CN114249977A - PET/TPU alloy material with excellent mechanical property and preparation method thereof - Google Patents

PET/TPU alloy material with excellent mechanical property and preparation method thereof Download PDF

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Publication number
CN114249977A
CN114249977A CN202111465968.8A CN202111465968A CN114249977A CN 114249977 A CN114249977 A CN 114249977A CN 202111465968 A CN202111465968 A CN 202111465968A CN 114249977 A CN114249977 A CN 114249977A
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pet
tpu
alloy material
compatilizer
hydroxyl
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CN114249977B (en
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王荣誉
高玉宝
宋红玮
陈洋
由可锦
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Meirui New Material Innovation Center Shandong Co ltd
Miracll Chemicals Co Ltd
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Meirui New Material Innovation Center Shandong Co ltd
Miracll Chemicals Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/04—Thermoplastic elastomer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Glanulating (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention discloses a PET/TPU alloy material with excellent mechanical property and a preparation method thereof. The alloy material comprises the following raw materials of PET, hydroxyl-terminated TPU and a compatilizer; the mass ratio of the PET to the hydroxyl-terminated TPU is 10-40% and 60-90% based on 100% of the total mass of the PET and the hydroxyl-terminated TPU; the compatilizer is isocyanate group blocked polyurethane, and the using amount of the compatilizer is 2-10% of the total mass of PET and hydroxyl group blocked TPU. The preparation method comprises the following steps: mixing PET and hydroxyl-terminated TPU into a uniform melt in a reactive twin-screw extruder by heating and shearing the twin-screws; feeding the compatilizer into a reactive double-screw extruder through a melt pump at a first exhaust port; the melt and the compatilizer are fully mixed and reacted under the action of a screw, and then are extruded out through a die head, and the PET/TPU alloy material with excellent mechanical property is obtained after water cooling, grain cutting, dehydration and drying.

Description

PET/TPU alloy material with excellent mechanical property and preparation method thereof
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a PET (polyethylene terephthalate)/TPU (thermoplastic polyurethane) alloy material with excellent mechanical property and a preparation method thereof.
Background
The polymer material occupies an important position in recycling economy, but most of materials recycled in the market are hard polymer materials, so that the application scenes of the recycled materials are greatly limited, the market is also lost, and therefore, the recycled materials with softer quality need to be developed.
Patent application CN104341747A introduces a novel PET composite material and a preparation method thereof, the alloy material introduced in the patent uses PET as a main material, the raw materials of polyurethane only comprise isocyanate and oligomer polyol, the reaction of the polyurethane formula is limited, only polyurethane with low polymerization degree can be formed, and the modification of the alloy material cannot achieve ideal effect; from the process of the patent, two kinds of isocyanate and polycarbophil are added into a high-speed mixer to be mixed and coated with inorganic particles, and the process causes the inorganic particles to be agglomerated together, difficult to disperse and difficult to achieve the desired effect; according to the formula of the hard plastic, the hard plastic is made of the hard plastic, and the purpose of the hard plastic is completely different from that of the invention to be realized.
Patent application CN104419128A relates to a recycled PET alloy and a preparation method thereof, the patent uses a plurality of materials for mixing, the main material is PET, the modified matrix is ABS, the effect of TPU-g-MAH in the patent technology is toughening agent, the addition amount is small, the expected effect of the materials is completely different, and the judgment of the added materials shows that the alloy material is engineering grade plastic with very high hardness, which is completely different from the expected effect of the invention.
The PET mineral water bottle is a material with a mature recycling system, but the hardness of the PET mineral water bottle is larger, the TPU is a material with a larger adjustable hardness range, and the TPU with the smaller hardness is combined with the PET with the larger hardness to prepare an alloy material which meets the use requirement and contains a certain proportion of recycled materials. However, the physical parameters of PET and TPU are greatly different, the compatibility of the materials is poor, and the performance of the alloy material is greatly reduced, so that an auxiliary agent capable of improving the compatibility of the PET and the TPU is needed to improve the performance of the material, but the conventional auxiliary agent cannot achieve the effect.
Disclosure of Invention
Aiming at the technical problems and the defects in the field, the invention provides the PET/TPU alloy material with excellent mechanical property, solves the problem of poor compatibility of the PET/TPU alloy, can improve the comprehensive performance of the material, and can improve the recycling property of the material and reduce the influence of waste plastics on the environment by adopting the recycled PET material.
