CN111154238A - Impact-resistant PET material and preparation method thereof - Google Patents
Impact-resistant PET material and preparation method thereof Download PDFInfo
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- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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Abstract
The invention discloses an impact-resistant PET material and a preparation method thereof, relating to the technical field of packaging materials, and the technical scheme is characterized in that the impact-resistant PET material comprises the following components in parts by weight: 50-60 parts of polyethylene glycol terephthalate, 6-8 parts of impact-resistant toughening agent, 4-6 parts of modified clay, 0.06-0.08 part of tackifying chain extender, 0.02-0.1 part of antioxidant and 0.5-1.5 parts of lubricant; the impact-resistant toughening agent consists of a maleic anhydride grafted polyethylene octene elastomer and an ethylene-acrylate-maleic anhydride terpolymer in a weight ratio of 1: 1. The impact-resistant PET material has excellent impact resistance.
Description
Technical Field
The invention relates to the technical field of packaging materials, in particular to an impact-resistant PET material and a preparation method thereof.
Background
PET refers to polyethylene terephthalate, which is prepared by exchanging dimethyl terephthalate with ethylene glycol or esterifying terephthalic acid with ethylene glycol to synthesize dihydroxy ethyl terephthalate, and then performing polycondensation reaction. The PET material has excellent gas, water, oil and odor barrier effects and good chemical stability, and thus can be used as a container for holding pesticides and other chemical agents.
In the prior art, a patent application publication No. CN109605654A discloses a manufacturing process of pesticide bottles, which comprises the following steps: step one, preparing modified titanium dioxide, namely uniformly mixing the titanium dioxide, a melt strength enhancer and a lubricant according to a mass ratio of 21:5:1, heating to completely melt the mixture, and uniformly stirring to obtain the modified titanium dioxide; and step two, preparing the anti-color-change agent, namely adding polyoxyethylene stearate and polycaprolactam powder into a ball mill according to the ratio of 2:1, and performing ball milling treatment for 35min to obtain the anti-color-change agent. Step three, manufacturing a bottle blank mold, wherein the bottle blank mold is manufactured by injecting a melting material into a mold by using an injection machine, 70 parts of PET powder, 13 parts of modified titanium dioxide and 3 parts of anti-discoloration agent are conveyed into a heated charging barrel from a hopper of the injection machine according to parts by weight, after heating, melting and plasticizing, the material is compressed and moves forwards by means of the thrust of a plunger or a screw, and is injected into a closed mold cavity through a nozzle at the front end of the charging barrel, and after cooling and shaping, the mold is opened to obtain a product; step four: the bottle blanks are sequenced and then sequentially enter an integrated bottle blowing machine, a bottle blank star wheel is arranged on the integrated bottle blowing machine, and workpieces are sequentially transmitted to a conveying chain wheel through the bottle blank star wheel; conveying the bottle blanks to a heating mechanism by a conveying chain wheel to heat the bottle blanks, wherein the bottle blanks are conveyed to a bottle blowing machine after being heated by the heating mechanism which adopts a drying oven; step five: carrying out bottle blowing operation, namely placing the preheated bottle blank into a prepared mould, carrying out high-pressure inflation on the bottle blank, and carrying out blowing and drawing on the bottle blank into a required bottle, wherein the blowing process of a bottle blowing machine is a bidirectional stretching process, and PET chains are bidirectionally extended, oriented and arranged in the bidirectional stretching process; step six: and taking out the bottle body after blowing from the bottle blowing machine.
The pesticide bottle prepared by the method has the advantage of difficult color change, but the PET resin has higher molecular chain rigidity and higher glass transition temperature, so that the impact resistance of a PET product is poorer, and after the PET pesticide bottle falls down, the bottle body is easy to crack, so that pesticide is exuded, the waste of medicines is caused, and the environment is polluted, so that the PET material with excellent impact resistance is required.
Disclosure of Invention
In view of the disadvantages of the prior art, a first object of the present invention is to provide an impact-resistant PET material having the advantage of excellent impact resistance.
