CN114589830A - Hydrolysis-resistant PET master batch and preparation method and application thereof - Google Patents
Hydrolysis-resistant PET master batch and preparation method and application thereof Download PDFInfo
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- CN114589830A CN114589830A CN202011436436.7A CN202011436436A CN114589830A CN 114589830 A CN114589830 A CN 114589830A CN 202011436436 A CN202011436436 A CN 202011436436A CN 114589830 A CN114589830 A CN 114589830A
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- 230000007062 hydrolysis Effects 0.000 title claims abstract description 87
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 87
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 83
- 230000000655 anti-hydrolysis Effects 0.000 claims abstract description 57
- 239000011347 resin Substances 0.000 claims abstract description 51
- 229920005989 resin Polymers 0.000 claims abstract description 51
- 238000001125 extrusion Methods 0.000 claims abstract description 46
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000001816 cooling Methods 0.000 claims abstract description 17
- 238000005469 granulation Methods 0.000 claims abstract description 17
- 230000003179 granulation Effects 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims description 184
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 114
- 239000000463 material Substances 0.000 claims description 14
- 229920002799 BoPET Polymers 0.000 claims description 13
- 150000001718 carbodiimides Chemical class 0.000 claims description 5
- 239000000835 fiber Substances 0.000 claims description 4
- 239000008204 material by function Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims 1
- 229920000642 polymer Polymers 0.000 claims 1
- 238000011143 downstream manufacturing Methods 0.000 abstract description 3
- 238000009700 powder processing Methods 0.000 abstract description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 94
- 230000000052 comparative effect Effects 0.000 description 29
- 238000004383 yellowing Methods 0.000 description 7
- 230000032683 aging Effects 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000001795 light effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- -1 polyethylene terephthalate Polymers 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
- B29K2067/003—PET, i.e. poylethylene terephthalate
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Abstract
The invention discloses a preparation method of hydrolysis-resistant PET master batch. The preparation method comprises the following steps: the hydrolysis-resistant PET master batch is prepared by a double-screw extruder, wherein the double-screw extruder comprises a main feeding port and a side feeding port; adding PET resin into a double-screw extruder through a main feeding port, adding an anti-hydrolysis agent into the double-screw extruder through a side feeding port, and carrying out melt mixing, extrusion, cooling and granulation on the PET resin and the anti-hydrolysis agent through the double-screw extruder; the hydrolysis-resistant PET master batch disclosed by the invention is excellent in color and does not yellow, so that the excellent service performance of a downstream photovoltaic back plate film is ensured; the hydrolysis resistance is high, and the mechanical property of the downstream photovoltaic back plate film is ensured; the concentration of the hydrolysis resistant agent is high, the addition amount is small in the blending process of downstream processing, the color influence caused by master batches is small, the downstream processing is convenient, and the problem of difficult powder processing is solved.
Description
Technical Field
The invention relates to an anti-hydrolysis PET master batch and a preparation method and application thereof.
Background
The main chain of polyethylene terephthalate (PET) molecules has rigid groups and molecular chains have high symmetry, so that the PET film has excellent physical and mechanical properties, heat resistance, electrical properties and film forming property and is low in price. Therefore, PET is widely used in engineering plastics, fiber textiles, and film industries. PET materials are widely used in photovoltaic back sheet films due to their excellent electrical insulation and moisture barrier properties, and in particular, in recent years, in order to eliminate the dependence on fluorine films, japanese has developed weather-resistant PET, and a photovoltaic back sheet with good weather resistance is prepared by multilayer compounding of modified PET and a common PET film, and this technology has become the mainstream technology in japan. However, the molecular structure of PET contains ester bonds, and the PET is easily degraded in natural environment, especially high-temperature and high-humidity environment, so that the phenomena of delamination, cracking, bubbles, yellowing and the like are caused, the output power of the photovoltaic cell is finally reduced, the service life is reduced, and therefore, the improvement of the hydrolysis resistance of the PET material is very important.
The solar photovoltaic back panel film material structure generally comprises structures such as TPT, TPE and PE, and is composed of three layers or two layers of materials, wherein P represents a polyester film BOPET (PET film), and is an important component material of the solar back panel film. In the using process, in order to ensure excellent efficiency conversion, the PET film has higher requirements on color besides ensuring certain transparency, if the PET film is yellow, the spectral transmittance is reduced, particularly the transmittance of blue light, and the blue light has the strongest light effect in the visible spectrum, so the color of the PET film is ensured as much as possible.
At present, the main method for improving the hydrolysis resistance of the PET material is to add a certain amount of carbodiimide hydrolysis resistant agent. The PET film is directly added in the film making process, and the addition amount is small, so that the dispersion is not uniform and the addition is inconvenient, so that the PET film is obtained by adding master batches in a blending, casting and biaxial stretching mode. The color of the master batch directly determines the color of the PET film, the higher the concentration of the hydrolysis resistant agent of the master batch is, the less the addition amount is in the blending process, and the smaller the color influence brought by the master batch is, so that the important point is how to prepare the PET master batch with high concentration of the hydrolysis resistant agent and excellent color.
