Polyamide-based polymer and preparation method thereof

Abstract

The invention provides a polyamide polymer and a preparation method thereof, and belongs to the technical field of polymers. Wherein the polyamide polymer is toughened or toughened and compatibilized by a vinyl polyolefin elastomer graft, and the polyamide polymer comprises the following components in parts by weight: 100 parts of polyamide or 110-140 parts of a polyamide alloy polymer; 5 to 20 parts of a vinyl polyolefin elastomer graft; 0.1 to 2 parts of an antioxidant; and 0.1-2 parts of a lubricant. Wherein the vinyl polyolefin elastomer graft is a graft of a vinyl polyolefin elastomer and maleic anhydride; the polyamide alloy polymer is selected from any one of an alloy polymer of polyamide and polyolefin and an alloy polymer of polyamide and glass fiber.

Description

Technical Field

[0001] The invention belongs to the technical field of polymers, and in particular relates to a polyamide polymer and a preparation method thereof, and more specifically relates to a vinyl polyolefin elastomer graft toughened polyamide, a toughened and volume-enhanced polyamide alloy polymer and a preparation method thereof. Background Art

[0002] Polyamide (PA) materials are widely used in industries such as automobiles, electronic appliances, packaging, daily necessities, and toys due to their superior comprehensive performance, low cost, and easy processing. However, polyamide materials have poor toughness, high notch sensitivity, and low heat resistance in low-temperature environments (0°C~-20°C), which limits the further application of polyamide materials. Although the toughening agents currently on the market can improve the impact resistance of PA, these toughening agents are expensive and cannot solve the problem of poor heat resistance of PA. In order to broaden the application scenarios of PA, PA is often blended with other polyolefin materials or fillers to form polyamide alloy polymers, but due to poor compatibility, the application of PA in toughening and capacity expansion is limited. Therefore, a general toughening and capacity expansion material with a suitable price and excellent comprehensive performance is designed. Summary of the invention

[0003] In view of the above problems, the present invention provides a polyamide polymer and a preparation method thereof, in order to at least partially solve the above technical problems. In this regard, the technical solution provided by the present invention is as follows.

[0004] As a first aspect of the present invention, a polyamide polymer toughened or toughened and expanded with a vinyl polyolefin elastomer graft is provided, which comprises, by weight: 100 parts of polyamide, or 110-140 parts of a polyamide alloy polymer; 5-20 parts of a vinyl polyolefin elastomer graft; 0.1-2 parts of an antioxidant and 0.1-2 parts of a lubricant; wherein the vinyl polyolefin elastomer graft is a graft of a vinyl polyolefin elastomer and maleic anhydride; and the polyamide alloy polymer is selected from any one of an alloy polymer of polyamide and polyolefin, and an alloy polymer of polyamide and glass fiber.

[0005] As a second aspect of the present invention, a method for preparing a polyamide polymer toughened or toughened and expanded with a vinyl polyolefin elastomer graft is provided, comprising: uniformly mixing 100 parts of polyamide, 5-20 parts of vinyl polyolefin elastomer graft, 0.1-2 parts of antioxidant and 0.1-2 parts of lubricant, feeding into a twin-screw extruder for blending, extrusion granulation, and obtaining a polyamide toughened with a vinyl polyolefin elastomer graft; or uniformly mixing 100 parts of polyamide, 10-40 parts of polyolefin or glass fiber, 5-20 parts of vinyl polyolefin elastomer graft, 0.1-2 parts of antioxidant and 0.1-2 parts of lubricant, feeding into a twin-screw extruder for blending, extrusion granulation, and obtaining a polyamide alloy polymer toughened and expanded with a vinyl polyolefin elastomer graft; wherein the vinyl polyolefin elastomer graft is obtained by grafting a vinyl polyolefin elastomer with maleic anhydride.

[0006] In the embodiment of the present invention, vinyl polyolefin elastomer (EPOE) is a non-polar compound, while polyamide (PA) is a polar compound. When the two are directly blended, the compatibility is poor, and it is difficult to achieve the purpose of using vinyl polyolefin elastomer to toughen polyamide. In view of the problem of poor compatibility between the two, the present invention proposes to graft-modify the vinyl polyolefin elastomer, and through the characteristics of the high branching degree of the vinyl polyolefin elastomer, maleic anhydride is grafted on its side chain, so that the vinyl polyolefin elastomer contains polar groups to improve the compatibility of mixing with polyamide, thereby achieving the purpose of using the vinyl polyolefin elastomer graft to toughen polyamide. The obtained vinyl polyolefin elastomer graft toughened polyamide has the advantages of excellent mechanical properties, thermal stability, and low cost. In addition, the vinyl polyolefin elastomer graft of the present invention can not only toughen polyamide and improve the disadvantage of poor strength of polyamide, but also improve the compatibility of polyamide with other polymer materials (such as polyolefin or glass fiber), thereby significantly improving the toughness and compatibility of the polyamide alloy polymer formed by polyamide and other polymer materials. In addition, the preparation method of the polyamide toughened by the vinyl polyolefin elastomer graft and the toughened and compatibility-enhanced polyamide alloy polymer in the present invention is relatively simple, highly repeatable, and low in cost, and can be industrially prepared. DETAILED DESCRIPTION

