A high-impact high-toughness bio-based nylon composite material and a preparation method thereof

Abstract

The application discloses a kind of high impact high toughness bio-based nylon composite material and preparation method thereof.The raw materials for preparing the nylon composite material include the following components by weight parts: 100 parts of bio-based nylon, 0-30 parts of toughening elastomer, 0.1-30 elastomer grafting compatibilizer and 0.2-0.6 parts of antioxidant;Wherein, the elastomer grafting compatibilizer is obtained by grafting modification of elastomer with itaconic anhydride, third monomer;The third monomer includes any one or combination of multiple of butyl acrylate, a-methyl styrene, maleic anhydride.The elastomer grafting compatibilizer provided by the application has the advantages of high grafting rate, low odor, high efficiency of compatibilization effect and high efficiency of toughening, and the bio-based nylon material toughened by elastomer and elastomer grafting compatibilizer has the advantages of high impact and high toughness, greatly solves the shortcomings of insufficient toughness of nylon material, and expands the application range of bio-based nylon material.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of toughening modification of nylon materials and synthesis of grafting compatibilizers, and particularly relates to a high-impact high-toughness bio-based nylon composite material and a preparation method thereof. BACKGROUND

[0002] Traditional nylons are mostly derived from non-renewable petroleum resources, and the high-temperature and high-pressure production process causes high emissions of wastewater and carbon dioxide, which has a negative impact on the environment. In order to reduce the environmental burden and reduce environmental pollution, the environmental protection and sustainable value of green fiber products gradually stand out, and bio-based nylon emerges as the times require.

[0003] However, whether it is a petroleum-based nylon such as nylon 6 or nylon 66 or a bio-based nylon such as nylon 56, there are problems of insufficient impact strength, poor toughness, and strong water absorption. At present, the most common method to improve the toughness of nylon materials is to use elastomers for toughening, but the elastomers and nylons often have compatibility problems, thereby limiting the application range of the nylon materials, especially the bio-based nylon materials. At this time, elastomer compatibilizers such as POE-g-MAH and SEBS-g-MAH are often added. However, the compatibilizers grafted with maleic anhydride (MAH) have problems of low grafting rate (<0.8%), large odor, and large steric hindrance of the anhydride after grafting due to the low reactivity, volatile, and irritating odor of maleic anhydride, thereby causing poor compatibility and greatly reducing the toughening effect on nylons.

[0004] Therefore, how to improve the compatibility of the toughening agent and the nylon, such as bio-based nylon 56, so as to improve the impact resistance and toughness of the nylon material, has become a crucial technical problem, which has far-reaching significance and value in the field of polymer composites. SUMMARY

[0005] The main purpose of the present application is to provide a high-impact high-toughness bio-based nylon composite material and a preparation method thereof to overcome the shortcomings of the prior art.

[0006] To achieve the foregoing purposes of the application, the technical solutions adopted by the present application include:

[0007] The present application provides a high-impact high-toughness bio-based nylon composite material, and the raw materials for preparing the nylon composite material include the following components calculated by weight parts: 100 parts of bio-based nylon, 0-30 parts of toughening elastomer, 0.1-30 parts of elastomer grafted compatibilizer, and 0.2-0.6 parts of antioxidant; wherein the elastomer grafted compatibilizer is obtained by grafting modification of the elastomer with itaconic anhydride and a third monomer; the third monomer includes any one or a combination of butyl acrylate (BA), alpha-methyl styrene (alpha-St), and maleic anhydride (MAH).

[0008] The application also provides a preparation method of the high-impact high-toughness bio-based nylon composite material.

[0009] The bio-based nylon, the toughening elastomer, the elastomer grafting compatibilizer and the antioxidant are uniformly mixed, and then the obtained material is input into a double screw extrusion device for melt blending extrusion, granulation treatment, so as to obtain the high-impact high-toughness bio-based nylon composite material.

[0010] The application also provides an elastomer grafting compatibilizer, and raw materials for preparing the elastomer grafting compatibilizer include the following components: an elastomer, a peroxide initiator, itaconic anhydride, a third monomer and a dispersing oil.

[0011] The application also provides a preparation method of the elastomer grafting compatibilizer.

[0012] The elastomer, the peroxide initiator, the itaconic anhydride, the third monomer and the dispersing oil are uniformly mixed, and then the obtained material is input into a double screw extrusion device for melt blending dynamic reaction extrusion, granulation and homogenization treatment, so as to obtain the elastomer grafting compatibilizer.