A PET/TPU alloy material with excellent mechanical properties comprises raw materials of PET, hydroxyl-terminated TPU and a compatilizer;
the mass ratio of the PET to the hydroxyl-terminated TPU is 10-40% and 60-90% based on 100% of the total mass of the PET and the hydroxyl-terminated TPU;
the compatilizer is isocyanate group blocked polyurethane, and the using amount of the compatilizer is 2-10% of the total mass of PET and hydroxyl group blocked TPU.
The hydroxyl-terminated TPU is stable in property and easy to store, and the hydroxyl-terminated TPU is used as a main material to form an alloy material with PET.
However, the compatibility of the hydroxyl-terminated TPU and PET is poor, and the molecular chains of the two materials are in a phase-separated state, so that the prepared material has poor performance and has great potential risk when being applied to an actual scene.
The polyurethane used as the compatilizer in the prior art is generally hydroxyl-terminated polyurethane, is not a reactive compatilizer and cannot form chemical crosslinking.
The compatilizer adopted by the invention is-NCO-terminated polyurethane, is a reactive compatilizer and has reaction activity, and hydroxyl-terminated TPU and PET terminal hydroxyl groups which are used as main materials can react with-NCO groups of the compatilizer, so that on one hand, molecular chains of the TPU can be prolonged, the strength of the TPU is improved, on the other hand, the PET and the molecular chains of the TPU can be connected together, the compatibility of the materials is improved, and the incompatible state of the two materials with larger physical property difference is converted into the state with higher compatibility.
If the-NCO-terminated TPU is directly used as a main material to be mixed and modified with PET, the actual production of the material has a big problem and is hardly feasible, because the-NCO-terminated TPU has active property, is easy to react with water or other substances, has uncontrollable structure after reaction, can be changed into a foaming-like thermosetting material, can not be reprocessed, is difficult to store in large quantity, and can not be used as the main material of an alloy material.
In a preferred embodiment, the PET/TPU alloy material with excellent mechanical properties is recycled and re-granulated PET, such as recycled mineral water bottle crushed material re-extruded and granulated particles.
In a preferred embodiment, the hydroxyl-terminated TPU is a polyester type TPU with a hardness of 70 to 90A. The polyester type TPU has more polar groups, so that more hydrogen bonds can be formed in the alloy material, the TPU with the hardness of 70-90A has higher forming speed and good mechanical property and hand feeling, and the adverse effect of introducing PET on the alloy material is compensated.
The isocyanate group-terminated polyurethane as the compatibilizing agent is preferably prepared by a method comprising the steps of:
(1) adding oligomer polyol into a vacuum heating stirring kettle, heating to 120-130 ℃, stirring after the oligomer polyol is completely melted, vacuumizing to remove water in the material, wherein the stirring vacuumizing time is 1-2 hours, and the vacuum degree is-0.09-0.1 MPa;
(2) when the water content of the oligomer polyol in the vacuum heating stirring kettle is lower than 0.05 wt%, cooling to 60-70 ℃, adding diisocyanate and a retarder into the vacuum heating stirring kettle, then heating to 100-110 ℃, continuously stirring and reacting for 1.5-2h, and maintaining the vacuum degree at-0.09-0.1 MPa;
(3) and then adding a catalyst into the vacuum heating stirring kettle, maintaining the vacuum degree of-0.09 to-0.1 MPa, defoaming until no obvious bubbles are generated (the time can be 0.5 to 1.5 hours), and finishing the reaction to obtain the isocyanate group-terminated polyurethane which can be used as a compatilizer.
The prepared compatilizer can be preserved by placing N2The replaced aluminum foil bag is filled with N2And sealing and storing.
The molecular weight of the oligomer polyol is preferably 1000-4000, and the oligomer polyol is preferably one or two of polyester polyol and polyether polyol, wherein the polyester polyol is preferably a polycondensate of adipic acid and one or more of ethylene glycol, 1, 2-propylene glycol, 1, 4-butanediol, diethylene glycol, neopentyl glycol, 1, 6-hexanediol, trimethylolpropane and glycerol, and the polyether polyol is preferably one or two of polytetrahydrofuran polyol and polypropylene oxide polyol.
In a preferred embodiment, the diisocyanate is one or more of toluene diisocyanate, diphenylmethane diisocyanate, 1, 5-naphthalene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and p-phenylene diisocyanate.