[0007] Polyolefin elastomer (POE) is a random copolymer with a high α-olefin content obtained by copolymerization of ethylene and α-olefin under the action of a catalyst. Since the molecular weight distribution index (PDI is generally 1.4-2.1) of polyolefin elastomer (POE) is relatively narrow, the side groups in the molecular structure can form connection points in the molecular structure to play a role of connection and buffering, so that the material can disperse and buffer the impact when it is impacted. However, POE has long side chains and poor compatibility with short-chain polyolefins such as polyethylene and polypropylene, which reduces the application of POE in toughening and capacity-enhancing alloy materials such as polyamides and polyolefins. In addition, the process requirements for the preparation of POE are relatively strict, and there are certain technical barriers in multiple links such as polymerization process, catalysts, and α-olefins, which cannot achieve larger-scale production.

[0008] In view of the current problems of POE, the present invention proposes to use vinyl polyolefin elastomer (EPOE) as raw material, and through grafting modification thereof, give EPOE polar groups, enhance its compatibility with polyamide, as well as with polymer materials such as polypropylene (PP) and polyethylene (PE), thereby achieving the purpose of using vinyl polyolefin elastomer grafts to toughen polyamide, toughen and compatibility polyamide and other polymer materials.

[0009] Specifically, as the first aspect of the present invention, a polyamide polymer toughened or toughened and expanded with a vinyl polyolefin elastomer graft is provided, which comprises, by weight: 100 parts of polyamide or 110-140 parts of polyamide alloy polymer; 5-20 parts of vinyl polyolefin elastomer graft; 0.1-2 parts of antioxidant and 0.1-2 parts of lubricant; wherein the vinyl polyolefin elastomer graft is a graft of vinyl polyolefin elastomer and maleic anhydride; and the polyamide alloy polymer is selected from any one of an alloy polymer of polyamide and polyolefin and an alloy polymer of polyamide and glass fiber.

[0010] In an embodiment of the present invention, vinyl polyolefin elastomer (EPOE) is a non-polar compound, while polyamide (PA) is a polar compound. When the two are directly blended, the compatibility is poor, and it is difficult to achieve the purpose of using EPOE to toughen polyamide. In this regard, the present invention proposes to graft maleic anhydride on EPOE, use maleic anhydride to give EPOE polar groups, and then mix the obtained vinyl polyolefin elastomer graft with polyamide, so that the compatibility is significantly improved, thereby achieving the purpose of using vinyl polyolefin elastomer graft to toughen polyamide. Alternatively, the vinyl polyolefin elastomer graft is mixed with polyamide and other polymer materials (such as polyolefin or glass fiber), and the compatibility is also significantly improved, thereby achieving the purpose of using vinyl polyolefin elastomer graft to toughen and compatibility polyamide and other polymer materials, thereby obtaining a polyamide alloy polymer. In addition, compared with POE, EPOE has a higher degree of branching and can be grafted with more maleic anhydride. The obtained vinyl polyolefin elastomer graft has significantly improved compatibility with polyamide, or significantly improved compatibility with polyamide and other polymer materials, thereby achieving the purpose of toughening polyamide or toughening and compatibility polyamide alloy polymers, and the obtained polyamide or polyamide alloy polymer has excellent mechanical properties and thermal stability.

[0011] Specifically, the polyamide polymer toughened by vinyl polyolefin elastomer grafts includes, by weight: 100 parts of polyamide, 5-20 parts of vinyl polyolefin elastomer grafts, 0.1-2 parts of antioxidants and 0.1-2 parts of lubricants. Alternatively, the polyamide polymer toughened and compatibilized by vinyl polyolefin elastomer grafts includes, by weight: 110-140 parts of polyamide alloy polymer (including 100 parts of polyamide, 10-40 parts of polyolefin or glass fiber), 5-20 parts of vinyl polyolefin elastomer grafts, 0.1-2 parts of antioxidants and 0.1-2 parts of lubricants.

[0012] According to an embodiment of the present invention, the vinyl polyolefin elastomer graft is a graft of vinyl polyolefin elastomer (EPOE) and maleic anhydride, wherein the maleic anhydride graft rate of the vinyl polyolefin elastomer graft is 0.5%-1.4%. The graft rate of maleic anhydride within this range ensures the compatibility of EPOE with polyamide. If the graft rate of maleic anhydride is less than 0.5%, it is easy to cause the compatibility of EPOE with polyamide to be poor and the purpose of toughening cannot be achieved; if the graft rate of maleic anhydride is greater than 1.4%, the cost will be increased and the toughening effect will not be significantly improved. Similarly, the graft rate of maleic anhydride within this range also ensures the compatibility of EPOE with polyamide and other polymer materials, thereby achieving the purpose of toughening and compatibility of polyamide and other polymer materials.