Disclosure of Invention
The invention aims to overcome the defects that the existing hydrolysis-resistant PET master batch cannot ensure the hydrolysis resistance and keep the color from yellowing, and provides a hydrolysis-resistant PET master batch, and a preparation method and application thereof.
The invention solves the technical problems through the following technical scheme:
a preparation method of hydrolysis-resistant PET master batch comprises the following steps:
the hydrolysis-resistant PET master batch is prepared by a double-screw extruder, and the double-screw extruder comprises a main feeding port and a side feeding port;
adding PET resin into the double-screw extruder through the main feeding port, adding an anti-hydrolysis agent into the double-screw extruder through the side feeding port, and carrying out melt mixing, extrusion, cooling and granulation on the PET resin and the anti-hydrolysis agent through the double-screw extruder;
the shell of the double-screw extruder comprises 8-12 heating cylinder bodies connected end to end, the main feeding port is arranged at the first heating cylinder body, and the side feeding port is arranged at any one of the heating cylinder bodies 2-4 sections away from the last heating cylinder body;
the heating cylinder body where the side feeding port is located is a side feeding area, the temperature of the side feeding area is 200-270 ℃, and the temperature of each heating cylinder body behind the side feeding area is 215-280 ℃;
the rotating speed of the extrusion is 200-400 r/min;
the mass addition amount of the anti-hydrolysis agent is 0% -30% but not 0%, and the mass addition amount of the anti-hydrolysis agent is the percentage of the mass of the anti-hydrolysis agent to the mass of the anti-hydrolysis PET master batch.
In the invention, the term "distance" that the side feeding port is arranged in any one of the heating cylinder bodies 2-4 sections away from the last heating cylinder body refers to the total number of the heating cylinder body in which the side feeding port is arranged, the last heating cylinder body and the heating cylinder bodies between the two heating cylinder bodies; for example, if there are 10 heating cylinders in total and the side feed port is located in the 8 th heating cylinder, the side feed port is located 3 heating cylinders apart from the last heating cylinder.
In the present invention, preferably, the hydrolysis-resistant PET masterbatch is composed of a hydrolysis-resistant agent and a PET resin.
In the present invention, the twin screw extruder may be conventional in the art, and is preferably a twin screw extruder commercially available from cokuron (Nanjing) machinery, Inc. with a model number of CTE 65.
In the present invention, the length-diameter ratio of the twin-screw extruder may be conventional in the art, and those skilled in the art know that if the length-diameter ratio of the twin-screw extruder is too low, the PET resin and the hydrolysis resistance agent are not sufficiently mixed; if the temperature is too high, the material extruded by the double-screw extruder is seriously degraded; preferably, the length-diameter ratio of the double-screw extruder is 20: 1-60: 1; more preferably 30:1 to 45: 1.
In the present invention, preferably, the number of the heating cylinders is 10 or 11.
In the present invention, preferably, the side feeding port is disposed in the section 8 or the section 9 of the heating cylinder.
In the invention, preferably, the mass addition amount of the hydrolysis resistant agent is 5-30%; more preferably 10% to 30%; even more preferably from 10% to 20%, for example 15% or 18%.
In the invention, the rotation speed of the extrusion is preferably 260-400 r/min; more preferably 300-360 r/min, such as 320r/min, 330r/min, 340r/min or 350 r/min.
In the present invention, the temperature of the side feeding zone is preferably 210 to 250 ℃, such as 215 ℃, 220 ℃, 230 ℃ or 240 ℃.
In the invention, the temperature of each heating cylinder body after the side feeding area is preferably 230-260 ℃, such as 235 ℃, 245 ℃ or 255 ℃.
In the present invention, the temperature of each heating cylinder before the side feeding zone can be conventional in the art, and those skilled in the art know that a suitable temperature is selected according to the melting temperature of the PET resin, preferably 270 to 290 ℃, for example 280 ℃.
In the invention, preferably, the number of the heating cylinders is 10-12, the temperature of the side feeding area is 215-250 ℃, the temperature of each heating cylinder behind the side feeding area is 215-260 ℃, the extrusion rotating speed is 320-350 r/min, and the addition amount of the hydrolysis resisting agent is 15-25%; more preferably, the number of the heating cylinders is 10 or 11, the temperature of the side feeding area is 215-240 ℃, the temperature of each heating cylinder behind the side feeding area is 235-255 ℃, and the addition amount of the anti-hydrolysis agent is 15-20%.
In a preferred embodiment of the present invention, the number of the heating cylinder sections is 10, the temperature of the side feeding region is 240 ℃, the temperature of each heating cylinder section arranged after the 8 th section and the side feeding region is 245-255 ℃, the extrusion rotation speed is 350r/min, and the addition amount of the hydrolysis resistant agent is 18%.
In another preferred embodiment of the invention, the number of the heating cylinder sections is 11, the temperature of the side feeding area is 220 ℃, the temperature of each heating cylinder section arranged after the 8 th section and the side feeding area is 235-255 ℃, the extrusion rotating speed is 320r/min, and the addition amount of the hydrolysis resisting agent is 15%.