The compatilizer prepared from the preferable oligomer polyalcohol and diisocyanate has a plurality of polar groups, and can generate hydrogen bonds with molecular chains of PET and hydroxyl-terminated TPU in an activated state such as high-temperature melting and the like, so that the strength of the material is further improved.
In a preferred embodiment, the retarder is an inorganic acid (e.g., phosphoric acid, etc.). The addition amount of the retarder is preferably 0.1 to 0.5 parts by mass based on 100 parts by mass of the total amount of the oligomer polyol and the diisocyanate.
In a preferred embodiment, the catalyst is one or more of dimorpholinodiethyl ether, N-methylmorpholine, N-ethylmorpholine, triethylene diamine, N-methylimidazole, stannous octoate and dibutyltin dilaurate. The amount of the catalyst added is preferably 1 to 10 parts by mass based on 100 parts by mass of the total amount of the oligomer polyol and the isocyanate.
In a preferred embodiment, the molar ratio (R value) of isocyanate groups in the diisocyanate to hydroxyl groups in the oligomeric polyol is greater than 1:1 and not greater than 3: 1.
The invention also provides a preparation method of the PET/TPU alloy material with excellent mechanical property, which comprises the following steps:
1) adding PET and hydroxyl-terminated TPU into a reactive twin-screw extruder, and mixing the PET and the hydroxyl-terminated TPU into a uniform melt through heating and shearing of twin screws;
2) feeding a compatilizer into a reactive double-screw extruder through a melt pump at a first exhaust port of the reactive double-screw extruder;
3) and (2) after the melt in the step 1) and the compatilizer are fully mixed and react under the action of a screw rod, extruding the mixture through a die head, and obtaining the PET/TPU alloy material with excellent mechanical property after water cooling, grain cutting, dehydration and drying.
When the compatilizer is added into a reactive twin-screw extruder, the blend of PET and hydroxyl-terminated TPU is heated and sheared into a molten state by twin screws, the molecular chain of the material is in a movable state, and the molecular chain in the activated state has reaction activity and can better react and crosslink with-NCO-terminated polyurethane.
In a preferred embodiment, the reactive twin-screw extruder has 14 sections, the feeding hole close to the main machine is the 1 st section, the first vent hole is the 6 th section, the second vent hole is the 11 th section, and the temperatures of the sections are set as follows: the temperature of the zone 1 is 200-220 ℃, the temperature of the zone 2-5 is 200-240 ℃, the temperature of the zone 6-10 is 220-245 ℃, the temperature of the zone 11-14 is 160-180 ℃, the temperature of the gear pump is 220-230 ℃, and the temperature of the die head is 220-230 ℃;
the rotating speed of the reactive double-screw extruder is 180 revolutions per minute, and the length-diameter ratio of the screw is 40-50: 1.
The melt pump may meter in a uniform rate to add a defined mass of compatibilizer. In a preferred embodiment, the melt pump is heated to a temperature of 60 ℃.
Compared with the prior art, the invention has the main advantages that:
physical properties of PET and hydroxyl-terminated TPU are greatly different, the simple blending of the PET and the hydroxyl-terminated TPU and the alloy prepared by adding a common compatilizer have layering and phase splitting phenomena, and the compatibility between the PET and the alloy cannot be improved, so that the alloy materials prepared from the PET and the hydroxyl-terminated TPU have poor performance and are difficult to apply. At present, the price of chemical raw materials is greatly increased and the pressure of the environment is continuously increased by the waste high polymer materials, so that the recycled PET bottle flake particles are not only favorable for reducing the pressure of the environment, but also favorable for reducing the cost of the composite material because the price of PET is relatively low. The compatilizer can solve the compatibility problem of the composite material, can prepare alloy materials with excellent comprehensive performance, can be applied to products such as sheaths and rubber coatings, has good mechanical performance and good hand feeling, reduces the cost of the alloy materials due to the application of the PET materials, realizes the recycling of resources, uses regenerated materials, and can effectively reduce carbon emission.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
Example 1