[0013] According to an embodiment of the present invention, ethylene polyolefin elastomer (EPOE), such as that produced by Hefei Zhongke Kele New Materials Co., Ltd., is only ethylene (CH 2 =CH 2 ) is a single raw material, which is obtained by polymerization reaction under the catalytic action of a main catalyst and a co-catalyst, wherein the main catalyst is a diimine nickel catalyst or a diimine palladium catalyst. Ethylene, as the only raw material for synthesizing vinyl polyolefin elastomers, significantly reduces the cost and technical difficulty of synthesizing EPOE compared to polyolefin elastomers (POE) obtained by copolymerization of ethylene and α-olefins, thereby reducing the cost of using vinyl polyolefin elastomer grafts to toughen polyamides. Furthermore, the diimine nickel catalyst has a structure as shown in formula (1). A diimine palladium catalyst can also be used. The diimine palladium catalyst has the same structure as the diimine nickel catalyst, the only difference being that nickel (Ni) is replaced by palladium (Pd).

[0014] Formula (1); where R 1 , R 8 are each independently selected from hydrogen, C 1 -C 6 Alkyl, halogen, halogen-substituted C 1 -C 6 Alkyl, nitro, C 1 -C 6 Any of alkoxy and trifluoromethyl; R 2 , R 7 , R 9 , R 12 are each independently selected from hydrogen, C 1 -C 6 Alkyl, halogen, halogen-substituted C 1 -C 6 Alkyl; R 3 , R 6 , R 10 , R 11 are each independently selected from hydrogen, C 1 -C 6 Alkyl, halogen, halogen-substituted C 1 -C 6 Any of alkyl, phenyl, and diphenylmethyl, R 4 , R 5 are each independently selected from hydrogen, C 1 -C 6 Alkyl, C 1 -C 6 Halogenated alkyl, phenyl, C 6 -C 30 substituted phenyl, X is selected from halogen, C 1 -C 6 Alkanes, C2 -C 6 The halogen is selected from Cl or Br.

[0015] According to an embodiment of the present invention, the co-catalyst used in the synthesis of EPOE is selected from at least one of alkylaluminoxane, alkylaluminum, phenylaluminum, alkylaluminum chloride, and borate. The molar ratio of the co-catalyst to the diimine nickel catalyst is (1-5000): 1, and the molar ratio of the co-catalyst to the diimine palladium catalyst is (1-5000): 1. The polymerization temperature is 30-150° C., the polymerization pressure is 0.1-3 MPa, and the polymerization time is 0.1-78 h.

[0016] According to an embodiment of the present invention, the antioxidant is selected from one or more of tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]pentaerythritol ester (antioxidant 1010), tris[2,4-di-tert-butylphenyl]phosphite (antioxidant 168), β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate octadecyl alcohol ester (antioxidant 1076), bis(2,4-dicumylphenyl)pentaerythritol diphosphite (antioxidant 9228), and distearyl thiodipropionate (antioxidant DSTDP); the lubricant is selected from at least one of ethylene bisstearamide (EBS) and pentaerythritol stearate (PETS).

[0017] According to an embodiment of the present invention, the melt index of EPOE is 3-13 g / 10 min, the number average molecular weight (M n ) is 100,000-200,000, molecular weight distribution index (PDI=M w / M n , M w The weight average molecular weight is 1.0-2.0, the branching degree is 30-60 branches / 1000 carbons, and the density is 0.860-0.9g / cm 3 , the melting point is 55-65 ° C. In an embodiment of the present invention, EPOE has a high degree of branching, and a higher grafting rate can be obtained when it is grafted with maleic anhydride, thereby significantly improving the compatibility of EPOE with maleic anhydride. In addition, EPOE has a wide range of melt index, which can effectively improve the mechanical properties and processing properties of polyamide, wherein the melt index can be selected from 3-5g / 10min, 5-9g / 10min, and 9-13g / 10min. The molecular weight distribution index of EPOE is narrow, and the number average molecular weight distribution is relatively uniform, which can reduce cracks when impacted, thereby improving the impact strength of polyamide.

[0018] According to an embodiment of the present invention, polyolefin is selected from polypropylene (PP) or polyethylene (PE). Because EPOE has a wide range of melt index, it can also effectively improve the mechanical properties of polyamide and polyolefin. The molecular weight distribution index of EPOE is narrow, and the number average molecular weight distribution is relatively uniform, which can reduce cracks when impacted, thereby improving the impact strength of polyamide and polyolefin. In addition, EPOE has shorter side chains and a molecular structure that is more similar to polypropylene (PP) and polyethylene (PE), making the vinyl polyolefin elastomer graft toughening and compatibilizing PP and PA, or PE and PA better.

[0019] As a second aspect of the present invention, a method for preparing a polyamide polymer toughened or toughened and expanded with a vinyl polyolefin elastomer graft is provided, comprising: uniformly mixing 100 parts of polyamide, 5-20 parts of vinyl polyolefin elastomer graft, 0.1-2 parts of antioxidant and 0.1-2 parts of lubricant, feeding into a twin-screw extruder for blending, extrusion granulation, and obtaining a polyamide toughened with a vinyl polyolefin elastomer graft; or uniformly mixing 100 parts of polyamide, 10-40 parts of polyolefin or glass fiber, 5-20 parts of vinyl polyolefin elastomer graft, 0.1-2 parts of antioxidant and 0.1-2 parts of lubricant, feeding into a twin-screw extruder for blending, extrusion granulation, and obtaining a polyamide alloy polymer toughened and expanded with a vinyl polyolefin elastomer graft; wherein the vinyl polyolefin elastomer graft is obtained by grafting a vinyl polyolefin elastomer (EPOE) with maleic anhydride.