In another preferred embodiment of the invention, the number of the heating cylinder sections is 10, the temperature of the side feeding area is 215 ℃, the temperature of each heating cylinder section after the side feeding area is arranged at the 9 th section and the side feeding area is 235 ℃, the extrusion rotating speed is 330r/min, and the addition amount of the anti-hydrolysis agent is 20%.
In the present invention, the PET resin may be conventional in the art, for example, a film-grade PET resin, a bottle-grade PET resin, or a fiber-grade PET resin; preferably PET resin commercially available from certified chemical fiber, type FG 720.
In the present invention, the hydrolysis resistance agent may be conventional in the art, and is mainly monomeric carbodiimide and polymeric carbodiimide; preferably commercially available from Shanghai Langyi functional materials, Inc. model number
1010 anti-hydrolysis agent.
The invention provides hydrolysis-resistant PET master batch prepared by the preparation method of the hydrolysis-resistant PET master batch.
The invention provides an anti-hydrolysis PET film which is prepared from the anti-hydrolysis PET master batch.
The invention provides an application of the hydrolysis-resistant PET film as a solar photovoltaic back panel film material.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
1. the hydrolysis-resistant PET master batch disclosed by the invention is excellent in color and free from yellowing, and the excellent service performance of the downstream photovoltaic back panel film is ensured.
2. The hydrolysis resistance PET master batch disclosed by the invention is high in hydrolysis resistance, and the mechanical property of a downstream photovoltaic back plate film is ensured.
3. The hydrolysis-resistant PET master batch disclosed by the invention is high in concentration of a hydrolysis-resistant agent, small in addition amount in the blending process of downstream processing, small in color influence brought by the master batch, convenient for downstream use and processing, and capable of overcoming the problem of difficult powder processing.
Drawings
FIG. 1 is a comparison of the apparent color (left) of the PET master batch obtained in comparative example 1 with the apparent color (right) of the PET master batch obtained in example 1.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
In the following examples and comparative examples, the PET resin used was commercially available from certified chemical fiber, type FG 720;
the hydrolysis resistant agent is commercially available from Shanghai Langyi functional materials Ltd, model number
1010。
The twin screw extruder used was commercially available from kyotong (nanjing) machinery ltd under the model CTE 65.
Example 1
Adding PET resin into a double-screw extruder through a main feeding port, adding an anti-hydrolysis agent into the double-screw extruder through a side feeding port, and carrying out melt mixing, extrusion, cooling and granulation on the PET resin and the anti-hydrolysis agent through the double-screw extruder to obtain the anti-hydrolysis PET master batch.
The length-diameter ratio of the double-screw extruder is 40:1, the shell of the double-screw extruder comprises 10 sections of heating cylinder bodies which are connected end to end, the main feeding port is arranged at the first section of heating cylinder body, and the side feeding port is arranged at the heating cylinder body which is 3 rd from the last section of heating cylinder body, namely, the heating cylinder body at the 8 th section.
The heating cylinder body where the side feeding port is located is a side feeding area, the temperature of the side feeding area is 240 ℃, and the temperature of each heating cylinder body behind the side feeding area is 245 ℃ and 255 ℃ in sequence; the temperatures of the heating cylinders of sections 1 to 7 are all 280 ℃.
Namely, the temperature of 10 sections of heating cylinder bodies is 280 ℃, 240 ℃, 245 ℃ and 255 ℃ in sequence.
The extrusion speed is 350 r/min.
The mass addition amount of the hydrolysis resistant agent is 18 percent.
The hydrolysis-resistant PET master batch prepared in the embodiment is shown in the right diagram of figure 1.
Example 2
Adding PET resin into a double-screw extruder through a main feeding port, adding an anti-hydrolysis agent into the double-screw extruder through a side feeding port, and carrying out melt mixing, extrusion, cooling and granulation on the PET resin and the anti-hydrolysis agent through the double-screw extruder to obtain the anti-hydrolysis PET master batch.
The length-diameter ratio of the double-screw extruder is 35:1, a shell of the double-screw extruder comprises 11 sections of heating cylinder bodies which are connected end to end, a main feeding port is arranged at the first section of heating cylinder body, and a side feeding port is arranged at a heating cylinder body which is 4 th section away from the last section of heating cylinder body, namely, the 8 th section of heating cylinder body.
The heating cylinder body where the side feeding port is located is a side feeding area, the temperature of the side feeding area is 220 ℃, and the temperature of each heating cylinder body behind the side feeding area is 235 ℃, 245 ℃ and 255 ℃ in sequence; the temperatures of the heating cylinders in sections 1 to 7 are all 280 ℃.
Namely, the temperature of the 11 sections of heating cylinder bodies is 280 ℃, 220 ℃, 235 ℃, 245 ℃ and 255 ℃ in sequence.
The extrusion speed was 320 r/min.
The mass addition amount of the hydrolysis resistant agent is 15%.
Example 3
Adding PET resin into a double-screw extruder through a main feeding port, adding an anti-hydrolysis agent into the double-screw extruder through a side feeding port, and carrying out melt mixing, extrusion, cooling and granulation on the PET resin and the anti-hydrolysis agent through the double-screw extruder to obtain the anti-hydrolysis PET master batch.