The second purpose of the invention is to provide a preparation method of the impact-resistant PET material.
In order to achieve the first object, the invention provides the following technical scheme: an impact-resistant PET material comprises the following components in parts by weight: 50-60 parts of polyethylene glycol terephthalate, 6-8 parts of impact-resistant toughening agent, 4-6 parts of modified clay, 0.06-0.08 part of tackifying chain extender, 0.02-0.1 part of antioxidant and 0.5-1.5 parts of lubricant; the impact-resistant toughening agent consists of a maleic anhydride grafted polyethylene octene elastomer and an ethylene-acrylate-maleic anhydride terpolymer in a weight ratio of 1: 1.
By adopting the technical scheme, the maleic anhydride grafted polyethylene octene elastomer (POE-g-MAH) has good flexibility, the ethylene-acrylic ester-maleic anhydride terpolymer (EMH) has good reactivity, crystallinity, fluidity and compatibility, and the impact-resistant toughening agent obtained by compounding the maleic anhydride grafted polyethylene octene elastomer and the ethylene-acrylic ester-maleic anhydride terpolymer has good compatibility with PET, so that the toughness and the impact resistance of the PET material can be greatly improved. By matching the tackifying chain extender and the nucleating agent modified argil, the crystallization rate of PET can be improved, the molding temperature is reduced, the molecular weight of PET is improved, and the viscosity of PET is enhanced, so that the mechanical property and the surface gloss of a product are improved.
①, adding water into pottery clay, stirring to obtain pottery clay suspension with pottery clay content of 10-15%, ②, taking 100 parts of pottery clay suspension by weight, adding 0.03-0.05 part of titanate coupling agent, heating to 90-100 ℃, stirring for 10-20min, adding 3-5 parts of modifier, heating to 140-160 ℃, stirring for 3-5h, cooling to room temperature, vacuum filtering to obtain precipitate, washing the precipitate with absolute ethyl alcohol to obtain washing matter, and drying the washing matter at 120 ℃ for 3-4h to obtain the modified pottery clay.
By adopting the technical scheme, the modified argil is used as a nucleating agent of the PET material, so that the crystallization rate of the PET material can be accelerated, and the impact resistance of the PET material can be further improved by matching the modified argil with the impact resistance toughening agent; firstly, the argil is pretreated by a titanate coupling agent, the titanate coupling agent is coupled with trace carboxyl or hydroxyl adsorbed on the surface of the argil through the chemical action of alkoxy of the titanate coupling agent, the dispersibility of the argil in water can be improved, and the modifying effect of the modifying agent on the argil can also be improved when the pretreated argil is modified by the modifying agent.
Further, the titanate coupling agent in step ② is a chelate solution of bis (dioctyloxypyrophosphate) ethylene titanate and triethanolamine.
By adopting the technical scheme, the chelate solution of bis (dioctyloxypyrophosphate) ethylene titanate and triethanolamine is a water-soluble coupling agent which is processed by a chelating technology and has excellent water stability, and the chelate solution is added into argil suspension to carry out and processing on argil at the temperature of 90-100 ℃, so that the stability of the suspension is improved, the modification efficiency of the modifying agent on argil is improved, and the modification effect is improved.
Further, the modifier in the step ② is prepared by taking 10-20 parts by weight of lithium bentonite, 2-4 parts by weight of hydrophobic fumed silica, 3-6 parts by weight of polyvinylpyrrolidone, 2-3 parts by weight of calcium acetate, 0.1-0.2 part by weight of silane coupling agent, 50-60 parts by weight of ethylene carbonate and 50-60 parts by weight of absolute ethyl alcohol, and stirring at the speed of 1000-2000r/min for 20-30min to obtain the modifier.