[0020] In the embodiment of the present invention, EPOE is first grafted with maleic anhydride to improve the polarity of EPOE. Subsequently, the raw materials required for preparing toughened polyamide and toughened and compatibilized polyamide alloy polymer are transported to a twin-screw extruder for blending and extrusion granulation to obtain a polyamide toughened by vinyl polyolefin elastomer graft, or a polyamide alloy polymer toughened and compatibilized by vinyl polyolefin elastomer graft. The preparation method is relatively simple, highly processable and repeatable.

[0021] According to an embodiment of the present invention, a vinyl polyolefin elastomer graft is obtained, comprising: in the presence of zinc hydroxide, an initiator initiates a grafting reaction between EPOE and maleic anhydride. The grafting rate of EPOE and maleic anhydride is 0.5%-1.4%; the initiator is selected from one or more of benzoyl peroxide (BPO), diisopropylbenzene peroxide (DCP), di-tert-butyl peroxide (DTBP), 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane (T101), 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxynonane (301), and di-tert-butylperoxyisopropylbenzene (BIPB).

[0022] Specifically, the method for preparing a vinyl polyolefin elastomer graft comprises: conveying EPOE, zinc hydroxide, an initiator and maleic anhydride into a premixer, mixing at 300-1000 rpm for 8-16 minutes to obtain a premix; then feeding the obtained premix into a twin-screw extruder, extruding after blending and cooling in the twin-screw extruder, initiating a grafting reaction on the vinyl polyolefin elastomer (EPOE) chain segment by an initiator during the extrusion process to graft maleic anhydride, and obtaining a vinyl polyolefin elastomer graft after pelletizing in a granulator. The body temperature of the twin-screw extruder is set at 180°C, the temperature of the first zone is set at 120±10°C, the temperature of the second zone is set at 180±10°C, the temperature of the third zone is set at 200±10°C, the temperature of the fourth zone is set at 200±10°C, and the speed of the twin-screw extruder is 400 rpm.

[0023] Specifically, the preparation method of polyamide toughened with vinyl polyolefin elastomer graft comprises: weighing polyamide, vinyl polyolefin elastomer graft, antioxidant and lubricant in proportion and conveying them into a premixer, mixing them at 800-1500 rpm for 10-20 minutes to obtain a premix; then feeding the obtained premix into a twin-screw extruder, blending and cooling the twin-screw extruder, and pelletizing the premix through a granulator to obtain polyamide toughened with vinyl polyolefin elastomer graft; wherein the body temperature of the twin-screw extruder is set to 180°C, the temperature of the first zone is set to 120±10°C, the temperature of the second zone is set to 180±10°C, the temperature of the third zone is set to 200±10°C, the temperature of the fourth zone is set to 200±10°C, and the speed of the twin-screw extruder is 500 rpm.

[0024] Specifically, the preparation method of a polyamide alloy polymer toughened and expanded with vinyl polyolefin elastomer grafts comprises: weighing polyamide, polyolefin or glass fiber, vinyl polyolefin elastomer grafts, antioxidants, and lubricants in proportion and conveying them to a premixer, mixing them at 800-1500 rpm for 10-20 minutes to obtain a premix; then feeding the obtained premix into a twin-screw extruder, blending and cooling the twin-screw extruder, and pelletizing the premix in a granulator to obtain a polyamide alloy polymer toughened and expanded with vinyl polyolefin elastomer grafts; wherein the body temperature of the twin-screw extruder is set to 180°C, the temperature of the first zone is set to 120±10°C, the temperature of the second zone is set to 180±10°C, the temperature of the third zone is set to 200±10°C, the temperature of the fourth zone is set to 200±10°C, and the speed of the twin-screw extruder is 500 rpm.

[0025] In summary, the present invention utilizes vinyl polyolefin elastomer grafted with maleic anhydride to toughen polyamide, toughen and compatibilize polyamide and other polymer materials (such as polyolefin or glass fiber), which can not only improve the disadvantage of poor strength of the obtained polyamide and polyamide alloy polymers, but also improve the toughness of polyamide and polyamide alloy polymers, and the thermal stability is also improved.

[0026] The technical solution of the present invention is further described in detail below in conjunction with specific embodiments.

[0027] Preparation of vinyl polyolefin elastomer (EPOE): 2 Under the atmosphere, a stirring bar, 250 equivalents of MAO (methylaluminoxane, used as a co-catalyst and to remove impurities such as water), and 48 mL of n-hexane were added to a 350 mL pressure bottle. The reaction temperature was adjusted to 100 ° C, the pressure of the ethylene gas was adjusted, and 2 mL of a dichloromethane solution of a diimine nickel catalyst was injected into the pressure bottle. The valve was closed and the pressure of the ethylene gas was adjusted to 20 bar. After reacting for 0.5 hours, the reaction was stopped. A 5% methanol hydrochloric acid solution was added to precipitate the solid, and the solid was washed three times with pure methanol and dried to obtain a vinyl polyolefin elastomer (EPOE). The obtained EPOE had a melt index of 4.3 g / 10 min, a number average molecular weight of 136,000, a molecular weight distribution index of 1.97, a degree of branching of 43 branches / 1000 carbons, and a density of 0.893 g / cm 3 , melting point is 57℃.