(1) 10kg of hydroxyl-terminated oligomer polyol with the molecular weight of 3000, which is prepared by the reaction of adipic acid and 1, 4-butanediol, is added into a vacuum heating stirring kettle, the temperature is gradually increased to 120-130 ℃, when the oligomer polyol is completely melted, stirring is carried out, the moisture in the materials is removed by vacuumizing, the stirring and vacuumizing time is 1-2h, and the vacuum degree is-0.09 to-0.1 MPa;
(2) taking 100ml of oligomer polyhydric alcohol from a discharge hole of a vacuum heating stirring kettle to test moisture, cooling the material to 60-70 ℃ when the moisture is lower than 0.05 wt%, adding 1.668kg of MDI (diphenylmethane diisocyanate) and 11.7g of phosphoric acid into the vacuum kettle, heating to 100-;
(3) adding 117g of dibutyltin dilaurate into the vacuum kettle, maintaining the vacuum degree to be between-0.09 and-0.1 MPa, and defoaming for 0.5 to 1.5 hours until no obvious bubbles are generated in a visible window of the vacuum kettle, and finishing the reaction;
(4) putting the prepared compatilizer into a reactor by using N2The replaced aluminum foil bag is filled with N2Sealing and storing;
(5) 30kg of PET which is purchased and recycled and re-granulated by Shandong co-creation macro new material science and technology Limited company and 70kg of TPU of grade E390C 1 produced by Meirui new material Limited company are mixed, the mixture is added into a reaction type double-screw extruder at a constant speed of 45kg/h through a feeder, the mixture is mixed into uniform melt through heating and shearing of double screws, the length-diameter ratio of the double-screw extruder is 42:1, and the temperature of a feeding zone 1 is 200 ℃; the 2-5 area is 240 ℃; the temperature of a 6-10 area is 220 ℃; the temperature of 11-14 areas is 160 ℃; the gear pump temperature is 230 ℃; the die temperature is 230 ℃;
(6) feeding a self-made compatilizer into a double-screw extruder at a constant speed of 1.35kg/h through a melt pump (the heating temperature is 60 ℃) at a first exhaust port (a 6 th area of the double-screw extruder) of the reactive double-screw extruder;
(7) and (3) fully mixing and reacting the blend and the compatilizer under the action of a screw, extruding the mixture through a die head, and performing water cooling, grain cutting, dehydration and drying to obtain the alloy material.
Example 2
(1) Adding 10kg of hydroxyl-terminated oligomer polyhydric alcohol with the molecular weight of 3000, which is prepared by the reaction of adipic acid and ethylene glycol, into a vacuum heating stirring kettle, gradually heating to 120-130 ℃, stirring after the oligomer polyhydric alcohol is completely melted, vacuumizing to remove moisture in the materials, stirring and vacuumizing for 1-2h, wherein the vacuum degree is-0.09 to-0.1 MPa;
(2) taking 100ml of oligomer polyhydric alcohol from a discharge hole of a vacuum heating stirring kettle to test moisture, cooling the material to 60-70 ℃ when the moisture is lower than 0.05 wt%, adding 1.668kg of MDI and 11.7g of phosphoric acid into the vacuum kettle, then heating to 100-110 ℃, continuing stirring for reaction for 1.5-2h, and maintaining the vacuum degree at-0.09 to-0.1 MPa;
(3) adding 117g of dibutyltin dilaurate into the vacuum kettle, maintaining the vacuum degree to be between-0.09 and-0.1 MPa, and defoaming for 0.5 to 1.5 hours until no obvious bubbles are generated in a visible window of the vacuum kettle, and finishing the reaction;
(4) putting the prepared compatilizer into a reactor by using N2The replaced aluminum foil bag is filled with N2Sealing and storing;
(5) 30kg of PET which is purchased and recycled and re-granulated by Shandong co-creation macro new material science and technology Limited company and 70kg of TPU of grade E390C 1 produced by Meirui new material Limited company are mixed, the mixture is added into a reaction type double-screw extruder at a constant speed of 45kg/h through a feeder, the mixture is mixed into uniform melt through heating and shearing of double screws, the length-diameter ratio of the double-screw extruder is 42:1, and the temperature of a feeding zone 1 is 200 ℃; the 2-5 area is 240 ℃; the temperature of a 6-10 area is 220 ℃; the temperature of 11-14 areas is 160 ℃; the gear pump temperature is 230 ℃; the die temperature is 230 ℃;
(6) feeding a self-made compatilizer into a double-screw extruder at a constant speed of 1.35kg/h through a melt pump (the heating temperature is 60 ℃) at a first exhaust port (a 6 th area of the double-screw extruder) of the reactive double-screw extruder;
(7) and (3) fully mixing and reacting the blend and the compatilizer under the action of a screw, extruding the mixture through a die head, and performing water cooling, grain cutting, dehydration and drying to obtain the alloy material.