According to the technical scheme, the modifier is prepared by mixing a silane coupling agent, ethylene carbonate and absolute ethyl alcohol with lithium bentonite, hydrophobic fumed silica, polyvinylpyrrolidone and calcium acetate as main raw materials, wherein the silane coupling agent can be chemically bonded with the lithium bentonite, the hydrophobic fumed silica, the polyvinylpyrrolidone and the calcium acetate firstly in the stirring process; then, the modified kaolin and the kaolin pretreated by the titanate coupling agent can be chemically bonded again, so that the dispersibility of the kaolin in the PET material can be improved, the agglomeration phenomenon of the modified kaolin and the PET material can be reduced, the modified kaolin and the PET material have good compatibility, the modified kaolin serving as a nucleating agent can improve the crystallization rate and shorten the molding period, the modified kaolin serving as an inorganic filler can strengthen and toughen the PET, and the modified kaolin and the kaolin are matched with an impact-resistant toughening agent to greatly improve the impact resistance of the PET so as to improve the drop resistance of the PET material.
Further, the silane coupling agent is one of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane and gamma- (methacryloyloxy) propyltrimethoxysilane.
By adopting the technical scheme, the gamma-aminopropyltriethoxysilane serving as the silane coupling agent is also called KH-550, the gamma-glycidoxypropyltrimethoxysilane serving as the silane coupling agent is also called KH-560, and the gamma- (methacryloyloxy) propyltrimethoxysilane serving as the silane coupling agent is also called KH-570, wherein KH-550, KH-560 and KH-570 are adopted as the silane coupling agents in the modifying agent, and when the silane coupling agent is used for modifying argil which is treated by the titanate coupling agent in advance, the adhesive force between the modifying agent and the argil can be improved, and the modifying effect is improved.
Further, the antioxidant is formed by mixing the antioxidant 1010 and the antioxidant 168 in a weight ratio of 1: 1.
By adopting the technical scheme, the chemical name of the antioxidant 1010 is tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, the chemical name of the antioxidant 168 is tri [ 2.4-di-tert-butylphenyl ] phosphite ester, and the antioxidant 1010 and the antioxidant 168 have a synergistic effect, so that the thermal oxidative degradation of PET can be prevented, and the processing stability of the PET can be improved.
Further, the lubricant is compounded by ethylene bis stearamide and stearic acid in a weight ratio of 3: 1.
By adopting the technical scheme, the lubricant compounded by ethylene bis stearamide and zinc stearate has good internal lubricity and external lubricity, can reduce melt viscosity, improve processability and improve the smoothness and smoothness of the surface of a product.
In order to achieve the second object, the invention provides the following technical scheme:
a preparation method of an impact-resistant PET material comprises the following steps:
s1, mixing materials: weighing the dried polyethylene glycol terephthalate according to the proportion, and blending for 10-20min to obtain a mixture;
s2, granulating: and melting, extruding and granulating the mixture at the temperature of 250-280 ℃ to obtain the impact-resistant PET material.
Further, the drying of the dried polyethylene terephthalate of S1 means drying at a temperature of 120-130 ℃ for 3-5 h.
By adopting the technical scheme, the PET particles have water absorption, can absorb external moisture in the placing process, and can cause the degradation of PET in the melting processing process, so that the viscosity of the PET is reduced, and the glossiness of the product is influenced; before processing, the PET is dried for 3-5h at the temperature of 120-130 ℃, so that the hydrolysis phenomenon of the PET in the processing process can be reduced, and the product quality is improved.
Further, in S2, the mixture is placed in a twin-screw extruder, and the temperatures in each zone are: the temperature of the first zone is 190-class 200 ℃, the temperature of the second zone is 210-class 220 ℃, the temperature of the third zone is 250-class 255 ℃, the temperature of the second zone is 255-class 260 ℃, the temperature of the third zone is 260-class 265 ℃, the temperature of the fourth zone is 265-class 270 ℃, the temperature of the fifth zone is 265-class 270 ℃, the temperature of the sixth zone is 260-class 265 ℃, the temperature of the seventh zone is 255-class 260 ℃, the temperature of the eighth zone is 255-class 260 ℃, the temperature of the head is 255-class 260 ℃ and the retention time is 3-5 min.