[0013] Compared with the prior art, the application has the following beneficial effects:

[0014] (1) The application uses bio-based itaconic anhydride as the first grafting monomer to replace the traditional maleic anhydride, and has the advantages of low boiling point, low odor, high reaction activity and flexible molecular chain, so that the prepared high-efficiency toughening compatibilizer not only has the effect of high-efficiency compatibility, but also has the effect of high-efficiency toughening.

[0015] (2) The elastomer / high-efficiency elastomer compatibilizer / nylon composite material prepared by the application not only maintains the advantages of high strength and high modulus of the nylon material, but also greatly improves the toughness of the nylon material, and the impact strength is increased by 10-15 times of that of pure nylon material. BRIEF DESCRIPTION OF DRAWINGS

[0016] In order to more clearly illustrate the technical solutions in the embodiments of the application or the prior art, the following will briefly introduce the drawings needed to be used in the embodiments or the prior art description. Obviously, the drawings in the following description are only some embodiments of the application, and for those skilled in the art, other drawings can also be obtained from these drawings without creative labor.

[0017] Figure 1is a compatibility mechanism diagram of the nylon and elastomer grafting compatibilizer in an exemplary embodiment of the present application;

[0018] Figures 2a-2b are grafting rate trend diagrams of different proportions of itaconic anhydride and different proportions of initiator in the embodiments of the present application, respectively;

[0019] Figures 3a-3b are impact strength, elongation at break trend diagrams and tensile strength, tensile modulus trend diagrams of the high impact high toughness PA56 in the application examples of the present application. DETAILED DESCRIPTION

[0020] In view of the defects of the prior art, the present inventors have obtained the technical solutions of the present application through long-term research and a large number of practices. The technical solutions of the present application will be described clearly and completely below. Obviously, the described embodiments are part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative labor fall within the scope of protection of the present application.

[0021] Specifically, as one aspect of the technical solutions of the present application, a high impact high toughness bio-based nylon composite material is involved. The raw materials for preparing the nylon composite material include the following components calculated by weight parts: 100 parts of bio-based nylon, 0-30 parts of toughening elastomer, 0.1-30 parts of elastomer grafting compatibilizer, and 0.2-0.6 parts of antioxidant; wherein the elastomer grafting compatibilizer is obtained by grafting modification of the elastomer with itaconic anhydride and a third monomer; the third monomer includes any one or a combination of multiple of butyl acrylate (BA), α-methyl styrene (α-St), and maleic anhydride (MAH).

[0022] In some preferred embodiments, the compatibility mechanism diagram of the nylon 56 and the elastomer grafting compatibilizer in the present application is as shown in Figure 1 .

[0023] In some preferred embodiments, the raw materials for preparing the nylon composite material include the following components calculated by weight parts: 100 parts of bio-based nylon, 0-30 parts of toughening elastomer, 0.1-30 parts of elastomer grafting compatibilizer, 0.1-0.3 parts of antioxidant 1010, and 0.1-0.3 parts of antioxidant 168.

[0024] In some preferred embodiments, the bio-based nylon includes any one or a combination of multiple of PA56, PA1010, PA11, PA610, and PA410, and is not limited thereto.

[0025] In some preferred embodiments, the elastomer used in the preparation of the elastomer grafted compatibilizer includes any one or more of a combination of ethylene octene copolymer (POE), styrene-hydrogenated butadiene-styrene copolymer (SEBS), olefin block copolymer (OBC), and the like, but is not limited thereto.

[0026] In some preferred embodiments, the toughening elastomer is the same as the elastomer used in the preparation of the elastomer grafted compatibilizer.

[0027] In some preferred embodiments, the method for preparing the elastomer grafted compatibilizer includes: uniformly mixing the elastomer, peroxide initiator, itaconic anhydride, third monomer, and dispersing oil, and then inputting the obtained material into a twin-screw extrusion device for melt blending dynamic reaction extrusion, pelletizing, and homogenization treatment to obtain the elastomer grafted compatibilizer.

[0028] Further, the mass ratio of the elastomer, peroxide initiator, itaconic anhydride, third monomer, and dispersing oil is 100:0.2-1:1-9:0.5-3:0.5-2.

