Toughening and compatibilizing agent, polyester polymer, preparation method

Abstract

The invention provides a toughening and compatibilizing agent, a polyester polymer, and a preparation method, and belongs to the technical field of polyester. In terms of weight, the toughening and compatibilizing agent suitable for polyester and its alloys includes: 100 parts of vinyl polyolefin elastomer, 1-5 parts of acrylate monomers, 0.1-1 parts of grafted comonomers, 0.01-0.5 parts of initiators, 0.1-4.5 parts of white oil additives, 0.01-1 parts of crosslinking inhibitors, 0.01-0.05 parts of antioxidants, and 0.01-0.05 parts of lubricants; wherein the branching degree of the vinyl polyolefin elastomer is 30-60 branches / 1000 carbons, the melt index is 1-20g / 10min, the number average molecular weight is 100,000-800,000, the molecular weight distribution index is 1.0-2.0, and the density is 0.8-0.9g / cm 3 ; The grafted comonomer is selected from styrene, divinylbenzene, C8-C 10 At least one of olefin or polyacrylate compounds.

Description

Technical Field

[0001] The present invention belongs to the technical field of polyesters, and particularly relates to a toughening and compatibilizing agent, a polyester polymer, and a preparation method, and more specifically relates to a toughening and compatibilizing agent applicable to polyesters and their alloys, polyesters, polyester alloy polymers, and their preparation methods. Background Art

[0002] Polyester resins are a general term for a class of resins containing ester functional groups in the main chain. Due to the characteristics of their own structures, they have advantages that general plastics do not have, such as physical properties, chemical stability, heat resistance, and environmental friendliness. Among them, polycarbonate (PC), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and alloy materials based on them are currently resins with relatively large usage in the polyester plastic modification industry. However, their common drawback is that they are relatively sensitive to notches. Notch sensitivity refers to the degree to which the mechanical properties (such as strength, toughness, etc.) of polyesters and their alloy materials change significantly when affected by notches (such as defects like cracks and scratches). Therefore, current efforts have been continuously made in the toughening modification of polyesters and their alloy materials. However, toughening agents applicable to polyesters and their alloy materials often have problems such as a relatively high usage amount (7wt%-10wt%), being relatively expensive, and affecting the processability of polyesters and their alloy materials. Summary of the Invention

[0003] In view of the above technical problems, the present invention provides a toughening and compatibilizing agent, a polyester polymer, and a preparation method, in order to at least partially solve the above technical problems. For this, the technical solutions provided by the present invention are as follows.

[0004] As a first aspect of the present invention, a toughening and compatibilizing agent applicable to polyesters and their alloys is provided. Calculated by weight parts, the toughening and compatibilizing agent includes: 100 parts of vinyl polyolefin elastomer, 1-5 parts of acrylate monomer, 0.1-1 part of graft co-monomer, 0.01-0.5 part of initiator, 0.1-4.5 parts of white oil additive, 0.01-1 part of crosslinking inhibitor, 0.01-0.05 part of antioxidant, 0.01-0.05 part of lubricant; wherein, the degree of branching of the vinyl polyolefin elastomer is 30-60 branches / 1000 carbons, the melt index is 1-20 g / 10 min, the number average molecular weight is 100,000-800,000, the molecular weight distribution index is 1.0-2.0, and the density is 0.8-0.9 g / cm 3 ; the graft co-monomer is selected from at least one of styrene, divinylbenzene, C8-C 10 olefins or polyacrylate compounds.

[0005] As a second aspect of the present invention, a preparation method of a toughening and compatibilizing agent applicable to polyester and its alloys is provided, including: uniformly mixing a vinyl polyolefin elastomer, an initiator, a white oil additive, an antioxidant, a lubricant, and a crosslinking inhibitor, and adding the mixture into a twin-screw extruder through a main feed port, and adding an acrylate monomer and a graft co-monomer into the twin-screw extruder through a liquid-phase feed port. After mixing and co-extrusion, a toughening and compatibilizing agent is obtained.

[0006] As a third aspect of the present invention, a polyester-based polymer toughened with a toughening and compatibilizing agent is provided. By weight, it includes: 100 parts of a polyester-based polymer, and 1-7 parts of the toughening and compatibilizing agent applicable to polyester and its alloys as described above; wherein, the polyester-based polymer includes polyester or a polyester alloy polymer, and the polyester alloy polymer is an alloy polymer of polyester and a polymer material; wherein, the polyester is selected from any one of polycarbonate, polyethylene terephthalate, and polybutylene terephthalate, and the polymer material is selected from any one of polybutylene terephthalate, acrylonitrile-butadiene-styrene copolymer, polyethylene terephthalate, polypropylene, and polyethylene-propylene copolymer.

[0007] As a fourth aspect of the present invention, a preparation method of a polyester-based polymer toughened with a toughening and compatibilizing agent is provided, including: uniformly mixing 100 parts of polyester and 1-7 parts of the toughening and compatibilizing agent applicable to polyester and its alloys as described above, and then feeding the mixture into a twin-screw extruder for blending and pelletizing to obtain a polyester toughened with the toughening and compatibilizing agent; or uniformly mixing 20-80 parts of polyester, 20-80 parts of a polymer material, totaling 100 parts; and 1-7 parts of the toughening and compatibilizing agent applicable to polyester and its alloys as described above, and then feeding the mixture into a twin-screw extruder for blending and pelletizing to obtain a polyester alloy polymer toughened and compatibilized with the toughening and compatibilizing agent.