In summary, compared with the prior art, the invention has the following beneficial effects:
1. the maleic anhydride grafted polyethylene octene elastomer (POE-g-MAH) has good flexibility, the ethylene-acrylic ester-maleic anhydride terpolymer (EMH) has good reaction activity, crystallinity, fluidity and compatibility, and the impact-resistant toughening agent obtained by compounding the maleic anhydride grafted polyethylene octene elastomer and the ethylene-acrylic ester-maleic anhydride terpolymer has good compatibility with PET, so that the toughness and the impact resistance of the PET material can be greatly improved. By matching the tackifying chain extender and the nucleating agent modified argil, the crystallization rate of PET can be improved, the molding temperature is reduced, the molecular weight of the PET is improved, and the viscosity of the PET is enhanced, so that the mechanical property and the surface gloss of a product are improved;
2. the modified argil is used as a nucleating agent of the PET material, so that the crystallization rate of the PET material can be increased, and the impact resistance of the PET material can be further improved through the matching of the modified argil and the impact resistance toughening agent; the modifier is prepared by mixing lithium bentonite, hydrophobic fumed silica, polyvinylpyrrolidone and calcium acetate serving as main raw materials with a silane coupling agent, ethylene carbonate and absolute ethyl alcohol, wherein the silane coupling agent can be chemically bonded with the lithium bentonite, the hydrophobic fumed silica, the polyvinylpyrrolidone and the calcium acetate firstly in the stirring process; then, the modified kaolin and the kaolin pretreated by the titanate coupling agent can be chemically bonded again, so that the dispersibility of the kaolin in the PET material can be improved, the agglomeration phenomenon of the modified kaolin and the PET material can be reduced, the modified kaolin and the PET material have good compatibility, the modified kaolin serving as a nucleating agent can improve the crystallization rate and shorten the molding period, the modified kaolin serving as an inorganic filler can strengthen and toughen the PET, and the modified kaolin and the kaolin are matched with an impact-resistant toughening agent to greatly improve the impact resistance of the PET so as to improve the drop resistance of the PET material.
Detailed Description
The present invention will be described in further detail below.
Preparation of modified Clay the titanate coupling agent in the following preparation is selected from chelate solutions of QX-311W bis (dioctyloxypyrophosphate) ethylene titanate and triethanolamine, available from Nanjing Schiff-base chemical Co., Ltd.; the lithium bentonite is selected from lithium bentonite with montmorillonite content more than or equal to 70 and granularity of 300 meshes provided by Xinyang Chengxiang Fei New Material science and technology Limited; the hydrophobic fumed silica is selected from hydrophobic fumed silica with model H-20 provided by Wake of Germany; the polyvinylpyrrolidone is selected from polyvinylpyrrolidone of type K30 available from Fujia of Shandong.
Preparation example 1: ① A suspension of clay having a clay content of 10% was prepared by adding water to clay and stirring;
② taking 10kg of lithium bentonite, 2kg of hydrophobic fumed silica, 3kg of polyvinylpyrrolidone, 2kg of calcium acetate, 0.1kg of gamma-aminopropyltriethoxysilane, 50kg of ethylene carbonate and 50kg of absolute ethyl alcohol, and stirring at the speed of 1000r/min for 20min to obtain the modifier;
③ taking 100kg of pottery clay suspension, adding 0.03kg of titanate coupling agent, heating to 90 ℃, keeping the temperature and stirring for 10min, adding 3kg of modifier, heating to 140 ℃, keeping the temperature and stirring for 3h, cooling to room temperature, performing vacuum filtration to obtain a precipitate, washing the precipitate with absolute ethyl alcohol to obtain a washed matter, and drying the washed matter at 100 ℃ for 3h to obtain the modified pottery clay.