[0028] Specifically, the structure of the nickel diimide catalyst used is as follows:

[0029] .

[0030] Preparation of grafted vinyl polyolefin elastomer: by weight, 100 parts of the above-prepared EPOE, 1.2 parts of maleic anhydride, 0.15 parts of 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane (initiator T101), and 0.3 parts of Zn(OH) 2 In zinc hydroxide (Zn(OH) 2 ), the initiator initiates the grafting reaction between EPOE and maleic anhydride to obtain maleic anhydride grafted product of vinyl polyolefin elastomer, referred to as EPOE-g-MAH, wherein the measured grafting rate is 0.73%.

[0031] Example 1

[0032] According to the amount of each component shown in Table 1, a vinyl polyolefin elastomer graft toughened polyamide was prepared, wherein, by weight, 100 parts of polyamide (PA-YH800), 10 parts of EPOE-g-MAH, 0.2 parts of antioxidant 1010, 0.2 parts of antioxidant 168, 0.2 parts of antioxidant DSTDP, and 0.2 parts of lubricant EBS (P-130) were weighed and mixed evenly, then sent into a premixer and mixed at 1500 rpm for 20 minutes to obtain a premix. Subsequently, the premix is ​​fed into a twin-screw extruder, blended in the twin-screw extruder, cooled, and pelletized by a granulator to obtain a polyamide toughened based on vinyl polyolefin elastomer grafts, wherein the body temperature of the twin-screw extruder is 180°C, the temperature of zone one is 120°C, the temperature of zone two is 180°C, the temperature of zone three is 200°C, the temperature of zone four is 200°C, and the main engine speed of the twin-screw extruder is 500 rpm.

[0033] Example 2

[0034] A vinyl polyolefin elastomer graft toughened and compatibilized polyamide alloy polymer was prepared according to the amounts of the components shown in Table 1, wherein, by weight, 100 parts of polyamide (PA-YH800), 20 parts of polypropylene (PP-K7227H), 10 parts of EPOE-g-MAH, 0.2 parts of antioxidant 1010, 0.2 parts of antioxidant 168, 0.2 parts of antioxidant DSTDP, and 0.2 parts of lubricant EBS (P-130) were weighed and mixed evenly, then fed into a premixer and mixed at 1500 rpm for 20 minutes to obtain a premix. Subsequently, the premix is ​​fed into a twin-screw extruder, blended in the twin-screw extruder, cooled, and pelletized by a granulator to obtain a polyamide alloy polymer toughened and expanded with vinyl polyolefin elastomer grafts, wherein the body temperature of the twin-screw extruder is 180°C, the temperature of zone 1 is 120°C, the temperature of zone 2 is 180°C, the temperature of zone 3 is 200°C, the temperature of zone 4 is 200°C, and the main engine speed of the twin-screw extruder is 500 rpm.

[0035] Comparative Example 1

[0036] The polyamide material was prepared according to the amount of each component shown in Table 1, wherein, by weight, 100 parts of polyamide (PA-YH800), 0.2 parts of antioxidant 1010, 0.2 parts of antioxidant 168, 0.2 parts of antioxidant DSTDP, and 0.2 parts of lubricant EBS (P-130) were mixed evenly, and then sent to a premixer, mixed at 1500 rpm for 20 minutes to obtain a premix. Subsequently, the premix was fed into a twin-screw extruder, blended in the twin-screw extruder, cooled, and pelletized in a granulator to obtain a polyamide material, wherein the body temperature of the twin-screw extruder was 180°C, the temperature of the first zone was 120°C, the temperature of the second zone was 180°C, the temperature of the third zone was 200°C, the temperature of the fourth zone was 200°C, and the main engine speed of the twin-screw extruder was 500 rpm.

[0037] Comparative Example 2

[0038] The polyamide alloy polymer was prepared according to the amount of each component shown in Table 1, wherein, by weight, 100 parts of polyamide (PA-YH800), 20 parts of polypropylene (PP-K7227H), 0.2 parts of antioxidant 1010, 0.2 parts of antioxidant 168, 0.2 parts of antioxidant DSTDP, and 0.2 parts of lubricant EBS (P-130) were mixed evenly, and then sent to a premixer and mixed at 1500 rpm for 20 minutes to obtain a premix. Subsequently, the premix was fed into a twin-screw extruder, blended in the twin-screw extruder, cooled, and pelletized in a granulator to obtain a polyamide alloy polymer, wherein the body temperature of the twin-screw extruder was 180°C, the temperature of the first zone was 120°C, the temperature of the second zone was 180°C, the temperature of the third zone was 200°C, the temperature of the fourth zone was 200°C, and the main engine speed of the twin-screw extruder was 500 rpm.