[0008] In an embodiment of the present invention, a graft reaction is carried out using an initiator, a vinyl polyolefin elastomer (EPOE), an acrylate monomer, and a graft co-monomer. The initiator and the graft co-monomer can achieve the grafting of the vinyl polyolefin elastomer and the acrylate monomer and at the same time improve the grafting rate. Among them, the acrylate monomer endows the vinyl polyolefin elastomer with polar groups, such as ester functional groups, through the graft reaction, changing the non-polar vinyl polyolefin elastomer into a polar one, while polyester is polar, and the compatibility between the two is good, so as to obtain a toughening and compatibilizing agent based on vinyl polyolefin elastomer applicable to polyester and its alloys. Further, the vinyl polyolefin elastomer has a low crystallinity (1-2%), a small molecular weight distribution index (PDI = 1.0-2.0), a low glass transition temperature (-50~-45°C), and a small density (0.8-0.9 g / cm 3),(which can play a toughening role after grafting), its relatively high melt index can improve the fluidity of polyester polymers (i.e., polyester, polyester alloy polymers). By utilizing the ester functional groups grafted onto the branches of vinyl polyolefin elastomers, the polarity of vinyl polyolefin elastomers is improved in the present invention. Subsequently, applying the toughening and compatibilizing agent based on vinyl polyolefin elastomers to polyester can achieve the effect of toughening polyester, or applying it to polyester and polymer materials to improve the compatibility between the two, and can achieve the effect of toughening and compatibilizing polyester and polymer materials, thereby obtaining polyester alloy polymers. In addition, by using the toughening and compatibilizing agent provided by the present invention, the obtained polyester and / or polyester alloy polymers have good mechanical properties and impact resistance. Detailed Embodiments

[0009] The embodiments of the present invention will be described below, but it should be understood that these descriptions are merely exemplary and are not intended to limit the scope of the present invention. In the following detailed description, for the sake of explanation, many specific details are set forth to provide a comprehensive understanding of the embodiments of the present invention. However, obviously, one or more embodiments can also be implemented without these specific details. In addition, in the following description, descriptions of well-known structures and technologies are omitted to avoid unnecessarily confusing the concepts of the present invention.

[0010] Currently, the commonly used toughening agents for polyester and its alloy materials mainly include acrylate resins (ACR), core-shell structured methyl methacrylate-butadiene-styrene copolymers (MBS), and ethylene-acrylate-glycidyl methacrylate copolymers. These toughening agents have problems such as relatively high addition amounts, being prone to aging and yellowing during the long-term use of thermal oxygen aging, being relatively expensive, and having poor fluidity which is not conducive to processing, thus restricting their use. Aiming at the problems of the toughening agents applicable to polyester and its alloy materials described above, the present invention proposes a toughening and compatibilizing agent based on vinyl polyolefin elastomers, and applying it to polyester and its alloys to achieve the purpose of toughening polyester, toughening and compatibilizing polyester and polymer materials, so that the obtained polyester and polyester alloy polymers have the advantages of excellent processability, impact resistance, heat resistance and low cost.

[0011] Specifically, as the first aspect of the present invention, a toughening and compatibilizing agent suitable for polyester and its alloys is provided. Calculated by weight parts, the toughening and compatibilizing agent includes: 100 parts of vinyl polyolefin elastomer, 1 - 5 parts of acrylate monomer, 0.1 - 1 part of graft co-monomer, 0.01 - 0.5 part of initiator, 0.1 - 4.5 parts of white oil additive, 0.01 - 1 part of crosslinking inhibitor, 0.01 - 0.05 part of antioxidant, 0.01 - 0.05 part of lubricant; wherein, the degree of branching of the vinyl polyolefin elastomer is 30 - 60 branches / 1000 carbons, the melt index is 1 - 20 g / 10 min, the number average molecular weight is 100,000 - 800,000, the molecular weight distribution index is 1.0 - 2.0, and the density is 0.8 - 0.9 g / cm 3 ; the graft co-monomer is selected from at least one of styrene, divinylbenzene, C8 - C 10 olefins or polyacrylate compounds.

[0012] In the embodiments of the present invention, the vinyl polyolefin elastomer (EPOE) is a non-polar polymer, while the polyester is a polar polymer. When the two are directly blended, the compatibility is poor, and it is difficult to achieve the toughening of polyester using the vinyl polyolefin elastomer, and it is also difficult to achieve the purpose of toughening and compatibilizing polyester and polymer materials to obtain a polyester alloy polymer. In this regard, the present invention uses an initiator to initiate the graft reaction of acrylate monomer and vinyl polyolefin elastomer to improve the polarity of the vinyl polyolefin elastomer. The acrylate monomer can connect the vinyl polyolefin elastomer and polyester as a "bridge" to improve the compatibility between the toughening and compatibilizing agent based on the vinyl polyolefin elastomer and polyester, and thus achieve the toughening of polyester using the vinyl polyolefin elastomer. The acrylate monomer can also connect the vinyl polyolefin elastomer, polyester and polymer materials as a "bridge" to improve the compatibility between the toughening and compatibilizing agent based on the vinyl polyolefin elastomer and polyester and polymer materials, and thus achieve the purpose of toughening and compatibilizing polyester and polymer materials using the vinyl polyolefin elastomer. The presence of the graft co-monomer can promote the occurrence of the graft reaction and also improve the grafting rate. The white oil additive is mainly used for lubrication and facilitating extrusion during the processing. The presence of the crosslinking inhibitor can avoid over-crosslinking. Through the synergistic effect of the graft co-monomer and the crosslinking inhibitor, the compatibility between the vinyl polyolefin elastomer and polyester can be significantly improved, so as to achieve the purpose of toughening polyester using the vinyl polyolefin elastomer; it can also significantly improve the compatibility between the vinyl polyolefin elastomer and polyester and polymer materials, so as to achieve the purpose of toughening and compatibilizing using the vinyl polyolefin elastomer. Further, by utilizing the characteristics of the vinyl polyolefin elastomer having a low crystallinity, a narrow molecular weight distribution, a low glass transition temperature and a small density, it can play a role in toughening polyester, toughening and compatibilizing polyester and polymer materials after grafting, and its relatively high melt index can improve the fluidity of polyester and polyester alloy polymer after grafting.

