CN116814001A - PP-PET alloy compatilizer and preparation method and application thereof - Google Patents
PP-PET alloy compatilizer and preparation method and application thereof Download PDFInfo
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- 239000000956 alloy Substances 0.000 title claims abstract description 69
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 26
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims abstract description 17
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003999 initiator Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 6
- 239000000314 lubricant Substances 0.000 claims description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 5
- 230000003078 antioxidant effect Effects 0.000 claims description 5
- 238000005469 granulation Methods 0.000 claims description 5
- 230000003179 granulation Effects 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 3
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 2
- 239000000155 melt Substances 0.000 abstract description 5
- 229920000642 polymer Polymers 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000000654 additive Substances 0.000 abstract description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 64
- 229920000139 polyethylene terephthalate Polymers 0.000 description 64
- 239000004743 Polypropylene Substances 0.000 description 34
- 229920001155 polypropylene Polymers 0.000 description 34
- 239000004033 plastic Substances 0.000 description 9
- 229920003023 plastic Polymers 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
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- 239000004593 Epoxy Substances 0.000 description 2
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- 238000005191 phase separation Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000012773 agricultural material Substances 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
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- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
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- 230000010534 mechanism of action Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
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- 229920006124 polyolefin elastomer Polymers 0.000 description 1
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- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
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Abstract
The invention belongs to the technical field of polymer additives, and discloses a PP-PET alloy compatilizer, a preparation method and application thereof. The PP-PET alloy compatilizer comprises, by weight, 10-55 parts of POE, 20-70 parts of PP, 0.02-0.8 part of an initiator and 0.4-1.5 parts of a first grafting monomer, wherein the first grafting monomer is MAH or/and GMA; preferably, the PP-PET alloy compatilizer further comprises a second grafting monomer, wherein the second grafting monomer is SEBS or styrene. According to the invention, POE is selected to play a role in toughening, on the basis of ensuring performance, PP is added to regulate the melt fingers, MAH or/and GMA is selected as a grafting monomer, and SEBS or styrene is introduced as a second grafting monomer to improve the grafting rate, so that the impact performance and compatibility of the alloy are improved, the sources of raw materials are wide, the processing process is simple and easy to implement, and the cost is controlled.
Description
Technical Field
The invention relates to the technical field of polymer additives, in particular to a preparation method of a PP-PET alloy compatilizer, and more particularly relates to a preparation method of a polymer additive capable of promoting compatibility between polypropylene (PP) and polyethylene terephthalate (PET).
Background
PP and PET are two commonly used plastics, but because of their great difference in polarity, crystallinity and melting point, problems such as phase separation, weak interfaces, poor mechanical properties, etc. occur when directly blending. Thus, it is desirable to add compatibilizers to improve their blending properties.
The application fields of the PP/PET compatilizer mainly comprise the following aspects:
plastic alloy: the PP/PET plastic alloy with excellent comprehensive performance, such as wear resistance, heat resistance, chemical resistance, high strength, high rigidity and the like, can be prepared by adding the compatilizer. The plastic alloy can be used in the fields of automobile parts, electronic and electric appliances, packaging materials and the like.
Plastic modification: by adding the compatilizer, certain properties of PP or PET, such as strengthening, toughening, flame retardance, antistatic and the like, can be improved. The modified plastic can be used in the fields of fibers, films, containers and the like.
And (3) plastic recycling: by adding the compatilizer, the recycling rate of the waste PP or PET can be improved, and the cost and the environmental pollution are reduced. The recycled plastic can be used in the fields of building materials, agricultural materials and the like.
The mechanism of action of the PP/PET compatilizer mainly comprises two types: firstly, the interfacial tension between PP and PET is reduced by physical action, namely intermolecular bonding force or association force, the interface layer thickness is increased, the particle size of a disperse phase is reduced, and a stable blending structure is formed; secondly, the PP and the PET are subjected to chemical crosslinking or grafting reaction by introducing reactive groups to form covalent bonds or hydrogen bonds, so that the interface bonding strength is improved, and the phase separation is inhibited.
Disclosure of Invention
The invention aims to overcome the defects of the background technology and provides a PP-PET alloy compatilizer and a preparation method and application thereof. In general, to increase the compatibility of PP/PET alloys, compatibilizers, such as graft copolymers or other polar compounds, are added to reduce interfacial tension, increase interfacial bond strength, and reduce dispersed phase size. The type, amount and grafting ratio of the compatibilizer are key factors affecting the performance of the PP-PET alloy. Because the impact toughness in the PP/PET alloy is poor, POE is selected to play a role in toughening, on the basis of ensuring the performance, a PP adjusting melt finger is added, MAH or/and GMA is selected as a grafting monomer, SEBS or styrene is introduced as a second grafting monomer for improving the grafting rate, the impact performance and the compatibility of the alloy are improved, the sources of raw materials are wide, the processing process is simple and easy to implement, and the cost is controlled.