Preparation example 2A argil suspension having an argil content of 12.5% was prepared by adding water to the argil ① and stirring;
② taking 15kg of lithium bentonite, 3g of hydrophobic fumed silica, 4.5kg of polyvinylpyrrolidone, 2.5kg of calcium acetate, 0.15kg of gamma-glycidyl ether oxypropyl trimethoxy silane, 55kg of ethylene carbonate and 55kg of absolute ethyl alcohol, and stirring at the speed of 1500r/min for 25min to obtain the modifier;
③ taking 100kg of pottery clay suspension, adding 0.04kg of titanate coupling agent, heating to 95 ℃, keeping the temperature and stirring for 15min, adding 4kg of modifier, heating to 150 ℃, keeping the temperature and stirring for 4h, cooling to room temperature, vacuum-filtering to obtain precipitate, washing the precipitate with absolute ethyl alcohol to obtain washed matter, and drying the washed matter at 110 ℃ for 3.5h to obtain the modified pottery clay.
Preparation example 3A argil suspension having an argil content of 15% was prepared by adding water to the argil ① and stirring;
② taking 20kg of lithium bentonite, 4kg of hydrophobic fumed silica, 6kg of polyvinylpyrrolidone, 3kg of calcium acetate, 0.2kg of gamma- (methacryloyloxy) propyl trimethoxy silane, 60kg of ethylene carbonate and 60kg of absolute ethyl alcohol, and stirring at the speed of 2000r/min for 30min to obtain the modifier;
③ taking 100kg of pottery clay suspension, adding 0.05kg of titanate coupling agent, heating to 100 ℃, keeping the temperature and stirring for 120min, adding 5kg of modifier, heating to 160 ℃, keeping the temperature and stirring for 5h, cooling to room temperature, performing vacuum filtration to obtain a precipitate, washing the precipitate with absolute ethyl alcohol to obtain a washed matter, and drying the washed matter at 120 ℃ for 4h to obtain the modified pottery clay.
Preparation example 4 this preparation differs from the modified kaolin preparation 1 in that no titanate coupling agent is added in step ③.
Preparation example 5 this preparation example differs from preparation example 1 of a modified clay in that no gamma-aminopropyltriethoxysilane was added in step ②.
Preparation example 6 this preparation differs from preparation example 1 of modified kaolin in that the modifier used in step ② is only gamma-aminopropyltriethoxysilane.
Examples
The polyethylene terephthalate in the following examples was selected from polyethylene terephthalate available from dupont, usa under the designation 530HTEJK 503; the maleic anhydride grafted polyethylene octene elastomer is selected from maleic anhydride grafted polyethylene octene elastomers available from AMPLIFY of America under the model number AMPLIFY M2265; the ethylene-acrylate-maleic anhydride terpolymer was selected from the ethylene-acrylate-maleic anhydride terpolymer supplied by arkema with model 2210; the tackifying chain extender is selected from the chain extenders provided by basf, germany under the trade name ADR-4370F.
Example 1: the impact-resistant PET is prepared by the following method:
s1, drying: drying polyethylene terephthalate for 3h at 120 ℃ to obtain dried polyethylene terephthalate;
s2, mixing materials: weighing 50kg of dried polyethylene glycol terephthalate, adding 3kg of maleic anhydride grafted polyethylene octene elastomer, 3kg of ethylene-acrylate-maleic anhydride terpolymer, 4kg of modified pottery clay (selected from preparation example 1 of the modified pottery clay), 0.06kg of tackifying chain extender, 10100.01 kg of antioxidant, 1680.01 kg of antioxidant, 0.375kg of ethylene bis stearamide and 0.125kg of stearic acid into a high-speed mixer, and blending for 10min at the speed of 3000r/min to obtain a mixture;
s3, granulating: placing the mixture in a double-screw extruder, wherein the temperature of each zone is as follows: the temperature of the first zone is 190 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 250 ℃, the temperature of the second zone is 255 ℃, the temperature of the third zone is 260 ℃, the temperature of the fourth zone is 265 ℃, the temperature of the fifth zone is 265 ℃, the temperature of the sixth zone is 260 ℃, the temperature of the seventh zone is 255 ℃, the temperature of the eighth zone is 255 ℃, the temperature of a machine head is 255 ℃, the retention time is 3min, and the impact-resistant PET material is obtained after melt extrusion granulation.