[0013] According to an embodiment of the present invention, a vinyl polyolefin elastomer, such as that produced by Hefei Zhongke Kele New Materials Co., Ltd., is obtained by polymerizing ethylene under the catalysis of a main catalyst and a cocatalyst. Among them, the main catalyst is a diimine nickel catalyst or a diimine palladium catalyst, and the cocatalyst is selected from any one of borate, alkylaluminoxane, alkylaluminum, phenylaluminum, and alkylaluminum chloride. The molar ratio of the cocatalyst to the diimine nickel catalyst is (1 - 5000):1; the molar ratio of the cocatalyst to the diimine palladium catalyst is (1 - 5000):1. The temperature of the polymerization reaction is 30 - 150 °C, the pressure of the polymerization reaction is 0.1 - 3 MPa, and the time of the polymerization reaction is 0.1 - 78 h. In the embodiment of the present invention, since the vinyl polyolefin elastomer is obtained by polymerizing reaction from a unique ethylene gas raw material, its cost is relatively low and the synthesis process is relatively simple.

[0014] Specifically, the main catalyst has the structure shown in formula (1). The diimine palladium catalyst and the diimine nickel catalyst exhibit high thermal stability and high polymerization activity in the ethylene polymerization reaction, and can obtain a vinyl polyolefin elastomer with a higher degree of branching and a higher molecular weight.

[0015] Formula (1); wherein, R1 and R8 each independently selected from hydrogen, C1 - C6 alkyl, halogen, halogen-substituted C1 - C6 alkyl, nitro, C1 - C6 alkoxy, trifluoromethyl; R2, R7, R9, R 12 each independently selected from hydrogen, C1 - C6 alkyl, halogen, halogen-substituted C1 - C6 alkyl; R3, R6, R 10 , R 11 each independently selected from hydrogen, C1 - C6 alkyl, halogen, halogen-substituted C1 - C6 alkyl, phenyl, diphenylmethyl, R4 and R5 each independently selected from hydrogen, C1 - C6 alkyl, C1 - C6 haloalkyl, phenyl, C6 - C 30 substituted phenyl, X selected from halogen, C1 - C6 alkane, C2 - C6 alkene, allyl or benzyl, halogen selected from Cl or Br; M selected from Ni or Pd.

[0016] According to an embodiment of the present invention, the crosslinking inhibitor is selected from at least one of p-benzoquinone, triphenyl phosphate, triphenyl phosphite, carbon tetrachloride, paraffin wax and oleic acid. In the embodiment of the present invention, during the grafting reaction of the vinyl polyolefin elastomer, side reactions of crosslinking and degradation generally occur. The crosslinking inhibitor mainly forms a donor-acceptor pair with the graft comonomer, making the double bond of the graft comonomer rich in electrons, increasing its reaction activity, thereby reducing the side reactions of crosslinking and degradation of the vinyl polyolefin elastomer, as well as the homopolymerization reaction of the graft comonomer.

[0017] According to an embodiment of the present invention, the acrylate monomer is selected from glycidyl methacrylate. The acrylate monomer in the present invention is mainly used to provide an ester group. After bridging with the vinyl polyolefin elastomer, it is mainly used to improve the compatibility between the toughening and compatibilizing agent and polyester to achieve the purpose of toughening, and to improve the compatibility between the toughening and compatibilizing agent, polyester and polymer material to achieve the purpose of toughening and compatibilizing. Further, based on 100 parts by weight of the vinyl polyolefin elastomer, the addition amount of the acrylate monomer should not be higher than 5 parts. If the addition amount is too high, excessive residues of the acrylate monomer in the toughening and compatibilizing agent will be difficult to remove and cause peculiar smells. If the addition amount is too small (less than 1 part), the toughening efficiency of the toughening and compatibilizing agent will be affected. Therefore, the acrylate monomer can be further preferably 2 - 4 parts.

[0018] According to an embodiment of the present invention, the initiator is selected from at least one of isopropyl t-butyl peroxycarbonate, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, 2-ethylhexyl t-butyl peroxycarbonate, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,2-bis(tert-butylperoxy)butane, t-amyl peroxy(2-ethylhexyl) carbonate, t-butyl peroxy-3,5,5-trimethylhexanoate, 1,3-bis(tert-butylperoxyisopropyl)benzene. The initiator in the present invention is mainly used to initiate the polymerization reaction of the vinyl polyolefin elastomer and the acrylate monomer. If the addition amount of the initiator is too much (such as greater than 0.5 part), it is easy to cause excessive crosslinking of the toughening and compatibilizing agent, forming gel and particulate substances (i.e., foreign matter points); if the addition amount of the initiator is too small (such as less than 0.01 part), it is easy to affect the grafting rate of the acrylate monomer, and then it is impossible to effectively improve the compatibility of the toughening and compatibilizing agent, nor can the purpose of toughening or toughening and compatibilizing be achieved. Further, the initiator can be preferably 0.05 part - 0.3 part.