[0029] Further, the elastomer includes any one or more of a combination of ethylene octene copolymer (POE), styrene-hydrogenated butadiene-styrene copolymer (SEBS), olefin block copolymer (OBC), and the like, but is not limited thereto.

[0030] Further, the peroxide initiator includes any one or more of a combination of 2,4-di-tert-butyl peroxide isopropyl benzene (BIBP), diisopropyl peroxydicarbonate (DIPP), di-tert-butyl peroxide (DTBP), tert-butyl peroxyacetate (TBPA), and the like, but is not limited thereto.

[0031] Further, the dispersing oil includes any one or more of a combination of white oil, epoxy soybean oil, paraffin oil, and the like, but is not limited thereto.

[0032] Another aspect of the embodiments of the present application also provides a method for preparing the aforementioned high-impact high-toughness bio-based nylon composite material, which includes:

[0033] uniformly mixing the bio-based nylon, toughening elastomer, elastomer grafted compatibilizer, and antioxidant, and then inputting the obtained material into a twin-screw extrusion device for melt blending extrusion and granulation treatment to obtain the high-impact high-toughness bio-based nylon composite material.

[0034] In some preferred embodiments, the process parameters adopted by the twin-screw extrusion device include: a zone 1 temperature of 130-150℃, a zone 2 temperature of 220-240℃, a zone 3 temperature of 230-250℃, a zone 4 temperature of 240-270℃, a zone 5 temperature of 245-265℃, a zone 6 temperature of 245-265℃, a zone 7 temperature of 245-265℃, a zone 8 temperature of 240-260℃, a zone 9 temperature of 240-260℃, a zone 10 temperature of 245-260℃, a zone 11 temperature of 245-260℃, a screw length-diameter ratio of 42:1-52:1, a screw rotation speed of 200-400rpm, and a feeding frequency of 50-70Hz.

[0035] In some more specific embodiments, the method for preparing the high-impact high-toughness bio-based nylon composite material includes the following steps:

[0036] (a) uniformly mixing the raw materials bio-based nylon, toughening elastomer, elastomer grafting compatibilizer, antioxidant 1010, and antioxidant 168 according to the mass fractions described above, and then adding them into a twin-screw extruder for melt blending extrusion granulation;

[0037] (b) after the extruded material is cooled by a cooling water tank and air-cooled by a blowing machine, uniformly granulating and homogenizing to obtain the high-impact high-toughness bio-based nylon material.

[0038] Further, the extrusion temperatures are, in sequence, a zone 1 temperature of 130-150℃, a zone 2 temperature of 220-240℃, a zone 3 temperature of 230-250℃, a zone 4 temperature of 240-270℃, a zone 5 temperature of 245-265℃, a zone 6 temperature of 245-265℃, a zone 7 temperature of 245-265℃, a zone 8 temperature of 240-260℃, a zone 9 temperature of 240-260℃, a zone 10 temperature of 245-260℃, and a zone 11 temperature of 245-260℃; the twin-screw melt extrusion adopts a screw length-diameter ratio of 42:1-52:1, a screw rotation speed of 200-400rpm, and a feeding frequency of 50-70Hz.

[0039] Another aspect of the embodiments of the present application also provides an elastomer grafting compatibilizer, and the raw materials for preparing the elastomer grafting compatibilizer include the following components: elastomer, peroxide initiator, itaconic anhydride, third monomer, and dispersing oil; wherein the third monomer includes any one or a combination of multiple of butyl acrylate (BA), alpha-methyl styrene (α-St), and maleic anhydride (MAH).

[0040] In the present application, due to the advantages of itaconic anhydride, such as high boiling point, high reactivity, high molecular chain flexibility and bio-based, the elastomer grafting compatibilizer has the advantages of high grafting rate, low odor, high efficient compatibility and high efficient toughening compared with the existing mature commercial elastomer grafting maleic anhydride (MAH), such as POE-g-MAH and SEBS-g-MAH. The bio-based nylon material toughened by the elastomer and the elastomer grafting compatibilizer has the advantages of high impact and high toughness, which greatly solves the shortcomings of insufficient toughness of the nylon material and expands the application range of the bio-based nylon material.

[0041] In some preferred embodiments, the raw materials for preparing the elastomer grafting compatibilizer include the following components by weight parts: 100 parts of elastomer, 0.2-1 parts of peroxide initiator, 1-9 parts of itaconic anhydride, 0.5-3 parts of third monomer and 0.5-2 parts of dispersing oil.

