinking agent Disintegating agent Decoupling auxiliary agent Antioxidant
Raw materials TH103 Triglycidyl isocyanurate Pyromellitic acid Nanometer aluminum chloride Antioxidant-1010
Proportion (parts by mass) 92.7 3 3 0.3 1
Comparative example 1
The present comparative example uses conventional glass fiber reinforced polyethylene terephthalate: KH-550 and glass fiber are mixed uniformly in advance, then added into a screw extruder in a side feeding mode, the length-diameter ratio of the screw is 28, and polyethylene terephthalate is obtained, and the proportions of the components are shown in Table 4.
Table 4 the proportions of the components for preparing polyethylene terephthalate
Raw materials CZ-5011 Alkali-free glass fiber KH-550 Compatibilizing agent CZ-5011
Proportion (parts by mass) 60 30 5 5 60
Comparative example 2
The preparation steps of the decoupling auxiliary nano aluminum chloride in the comparative example are the same as those of the example 3, and the specific difference is that: the polyethylene terephthalate was prepared without adding a crosslinking agent, and the formulation of each component is shown in Table 5.
Table 5 the proportions of the components for preparing polyethylene terephthalate
Comparative example 3
The preparation steps of the decoupling auxiliary nano aluminum chloride in the comparative example are the same as those of the example 3, and the specific difference is that: the preparation of polyethylene terephthalate is directly carried out by adopting a crosslinking scheme without adding a decoupling agent and a decoupling auxiliary agent, and the formula of each component is shown in Table 6.
Table 6 proportions of the components for preparing polyethylene terephthalate
Raw materials TH-103 Triglycidyl isocyanurate Polyethylene polyamine Antioxidant-1010
Proportion (parts by mass) 92.7 6 1 1
Performance test: the polyethylene terephthalates prepared in examples 1 to 3 and comparative examples 1 to 3 were respectively subjected to performance tests, and the test results are shown in Table 7.
TABLE 7 Performance test of polyethylene terephthalate
As can be seen from a comparison of example 1 and comparative example 1, the use of glass fiber reinforcement first requires the use of side feeds, requiring the addition of feeding devices and the retrofitting of the equipment. In addition, the density of the glass fiber is far higher than that of the polymer, so that the specific gravity of the PET material obtained by reinforcing the glass fiber in comparative example 1 is increased, and the lightweight application of the PET is seriously affected. Although various compatibilizers were used to improve compatibility in comparative example 1, it was unavoidable that the mechanical properties and heat resistance of PET in comparative example 1 were lower than those of polyethylene terephthalate obtained in example 1 in combination.
As can be seen from the comparison of example 3 and comparative example 2, the addition of the crosslinking agent in the preparation of polyethylene terephthalate can effectively raise the heat distortion temperature and mechanical strength of PET, because the crosslinking agent crosslinks the linear PET segments to form a three-dimensional bulk structure, which can inhibit segment slip.
As can be seen from a comparison of example 3 and comparative example 3, the PET properties of comparative example 3 using direct crosslinking to the thermoset are superior to those of the present invention, but the thermoset PET cannot be melt processed again. The sample bars of comparative example 3 and example 3 were simultaneously placed at 500 ℃, and example 3 exhibited a softening flow phenomenon because the deblocking agent was subjected to transesterification reaction under the catalysis of the deblocking aid at high temperature to form a dynamic covalent cross-linking network, thereby ensuring the fluidity of the reinforced PET material at high temperature, whereas comparative example 3 exhibited only warpage and surface oxidation, without any softening flow, and thus failed to perform secondary processing, as shown in FIG. 5, comparative example 3 was unsuitable for the current extrusion, injection molding process, severely limiting the use of PET.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be appreciated by persons skilled in the art that the above embodiments are not intended to limit the invention in any way, and that all technical solutions obtained by means of equivalent substitutions or equivalent transformations fall within the scope of the invention.

Claims (8)

1. The high-strength heat-resistant polyethylene terephthalate is characterized by being prepared from the following components in parts by weight: 90-95 parts of polyethylene terephthalate matrix, 2-5 parts of cross-linking agent, 2-5 parts of decoupling agent, 0.07-0.5 part of decoupling auxiliary agent and 0.5-2 parts of antioxidant; the cross-linking agent has the structure thatN is more than or equal to 2, Y is a main chain, R is one or more of hydroxyl, carboxyl and epoxy groups, the decoupling agent is one of pyromellitic acid, 4' -diphenyl ether dicarboxylic acid or 2-hydroxy-3-naphthoic acid, and the decoupling auxiliary agent is nano aluminum chloride.
2. The high-strength heat-resistant polyethylene terephthalate according to claim 1, wherein the intrinsic viscosity of the polyethylene terephthalate matrix is 0.5-1 dl/g, and the carboxyl end group content is less than 0.05mmol/g.
3. The high strength and heat resistance polyethylene terephthalate according to claim 2, wherein the polyethylene terephthalate matrix is one of CZ-5011, BG80, or TH 103.
4. The high strength and heat resistance polyethylene terephthalate according to claim 1, wherein the cross-linking agent is one of bisphenol a diglycidyl ether, 2-hydroxypropane-1, 2, 3-tricarboxylic acid, or triglycidyl isocyanurate.
5. The high strength and heat resistance polyethylene terephthalate according to claim 1, wherein the antioxidant is one of antioxidant-1010, antioxidant-1076, or antioxidant-3114.
6. The high-strength heat-resistant polyethylene terephthalate according to claim 1, characterized in that the preparation steps of the nano aluminum chloride are as follows:
S1, adding aluminum ammonium sulfate and a surfactant into deionized water, and stirring until the aluminum ammonium sulfate and the surfactant are completely dissolved to obtain mother liquor A;
s2, stirring the mother solution A, and simultaneously dropwise adding an ammonium hydroxide solution into the mother solution A to react to obtain an intermediate suspension B;
S3, placing the suspension B in an ice-water bath, starting an ultrasonic probe, stirring, dropwise adding hydrochloric acid, and reacting to obtain a nano aluminum chloride dispersion;
And S4, carrying out vacuum suction filtration, cleaning and vacuum drying on the nano aluminum chloride dispersion liquid to obtain the nano aluminum chloride.
7. The high strength and heat resistant polyethylene terephthalate according to claim 6, wherein the surfactant is one of OP-10, sodium dodecyl benzene sulfonate, or tween-20.
8. The method for preparing high-strength heat-resistant polyethylene terephthalate according to claim 1, comprising the following specific steps: uniformly mixing a polyethylene terephthalate matrix, a cross-linking agent, a decoupling auxiliary agent and an antioxidant in a high-speed mixer according to a certain proportion, adding the obtained mixture into a screw extruder for blending extrusion, and granulating to obtain the high-strength heat-resistant polyethylene terephthalate.
CN202211581144.1A 2022-12-09 2022-12-09 High-strength heat-resistant polyethylene terephthalate and preparation method thereof Active CN115850925B (en)

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