[0019] According to an embodiment of the present invention, the antioxidant is selected from at least one of hindered phenols, hindered amines, phosphites, and aromatic amine antioxidants. Further, the antioxidant is selected from at least one of pentaerythritol tetrakis [β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (antioxidant 1010), octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (antioxidant 1076), tris(2,4-di-tert-butylphenyl) phosphite (antioxidant 168), dibutylhydroxytoluene, butylated hydroxyanisole, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 4,4'-thiobis(6-tert-butyl-m-cresol), dipentaerythritol diphosphite distearyl ester, dipentaerythritol diphosphite dioctadecyl ester, dilauryl thiodipropionate, distearyl thiodipropionate, tris(nonylphenyl) phosphite, and tris(nonylphenyl) phosphite. On the one hand, the antioxidant of the present invention is used to avoid aging during the preparation of the toughening and compatibilizing agent, which affects the service life. On the other hand, it is used to inhibit the aging of polyester and polyester alloy polymers and extend the service life.

[0020] According to an embodiment of the present invention, the lubricant is selected from at least one of white oil, stearic acid, calcium stearate, zinc stearate, and ethylene bisstearamide. The lubricant in the toughening and compatibilizing agent of the present invention is mainly used for lubrication to ensure the fluidity and processability of the toughening and compatibilizing agent, polyester, and polyester alloy polymers. The white oil additive or white oil is selected from No. 5 white oil, which can be used as a lubricant and a demolding agent, reduce the friction between the plastic melt and the mold, make the plastic products easier to demold, improve production efficiency and product quality, and also improve the flexibility and transparency of plastics. In this embodiment, it can also be used as an active diluent and a plasticizer for the initiator.

[0021] According to an embodiment of the present invention, the graft co-monomer is selected from at least one of styrene, divinylbenzene, C8-C 10 olefins, or polyacrylate compounds, where the C8-C 10 olefins can be selected from 1-octene and 1-decene; the polyacrylate compounds are selected from at least one of pentaerythritol triacrylate, pentaerythritol tetraacrylate, diethylene glycol diacrylate, trimellitic anhydride triacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, and trimethylolpropane trimethacrylate. The graft co-monomer in the present invention contains vinyl and / or acrylate groups, which can connect the vinyl polyolefin elastomer and the acrylate monomer together through chemical bonds to form a graft copolymer. In other words, the graft co-monomer is mainly used to promote the grafting of the vinyl polyolefin elastomer and the acrylate monomer and improve the grafting rate.

[0022] As a second aspect of the present invention, a method for preparing a toughening and compatibilizing agent suitable for polyester and its alloys is provided, comprising: uniformly mixing a vinyl polyolefin elastomer, an initiator, a white oil auxiliary agent, an antioxidant, a lubricant, and a crosslinking inhibitor, and then adding the mixture into a twin-screw extruder through a main feeding port, and adding an acrylate monomer and a graft comonomer into the twin-screw extruder through a liquid-phase feeding port, and after mixing and co-extruding, obtaining the toughening and compatibilizing agent.

[0023] In an embodiment of the present invention, according to the above weight parts, the vinyl polyolefin elastomer, the initiator, the white oil auxiliary agent, the antioxidant, the lubricant, and the crosslinking inhibitor are uniformly mixed and then added into the twin-screw extruder through the main feeding port; the acrylate monomer and the graft comonomer are uniformly mixed and then added into the twin-screw extruder through the liquid-phase side feeding port. The temperatures of each section of the twin-screw extruder are controlled for melt extrusion, and a graft reaction is carried out during the extrusion process. After pelletizing, a toughening and compatibilizing agent suitable for polyester and its alloys is obtained. Compared with the products of traditional polymerization reaction extrusion processes, the toughening and compatibilizing agent suitable for polyester and its alloys produced by the preparation method provided by the present invention has the advantages of higher graft efficiency, fewer particulate matters, lower gel content, and less residue of unreacted acrylate monomers. Moreover, compared with the reaction polymerization process, the extrusion graft process in the present invention has significant advantages in continuous production and cost control methods, and has excellent processability.

[0024] According to an embodiment of the present invention, the length-diameter ratio of the screw of the twin-screw extruder is greater than or equal to 48, the screw speed is 200 - 600 rpm, the temperatures of each zone are 60°C, 80°C, 120°C, 140°C, 180°C, 190°C, 190°C, 190°C, 190°C, 170°C in sequence, the residence time is greater than 40 s, and there is at least one shear block with a shear angle greater than 45° in the reaction zone.

[0025] As a third aspect of the present invention, a polyester-based polymer toughened with a toughening and compatibilizing agent is provided, comprising: 100 parts of a polyester-based polymer, and 1 - 7 parts of the toughening and compatibilizing agent suitable for polyester and its alloys as described above; wherein, the polyester-based polymer includes a polyester or a polyester alloy polymer, and the polyester alloy polymer is an alloy polymer of a polyester and a polymer material; wherein, the polyester is selected from any one of polycarbonate (PC), polyethylene terephthalate (PET), and polybutylene terephthalate (PBT), and the polymer material is selected from any one of polybutylene terephthalate (PBT), acrylonitrile-butadiene-styrene copolymer (ABS), polyethylene terephthalate (PET), polypropylene (PP), and polyethylene-propylene copolymer (PO).

[0026] In an embodiment of the present invention, the structure of polyester is designed, and vinyl polyolefin elastomer is grafted with acrylate monomers to obtain a toughening and compatibilizing agent. This toughening and compatibilizing agent has a chemical structure and properties similar to those of polyester and polymer materials, and has good compatibility. Applying the toughening and compatibilizing agent to polyester can achieve the purpose of toughening, so that the obtained toughened polyester has excellent processing performance and impact resistance. Applying the toughening and compatibilizing agent to toughened and compatibilized polyester and polymer materials, the toughening and compatibilizing agent based on vinyl polyolefin elastomer forms a bridge between the two alloys of polyester and polymer materials. This toughening and compatibilizing agent improves the compatibility of polyester and polymer materials, achieving the purpose of toughening and compatibilizing, so that the obtained polyester alloy polymer has excellent impact resistance.