[0039] Comparative Example 3

[0040] Polyamide toughened with Nengzhiguang N413 toughening agent was prepared according to the amount of each component shown in Table 1, which includes, by weight: 100 parts of polyamide (PA-YH800), 10 parts of Nengzhiguang N413 toughening agent (a toughening agent formed by POE grafted with maleic anhydride, with a grafting rate of 0.4%-0.8%), 0.2 parts of antioxidant 1010, 0.2 parts of antioxidant 168, 0.2 parts of antioxidant DSTDP, and 0.2 parts of lubricant EBS (P-130). After mixing evenly, the mixture was sent into a premixer and mixed at 1500 rpm for 20 minutes to obtain a premix. Subsequently, the premix is ​​fed into a twin-screw extruder, blended in the twin-screw extruder and then cooled, and pelletized by a pelletizer to obtain polyamide toughened with Energy Light N413 toughening agent, wherein the body temperature of the twin-screw extruder is 180°C, the temperature of zone one is 120°C, the temperature of zone two is 180°C, the temperature of zone three is 200°C, the temperature of zone four is 200°C, and the main engine speed of the twin-screw extruder is 500 rpm.

[0041] Comparative Example 4

[0042] A polyamide alloy polymer toughened and expanded with Nengzhiguang N413 toughening agent was prepared according to the amounts of each component shown in Table 1, wherein, by weight, the components include: 100 parts of polyamide (PA-YH800), 20 parts of polypropylene (PP-K7227H), 10 parts of Nengzhiguang N413 toughening agent, 0.2 parts of antioxidant 1010, 0.2 parts of antioxidant 168, 0.2 parts of antioxidant DSTDP, and 0.2 parts of lubricant EBS (P-130). After mixing evenly, the mixture was sent into a premixer and mixed at 1500 rpm for 20 minutes to obtain a premix. Subsequently, the premix is ​​fed into a twin-screw extruder, blended in the twin-screw extruder and then cooled, and pelletized by a granulator to obtain a polyamide alloy polymer toughened and expanded with the Energy Light N413 toughening agent. The body temperature of the twin-screw extruder is 180°C, the temperature of zone one is 120°C, the temperature of zone two is 180°C, the temperature of zone three is 200°C, the temperature of zone four is 200°C, and the main engine speed of the twin-screw extruder is 500 rpm.

[0043] Table 1

[0044]

[0045] The polymers obtained from the above-mentioned Examples 1 to 2 and Comparative Examples 1 to 4 were tested for melt flow rate, density, tensile strength, breaking strain, flexural modulus, and notched impact. The specific test results are shown in Table 2.

[0046] The test method for melt flow rate is: using the test method of ASTM D1238, the temperature is 275°C, the weight is 5.0 kg, the experiment is repeated 3 times, and the experimental results are recorded.

[0047] The method for tensile strength and fracture strain is as follows: According to the test method of GB / T1040-2018, a universal tensile testing machine is used to control the tensile rate to 50 mm / min for material tensile testing. The tensile test is repeated five times and the experimental results are recorded.

[0048] The testing method of the bending modulus is: according to the testing method of GB / T9341-2008, using a bending tester, timing the bending time to 3 minutes, repeating the experiment 3 times, and recording the experimental results.

[0049] The testing method of the notch impact test is: according to the testing methods of GB / T1843-2008 and GB / T1043.1-2008, the test is carried out using a cantilever beam and a simply supported beam notch testing machine respectively, the experiment is repeated five times, and the experimental results are recorded.

[0050] Table 2

[0051]

[0052] It can be seen from Table 2 above that the use of maleic anhydride grafts of vinyl polyolefin elastomers to toughen polyamide is comparable to the use of commercially available Energy Light N413 toughening agent (POE grafted maleic anhydride toughening agent) to toughen polyamide in terms of tensile strength, impact strength, fracture strain and other properties (such as Example 1 and Comparative Example 3), and after the use of maleic anhydride grafts of vinyl polyolefin elastomers to toughen polyamide, the Vicat softening temperature of the polyamide exceeds that of the commercially available Energy Light N413 toughening agent (POE graft) toughened polyamide, making the maleic anhydride grafts of vinyl polyolefin elastomers have a wider range of applications. Furthermore, by comparing Example 1 with Comparative Example 1, it can be found that the flexural modulus and impact strength of the polyamide toughened with the maleic anhydride graft of vinyl polyolefin elastomer are greatly improved, indicating that the maleic anhydride graft of vinyl polyolefin elastomer as the main modifier not only improves the disadvantage of poor strength of polyamide, but also greatly improves the toughness of the toughened polyamide, and various mechanical properties are on par with those of the polyamide toughened with the commercially available Energy Light N413 toughening agent (POE grafted maleic anhydride toughening agent), and the thermal stability even exceeds that of the commercially available N413 toughening agent, indicating that the polyamide toughened with the maleic anhydride graft of vinyl polyolefin elastomer can meet the use requirements of engineering plastic parts in the automotive and other fields, and has great application prospects. Furthermore, by comparing Example 2 with Comparative Example 2, the mechanical properties of the obtained alloy polymers of polyamide and polypropylene were improved after toughening and compatibilization using the maleic anhydride graft of vinyl polyolefin elastomer, indicating that the maleic anhydride graft of vinyl polyolefin elastomer can better improve the compatibility of polyamide and polypropylene, and the toughening and compatibilization properties of the maleic anhydride graft of vinyl polyolefin elastomer are slightly higher than the toughening and compatibilization properties of the Nengzhiguang N413 toughening agent (such as Example 2 and Comparative Example 4).