In order to achieve the aim of the invention, the PP-PET alloy compatilizer comprises 10-55 parts by weight of POE, 20-70 parts by weight of PP, 0.02-0.8 part by weight of initiator and 0.4-1.5 parts by weight of first grafting monomer, wherein the first grafting monomer is MAH or/and GMA.
Further, in some embodiments of the present invention, the PP-PET alloy compatibilizer further comprises a second grafting monomer, wherein the second grafting monomer is SEBS or styrene.
Preferably, in some embodiments of the present invention, white oil is added to the SEBS to improve processability.
Preferably, in some embodiments of the present invention, the PP-PET alloy compatilizer comprises, by weight, 10-55 parts of POE, 20-70 parts of PP, 0.02-0.8 part of initiator, 0.4-1.5 parts of MAH or/and GMA, 15-40 parts of SEBS, and 10-30 parts of white oil.
Preferably, in some embodiments of the present invention, the PP-PET alloy compatilizer comprises, by weight, 10-55 parts of POE, 20-70 parts of PP, 0.02-0.8 part of initiator, 0.4-1.5 parts of MAH or/and GMA, and 0.3-0.6 part of styrene.
Further, in some embodiments of the invention, the initiator is DCP or/and bis 25.
On the other hand, the invention also provides a preparation method of the PP-PET alloy compatilizer, which comprises the following steps:
(1) Drying PP and POE to reduce the water content to below 0.1%, and keeping the PP and POE for later use;
(2) Adding the first grafting monomer, the second grafting monomer and the initiator into a stirring tank for stirring (if SEBS is added, standing is needed to fully disperse white oil into the SEBS);
(3) Adding PP, PP and POE on the basis of the step (2), and uniformly stirring for later use;
(4) Pouring the mixed materials into a double-screw extruder, and carrying out melt extrusion granulation.
In still another aspect, the invention also provides an application of the PP-PET alloy compatilizer, wherein the application is that the compatilizer is added into the PP-PET alloy, and the addition amount is 3-15% of the PP-PET alloy.
Further, in some embodiments of the invention, the amount added is 5-10% of the PP-PET alloy.
Further, in some embodiments of the present invention, the PP and PET in the PP-PET alloy are in the range of 5 to 8:2-5 by mass.
In still another aspect, the invention also provides a PP-PET alloy, wherein the PP and PET in the PP-PET alloy are mixed according to the ratio of 5-8:2-5, comprising the PP-PET alloy compatilizer of the invention, wherein the mass ratio of the PP-PET alloy compatilizer is 3-15%, preferably 5-10% of that of the PP-PET alloy.
Further, in some embodiments of the present invention, a lubricant is also included in the PP-PET alloy; preferably, the lubricant is EBS.
Further, in some embodiments of the present invention, the PP-PET alloy further comprises an antioxidant; preferably, the antioxidant is antioxidant 1010 and/or antioxidant 168.
In still another aspect, the present invention also provides a method for preparing the PP-PET alloy, the method comprising the steps of:
(1) Drying PP and PET, and removing water;
(2) Mixing the dried PP and PET according to the required mass ratio, and adding a PP-PET alloy compatilizer and other auxiliary agents (such as a lubricant and an antioxidant, for example);
(3) And (3) carrying out melt blending on the raw materials mixed in the step (2), controlling the melting temperature and the screw rotating speed, then sending the raw materials into a double-screw extruder for extrusion, and carrying out post-treatment such as cooling, granulating, drying and the like on the extruded melt to obtain PP-PET alloy particles.
Compared with the prior art, the invention has the following advantages:
(1) The compatibilizing agent of the present invention can reduce or eliminate the mutual repulsion effect between the two polymers through the interaction between the PP and PET molecules, so that the compatibilizing agent is better compatible when being mixed. In the PP-PET granulation process, the processing performance can be improved due to the improvement of the compatibility, the particles with uniform thickness and stable performance can be obtained, the surface between the particles can be smooth in the injection molding process, and the phenomena of skinning, layering and the like of a finished piece can be obviously inhibited.