[0027] According to an embodiment of the present invention, the polyester alloy polymer is selected from any one of the alloy polymers of polycarbonate (PC) and polybutylene terephthalate (PBT), the alloy polymer of polycarbonate (PC) and acrylonitrile-butadiene-styrene copolymer (ABS), the alloy polymer of polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), the alloy polymer of polyethylene terephthalate (PET) and polypropylene (PP), and the alloy polymer of polyethylene terephthalate (PET) and polyethylene-propylene copolymer (PO).

[0028] As the fourth aspect of the present invention, a preparation method of a toughened polyester-based polymer with a toughening and compatibilizing agent is provided, including: after uniformly mixing 100 parts of polyester and 1-7 parts of the toughening and compatibilizing agent applicable to polyester and its alloys as described above, feeding them into a twin-screw extruder for blending and pelletizing to obtain a polyester toughened by the toughening and compatibilizing agent; or mixing 20-80 parts of polyester, 20-80 parts of polymer materials, totaling 100 parts; and 1-7 parts of the toughening and compatibilizing agent applicable to polyester and its alloys as described above, uniformly mixing them, feeding them into a twin-screw extruder for blending and pelletizing to obtain a polyester alloy polymer toughened and compatibilized by the toughening and compatibilizing agent.

[0029] In an embodiment of the present invention, due to the good polarity of the toughening and compatibilizing agent, when it is mixed with polyester, the compatibility between the two is good. Thus, the polyester can be toughened by using the toughening and compatibilizing agent based on vinyl polyolefin elastomer, and the preparation method is relatively simple and the toughening efficiency is relatively high. Or, when the toughening and compatibilizing agent is mixed with polyester and polymer materials, the compatibility among the three is good. Thus, the polyester and polymer materials can be toughened and compatibilized by using the toughening and compatibilizing agent based on vinyl polyolefin elastomer to obtain a polyester alloy polymer, and the preparation method is relatively simple and the toughening and compatibilizing efficiency is relatively high.

[0030] It should be noted that: in the above preparation methods of toughening polyester with the toughening compatibilizer and toughening and compatibilizing polyester alloy polymer with the toughening compatibilizer, the parameters of the twin-screw extruder involved are the same as those of the twin-screw extruder used in the preparation method of the toughening compatibilizer for polyester and its alloy in the above embodiments, and will not be elaborated in detail here.

[0031] The technical solutions and advantages of the present invention will be further described in detail below in conjunction with specific embodiments.

[0032] Testing methods

[0033] Melt flow rate (i.e., melt index, unit: g / 10min): The test condition is that the melt (such as the toughening compatibilizer for polyester and its alloy) passes through a standard capillary at 190 °C and 2.16 kg, and the number of grams of the melt flowing out within 10 min is measured.

[0034] Gel content: Weigh a certain amount of the toughening compatibilizer for polyester and its alloy, dissolve it in a solvent (such as toluene), dissolve it at 140 °C, and calculate the ratio of the undissolved substance to the total mass taken as the gel content.

[0035] Odor: Put the toughening compatibilizer for polyester and its alloy into a dryer and keep it at 80 °C for 2 h.

[0036] Example 1

[0037] Prepare the toughening compatibilizer A for polyester and its alloy, including: Mix 10 kg of vinyl polyolefin elastomer, 2 g of antioxidant (including antioxidant 1010 and antioxidant 168, with a mass ratio of 2:1), 1 g of calcium stearate (lubricant), 180 g of No. 5 white oil additive, and 20 g of 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane (initiator) evenly through a mixer, and add them from the main feeding port of the twin-screw extruder; Add a mixture of 200 g of glycidyl methacrylate (GMA) and 20 g of graft comonomer (styrene) from the liquid-phase feeding port of the twin-screw extruder, where the feeding amounts of the main feeding port and the liquid-phase feeding port are 30 kg / h and 2 kg / h respectively. Turn on the vacuum system, and the temperature of the twin-screw extruder used is set at 60 °C, 80 °C, 120 °C, 140 °C, 180 °C, 190 °C, 190 °C, 190 °C, 190 °C, 170 °C. The length-diameter ratio of the screw of the twin-screw extruder is 48, the screw speed is 250 rpm, and the residence time of the melt in the screw is 60 s. After extrusion and pelletization, the toughening compatibilizer A for polyester and its alloy is obtained. Among them, the degree of branching of the vinyl polyolefin elastomer is 45 branches / 1000 carbons, the melt index is 5 g / 10min, the number-average molecular weight is 600,000, the molecular weight distribution index is 1.5, and the density is 0.895 g / cm 3 .

[0038] Example 2

[0039] The toughening and compatibilizing agent B suitable for polyester and its alloys was prepared by the same method as in Example 1, with the only difference being that 5 g of p-benzoquinone (crosslinking inhibitor) was added to the main feed port of the twin-screw extruder.

[0040] Example 3

[0041] The toughening and compatibilizing agent C suitable for polyester and its alloys was prepared by the same method as in Example 1, with the only difference being that 10 g of p-benzoquinone (crosslinking inhibitor) was added to the main feed port of the twin-screw extruder.

[0042] Example 4

[0043] The toughening and compatibilizing agent D suitable for polyester and its alloys was prepared by the same method as in Example 1, with the only difference being that 20 g of p-benzoquinone (crosslinking inhibitor) was added to the main feed port of the twin-screw extruder.