The length-diameter ratio of the double-screw extruder is 35:1, a shell of the double-screw extruder comprises 10 heating cylinder bodies which are connected end to end, a main feeding port is arranged at the first heating cylinder body, and a side feeding port is arranged at the heating cylinder body which is 2 nd section away from the last heating cylinder body, namely, the heating cylinder body 9 th section.
The heating cylinder body where the side feeding port is located is a side feeding area, the temperature of the side feeding area is 215 ℃, and the temperature of the heating cylinder body behind the side feeding area is 235 ℃; the temperature of the heating cylinder bodies in the 1 st to 7 th sections is 280 ℃; the temperature of the heating cylinder in section 8 is 270 ℃.
Namely, the temperature of 10 sections of heating cylinders is 280 ℃, 270 ℃, 215 ℃ and 235 ℃ in sequence.
The extrusion speed was 330 r/min.
The mass addition amount of the hydrolysis resistant agent is 20%.
Example 4
Adding PET resin into a double-screw extruder through a main feeding port, adding an anti-hydrolysis agent into the double-screw extruder through a side feeding port, and carrying out melt mixing, extrusion, cooling and granulation on the PET resin and the anti-hydrolysis agent through the double-screw extruder to obtain the anti-hydrolysis PET master batch.
The length-diameter ratio of the double-screw extruder is 40:1, a shell of the double-screw extruder comprises 8 sections of heating cylinder bodies which are connected end to end, a main feeding port is arranged at the first section of heating cylinder body, and a side feeding port is arranged at the heating cylinder body which is 3 rd from the last section of heating cylinder body, namely, the 6 th section of heating cylinder body.
The heating cylinder body where the side feeding port is located is a side feeding area, the temperature of the side feeding area is 230 ℃, and the temperature of each heating cylinder body behind the side feeding area is 260 ℃ and 250 ℃ in sequence; the temperature of the heating cylinder bodies from 1 to 4 sections is 280 ℃; the temperature of the heating cylinder in section 5 is 270 ℃.
Namely, the temperature of the 8 sections of heating cylinders is 280 ℃, 270 ℃, 230 ℃, 260 ℃ and 250 ℃ in sequence.
The extrusion speed was 340 r/min.
The mass addition amount of the hydrolysis resistant agent is 20%.
Example 5
Adding PET resin into a double-screw extruder through a main feeding port, adding an anti-hydrolysis agent into the double-screw extruder through a side feeding port, and carrying out melt mixing, extrusion, cooling and granulation on the PET resin and the anti-hydrolysis agent through the double-screw extruder to obtain the anti-hydrolysis PET master batch.
The length-diameter ratio of the double-screw extruder is 45:1, a shell of the double-screw extruder comprises 12 sections of heating cylinder bodies which are connected end to end, a main feeding port is arranged at the first section of heating cylinder body, and a side feeding port is arranged at the 4 th section of heating cylinder body which is away from the last section of heating cylinder body, namely the 9 th section of heating cylinder body.
The heating cylinder body where the side feeding port is located is a side feeding area, the temperature of the side feeding area is 250 ℃, and the temperature of each heating cylinder body behind the side feeding area is 260 ℃, 265 ℃ and 245 ℃ in sequence; the temperatures of the heating cylinders in sections 1 to 8 are all 280 ℃.
Namely, the temperature of the 12 sections of heating cylinders is 280 ℃, 250 ℃, 260 ℃, 265 ℃ and 245 ℃ in sequence.
The extrusion speed is 350 r/min.
The mass addition amount of the hydrolysis resistant agent is 25%.
Example 6
Adding PET resin into a double-screw extruder through a main feeding port, adding an anti-hydrolysis agent into the double-screw extruder through a side feeding port, and carrying out melt mixing, extrusion, cooling and granulation on the PET resin and the anti-hydrolysis agent through the double-screw extruder to obtain the anti-hydrolysis PET master batch.
The length-diameter ratio of the double-screw extruder is 35:1, a shell of the double-screw extruder comprises 10 sections of heating cylinder bodies which are connected end to end, a main feeding port is arranged at the first section of heating cylinder body, and a side feeding port is arranged at the heating cylinder body which is 3 rd from the last section of heating cylinder body, namely, the heating cylinder body at the 8 th section.
The heating cylinder body where the side feeding port is located is a side feeding area, the temperature of the side feeding area is 200 ℃, and the temperature of each heating cylinder body behind the side feeding area is 225 ℃ and 235 ℃ in sequence; the temperature of the heating cylinder bodies in the sections 1 to 5 is 280 ℃; the temperatures of the heating cylinders in sections 6 and 7 are both 270 ℃.
Namely, the temperature of 10 sections of heating cylinders is 280 ℃, 270 ℃, 200 ℃, 225 ℃ and 235 ℃ in sequence.
The extrusion speed was 330 r/min.
The mass addition amount of the hydrolysis resistant agent is 20%.
Example 7
Adding PET resin into a double-screw extruder through a main feeding port, adding an anti-hydrolysis agent into the double-screw extruder through a side feeding port, and carrying out melt mixing, extrusion, cooling and granulation on the PET resin and the anti-hydrolysis agent through the double-screw extruder to obtain the anti-hydrolysis PET master batch.