[0042] In some preferred embodiments, the elastomer includes any one or more of a combination of ethylene octene copolymer (POE), styrene-hydrogenated butadiene-styrene copolymer (SEBS) and olefin block copolymer (OBC), and is not limited thereto.

[0043] In some preferred embodiments, the peroxide initiator includes any one or more of a combination of 2,4-di-tert-butyl peroxide isopropyl benzene (BIBP), diisopropyl peroxide dicarbonate (DIPP), di-tert-butyl peroxide (DTBP) and tert-butyl peroxide acetate (TBPA), and is not limited thereto.

[0044] In some preferred embodiments, the itaconic anhydride is prepared by dehydration after bio-fermentation of agricultural and sideline products such as starch, sucrose, wood chips or straw.

[0045] In some preferred embodiments, the dispersing oil includes any one or more of a combination of white oil, epoxy soybean oil and paraffin oil, and is not limited thereto.

[0046] Another aspect of the embodiments of the present application also provides a preparation method of the aforementioned elastomer grafting compatibilizer, which includes:

[0047] The elastomer, peroxide initiator, itaconic anhydride, third monomer and dispersing oil are uniformly mixed, and then the obtained material is input into a double screw extrusion device for melt blending dynamic reaction extrusion, granulation and homogenization treatment to prepare the elastomer grafting compatibilizer.

[0048] In some preferred embodiments, the process parameters adopted by the twin-screw extrusion device include: a zone temperature of 130-150°C, a zone temperature of 140-160°C, a zone temperature of 160-180°C, a zone temperature of 170-190°C, a zone temperature of 170-190°C, a zone temperature of 175-195°C, a zone temperature of 175-195°C, a zone temperature of 170-190°C, a zone temperature of 170-190°C, a zone temperature of 170-185°C, a zone temperature of 170-185°C, a zone temperature of 165-185°C, a screw length-diameter ratio of 42:1-52:1, a main screw rotation speed of 200-400 rpm, and a feeding screw rotation speed of 20-40 rpm.

[0049] In some more specific embodiments, the method for preparing the elastomer grafting compatibilizer comprises the following steps:

[0050] (a) uniformly mixing the elastomer and the dispersing oil according to the mass fractions described above, then adding the peroxide initiator, itaconic anhydride and the third monomer and mixing again;

[0051] (b) adding the uniformly mixed materials into a twin-screw extruder for melt blending dynamic reaction extrusion;

[0052] (c) water-cooling or air-cooling the extruded materials, cutting them into uniformly sized particles by a particle cutter, and finally homogenizing for 2-4 h.

[0053] Further, the extrusion temperatures are in turn a zone temperature of 130-150°C, a zone temperature of 140-160°C, a zone temperature of 160-180°C, a zone temperature of 170-190°C, a zone temperature of 170-190°C, a zone temperature of 175-195°C, a zone temperature of 175-195°C, a zone temperature of 170-190°C, a zone temperature of 170-190°C, a zone temperature of 170-185°C, a zone temperature of 170-185°C, a zone temperature of 165-185°C, a screw length-diameter ratio of 42:1-52:1 for the twin-screw melt extrusion, a main screw rotation speed of 200-400 rpm, and a feeding screw rotation speed of 20-40 rpm.

[0054] The technical solutions of the present application will be further described in detail below in combination with several preferred embodiments and the accompanying drawings. The embodiments are implemented on the premise of the technical solutions of the present application, and detailed implementation manners and specific operation processes are given, but the protection scope of the present application is not limited to the following embodiments.

[0055] In the following examples, the experimental materials used are commercially available from conventional biochemical reagent companies unless otherwise specified.

[0056] Elastomer grafting compatibilizer examples:

[0057] The extrusion temperature of the twin-screw extruder in Examples 1-12 and Comparative Examples 1-2 is 140°C for Zone 1, 150°C for Zone 2, 170°C for Zone 3, 180°C for Zone 4, 180°C for Zone 5, 185°C for Zone 6, 185°C for Zone 7, 180°C for Zone 8, 180°C for Zone 9, 180°C for Zone 10, 175°C for Zone 11, and 175°C for Zone 12, respectively.