[0044] Comparative Example 1

[0045] The toughening and compatibilizing agent E suitable for polyester and its alloys was prepared by the same method as in Example 4, with the only difference being that the vinyl polyolefin elastomer was replaced with an ethylene-octene copolymer elastomer, namely POE-8200 purchased from Dow Chemical Company, with a melt index of 5.0 g / 10 min.

[0046] Furthermore, the properties of the toughening and compatibilizing agents for polyester and its alloys in the above Examples 1 - 4 and Comparative Example 1 were tested, and the specific test results are shown in Table 1.

[0047] Table 1

[0048]

[0049] As can be seen from Table 1, in the case of not adding a crosslinking inhibitor, the obtained toughening and compatibilizing agent for polyester and its alloys had an obvious pungent odor at 80 °C for 2 h. This was mainly because there were free acrylate groups in the toughening and compatibilizing agent, and the melt index of the obtained toughening and compatibilizing agent was relatively low, indicating low fluidity and difficult processing. Furthermore, by adding a crosslinking inhibitor and increasing its addition amount, the generation of odor could be significantly reduced, and the melt index of the obtained toughening and compatibilizing agent continuously increased, indicating that the fluidity and processability of the toughening and compatibilizing agent were continuously improved.

[0050] Further, toughening and compatibilizing agent D in Example 4 and toughening and compatibilizing agent E in Comparative Example 1 were respectively added to polycarbonate (PC) and polybutylene terephthalate (PBT) polymer materials to prepare a polyester alloy polymer toughened and compatibilized by the toughening and compatibilizing agent. The specific preparation process is as follows.

[0051] Comparative Example 2

[0052] 30 parts of PC, 70 parts of PBT, totaling 100 parts; and 0 parts of the toughening and compatibilizing agent D in Example 4 above were mixed evenly and then fed into a twin-screw extruder for blending and extrusion granulation to obtain PC-PBT alloy polymer A. The temperature of the twin-screw extruder was 60°C, 80°C, 120°C, 140°C, 180°C, 190°C, 190°C, 190°C, 190°C, 170°C. The length-diameter ratio of the screw of the twin-screw extruder was 48, the screw speed was 250 rpm, and the residence time of the melt in the screw was 60 s.

[0053] Example 5

[0054] PC-PBT alloy polymer B toughened and compatibilized by toughening and compatibilizing agent D in Example 4 was prepared by the same method as in Comparative Example 2. The only difference was that the addition amount of toughening and compatibilizing agent D in Example 4 was 3 parts (i.e., 3%).

[0055] Example 6

[0056] PC-PBT alloy polymer C toughened and compatibilized by toughening and compatibilizing agent D in Example 4 was prepared by the same method as in Comparative Example 2. The only difference was that the addition amount of toughening and compatibilizing agent D in Example 4 was 5 parts (i.e., 5%).

[0057] Example 7

[0058] PC-PBT alloy polymer D toughened and compatibilized by toughening and compatibilizing agent D in Example 4 was prepared by the same method as in Comparative Example 2. The only difference was that the addition amount of the toughening and compatibilizing agent in Example 4 was 7 parts (i.e., 7%).

[0059] Comparative Example 3

[0060] PC-PBT alloy polymer toughened and compatibilized by toughening and compatibilizing agent E in Comparative Example 1 was prepared by the same method as in Example 7. The only difference was that the addition amount of toughening and compatibilizing agent E in Comparative Example 1 was 7 parts (i.e., 7%).

[0061] Further, the properties of the PC-PBT alloy polymers toughened and compatibilized by the toughening and compatibilizing agents in Examples 5 - 7 and Comparative Examples 2 - 3 were tested. The specific test results are shown in Table 2.

[0062] Test method

[0063] Density test: Refer to GB∕T4472-2011 and combine with the principle of the drainage method to determine the density.

[0064] Melt index determination: (i.e., melt flow rate, unit: g / 10min): According to the standard ISO 1133, the number of grams of the molten material flowing out through the standard capillary within 10 minutes when the molten material (such as PC-PBT alloy polymer) is melted at 250°C under 5 kg.

[0065] Tensile strength determination: According to the standard ISO 527, install the sample to be tested on the tensile testing machine, start applying tensile load to the sample to be tested, and record the tensile force and elongation. Among them, the tensile speed is set at a constant rate of 50 mm / min.

[0066] Elongation at break determination: Refer to the standard ISO 527. After cutting out the test sample with standard size from the sample to be tested, place it on the tensile testing machine. Among them, the tensile speed is set at a constant rate of 50 mm / min and record.

[0067] Flexural modulus and flexural strength determination: Refer to the standard ISO 178, install the sample to be tested on the flexural testing machine, set parameters such as the loading speed and maximum load of the flexural testing machine. Start the flexural testing machine, start applying flexural load to the sample to be tested, and record the relationship between the load and the deformation of the sample to be tested.

[0068] Notched impact strength determination: Refer to the standard ISO 180, install the sample to be tested on the impact testing machine at room temperature (25°C), set the impact speed and impact energy to conduct the impact test.

[0069] Notched impact strength at low temperature (-20°C) determination: Refer to the standard ISO 180, install the sample to be tested on the impact testing machine in a low-temperature test chamber (-20°C), set the impact speed and impact energy to conduct the impact test.