The length-diameter ratio of the double-screw extruder is 35:1, a shell of the double-screw extruder comprises 10 sections of heating cylinder bodies which are connected end to end, a main feeding port is arranged at the first section of heating cylinder body, and a side feeding port is arranged at the heating cylinder body which is 3 rd from the last section of heating cylinder body, namely, the heating cylinder body at the 8 th section.
The heating cylinder body where the side feeding port is located is a side feeding area, the temperature of the side feeding area is 200 ℃, and the temperature of each heating cylinder body behind the side feeding area is 280 ℃; the temperature of the heating cylinder bodies in the sections 1 to 5 is 280 ℃; the temperatures of the heating cylinders in sections 6 and 7 are both 270 ℃.
Namely, the temperature of 10 sections of heating cylinder bodies is 280 ℃, 270 ℃, 200 ℃, 280 ℃ and 280 ℃ in sequence.
The extrusion speed was 330 r/min.
The mass addition amount of the hydrolysis resistant agent is 20%.
Example 8
Adding PET resin into a double-screw extruder through a main feeding port, adding an anti-hydrolysis agent into the double-screw extruder through a side feeding port, and carrying out melt mixing, extrusion, cooling and granulation on the PET resin and the anti-hydrolysis agent through the double-screw extruder to obtain the anti-hydrolysis PET master batch.
The length-diameter ratio of the double-screw extruder is 35:1, a shell of the double-screw extruder comprises 10 sections of heating cylinder bodies which are connected end to end, a main feeding port is arranged at the first section of heating cylinder body, and a side feeding port is arranged at the heating cylinder body which is 3 rd from the last section of heating cylinder body, namely, the heating cylinder body at the 8 th section.
The heating cylinder body where the side feeding port is located is a side feeding area, the temperature of the side feeding area is 270 ℃, and the temperature of each heating cylinder body behind the side feeding area is 215 ℃ and 235 ℃ in sequence; the temperatures of the heating cylinders in sections 1 to 7 are all 280 ℃.
Namely, the temperature of 10 sections of heating cylinders is 280 ℃, 270 ℃, 215 ℃ and 235 ℃ in sequence.
The extrusion speed is 400 r/min.
The mass addition amount of the hydrolysis resistant agent is 20%.
Comparative example 1
Adding PET resin into a double-screw extruder through a main feeding port, adding an anti-hydrolysis agent into the double-screw extruder through a side feeding port, and carrying out melt mixing, extrusion, cooling and granulation on the PET resin and the anti-hydrolysis agent through the double-screw extruder to obtain the anti-hydrolysis PET master batch.
The length-diameter ratio of the double-screw extruder is 35:1, a shell of the double-screw extruder comprises 10 sections of heating cylinder bodies which are connected end to end, a main feeding port is arranged at the first section of heating cylinder body, and a side feeding port is arranged at the heating cylinder body which is 3 rd from the last section of heating cylinder body, namely, the heating cylinder body at the 8 th section.
The heating cylinder body where the side feeding port is located is a side feeding area, the temperature of the side feeding area is 270 ℃, and the temperature of each heating cylinder body behind the side feeding area is 265 ℃; the temperatures of the heating cylinders of sections 1 to 7 are all 280 ℃.
Namely, the temperature of 10 sections of heating cylinders is 280 ℃, 240 ℃, 265 ℃ and 265 ℃ in sequence.
The extrusion speed is 180 r/min.
The mass addition amount of the hydrolysis resistant agent is 15%.
The hydrolysis-resistant PET master batch prepared by the comparative example is shown in the left diagram of fig. 1.
Comparative example 2
Adding PET resin into a double-screw extruder through a main feeding port, adding an anti-hydrolysis agent into the double-screw extruder through a side feeding port, and carrying out melt mixing, extrusion, cooling and granulation on the PET resin and the anti-hydrolysis agent through the double-screw extruder to obtain the anti-hydrolysis PET master batch.
The length-diameter ratio of the double-screw extruder is 35:1, a shell of the double-screw extruder comprises 15 sections of heating cylinder bodies which are connected end to end, a main feeding port is arranged at the first section of heating cylinder body, and a side feeding port is arranged at a heating cylinder body which is 4 th section away from the last section of heating cylinder body, namely 12 th section of heating cylinder body.
The heating cylinder body where the side feeding port is located is a side feeding area, the temperature of the side feeding area is 260 ℃, and the temperature of each heating cylinder body behind the side feeding area is 270 ℃; the temperatures of the heating cylinders in sections 1 to 11 are all 280 ℃.
Namely, the temperature of the 12 sections of heating cylinders is 280 ℃, 260 ℃, 270 ℃ and 270 ℃ in sequence.
The extrusion speed is 350 r/min.
The mass addition amount of the hydrolysis resistant agent is 20%.
Comparative example 3
Adding PET resin into a double-screw extruder through a main feeding port, adding an anti-hydrolysis agent into the double-screw extruder through a side feeding port, and carrying out melt mixing, extrusion, cooling and granulation on the PET resin and the anti-hydrolysis agent through the double-screw extruder to obtain the anti-hydrolysis PET master batch.