[0053] Example 3

[0054] According to the amount of each component shown in Table 3, a vinyl polyolefin elastomer graft toughened and expanded polyamide alloy polymer was prepared, wherein, by weight, 100 parts of polyamide (PA-YH800), 30 parts of glass fiber (GF-988A), 10 parts of EPOE-g-MAH, 0.2 parts of antioxidant 1010, 0.2 parts of antioxidant 168, 0.2 parts of antioxidant DSTDP, and 0.2 parts of lubricant EBS (P-130) were weighed and mixed evenly, then sent to a premixer and mixed at 1500 rpm for 20 minutes to obtain a premix. Subsequently, the premix is ​​fed into a twin-screw extruder, blended in the twin-screw extruder, cooled, and pelletized by a granulator to obtain a polyamide alloy polymer toughened and expanded with vinyl polyolefin elastomer grafts, wherein the body temperature of the twin-screw extruder is 180°C, the temperature of zone 1 is 120°C, the temperature of zone 2 is 180°C, the temperature of zone 3 is 200°C, the temperature of zone 4 is 200°C, and the main engine speed of the twin-screw extruder is 500 rpm.

[0055] Comparative Example 5

[0056] According to the amount of each component shown in Table 3, the alloy polymer of polyamide and glass fiber is prepared, wherein, by weight, it includes: 100 parts of polyamide (PA-YH800), 30 parts of glass fiber (GF-988A), 0.2 parts of antioxidant 1010, 0.2 parts of antioxidant 168, 0.2 parts of antioxidant DSTDP, and 0.2 parts of lubricant EBS (P-130), after being mixed evenly, it is sent to a premixer and mixed at 1500 rpm for 20 minutes to obtain a premix. Subsequently, the premix is ​​fed into a twin-screw extruder, and after being blended in the twin-screw extruder, it is cooled and pelletized by a granulator to obtain a polymer of polyamide and glass fiber, wherein the body temperature of the twin-screw extruder is 180°C, the temperature of the first zone is 120°C, the temperature of the second zone is 180°C, the temperature of the third zone is 200°C, the temperature of the fourth zone is 200°C, and the main engine speed of the twin-screw extruder is 500 rpm.

[0057] Comparative Example 6

[0058] A polyamide alloy polymer toughened and expanded with Nengzhiguang N413 toughening agent was prepared according to the amounts of each component shown in Table 3, wherein, by weight, the components include: 100 parts of polyamide (PA-YH800), 30 parts of glass fiber (GF-988A), 10 parts of Nengzhiguang N413 toughening agent, 0.2 parts of antioxidant 1010, 0.2 parts of antioxidant 168, 0.2 parts of antioxidant DSTDP, and 0.2 parts of lubricant EBS (P-130). After mixing evenly, the mixture was sent into a premixer and mixed at 1500 rpm for 20 minutes to obtain a premix. Subsequently, the premix is ​​fed into a twin-screw extruder, blended in the twin-screw extruder and then cooled, and pelletized by a granulator to obtain a polyamide alloy polymer toughened and expanded with the Energy Light N413 toughening agent. The body temperature of the twin-screw extruder is 180°C, the temperature of zone one is 120°C, the temperature of zone two is 180°C, the temperature of zone three is 200°C, the temperature of zone four is 200°C, and the main engine speed of the twin-screw extruder is 500 rpm.

[0059] Comparative Example 7

[0060] A polyamide alloy polymer toughened and expanded with Nengzhiguang N406 toughening agent was prepared according to the amounts of the components shown in Table 3, wherein, by weight, the components include: 100 parts of polyamide (PA-YH800), 30 parts of glass fiber (GF-988A), 10 parts of Nengzhiguang N406 (a toughening agent formed by grafting maleic anhydride with a grafting rate of 0.45%-0.8%), 0.2 parts of antioxidant 1010, 0.2 parts of antioxidant 168, 0.2 parts of antioxidant DSTDP, and 0.2 parts of lubricant EBS (P-130). After mixing evenly, the mixture was sent into a premixer and mixed at 1500 rpm for 20 minutes to obtain a premix. Subsequently, the premix is ​​fed into a twin-screw extruder, blended in the twin-screw extruder and then cooled, and pelletized by a granulator to obtain a polyamide alloy polymer toughened and expanded with the Energy Light N406 toughening agent. The body temperature of the twin-screw extruder is 180°C, the temperature of zone one is 120°C, the temperature of zone two is 180°C, the temperature of zone three is 200°C, the temperature of zone four is 200°C, and the main engine speed of the twin-screw extruder is 500 rpm.

[0061] Table 3

[0062]

[0063] The polymers obtained in the above Example 3 and Comparative Examples 5 to 7 were tested for melt flow rate, density, tensile strength, breaking strain, flexural modulus, and notched impact. The specific test results are shown in Table 4.