[0070] Table 2

[0071]

[0072] As can be seen from Table 2, without adding a toughening and compatibilizing agent, the prepared PC-PBT alloy polymer has a low elongation at break and poor impact resistance. Further, as the addition amount of the toughening and compatibilizing agent increases, the melt index, tensile strength, flexural strength, and flexural modulus of the obtained PC-PBT alloy polymer gradually decrease, while the elongation at break and impact resistance gradually increase, indicating that the toughening and compatibilizing agent in the embodiments of the present invention achieves the purpose of toughening and compatibilizing PC and PBT. Furthermore, by comparing the PC-PBT alloy polymers obtained in Example 7 and Comparative Example 3, it can be found that the PC-PBT alloy polymer in Example 7 of the present invention has a lower melt index and tensile strength, and higher elongation at break, flexural strength, flexural modulus, and impact resistance. This shows that the toughening and compatibilizing agent based on ethylene vinyl olefin elastomer (EPOE) in the embodiments of the present invention has a significant toughening effect, and has a better toughening effect than the toughening and compatibilizing agent based on polyolefin elastomer (POE) with the same addition amount, whether at room temperature or at low temperature (-20°C). Combining the cost advantages of ethylene vinyl olefin elastomer (EPOE) and polyolefin elastomer (POE), the toughening and compatibilizing agent provided by the present invention has a higher cost performance advantage, and it can be applied to fields such as automobile bumpers, communication equipment casings, and mechanical structural parts.

[0073] Example 8

[0074] 80 parts of PET and 20 parts of PP, totaling 100 parts; and 5 parts of the toughening and compatibilizing agent in Example 3 above were mixed evenly and then fed into a twin-screw extruder for blending and extrusion granulation to obtain the PET-PP alloy polymer toughened and compatibilized by the toughening and compatibilizing agent in Example 3. The temperature of the twin-screw extruder was 60°C, 80°C, 120°C, 140°C, 180°C, 190°C, 190°C, 190°C, 190°C, 170°C. The length-diameter ratio of the screw of the twin-screw extruder was 48, the screw speed was 250 rpm, and the residence time of the melt in the screw was 60 s.

[0075] Example 9

[0076] The PET-PP alloy polymer toughened and compatibilized by the toughening and compatibilizing agent was prepared by the same method as in Example 8, and the only difference was that the toughening and compatibilizing agent in Example 4 was used, and the addition amount was 5 parts.

[0077] Comparative Example 4

[0078] The PET-PP alloy polymer toughened and compatibilized by the toughening and compatibilizing agent was prepared by the same method as in Example 8, and the only difference was that 5 parts of Arkema EMA AX8900 toughening and compatibilizing agent was applied to PET and PP for compatibilization.

[0079] Furthermore, the properties of the toughened and compatibilized PET-PP alloy polymers with the toughening and compatibilizing agent in the above Examples 8 - 9 and Comparative Example 4 were tested, and the specific test results are shown in Table 3.

[0080] Determination of the melt index in Table 3: Referring to the standard ISO 1133, the number of grams of the molten material (such as the PET-PP alloy polymer toughened with the toughening and compatibilizing agent) flowing out through the standard capillary within 10 min at 270°C and 5 kg.

[0081] Table 3

[0082]

[0083] As can be seen from Table 3, when using the toughening and compatibilizing agent based on vinyl polyolefin elastomer of the present invention to toughen and compatibilize PET and PP, it has excellent compatibility and processability, and excellent impact resistance. Further, in view of the low dielectric loss of polypropylene (PP), this PET-PP alloy polymer is expected to be applied in the field of 5G materials.

[0084] Example 10

[0085] After mixing 100 parts of PBT and 5 parts of the toughening and compatibilizing agent in the above Example 3 evenly, they were sent into a twin-screw extruder for blending and extrusion granulation to obtain the PBT polymer toughened with the toughening and compatibilizing agent in Example 3. The temperature of the twin-screw extruder was 60°C, 80°C, 120°C, 140°C, 180°C, 190°C, 190°C, 190°C, 190°C, 170°C. The length-diameter ratio of the screw of the twin-screw extruder was 48, the screw speed was 250 rpm, and the residence time of the melt in the screw was 60 s.

[0086] Comparative Example 5

[0087] The difference from Example 10 was that the toughening and compatibilizing agent in Example 3 was not added, and the other conditions were the same.

[0088] Furthermore, the properties of the PBT polymers in the above Example 10 and Comparative Example 5 were tested, and the specific test results are shown in Table 4.

[0089] Table 4

[0090]

[0091] As can be seen from Table 4, when toughening PBT with the toughening and compatibilizing agent based on vinyl polyolefin elastomer of the present invention, the obtained PBT polymer has excellent impact resistance.

[0092] In summary, the present invention mixes acrylate monomers, vinyl polyolefin elastomers, graft comonomers, initiators, white oil additives, antioxidants, crosslinking inhibitors, and lubricants, and extrudes and granulates them through a twin-screw extruder to obtain a toughening and compatibilizing agent suitable for polyesters and their alloys. Compared with the existing toughening agents with a linear structure, the vinyl polyolefin elastomer has a higher degree of branching and a larger free volume, and after grafting acrylate monomers, it has a higher toughening efficiency. Compared with the core-shell structured toughening agents, the preparation method of the toughening and compatibilizing agent provided by the present invention is simpler. The present invention does not require the use of solvents, has less investment, is easier to obtain equipment, has less pollutant emissions in the process route, is simpler in process control, and has a low residual monomer content and stable composition in the toughening and compatibilizing agent, polyester, and polyester alloy polymer. The toughening and compatibilizing agent is relatively simple to use and can be used for toughening modification in polylactic acid, polyester, and alloy materials composed of polyester and polymer materials, and thus can be widely used in fields such as medical treatment, packaging, household appliances, automobiles, and aviation, and has very broad application prospects and industrialization value.