The length-diameter ratio of the double-screw extruder is 35:1, a shell of the double-screw extruder comprises 10 sections of heating cylinder bodies which are connected end to end, a main feeding port is arranged at the first section of heating cylinder body, and a side feeding port is arranged at the heating cylinder body which is 3 rd from the last section of heating cylinder body, namely, the heating cylinder body at the 8 th section.
The heating cylinder body where the side feeding port is located is a side feeding area, the temperature of the side feeding area is 280 ℃, and the temperature of each heating cylinder body behind the side feeding area is 245 ℃; the temperatures of the heating cylinders in sections 1 to 7 are all 280 ℃.
Namely, the temperature of 10 sections of heating cylinders is 280 ℃, 245 ℃ and 245 ℃ in sequence.
The extrusion speed was 330 r/min.
The mass addition amount of the hydrolysis resistant agent is 20%.
Comparative example 4
Adding PET resin into a double-screw extruder through a main feeding port, adding an anti-hydrolysis agent into the double-screw extruder through a side feeding port, and carrying out melt mixing, extrusion, cooling and granulation on the PET resin and the anti-hydrolysis agent through the double-screw extruder to obtain the anti-hydrolysis PET master batch.
The length-diameter ratio of the double-screw extruder is 35:1, a shell of the double-screw extruder comprises 10 sections of heating cylinder bodies which are connected end to end, a main feeding port is arranged at the first section of heating cylinder body, and a side feeding port is arranged at the heating cylinder body which is 3 rd from the last section of heating cylinder body, namely, the heating cylinder body at the 8 th section.
The heating cylinder body where the side feeding port is located is a side feeding area, the temperature of the side feeding area is 260 ℃, and the temperature of each heating cylinder body behind the side feeding area is 290 ℃; the temperature of the heating cylinder bodies in the sections 1 to 5 is 280 ℃; the temperatures of the heating cylinders in sections 6 and 7 are both 270 ℃.
Namely, the temperature of 10 sections of heating cylinders is 280 ℃, 270 ℃, 260 ℃, 290 ℃ and 290 ℃ in sequence.
The extrusion speed was 330 r/min.
The mass addition amount of the hydrolysis resistant agent is 20%.
Comparative example 5
Adding PET resin into a double-screw extruder through a main feeding port, adding an anti-hydrolysis agent into the double-screw extruder through a side feeding port, and carrying out melt mixing, extrusion, cooling and granulation on the PET resin and the anti-hydrolysis agent through the double-screw extruder to obtain the anti-hydrolysis PET master batch.
The length-diameter ratio of the double-screw extruder is 35:1, a shell of the double-screw extruder comprises 10 sections of heating cylinder bodies which are connected end to end, a main feeding port is arranged at the first section of heating cylinder body, and a side feeding port is arranged at the heating cylinder body which is 3 rd from the last section of heating cylinder body, namely, the heating cylinder body at the 8 th section.
The heating cylinder body where the side feeding port is located is a side feeding area, the temperature of the side feeding area is 270 ℃, and the temperature of each heating cylinder body behind the side feeding area is 265 ℃; the temperatures of the heating cylinders of sections 1 to 7 are all 280 ℃.
Namely, the temperature of 10 sections of heating cylinders is 280 ℃, 270 ℃, 265 ℃ and 265 ℃ in sequence.
The extrusion speed is 450 r/min.
The mass addition amount of the hydrolysis resistant agent is 15%.
Comparative example 6
Adding PET resin into a double-screw extruder through a main feeding port, adding an anti-hydrolysis agent into the double-screw extruder through a side feeding port, and carrying out melt mixing, extrusion, cooling and granulation on the PET resin through the double-screw extruder to obtain blank PET master batches.
The length-diameter ratio of the double-screw extruder is 35:1, a shell of the double-screw extruder comprises 10 sections of heating cylinder bodies which are connected end to end, a main feeding port is arranged at the first section of heating cylinder body, and a side feeding port is arranged at the heating cylinder body which is 3 rd from the last section of heating cylinder body, namely, the heating cylinder body at the 8 th section.
The heating cylinder body where the side feeding port is located is a side feeding area, the temperature of the side feeding area is 270 ℃, and the temperature of each heating cylinder body behind the side feeding area is 215 ℃; the temperature of the heating cylinder in sections 1 to 7 is 235 ℃.
Namely, the temperature of 10 sections of heating cylinders is 280 ℃, 270 ℃, 215 ℃ and 235 ℃ in sequence.
The extrusion speed is 350 r/min.
The mass addition amount of the hydrolysis resistant agent is 0 percent.
Comparative example 7
According to the technical scheme of the embodiment 2 of the prior art (application publication number: CN 103627152A), the hydrolysis-resistant PET master batch is prepared by using the PET raw material.
Comparative example 8
The materials, procedure and equipment were as in example 1, except that the temperature in the side feed zone was 180 ℃.
Because the temperature of the side feeding area is too low, the viscosity of the melt of the PET resin is suddenly increased after the melt reaches the area, so that the screw is locked and cannot be implemented.
Comparative example 9
The raw materials, operation steps and equipment were the same as those in example 1, except that the total number of the heating cylinders was 6.
Because the screw rod is too short, the plasticizing effect of the front section of the PET resin is poor, and the mixing of the hydrolysis resistant agent is not uniform after the hydrolysis resistant agent is added.