[0058] Example 1

[0059] After 100 parts of SEBS and 1 part of epoxy soybean oil are uniformly mixed, 0.6 parts of DIPP, 1 part of itaconic anhydride, and 1 part of BA are added and uniformly mixed, and then the mixture is fed into a twin-screw extruder for melt blending reaction extrusion. The length-diameter ratio of the screw used in the melt extrusion of the twin screw is 48:1, and the screw rotation speed is 300 rpm. After extrusion, the product is water-cooled and pelletized, and then homogenized to obtain high-efficiency compatibilizer particles (i.e., elastomer grafted compatibilizer). The grafting rate of the compatibilizer after purification is 0.667%.

[0060] Example 2

[0061] After 100 parts of SEBS and 1 part of epoxy soybean oil are uniformly mixed, 0.6 parts of DIPP, 3 parts of itaconic anhydride, and 1 part of BA are added and uniformly mixed, and then the mixture is fed into a twin-screw extruder for melt blending reaction extrusion. The length-diameter ratio of the screw used in the melt extrusion of the twin screw is 48:1, and the screw rotation speed is 300 rpm. After extrusion, the product is water-cooled and pelletized, and then homogenized to obtain high-efficiency compatibilizer particles. The grafting rate of the compatibilizer after purification is 0.806%.

[0062] Example 3

[0063] After 100 parts of SEBS and 1 part of epoxy soybean oil are uniformly mixed, 0.6 parts of DIPP, 5 parts of itaconic anhydride, and 1 part of BA are added and uniformly mixed, and then the mixture is fed into a twin-screw extruder for melt blending reaction extrusion. The length-diameter ratio of the screw used in the melt extrusion of the twin screw is 48:1, and the screw rotation speed is 300 rpm. After extrusion, the product is water-cooled and pelletized, and then homogenized to obtain high-efficiency compatibilizer particles. The grafting rate of the compatibilizer after purification is 1.30%.

[0064] Example 4

[0065] Example 1

[0066] Example 2

[0067] Example 3

[0068] Example 4

[0069] Example 5

[0070] Example 6

[0071] Example 7

[0072] Example 8

[0073] Example 9

[0074] Example 9

[0075] According to the following mass fraction: 100 parts of SEBS, 1 part of epoxy soybean oil is uniformly mixed, then 1 part of DIPP, 5 parts of itaconic anhydride, 1 part of BA is uniformly mixed, then added into the branch twin screw extruder for melt blending reaction extrusion, the screw length diameter ratio of 48:1 is adopted for the twin screw melt extrusion, the screw rotation speed is 300 rpm, after extrusion, water cooling and granulation, after homogenization, high efficiency compatilizer particles are obtained, the grafting rate of the compatilizer measured after purification is 1.129%.

[0076] Example 10

[0077] According to the following mass fraction: 100 parts of POE, 1 part of epoxy soybean oil is uniformly mixed, then 0.6 parts of BIBP, 5 parts of itaconic anhydride, 3 parts of alpha-methyl styrene is uniformly mixed, then added into the branch twin screw extruder for melt blending reaction extrusion, the screw length diameter ratio of 48:1 is adopted for the twin screw melt extrusion, the screw rotation speed is 300 rpm, after extrusion, water cooling and granulation, after homogenization, high efficiency compatilizer particles are obtained, the grafting rate of the compatilizer measured after purification is 1.032%.

[0078] Example 11

[0079] According to the following mass fraction: 100 parts of OBC, 0.5 parts of white oil is uniformly mixed, then 0.6 parts of DTBP, 5 parts of itaconic anhydride, 0.5 parts of MAH is uniformly mixed, then added into the branch twin screw extruder for melt blending reaction extrusion, the screw length diameter ratio of 48:1 is adopted for the twin screw melt extrusion, the screw rotation speed is 300 rpm, after extrusion, water cooling and granulation, after homogenization, high efficiency compatilizer particles are obtained, the grafting rate of the compatilizer measured after purification is 0.928%.

[0080] Example 12

[0081] According to the following mass fraction: 100 parts of SEBS, 2 parts of paraffin oil is uniformly mixed, then 0.6 parts of TBPA, 5 parts of itaconic anhydride, 0.5 parts of alpha-methyl styrene is uniformly mixed, then added into the branch twin screw extruder for melt blending reaction extrusion, the screw length diameter ratio of 48:1 is adopted for the twin screw melt extrusion, the screw rotation speed is 300 rpm, after extrusion, water cooling and granulation, after homogenization, high efficiency compatilizer particles are obtained, the grafting rate of the compatilizer measured after purification is 0.976%.