(2) Because the PP has certain toughness, the compatilizer selects the polyolefin elastomer, the elastomer has good compatibility with the PP phase, improves the toughness of a matrix, compensates the brittleness of PET, has good oil resistance, fat resistance, dilute acid resistance and dilute alkali resistance, resists most solvents and has good barrier property, and the compatilizer can react with the end group of the PET after grafting modification, so the compatibility with the PET is improved, and the compatilizer can be selected to obtain excellent high polymer alloy materials by combining the advantages of the PP and the PET.
Drawings
FIG. 1 is a scanning electron micrograph of a PP/PET alloy without a compatibilizer;
FIG. 2 is a photograph of a PP/PET alloy electron microscope of example 3 of the present invention, which is a PET dispersed in a spherical form, and it can be seen that the PET of example 3 is more uniformly distributed and the dispersed phase is finer, and that in the hole from which PET was pulled out, there is a significant plastic deformation around the hole left in FIG. 2, so that it can be considered that the compatibility effect of the additive example 3 is better.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. It is to be understood that the following description is intended to be illustrative of the invention and not restrictive.
The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.
Furthermore, the descriptions of the terms "one embodiment," "some embodiments," "examples," "particular examples," or "some examples," etc., described below mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily for the same embodiment or example. The technical features of the respective embodiments of the present invention may be combined with each other as long as they do not collide with each other.
The device information used in the present invention is shown in the following table.
The preparation method of the PP-PET alloy compatilizer comprises the following steps:
(1) Drying SEBS, PP, POE to reduce the water content to below 0.1%, and keeping for later use;
(2) Adding the first grafting monomer, the second grafting monomer and the initiator into a stirring cylinder for stirring (if SEBS is added, standing for 16-32h is needed to fully disperse white oil into the SEBS);
(3) Adding PP, PP and POE on the basis of the step (2), and uniformly stirring for later use;
(4) Pouring the mixed materials into a double-screw extruder, and carrying out melt extrusion granulation.
Wherein, the processing conditions of the melt extrusion granulation are as follows:
| temperature zone | 1 | 2 | 3 | 4 | 5 | 6 | 7 | Machine head |
| Lower temperature limit | 80 | 100 | 140 | 170 | 170 | 170 | 170 | 150 |
| Upper limit of temperature | 160 | 170 | 190 | 210 | 210 | 210 | 210 | 190 |
The rotating speed of the screw extruder is between 200 and 300rpm, the rotating speed of the high-speed stirring cylinder is between 300 and 600rpm, and the stirring time is between 2 and 7 minutes.
The preparation method of the PP-PET alloy for testing mainly comprises the following steps:
(1) Drying PP and PET in a drying oven to remove water;
(2) The dried PP and PET were processed according to a ratio of 7:3, mixing the materials according to the mass ratio, and adding 10% of PP-PET alloy compatilizer, lubricant EBS and antioxidant 1010;
(3) Carrying out melt blending on the mixed raw materials, and controlling the melting temperature and the screw rotating speed; and then feeding the mixture into a double screw for extrusion, and carrying out post-treatment such as cooling, granulating, drying and the like on the extruded melt to obtain PP-PET alloy particles.
Wherein, the conditions for producing the test particles, namely PP-PET alloy melt blending are as follows:
| temperature zone | 1 | 2 | 3 | 4 | 5 | 6 | 7 | Machine head |
| Lower temperature limit | 130 | 150 | 170 | 190 | 210 | 210 | 210 | 180 |
| Upper limit of temperature | 160 | 180 | 210 | 230 | 250 | 250 | 250 | 230 |
The rotating speed of the screw extruder is between 250 and 400rpm
After PP-PET alloy particles are obtained, injection molding is carried out according to the following conditions:
| temperature zone | 1 | 2 | 3 | 4 | 5 |
| Lower temperature limit | 210 | 210 | 230 | 230 | 230 |
| Upper limit of temperature | 240 | 240 | 260 | 260 | 260 |
Wherein the injection pressure is between 30 and 70Mpα, the holding pressure is between 30 and 70Mpα, and the holding time is between 3 and 30s.
The prepared resin is molded into standard sample bars to obtain mechanical test data (wherein the detection standard of tensile strength and elongation at break is GB/T1040-92, the detection standard of impact strength is GB/T1843-2008), melt index (measured under the condition of 190 ℃ C., 2.16kg, the detection standard is GB/T3682-2000) and an SEM scanning electron microscope.
The following are tables of the amounts (%) of the respective components in examples 1 to 8 of the present invention and the results of the effect detection.