Comparative example 10
The raw materials, operation steps and equipment were the same as in example 1, but the temperature after the side feeding zone was 200 ℃ and the melt viscosity increased greatly, resulting in screw locking and failure to perform.
Comparative example 11
The raw materials, operation steps and equipment were the same as in example 1, except that the addition amount of the hydrolysis-resistant agent was 40%.
The addition of the hydrolysis resistant agent is too much to be fully compatible with the PET resin, and the phenomenon is that liquid emerges from the side feeding section.
Effects of the embodiment
The PET master batches prepared in the above examples 1 to 8 and comparative examples 1 to 7 were subjected to color model tests, and the test results are shown in table 1.
The Lab color model in the embodiment of the effect is disclosed in the national standard GB/T7921-2008, wherein L refers to brightness, and a and b are two color channels. Wherein, the colors included in a are from dark green (low brightness value) to gray (medium brightness value) to bright pink red (high brightness value); b is from bright blue (low luminance value) to gray (medium luminance value) to yellow (high luminance value). Therefore, the value of b can reflect the yellowing degree of the prepared hydrolysis-resistant PET master batch.
TABLE 1 Lab values of PET master batches prepared under different process conditions
As can be seen from the comparison results, the color of the PET master batch prepared by the embodiment of the invention is obviously superior to that of comparative examples 1-5 and 7, and is closer to that of blank PET particles.
In order to further compare the excellent performance of the hydrolysis resistant PET master batch prepared by the invention, the master batch and the blank particles are blended according to the same 1% of the addition amount of the hydrolysis resistant agent to prepare the PET photovoltaic back panel film, the color test of the film is shown in Table 2, and the light transmittance is shown in Table 3. The prepared sample strips were subjected to ultraviolet light aging, and the tensile strength thereof was measured, with the results shown in Table 4.
TABLE 2 Lab values of PET photovoltaic back panel films prepared from PET master batches of different processing techniques
Table 3. light transmittance of PET photovoltaic back plate film prepared from PET master batches by different processing technologies
TABLE 4 ultraviolet aging tensile strength of PET photovoltaic backboard films prepared by different processing techniques of PET master batches
| Tensile Strength (MPa) | Aging for 0h | Aging for 24h | Aging for 48h | Aging for 60h |
| Example 1 | 126.2 | 112.7 | 108.5 | 104.0 |
| Example 2 | 125.8 | 112.4 | 108.2 | 103.6 |
| Example 3 | 126.8 | 113.2 | 109.0 | 104.2 |
| Example 4 | 125.2 | 110.6 | 106.2 | 102.4 |
| Example 5 | 125.4 | 112.6 | 108.0 | 103.8 |
| Example 6 | 126.3 | 112.2 | 108.6 | 103.6 |
| Example 7 | 125.0 | 108.9 | 106.4 | 102.0 |
| Example 8 | 125.2 | 108.6 | 106.2 | 101.6 |
| Comparative example 1 | 124.8 | 106.2 | 90.6 | 80.3 |
| Comparative example 2 | 125.2 | 106.5 | 91.2 | 83.4 |
| Comparative example 3 | 125.0 | 106.5 | 90.8 | 83.6 |
| Comparative example 4 | 124.9 | 105.9 | 90.2 | 81.9 |
| Comparative example 5 | 125.2 | 105.8 | 90.6 | 82.5 |
| Comparative example 6 | 124.8 | 102.4 | 60.6 | 30.5 |
| Comparative example 7 | 125.6 | 103.2 | 85.3 | 75.8 |
As can be seen from tables 2, 3 and 4, the color, the light transmittance and the sum of the color and the light transmittance of the PET photovoltaic back panel film prepared from the hydrolysis-resistant PET masterbatch of the embodiments 1 to 8 of the invention are superior to those of the comparative examples 1 to 7.
In conclusion, by comprehensively comparing the PET photovoltaic back panel films prepared from the hydrolysis-resistant PET master batches in different processes, the comprehensive performance of the photovoltaic back panel film prepared from the PET master batches in the process is obviously superior to that of the existing process. If the hydrolysis-resistant PET master batch with excellent color, high content of hydrolysis-resistant agent and high PET concentration is to be obtained, the raw materials and the process parameters need to be matched with each other.
For example, the extrusion speed of comparative example 1 is too low, the total number of heating cylinders of comparative example 2 is too high, the extrusion process is lengthened, the material stays in the screw for too long time, the degradation is serious, and the prepared PET master batch is yellowed. In comparative example 3, the temperature in the side feed zone was too high, 280 ℃, resulting in yellowing of the material at high temperature.
In comparative example 4, the temperature of each heating cylinder after the side feeding zone was too high, 290 ℃, resulting in yellowing of the material at high temperature. In comparative example 5, the extrusion speed was 450r/min, and the shear heat effect of the screw was increased, resulting in yellowing of the material due to degradation.