[0093] The specific embodiments described above further elaborate on the purpose, technical solutions, and beneficial effects of the present invention. It should be understood that the above are only specific embodiments of the present invention and are not used to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Claims

1. A toughened polyester polymer toughened with a toughening and compatibilizing agent, characterized in that, By weight parts, it includes: 100 parts of polyester polymer, 1 - 7 parts of toughening and compatibilizing agent suitable for polyester and its alloys; Among them, the polyester polymer includes polyester or polyester alloy polymer, and the polyester alloy polymer is an alloy polymer of the polyester and a polymer material; Among them, the toughening and compatibilizing agent suitable for polyester and its alloys includes: 100 parts of vinyl polyolefin elastomer, 1 - 5 parts of acrylate monomer, 0.1 - 1 part of graft comonomer, 0.01 - 0.5 part of initiator, 0.1 - 4.5 parts of white oil additive, 0.01 - 1 part of crosslinking inhibitor, 0.01 - 0.05 part of antioxidant, 0.01 - 0.05 part of lubricant; Among them, the degree of branching of the vinyl polyolefin elastomer is 30 - 60 branches / 1000 carbons, the melt index is 1 - 20 g / 10 min, the number average molecular weight is 100,000 - 800,000, the molecular weight distribution index is 1.0 - 2.0, and the density is 0.8 - 0.9 g / cm 3 ; The graft co-monomer is selected from at least one of styrene, divinylbenzene, C8-C 10 olefins or polyacrylate compounds; The crosslinking inhibitor is selected from p - benzoquinone, and the acrylate monomer is selected from glycidyl methacrylate; The polyacrylate compound is selected from at least one of pentaerythritol triacrylate, pentaerythritol tetraacrylate, diethylene glycol diacrylate, trimellitic anhydride triacrylate, 1,4 - butanediol dimethacrylate, 1,6 - hexanediol dimethacrylate, trimethylolpropane trimethacrylate; 2. The toughened polyester polymer toughened by the toughening and compatibilizing agent according to claim 1, characterized in that The initiator is selected from at least one of isopropyl peroxycarbonate t - butyl, 2,5 - dimethyl - 2,5 - bis(tert - butylperoxy)hexane, 2 - ethylhexyl peroxycarbonate t - butyl, 1,1 - bis(tert - butylperoxy)-3,3,5 - trimethylcyclohexane, 1,1 - bis(tert - butylperoxy)cyclohexane, 2,2 - bis(tert - butylperoxy)butane, tert - amyl peroxy(2 - ethylhexyl) carbonate, tert - butyl peroxy - 3,5,5 - trimethylhexanoate, 1,3 - bis(tert - butylperoxyisopropyl)benzene; The white oil additive is selected from No. 5 white oil; The antioxidant is selected from at least one of hindered phenol, hindered amine, phosphite and aromatic amine antioxidants; The lubricant is selected from at least one of white oil, stearic acid, calcium stearate, zinc stearate, ethylene bisstearamide; 3. The toughened polyester polymer toughened by the toughening and compatibilizing agent according to claim 1, characterized in that, The vinyl polyolefin elastomer is obtained by polymerization of ethylene under the catalytic action of a main catalyst and a cocatalyst; Among them, the main catalyst is a diimine nickel catalyst or a diimine palladium catalyst; the cocatalyst is selected from any one of borate, alkylaluminoxane, alkylaluminum, phenylaluminum, alkylaluminum chloride; 4. The toughened polyester polymer toughened by the toughening and compatibilizing agent according to claim 1, characterized in that, The polyester is selected from any one of polycarbonate, polyethylene terephthalate, polybutylene terephthalate, and the polymer material is selected from any one of polybutylene terephthalate, acrylonitrile - butadiene - styrene copolymer, polyethylene terephthalate, polypropylene, polyethylene - polypropylene copolymer; 5. The polyester polymer toughened with the toughening and compatibilizing agent according to claim 4, characterized in that, The polyester alloy polymer is selected from any one of an alloy polymer of polycarbonate and polybutylene terephthalate, an alloy polymer of polycarbonate and acrylonitrile - butadiene - styrene copolymer, an alloy polymer of polyethylene terephthalate and polybutylene terephthalate, an alloy polymer of polyethylene terephthalate and polypropylene, an alloy polymer of polyethylene terephthalate and polyethylene - polypropylene copolymer; 6. A method for preparing a toughened polyester polymer toughened with a toughening and compatibilizing agent as described in any one of claims 1-5, characterized in that, The preparation method includes: After uniformly mixing 100 parts of polyester and 1 - 7 parts of a toughening and compatibilizing agent suitable for polyester and its alloys, feeding them into a twin-screw extruder for blending and then pelletizing, polyester toughened by the toughening and compatibilizing agent is obtained; or After uniformly mixing 20 - 80 parts of polyester, 20 - 80 parts of polymer material, totaling 100 parts; and 1 - 7 parts of a toughening and compatibilizing agent suitable for polyester and its alloys as described in any one of claims 1 - 5, feeding them into a twin-screw extruder for blending and then pelletizing, a polyester alloy polymer toughened and compatibilized by the toughening and compatibilizing agent is obtained.

7. The preparation method according to claim 6, characterized in that, The toughening and compatibilizing agent suitable for polyester and its alloys is obtained through the following preparation method: After uniformly mixing a vinyl polyolefin elastomer, an initiator, a white oil additive, an antioxidant, a lubricant, and a crosslinking inhibitor, adding them into a twin-screw extruder through the main feed port, and adding an acrylate monomer and a graft comonomer into the twin-screw extruder through the liquid-phase feed port, and then performing mixed co-extrusion, the toughening and compatibilizing agent is obtained.

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