Example 2: the impact-resistant PET is prepared by the following method:
s1, drying: drying polyethylene terephthalate at 125 ℃ for 4h to obtain dried polyethylene terephthalate;
s2, mixing materials: weighing 55kg of dried polyethylene glycol terephthalate, putting the dried polyethylene glycol terephthalate into a high-speed mixer, adding 3.5kg of maleic anhydride grafted polyethylene octene elastomer, 3.5kg of ethylene-acrylate-maleic anhydride terpolymer, 5kg of modified pottery clay (selected from preparation example 2 of the modified pottery clay), 0.07kg of tackifying chain extender, 10100.03 kg of antioxidant, 1680.03 kg of antioxidant, 0.75kg of ethylene bis stearamide and 0.25kg of stearic acid, and blending for 15min at the speed of 3000r/min to obtain a mixture;
s3, granulating: placing the mixture in a double-screw extruder, wherein the temperature of each zone is as follows: the temperature of the first zone is 195 ℃, the temperature of the second zone is 215 ℃, the temperature of the third zone is 252 ℃, the temperature of the second zone is 257 ℃, the temperature of the third zone is 262 ℃, the temperature of the fourth zone is 267 ℃, the temperature of the fifth zone is 267 ℃, the temperature of the sixth zone is 262 ℃, the temperature of the seventh zone is 257 ℃, the temperature of the eighth zone is 257 ℃, the temperature of a machine head is 257 ℃, the retention time is 4min, and the impact-resistant PET material is obtained after melt extrusion granulation.
Example 3: the impact-resistant PET is prepared by the following method:
s1, drying: drying polyethylene terephthalate for 5 hours at the temperature of 130 ℃ to obtain dried polyethylene terephthalate;
s2, mixing materials: weighing 60kg of dried polyethylene glycol terephthalate, adding 4kg of maleic anhydride grafted polyethylene octene elastomer, 4kg of ethylene-acrylate-maleic anhydride terpolymer, 6kg of modified pottery clay (selected from preparation example 3 of the modified pottery clay), 0.08kg of tackifying chain extender, 10100.05 kg of antioxidant, 1680.05 kg of antioxidant, 1.125kg of ethylene bis stearamide and 0.375kg of stearic acid into a high-speed mixer, and blending at the speed of 3000r/min for 20min to obtain a mixture;
s3, granulating: placing the mixture in a double-screw extruder, wherein the temperature of each zone is as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 220 ℃, the temperature of the third zone is 255 ℃, the temperature of the second zone is 260 ℃, the temperature of the third zone is 265 ℃, the temperature of the fourth zone is 270 ℃, the temperature of the fifth zone is 270 ℃, the temperature of the sixth zone is 265 ℃, the temperature of the seventh zone is 260 ℃, the temperature of the eighth zone is 260 ℃, the temperature of a machine head is 260 ℃, the retention time is 5min, and the impact-resistant PET material is obtained after melt extrusion granulation.
Table 1 examples 1-3 raw material usage meter
Comparative example
Comparative example 1: this comparative example differs from example 1 in that the maleic anhydride grafted polyethylene octene elastomer and the ethylene-acrylate-maleic anhydride terpolymer were not added to the feed.
Comparative example 2: this comparative example is different from example 1 in that the modified kaolin in the raw material was replaced with the same amount of calcium carbonate.
Comparative example 3: this comparative example is different from example 1 in that the modified kaolin was selected from those prepared in preparation example 4 of modified kaolin.
Comparative example 4: this comparative example is different from example 1 in that the modified kaolin was selected from those prepared in preparation example 5 of modified kaolin.
Comparative example 5: this comparative example is different from example 1 in that the modified kaolin was selected from those prepared in preparation example 6 of modified kaolin.