Claims (10)
1. The preparation method of the hydrolysis-resistant PET master batch is characterized by comprising the following steps:
the hydrolysis-resistant PET master batch is prepared by a double-screw extruder, and the double-screw extruder comprises a main feeding port and a side feeding port;
adding PET resin into the double-screw extruder through the main feeding port, adding an anti-hydrolysis agent into the double-screw extruder through the side feeding port, and carrying out melt mixing, extrusion, cooling and granulation on the PET resin and the anti-hydrolysis agent through the double-screw extruder;
the shell of the double-screw extruder comprises 8-12 sections of heating cylinder bodies connected end to end, the main feeding port is arranged at the first section of heating cylinder body, and the side feeding port is arranged at any one of the heating cylinder bodies 2-4 sections away from the last section of heating cylinder body;
the heating cylinder body where the side feeding port is located is a side feeding area, the temperature of the side feeding area is 200-270 ℃, and the temperature of each heating cylinder body behind the side feeding area is 215-280 ℃;
the rotating speed of the extrusion is 200-400 r/min;
the mass addition amount of the hydrolysis-resistant agent is 0-30% but not 0%, and the mass addition amount of the hydrolysis-resistant agent is the percentage of the mass of the hydrolysis-resistant agent to the mass of the hydrolysis-resistant PET master batch.
2. The method for preparing the hydrolysis-resistant PET masterbatch according to claim 1, wherein the hydrolysis-resistant PET masterbatch is composed of a hydrolysis-resistant agent and PET resin;
and/or, the twin screw extruder is commercially available from kyron mikyo machines ltd under model number CTE 65;
and/or the PET resin is film-grade PET resin, bottle-grade PET resin or fiber-grade PET resin; preferably commercially available from certified chemical fibers, the model number is FG 720;
and/or the hydrolysis-resistant agent is one or more of monomer type carbodiimide and polymer type carbodiimide; preferably commercially available from Shanghai Langyi functional materials, Inc. under the model number
1010；
And/or the length-diameter ratio of the double-screw extruder is 20: 1-60: 1; preferably 30:1 to 45: 1.
3. The method for preparing the hydrolysis-resistant PET master batch according to claim 1, wherein the number of the heating cylinders is 10 or 11;
and/or the side feeding port is arranged on the section 8 or the section 9 of the heating cylinder body.
4. The preparation method of the hydrolysis-resistant PET master batch of claim 1, wherein the mass addition amount of the hydrolysis-resistant agent is 5-30%; preferably 10% -30%; more preferably from 10% to 20%, for example 15% or 18%;
and/or the rotating speed of the extrusion is 260-400 r/min; preferably 300-360 r/min, such as 320r/min, 330r/min, 340r/min or 350 r/min.
5. The method for preparing the hydrolysis-resistant PET masterbatch according to claim 1, wherein the temperature of the side feeding zone is 210-250 ℃, such as 215 ℃, 220 ℃, 230 ℃ or 240 ℃;
and/or the temperature of each heating cylinder body behind the side feeding area is 230-260 ℃, such as 235 ℃, 245 ℃ or 255 ℃;
and/or the temperature of each heating cylinder before the side feeding area is 270-290 ℃, such as 280 ℃.
6. The preparation method of the hydrolysis-resistant PET master batch as claimed in claim 1, wherein the number of the heating cylinders is 10-12, the temperature of the side feeding area is 215-250 ℃, the temperature of each heating cylinder behind the side feeding area is 215-260 ℃, the extrusion rotation speed is 320-350 r/min, and the addition amount of the hydrolysis-resistant agent is 15-25%;
preferably, the number of the heating cylinders is 10 or 11, the temperature of the side feeding area is 215-240 ℃, the temperature of each heating cylinder behind the side feeding area is 235-255 ℃, and the addition amount of the anti-hydrolysis agent is 15-20%.
7. The preparation method of the hydrolysis-resistant PET master batch as claimed in claim 6, wherein the number of the heating cylinder sections is 10, the temperature of the side feeding area is 240 ℃, the side feeding area is arranged at the 8 th section, the temperature of each heating cylinder section behind the side feeding area is 245-255 ℃, the extrusion rotation speed is 350r/min, and the addition amount of the hydrolysis-resistant agent is 18%;
and/or the number of the heating cylinder bodies is 11, the temperature of the side feeding area is 220 ℃, the temperature of each heating cylinder body arranged behind the 8 th section and the side feeding area is 235-255 ℃, the extrusion rotating speed is 320r/min, and the addition amount of the hydrolysis resisting agent is 15%;
and/or the number of the heating cylinder bodies is 10, the temperature of the side feeding area is 215 ℃, the temperature of each heating cylinder body arranged behind the 9 th section and the side feeding area is 235 ℃, the extrusion rotating speed is 330r/min, and the addition amount of the hydrolysis resisting agent is 20%.
8. The hydrolysis-resistant PET master batch prepared by the preparation method of the hydrolysis-resistant PET master batch of any one of claims 1-7.
9. An hydrolysis-resistant PET film obtained from the hydrolysis-resistant PET master batch according to claim 8.
10. Use of the hydrolysis-resistant PET film of claim 9 as a solar photovoltaic back sheet material.
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| CN104080834A (en) * | 2012-02-03 | 2014-10-01 | 富士胶片株式会社 | Resin composition, method for producing same, polyethylene terephthalate film, and solar cell module backing sheet |
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