[0064] Table 4

[0065]

[0066] As shown in Table 4, by comparing Example 3 with Comparative Examples 5-7, the alloy polymer of polyamide and glass fiber toughened and compatibilized by maleic anhydride grafts of vinyl polyolefin elastomer (i.e., polyamide alloy polymer) has better properties such as tensile strength, impact strength, and fracture strain than the alloy polymer of polyamide and glass fiber toughened and compatibilized by the commercially available Energy Light N413 toughener and Energy Light N406 toughener (which is a graft of polyolefin elastomer (POE) grafted with maleic anhydride), and after the polyamide and glass fiber are toughened and compatibilized by the maleic anhydride grafts of vinyl polyolefin elastomer, the Vicat softening temperature of the alloy polymer of polyamide and glass fiber obtained exceeds that of the alloy polymer of polyamide and glass fiber toughened and compatibilized by the commercially available Energy Light N413 toughener and Energy Light N406 toughener, which makes the maleic anhydride grafts of vinyl polyolefin elastomer have a wider range of applications. Furthermore, by comparing Example 3 with Comparative Example 5, it is found that after toughening and increasing the volume using maleic anhydride grafts of vinyl polyolefin elastomers, the fracture strain and impact strength of the obtained alloy polymer of polyamide and glass fiber are greatly improved, which shows that the use of maleic anhydride grafts of vinyl polyolefin elastomers as the main modifier not only improves the disadvantage of poor fracture strength of the alloy polymer of polyamide and glass fiber, but also greatly improves the toughness of the alloy polymer of polyamide and glass fiber, and the various mechanical properties exceed the alloy polymer of polyamide and glass fiber toughened by the commercially available N413 toughening agent and N406 toughening agent (toughening agent formed by POE grafted maleic anhydride). The alloy polymer of polyamide and glass fiber toughened and increased in volume using maleic anhydride grafts of vinyl polyolefin elastomers can meet the use requirements of engineering plastic parts in the automotive and other fields, has a large application prospect, and can be well applied to engineering plastic parts in the automotive and other fields.

[0067] The specific embodiments described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A polyamide polymer toughened or toughened and compatibilized by grafting vinyl polyolefin elastomer, characterized in that: In parts by weight, it includes: 100 parts of polyamide, or 110-140 parts of polyamide alloy polymer; 5-20 parts of vinyl polyolefin elastomer graft; 0.1-2 parts antioxidant; and 0.1-2 parts of lubricant; Wherein, the vinyl polyolefin elastomer graft is a graft of vinyl polyolefin elastomer and maleic anhydride; The polyamide alloy polymer is selected from any one of an alloy polymer of polyamide and polyolefin and an alloy polymer of polyamide and glass fiber; The vinyl polyolefin elastomer is obtained by polymerization reaction with ethylene as a single raw material under the catalytic action of a main catalyst and a co-catalyst. The vinyl polyolefin elastomer has a melt index of 3-13 g / 10 min, a number average molecular weight of 100,000-200,000, a molecular weight distribution index of 1.0-2.0, a branching degree of 30-60 branches / 1000 carbons, and a density of 0.860-0.9 g / cm 3 , melting point is 55-65℃.

2. The polyamide polymer according to claim 1, characterized in that The maleic anhydride grafting rate of the vinyl polyolefin elastomer graft is 0.5%-1.4%.

3. The polyamide polymer according to claim 1, characterized in that The main catalyst is a diimine nickel catalyst or a diimine palladium catalyst.

4. The polyamide polymer according to claim 1, characterized in that: The antioxidant is selected from one or more of tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester, tris[2,4-di-tert-butylphenyl] phosphite, β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, bis(2,4-dicumylphenyl) pentaerythritol diphosphite, and distearyl thiodipropionate; The lubricant is selected from at least one of ethylene bis stearic acid amide and pentaerythritol stearate.

5. The polyamide polymer according to claim 1, characterized in that: The polyolefin is selected from polypropylene or polyethylene.

6. A method for preparing a polyamide polymer toughened or toughened and compatibilized by grafting a vinyl polyolefin elastomer as claimed in any one of claims 1 to 5, characterized in that: The preparation method comprises: 100 parts of polyamide, 5-20 parts of vinyl polyolefin elastomer graft, 0.1-2 parts of antioxidant and 0.1-2 parts of lubricant are mixed evenly, and then sent into a twin-screw extruder for blending and extrusion granulation to obtain a polyamide toughened by vinyl polyolefin elastomer graft; or 100 parts of polyamide, 10-40 parts of polyolefin or glass fiber, 5-20 parts of vinyl polyolefin elastomer graft, 0.1-2 parts of antioxidant and 0.1-2 parts of lubricant are mixed evenly, and then sent into a twin-screw extruder for blending and extrusion granulation to obtain a polyamide alloy polymer toughened and expanded by vinyl polyolefin elastomer graft; The vinyl polyolefin elastomer graft product is obtained by grafting vinyl polyolefin elastomer with maleic anhydride.

7. The preparation method according to claim 6, characterized in that: The vinyl polyolefin elastomer graft product is obtained, comprising: In the presence of zinc hydroxide, an initiator initiates a grafting reaction between the vinyl polyolefin elastomer and the maleic anhydride; Wherein, the grafting rate of the vinyl polyolefin elastomer and maleic anhydride is 0.5%-1.4%.

8. The preparation method according to claim 7, characterized in that: The initiator is selected from one or more of benzoyl peroxide, diisopropylbenzene peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxynonane, and di-tert-butylperoxyisopropylbenzene.

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