Performance testing
Preparing a PET material by adopting the methods of the embodiments 1-3 and the comparative examples 1-5, respectively placing the prepared PET materials into a double-screw injection molding machine for injection molding, wherein the injection nozzle temperature of the injection molding machine is 280 ℃, the front section temperature is 275 ℃, the middle section temperature is 270 ℃, the rear section temperature is 265 ℃, and the injection pressure is 90MPa to obtain a sample; the properties of the test specimens were measured in the following manner, and the results are shown in Table 2.
Tensile property: according to GB/T1040-2018, part 1 of the determination of tensile properties of plastics: the method in general rules "measures the tensile strength of a specimen;
bending property: the flexural strength and flexural modulus of the test specimens were measured according to the method in GB/T9341-2008 "measurement of Plastic flexural Properties";
impact strength: the impact strength of the test specimen with or without notches was measured according to the method in GB/T1843-2008 "measurement of impact strength of Plastic cantilever Beam";
melt index: part 1 of the determination of the melt Mass Flow Rate (MFR) and melt volume flow rate (MVR) of the thermoplastics according to GB/T3682-2018: standard methods for testing.
TABLE 2 Performance test Table for PET materials in examples 1 to 3 and comparative examples 1 to 5
As can be seen from the data in Table 2, the PET materials in examples 1-3 have good tensile property, bending property and impact resistance, which indicates that the PET materials prepared by the method of the invention have excellent toughness and impact resistance; the melt index is a value of the fluidity of the plastic material during processing, the larger the value, the better the processing fluidity, and the melt index in examples 1 to 3 is more than 20g/10min, which shows that the PET material of the invention also has good processing performance.
The raw material of comparative example 1 was not added with maleic anhydride grafted polyethylene octene elastomer and ethylene-acrylate-maleic anhydride terpolymer; compared with example 1, the tensile strength, flexural modulus and impact strength of the PET in comparative example 1 are obviously reduced, which shows that the mechanical properties of the PET material can be obviously improved by adding the maleic anhydride grafted polyethylene octene elastomer and the ethylene-acrylate-maleic anhydride terpolymer.
In comparative example 2, the modified kaolin in the raw material was replaced with an equal amount of calcium carbonate; compared with example 1, the tensile strength, bending modulus, impact strength and melt index of PET in comparative example 2 are obviously reduced, which shows that the modified argil of the invention can not only improve the mechanical property of PET material, but also improve the processing property compared with the traditional calcium carbonate.
The modified kaolin of comparative example 3 was prepared from the modified kaolin prepared in preparation example 4, in which no titanate coupling agent was added in step ③, and the modified kaolin of comparative example 4 was prepared from the modified kaolin prepared in preparation example 5, in which no gamma-aminopropyltriethoxysilane was added in step ②, which shows that the titanate coupling agent and gamma-aminopropyltriethoxysilane added during the preparation of the modified kaolin improve the modifying effect of the modified kaolin to improve the performance of the PET material compared to example 1, and that the compatibility of the inorganic filler with the polymer is improved by the titanate coupling agent and gamma-aminopropyltriethoxysilane added during the preparation of the modified kaolin, and that the silane coupling agent and the titanate coupling agent both improve the processability of the PET material.
The modified kaolin clay of the comparative example 5 is prepared by selecting the modified kaolin clay from the preparation example 6 of the modified kaolin clay, the modifier in the step ② of the preparation is only gamma-aminopropyltriethoxysilane, compared with the example 1, the tensile strength, the bending modulus, the impact strength and the melt index of the PET material in the comparative example 5 are obviously reduced, the mechanical property of the modified kaolin clay of the invention can be obviously improved after the modified kaolin clay is treated by the modifier, and the comparison among the examples 1, the comparative example 3 and the comparative example 4 with the comparative example 5 shows that the mechanical property of the PET material can be improved and the processing property of the PET material can also be improved.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Claims (10)
1. An impact-resistant PET material characterized by: the paint comprises the following components in parts by weight: 50-60 parts of polyethylene glycol terephthalate, 6-8 parts of impact-resistant toughening agent, 4-6 parts of modified clay, 0.06-0.08 part of tackifying chain extender, 0.02-0.1 part of antioxidant and 0.5-1.5 parts of lubricant;
the impact-resistant toughening agent consists of a maleic anhydride grafted polyethylene octene elastomer and an ethylene-acrylate-maleic anhydride terpolymer in a weight ratio of 1: 1.