Compared with the example shown in Table 2 in the paper of Jiangsu Limited liability company of the best Yi Rong compatilizer, the improvement of the mechanical properties of the alloy by the PP-PET alloy compatilizer is obviously better.
The impact strength represents the toughening effect, the melt index represents the compatibilizing effect, and the compatilizer can play a good role in toughening and compatibilizing the alloy. From the results of the examples, it is found that the impact properties and compatibility of the alloy are affected by the height of the melt fingers, and therefore, the melt fingers are properly adjusted by adding PP. The PET has benzene ring, so in order to improve the compatibility of the polyolefin matrix and PET, SEBS which has both the benzene ring and the polyolefin structure and is flexible is selected as an alternative, and white oil is added at the same time to improve the processing performance. In the process of selecting the grafting monomer, because of the nature of MAH structure, the addition reaction between the monomers is difficult to occur, so that in order to improve the grafting rate, a second grafting monomer needs to be introduced, and styrene is selected from the structural consideration of PET. Whereas PET is carboxyl or hydroxyl terminated, and epoxy has theoretically higher reactivity than MAH, so GMA with epoxy can also be selected as the first monomer to be added to the compatibilizer.
It will be readily appreciated by those skilled in the art that the foregoing is merely illustrative of the present invention and is not intended to limit the invention, but any modifications, equivalents, improvements or the like which fall within the spirit and principles of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The PP-PET alloy compatilizer is characterized by comprising, by weight, 10-55 parts of POE, 20-70 parts of PP, 0.02-0.8 part of an initiator and 0.4-1.5 parts of a first grafting monomer, wherein the first grafting monomer is MAH or/and GMA.
2. The PP-PET alloy compatibilizer of claim 1 further comprising a second grafting monomer, wherein said second grafting monomer is SEBS or styrene; preferably, white oil is added to the SEBS.
3. The PP-PET alloy compatilizer according to claim 2, wherein the PP-PET alloy compatilizer comprises, by weight, 10-55 parts of POE, 20-70 parts of PP, 0.02-0.8 part of an initiator, 0.4-1.5 parts of MAH or/and GMA, 15-40 parts of SEBS and 10-30 parts of white oil.
4. The PP-PET alloy compatilizer according to claim 2, wherein the PP-PET alloy compatilizer comprises, by weight, 10-55 parts of POE, 20-70 parts of PP, 0.02-0.8 part of an initiator, 0.4-1.5 parts of MAH or/and GMA and 0.3-0.6 part of styrene.
5. The PP-PET alloy compatibilizer of claim 1 wherein said initiator is DCP or/and bis 25.
6. A process for the preparation of a PP-PET alloy compatibilizer according to any one of claims 1 to 5, characterized in that it comprises the steps of:
(1) Drying PP and POE to reduce the water content to below 0.1%, and keeping the PP and POE for later use;
(2) Adding the first grafting monomer, the second grafting monomer and the initiator into a stirring cylinder for stirring, if SEBS is added, standing is needed to fully disperse white oil into the SEBS;
(3) Adding PP, PP and POE on the basis of the step (2), and uniformly stirring for later use;
(4) Pouring the mixed materials into a double-screw extruder, and carrying out melt extrusion granulation.
7. Use of a compatibilising agent for PP-PET alloys according to any of claims 1-5, characterised in that the compatibilising agent is added to the PP-PET alloy in an amount of 3-15% of the PP-PET alloy.
8. The use of the PP-PET alloy compatibiliser according to claim 7, wherein the addition is 5-10% of the PP-PET alloy; preferably, the PP and PET in the PP-PET alloy are mixed according to a ratio of 5-8:2-5 by mass.
9. A PP-PET alloy, wherein PP and PET in the PP-PET alloy are mixed according to a ratio of 5-8:2-5, comprising the PP-PET alloy compatibiliser of any of claims 1-5, and the PP-PET alloy compatibiliser comprises 3-15%, preferably 5-10% by mass of the PP-PET alloy.
10. The PP-PET alloy of claim 9 further comprising a lubricant therein; preferably, the lubricant is EBS; preferably, the PP-PET alloy also comprises an antioxidant; preferably, the antioxidant is antioxidant 1010 and/or antioxidant 168.
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| CN202310872145.XA CN116814001A (en) | 2023-07-17 | 2023-07-17 | PP-PET alloy compatilizer and preparation method and application thereof |
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| CN202310872145.XA CN116814001A (en) | 2023-07-17 | 2023-07-17 | PP-PET alloy compatilizer and preparation method and application thereof |
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