[0082] Comparative Example 1

[0083] The following are mixed uniformly according to the following mass fractions: 100 parts of SEBS, 1 part of epoxy soybean oil, 0.6 parts of DIPP, 5 parts of maleic anhydride, and 1 part of BA. After uniform mixing, they are added to a twin-screw extruder for melt blending reaction extrusion. The screw length-diameter ratio used for the twin-screw melt extrusion is 48:1, and the screw rotation speed is 300 rpm. After extrusion, water cooling and granulation, and homogenization, high-efficiency compatibilizer particles are obtained. The grafting rate of the compatibilizer after purification is 0.579%.

[0084] Comparative Example 2

[0085] The method is the same as in Example 3, except that the monomer BA is absent. As shown in Table 1, the grafting rate of Comparative Example 2 is 0.579%, which is significantly lower than that of Example 3. Figure 2a and Figure 2b As shown in Table 1, the grafting rate of Comparative Example 1 and Example 3 is obtained. Itaconic anhydride as the first grafting monomer has a grafting rate of 1.3%, which is significantly higher than that of maleic anhydride as the first grafting monomer (grafting rate is only 0.579%). At the same time, with the increase of itaconic anhydride content and initiator content, the grafting rate shows a trend of first increasing and then remaining stable, and the highest grafting rate scheme is 0.6% initiator DIPP and 5% itaconic anhydride. As can be seen from Examples 10-12, this method is also applicable to grafting itaconic anhydride on POE and OBC elastomers.

[0086] Table 1 Raw materials and test results of Examples 1-12 and Comparative Example 1

[0087]

[0088]

[0089] Application Example of High-Impact High-Toughness Bio-Based Nylon Composite Material

[0090] In Application Examples 1-4 and Comparative Examples 1-3, the extrusion temperatures of the twin-screw extruder are as follows: Zone 1 temperature 140°C, Zone 2 temperature 230°C, Zone 3 temperature 240°C, Zone 4 temperature 250°C, Zone 5 temperature 260°C, Zone 6 temperature 260°C, Zone 7 temperature 260°C, Zone 8 temperature 260°C, Zone 9 temperature 250°C, Zone 10 temperature 250°C, and Zone 11 temperature 245°C.

[0091] Application Example 1

[0092] According to the mass fractions, 100 parts of PA56, 17.5 parts of SEBS, 2.5 parts of ITA-g-SEBS (Example 3), 0.2 parts of antioxidant 1010 and 0.2 parts of antioxidant 168 are uniformly mixed, then added to the main feeding hopper of the twin-screw extruder, and melt blended and extruded to obtain SEBS toughened PA56 composite material.

[0093] Application Example 2

[0094] PA56 100 parts, SEBS 10 parts, ITA-g-SEBS (Example 3) 10 parts, antioxidant 1010 and 168 each 0.2 parts were uniformly mixed and then added to the main feeding hopper of a twin-screw extruder for melt blending extrusion and granulation, with the screw rotation speed adjusted to 300 rpm and the main feeding speed to 50 rpm, to obtain a SEBS toughened PA56 composite material.

[0095] Application Example 3

[0096] PA56 100 parts, SEBS 10 parts, ITA-g-SEBS (Example 3) 10 parts, antioxidant 1010 and 168 each 0.2 parts were uniformly mixed and then added to the main feeding hopper of a twin-screw extruder for melt blending extrusion and granulation, with the screw rotation speed adjusted to 300 rpm and the main feeding speed to 50 rpm, to obtain a SEBS toughened PA56 composite material.

[0097] Application Example 4

[0098] PA56 100 parts, ITA-g-SEBS (Example 3) 20 parts, antioxidant 1010 and 168 each 0.2 parts were uniformly mixed and then added to the main feeding hopper of a twin-screw extruder for melt blending extrusion and granulation, with the screw rotation speed adjusted to 300 rpm and the main feeding speed to 50 rpm, to obtain a SEBS toughened PA56 composite material.