2. The impact-resistant PET material is characterized in that the modified pottery clay is prepared by adding ① water into pottery clay, and stirring to obtain a pottery clay suspension with a pottery clay content of 10-15%;
② taking 100 parts by weight of pottery clay suspension, adding 0.03-0.05 part of titanate coupling agent, heating to 90-100 ℃, stirring for 10-20min under heat preservation, adding 3-5 parts of modifier, heating to 140 ℃ and 160 ℃, stirring for 3-5h under heat preservation, cooling to room temperature, vacuum filtering to obtain precipitate, washing the precipitate with absolute ethyl alcohol to obtain a washed matter, and drying the washed matter at 120 ℃ for 3-4h to obtain the modified pottery clay.
3. The impact-resistant PET material as claimed in claim 2, wherein the titanate coupling agent in step ② is a chelate solution of bis (dioctyloxypyrophosphate) ethylene titanate and triethanolamine.
4. The impact-resistant PET material as claimed in claim 2, wherein the modifier in step ② is prepared by taking 10-20 parts by weight of lithium bentonite, 2-4 parts by weight of hydrophobic fumed silica, 3-6 parts by weight of polyvinylpyrrolidone, 2-3 parts by weight of calcium acetate, 0.1-0.2 part by weight of silane coupling agent, 50-60 parts by weight of ethylene carbonate and 50-60 parts by weight of absolute ethyl alcohol, and stirring at a speed of 1000-2000r/min for 20-30min to obtain the modifier.
5. An impact-resistant PET material according to claim 4, characterized in that: the silane coupling agent is one of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane and gamma- (methacryloyloxy) propyltrimethoxysilane.
6. An impact-resistant PET material according to claim 1, characterized in that: the antioxidant is prepared by mixing an antioxidant 1010 and an antioxidant 168 in a weight ratio of 1: 1.
7. An impact-resistant PET material according to claim 1, characterized in that: the lubricant is compounded by ethylene bis stearamide and stearic acid in a weight ratio of 3: 1.
8. A process for the preparation of an impact-resistant PET material as claimed in any of claims 1 to 7, characterized in that: the method comprises the following steps:
s1, mixing materials: weighing the dried polyethylene glycol terephthalate according to the proportion, and blending for 10-20min to obtain a mixture;
s2, granulating: and melting, extruding and granulating the mixture at the temperature of 250-280 ℃ to obtain the impact-resistant PET material.
9. The method for preparing an impact-resistant PET material according to claim 8, wherein the method comprises the following steps: the dried polyethylene terephthalate of S1 is dried at the temperature of 120-130 ℃ for 3-5 h.
10. The method for preparing an impact-resistant PET material according to claim 8, wherein the method comprises the following steps: s2, placing the mixture into a double-screw extruder, wherein the temperature of each zone is as follows: the temperature of the first zone is 190-class 200 ℃, the temperature of the second zone is 210-class 220 ℃, the temperature of the third zone is 250-class 255 ℃, the temperature of the second zone is 255-class 260 ℃, the temperature of the third zone is 260-class 265 ℃, the temperature of the fourth zone is 265-class 270 ℃, the temperature of the fifth zone is 265-class 270 ℃, the temperature of the sixth zone is 260-class 265 ℃, the temperature of the seventh zone is 255-class 260 ℃, the temperature of the eighth zone is 255-class 260 ℃, the temperature of the head is 255-class 260 ℃ and the retention time is 3-5 min.
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| CN112940460A (en) * | 2021-04-14 | 2021-06-11 | 广东宇豪新材料科技有限公司 | Shock-resistant supramolecular composite |
| CN113956620A (en) * | 2021-07-27 | 2022-01-21 | 黄山鑫赢再生资源有限公司 | Preparation method of high-viscosity recycled PET plastic particles |
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