Example 3
(1) 10kg of hydroxyl-terminated oligomer polyol with the molecular weight of 3000, which is prepared by the reaction of adipic acid and 1, 2-propylene glycol, is added into a vacuum heating stirring kettle, the temperature is gradually increased to 120-130 ℃, when the oligomer polyol is completely melted, stirring is carried out, the moisture in the materials is removed by vacuumizing, the stirring and vacuumizing time is 1-2h, and the vacuum degree is-0.09 to-0.1 MPa;
(2) taking 100ml of oligomer polyhydric alcohol from a discharge hole of a vacuum heating stirring kettle to test moisture, cooling the material to 60-70 ℃ when the moisture is lower than 0.05 wt%, adding 1.668kg of MDI and 11.7g of phosphoric acid into the vacuum kettle, then heating to 100-110 ℃, continuing stirring for reaction for 1.5-2h, and maintaining the vacuum degree at-0.09 to-0.1 MPa;
(3) adding 117g of dibutyltin dilaurate into the vacuum kettle, maintaining the vacuum degree to be between-0.09 and-0.1 MPa, and defoaming for 0.5 to 1.5 hours until no obvious bubbles are generated in a visible window of the vacuum kettle, and finishing the reaction;
(4) putting the prepared compatilizer into a reactor by using N2The replaced aluminum foil bag is filled with N2Sealing and storing;
(5) 30kg of PET which is purchased and recycled and re-granulated by Shandong co-creation macro new material science and technology Limited company and 70kg of TPU of grade E390C 1 produced by Meirui new material Limited company are mixed, the mixture is added into a reaction type double-screw extruder at a constant speed of 45kg/h through a feeder, the mixture is mixed into uniform melt through heating and shearing of double screws, the length-diameter ratio of the double-screw extruder is 42:1, and the temperature of a feeding zone 1 is 200 ℃; the 2-5 area is 240 ℃; the temperature of a 6-10 area is 220 ℃; the temperature of 11-14 areas is 160 ℃; the gear pump temperature is 230 ℃; the die temperature is 230 ℃;
(6) feeding a self-made compatilizer into a double-screw extruder at a constant speed of 1.35kg/h through a melt pump (the heating temperature is 60 ℃) at a first exhaust port (a 6 th area of the double-screw extruder) of the reactive double-screw extruder;
(7) and (3) fully mixing and reacting the blend and the compatilizer under the action of a screw, extruding the mixture through a die head, and performing water cooling, grain cutting, dehydration and drying to obtain the alloy material.
Example 4
(1) Adding 10kg of polytetrahydrofuran ether glycol with the molecular weight of 3000 into a vacuum heating stirring kettle, gradually heating to 120-130 ℃, stirring after oligomer polyol is completely melted, vacuumizing to remove water in the material, wherein the stirring vacuumizing time is 1-2h, and the vacuum degree is-0.09 to-0.1 MPa;
(2) taking 100ml of oligomer polyhydric alcohol from a discharge hole of a vacuum heating stirring kettle to test moisture, cooling the material to 60-70 ℃ when the moisture is lower than 0.05 wt%, adding 1.668kg of MDI and 11.7g of phosphoric acid into the vacuum kettle, then heating to 100-110 ℃, continuing stirring for reaction for 1.5-2h, and maintaining the vacuum degree at-0.09 to-0.1 MPa;
(3) adding 117g of dibutyltin dilaurate into the vacuum kettle, maintaining the vacuum degree to be between-0.09 and-0.1 MPa, and defoaming for 0.5 to 1.5 hours until no obvious bubbles are generated in a visible window of the vacuum kettle, and finishing the reaction;
(4) putting the prepared compatilizer into a reactor by using N2The replaced aluminum foil bag is filled with N2Sealing and storing;
(5) 30kg of PET which is purchased and recycled and re-granulated by Shandong co-creation macro new material science and technology Limited company and 70kg of TPU of grade E390C 1 produced by Meirui new material Limited company are mixed, the mixture is added into a reaction type double-screw extruder at a constant speed of 45kg/h through a feeder, the mixture is mixed into uniform melt through heating and shearing of double screws, the length-diameter ratio of the double-screw extruder is 42:1, and the temperature of a feeding zone 1 is 200 ℃; the 2-5 area is 240 ℃; the temperature of a 6-10 area is 220 ℃; the temperature of 11-14 areas is 160 ℃; the gear pump temperature is 230 ℃; the die temperature is 230 ℃;
(6) feeding a self-made compatilizer into a double-screw extruder at a constant speed of 1.35kg/h through a melt pump (the heating temperature is 60 ℃) at a first exhaust port (a 6 th area of the double-screw extruder) of the reactive double-screw extruder;
(7) and (3) fully mixing and reacting the blend and the compatilizer under the action of a screw, extruding the mixture through a die head, and performing water cooling, grain cutting, dehydration and drying to obtain the alloy material.