[0099] Application Comparative Example 1

[0100] PA56 100 parts, SEBS 20 parts, antioxidant 1010 and 168 each 0.2 parts were uniformly mixed and then added to the main feeding hopper of a twin-screw extruder for melt blending extrusion and granulation, with the screw rotation speed adjusted to 300 rpm and the main feeding speed to 50 rpm, to obtain a SEBS toughened PA56 composite material.

[0101] Application Comparative Example 2

[0102] PA56 100 parts, SEBS 15 parts, the compatibilizer of Comparative Example 1 5 parts, antioxidant 1010 and 168 each 0.2 parts were uniformly mixed and then added to the main feeding hopper of a twin-screw extruder for melt blending extrusion and granulation, with the screw rotation speed adjusted to 300 rpm and the main feeding speed to 50 rpm, to obtain a toughened PA56 composite material.

[0103] Application Comparative Example 3

[0104] The PA56 100 parts, SEBS 15 parts, comparative example 2 compatibilizer 5 parts, antioxidants 1010 and 168 0.2 parts each, were uniformly mixed, then added to the main feeding hopper of the twin-screw extruder, and melt blending extrusion granulation was carried out, the screw rotation speed was adjusted to 300 rpm and the main feeding speed was 50 rpm, to obtain a toughened PA56 composite material.

[0105] In order to facilitate the comparison of toughening and compatibilization effects, the present application measures that the impact strength of pure PA56 without toughening is 5.25kJ / m 2 , the elongation at break is 3.28%, the tensile strength and tensile modulus are 73.4MPa and 2842.3MPa respectively.

[0106] As Figure 3a shown, by comparing comparative example 1 and application examples 1-5, it can be seen that pure SEBS toughening has poor toughening effect on nylon 56, and the impact strength and elongation at break do not increase significantly. At the same time, with the increase of the proportion of SEBS-g-ITA, the impact strength can be increased to 63.8kJ / m 2 , which is more than 10 times that of pure PA56 and pure SEBS toughened PA56. By comparing comparative examples 2-3 and application example 3, it is found that whether MAH or no third monomer is added, the toughening effect is significantly poorer than that of the toughening compatibilizer of application example 3.

[0107] As Figure 3b shown, after toughening and compatibilization, the tensile strength and tensile modulus of nylon 56 slightly decrease, but still maintain a high value, and the tensile strength after toughening and compatibilization can be maintained at more than 52MPa, and the tensile modulus can be maintained at more than 1700MPa.

[0108] In addition, the present inventors have also carried out tests with other raw materials, process operations and process conditions described in the present specification according to the aforementioned embodiments, and all have obtained relatively ideal results.

[0109] It should be understood that the technical solutions of the present application are not limited to the specific implementation cases described above, and any technical modification made according to the technical solutions of the present application without departing from the purpose of the present application and the scope protected by the claims, falls within the protection scope of the present application.

Claims

1. A high impact high toughness bio-based nylon composite, characterized in that, The raw materials for preparing the nylon composite include the following components by weight: 100 parts of bio-based nylon, 0-30 parts of toughening elastomer, 0.1-30 parts of elastomer grafted compatilizer, and 0.2-0.6 parts of antioxidant; wherein the elastomer grafted compatilizer is obtained by grafting modification of an elastomer with itaconic anhydride and a third monomer; the mass ratio of the itaconic anhydride, the third monomer and the elastomer is 1-9:0.5-3:100; the third monomer includes any one or combination of butyl acrylate, alpha-methyl styrene, maleic anhydride.

2. The high-impact high-toughness bio-based nylon composite of claim 1, wherein, The raw materials for preparing the nylon composite include the following components by weight: 100 parts of bio-based nylon, 0-30 parts of toughening elastomer, 0.1-30 parts of elastomer grafted compatilizer, 0.1-0.3 parts of antioxidant 1010, and 0.1-0.3 parts of antioxidant 168.

3. The high-impact high-toughness bio-based nylon composite of claim 1, wherein: The bio-based nylon includes any one or combination of PA56, PA1010, PA11, PA610, PA410.

4. The high-impact high-toughness bio-based nylon composite of claim 1, wherein: The elastomer used in the preparation of the elastomer grafted compatilizer includes any one or combination of ethylene octene copolymer, styrene-hydrogenated butadiene-styrene copolymer, and olefin block copolymer.

5. The high-impact high-toughness bio-based nylon composite of claim 1, wherein: The toughening elastomer is the same as the elastomer used in the preparation of the elastomer grafted compatilizer.