Comparative example 1
(1) 30kg of PET which is purchased and recycled and re-granulated by Shandong co-creation macro new material science and technology Limited, 70kg of TPU of E390C 1 brand which is produced by Meirui new material Co Ltd and 10kg of SEBS-g-MAH which is purchased from American Keteng are mixed, the mixture is added into a reaction type double screw extruder at a constant speed of 45kg/h through a feeder, the mixture is mixed into uniform melt through heating and shearing of double screws, the length-diameter ratio of the double screw extruder is 42:1, and the temperature of a feeding 1 area is 200 ℃; the 2-5 area is 240 ℃; the temperature of a 6-10 area is 220 ℃; the temperature of 11-14 areas is 160 ℃; the gear pump temperature is 230 ℃; the die temperature is 230 ℃;
(2) and (3) fully mixing and reacting the blend and the compatilizer under the action of a screw, extruding the mixture through a die head, and performing water cooling, grain cutting, dehydration and drying to obtain the alloy material.
Comparative example 2
(1) 30kg of PET which is purchased and recycled and re-granulated by Shandong co-creation macro new material science and technology Limited, 70kg of TPU of E390C 1 brand which is produced by Meirui new material Co Ltd and 10kg of POE-g-MAH which is purchased from Dow USA are mixed, the mixture is uniformly added into a reaction type double-screw extruder at the speed of 45kg/h through a feeder, the mixture is mixed into uniform melt through heating and shearing of double screws, the length-diameter ratio of the double-screw extruder is 42:1, and the temperature of a feeding 1 area is 200 ℃; the 2-5 area is 240 ℃; the temperature of a 6-10 area is 220 ℃; the temperature of 11-14 areas is 160 ℃; the gear pump temperature is 230 ℃; the die temperature is 230 ℃;
(2) and (3) fully mixing and reacting the blend and the compatilizer under the action of a screw, extruding the mixture through a die head, and performing water cooling, grain cutting, dehydration and drying to obtain the alloy material.
The performance test results of the alloy materials obtained in the examples and the comparative examples are shown in the following table 1.
TABLE 1
Figure BDA0003391475520000091
As can be seen from the table 1, aiming at the hydroxyl-terminated TPU/PET alloy material system provided by the invention, the isocyanate-terminated polyurethane compatilizer is adopted, compared with the conventional compatilizer, the mechanical property of the prepared alloy material is obviously improved, the strength and the elongation at break of the material are higher, the application in more scenes can be met, the hardness of the material is lower, the hand feeling is good, the hard texture of plastic is not existed any more, and the using amount of the compatilizer is less.
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.

Claims (10)

1. A PET/TPU alloy material with excellent mechanical properties is characterized in that the raw materials comprise PET, hydroxyl-terminated TPU and a compatilizer;
the mass ratio of the PET to the hydroxyl-terminated TPU is 10-40% and 60-90% based on 100% of the total mass of the PET and the hydroxyl-terminated TPU;
the compatilizer is isocyanate group blocked polyurethane, and the using amount of the compatilizer is 2-10% of the total mass of PET and hydroxyl group blocked TPU.
2. The excellent mechanical property PET/TPU alloy material of claim 1, wherein the PET is recycled regranulated PET.
3. The PET/TPU alloy material with excellent mechanical properties as claimed in claim 1, wherein the hydroxyl terminated TPU is a polyester TPU with a hardness of 70-90A.
4. The PET/TPU alloy material with excellent mechanical properties as claimed in any one of claims 1 to 3, wherein the isocyanate group-terminated polyurethane as the compatibilizer is prepared by a method comprising the steps of:
(1) adding oligomer polyol into a vacuum heating stirring kettle, heating to 120-130 ℃, stirring after the oligomer polyol is completely melted, vacuumizing to remove water in the material, wherein the stirring vacuumizing time is 1-2 hours, and the vacuum degree is-0.09-0.1 MPa;
(2) when the water content of the oligomer polyol in the vacuum heating stirring kettle is lower than 0.05 wt%, cooling to 60-70 ℃, adding diisocyanate and a retarder into the vacuum heating stirring kettle, then heating to 100-110 ℃, continuously stirring and reacting for 1.5-2h, and maintaining the vacuum degree at-0.09-0.1 MPa;
(3) and then adding a catalyst into the vacuum heating stirring kettle, maintaining the vacuum degree of-0.09 to-0.1 MPa, defoaming until no obvious bubbles are generated, and finishing the reaction to obtain the isocyanate group terminated polyurethane which can be used as a compatilizer.
5. The PET/TPU alloy material with excellent mechanical properties as claimed in claim 4, wherein the molecular weight of the oligomer polyol is 1000-4000, and the oligomer polyol is one or two selected from polyester polyol and polyether polyol, wherein the polyester polyol is one or more polycondensates of adipic acid and one or more of ethylene glycol, 1, 2-propylene glycol, 1, 4-butanediol, diethylene glycol, neopentyl glycol, 1, 6-hexanediol, trimethylolpropane and glycerol, and the polyether polyol is one or two selected from polytetrahydrofuran polyol and polypropylene oxide polyol;
the diisocyanate is one or more of toluene diisocyanate, diphenylmethane diisocyanate, 1, 5-naphthalene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and p-phenylene diisocyanate.
6. The PET/TPU alloy material with excellent mechanical properties as claimed in claim 4, wherein the retarder is an inorganic acid; the addition amount of the retarder is 0.1-0.5 parts by mass based on 100 parts by mass of the total amount of the oligomer polyol and the diisocyanate;
the catalyst is one or more of dimorpholinyl diethyl ether, N-methylmorpholine, N-ethylmorpholine, triethylene diamine, N-methylimidazole, stannous octoate and dibutyltin dilaurate; the amount of the catalyst added is 1 to 10 parts by mass based on 100 parts by mass of the total amount of the oligomer polyol and the diisocyanate.
7. The PET/TPU alloy material with excellent mechanical properties as set forth in claim 4, wherein the molar ratio of isocyanate groups in the diisocyanate to hydroxyl groups in the oligomer polyol is greater than 1:1 and not greater than 3: 1.
8. The preparation method of the PET/TPU alloy material with excellent mechanical properties as claimed in any one of claims 1 to 7, comprising the steps of:
1) adding PET and hydroxyl-terminated TPU into a reactive twin-screw extruder, and mixing the PET and the hydroxyl-terminated TPU into a uniform melt through heating and shearing of twin screws;
2) feeding a compatilizer into a reactive double-screw extruder through a melt pump at a first exhaust port of the reactive double-screw extruder;
3) and (2) after the melt in the step 1) and the compatilizer are fully mixed and react under the action of a screw rod, extruding the mixture through a die head, and obtaining the PET/TPU alloy material with excellent mechanical property after water cooling, grain cutting, dehydration and drying.
9. The method for preparing a PET/TPU alloy material with excellent mechanical properties as claimed in claim 8, wherein the reactive twin-screw extruder has 14 zones, the feeding hole close to the main machine is the 1 st zone, the first vent hole is the 6 th zone, the second vent hole is the 11 th zone, and the temperatures of the zones are set as follows: the temperature of the zone 1 is 200-220 ℃, the temperature of the zone 2-5 is 200-240 ℃, the temperature of the zone 6-10 is 220-245 ℃, the temperature of the zone 11-14 is 160-180 ℃, the temperature of the gear pump is 220-230 ℃, and the temperature of the die head is 220-230 ℃;
the rotating speed of the reactive double-screw extruder is 180 revolutions per minute, and the length-diameter ratio of the screw is 40-50: 1.
10. The method for preparing PET/TPU alloy material with excellent mechanical properties as claimed in claim 8, wherein the heating temperature of the melt pump is 60 ℃.
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GB1513197A (en) * 1975-10-20 1978-06-07 Mobay Chemical Corp Poly(butyleneterephthalate)-polyurethane blends
US4034016A (en) * 1976-07-15 1977-07-05 Mobay Chemical Corporation Ternary polyblends prepared from polybutylene terephthalates, polyurethanes and aromatic polycarbonates
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