6. The high-impact high-toughness bio-based nylon composite of claim 1, wherein, The preparation method of the elastomer grafted compatilizer includes: uniformly mixing the elastomer, peroxide initiator, itaconic anhydride, third monomer, and dispersing oil, then inputting the obtained material into a double screw extrusion device for melt blending dynamic reaction extrusion, granulation, and homogenization treatment to obtain the elastomer grafted compatilizer.

7. The high-impact high-toughness bio-based nylon composite of claim 6, wherein: The mass ratio of the elastomer, peroxide initiator, itaconic anhydride, third monomer, and dispersing oil is 100:0.2-1:1-9:0.5-3:0.5-2.

8. The high-impact high-toughness bio-based nylon composite of claim 6, wherein: The elastomer includes any one or combination of ethylene octene copolymer, styrene-hydrogenated butadiene-styrene copolymer, and olefin block copolymer.

9. The high-impact high-toughness bio-based nylon composite of claim 6, wherein: The peroxide initiator includes any one or combination of 2,4-di-tert-butyl cumyl peroxide, diisopropyl peroxydicarbonate, di-tert-butyl peroxide, and tert-butyl peroxyacetate.

10. The high-impact high-toughness bio-based nylon composite of claim 6, wherein: The dispersing oil includes any one or combination of white oil, epoxy soybean oil, and paraffin oil.

11. The method of making a high-impact high-toughness bio-based nylon composite of any one of claims 1-10, wherein, The method includes: Uniformly mixing bio-based nylon, toughening elastomer, elastomer grafted compatilizer, and antioxidant, then inputting the obtained material into a double screw extrusion device for melt blending extrusion and granulation treatment to obtain high impact and high toughness bio-based nylon composite.

12. The method of claim 11, wherein, The process parameters of the double screw extrusion device include: the temperature of the first zone is 130-150℃, the temperature of the second zone is 220-240℃, the temperature of the third zone is 230-250℃, the temperature of the fourth zone is 240-270℃, the temperature of the fifth zone is 245-265℃, the temperature of the sixth zone is 245-265℃, the temperature of the seventh zone is 245-265℃, the temperature of the eighth zone is 240-260℃, the temperature of the ninth zone is 240-260℃, the temperature of the tenth zone is 245-260℃, the temperature of the eleventh zone is 245-260℃, the length-diameter ratio of the screw is 42:1-52:1, the rotation speed of the screw is 200-400rpm, and the feeding frequency is 50-70Hz.

13. An elastomer grafting compatibilizer characterized by, The raw materials for preparing the elastomer grafting compatibilizer include the following components: an elastomer, a peroxide initiator, itaconic anhydride, a third monomer, and a dispersing oil; wherein the third monomer includes any one or a combination of multiple of butyl acrylate, alpha-methyl styrene, and maleic anhydride; the raw materials for preparing the elastomer grafting compatibilizer include the following components in parts by weight: 100 parts of the elastomer, 0.2-1 parts of the peroxide initiator, 1-9 parts of itaconic anhydride, 0.5-3 parts of the third monomer, and 0.5-2 parts of the dispersing oil.

14. The elastomer grafting compatibilizer of claim 13, wherein: The elastomer includes any one or a combination of multiple of ethylene octene copolymer, styrene-hydrogenated butadiene-styrene copolymer, and olefin block copolymer.

15. The elastomer grafting compatibilizer of claim 13, wherein: The peroxide initiator includes any one or a combination of multiple of 2,4-di-tert-butyl cumyl peroxide, diisopropyl peroxydicarbonate, di-tert-butyl peroxide, and tert-butyl peroxyacetate.

16. The elastomer grafting compatibilizer of claim 13, wherein: The itaconic anhydride is obtained by dehydration after bio-fermentation of agricultural and sideline products such as starch, sucrose, wood chips, or straw.

17. The elastomer grafting compatibilizer of claim 13, wherein: The dispersing oil includes any one or a combination of multiple of white oil, epoxy soybean oil, and paraffin oil.

18. The process for preparing the elastomer grafting compatibilizer according to any one of claims 13 to 17, wherein The method comprises the following steps: The elastomer, the peroxide initiator, the itaconic anhydride, the third monomer, and the dispersing oil are uniformly mixed, and then the obtained material is input into a double screw extrusion device for melt blending dynamic reaction extrusion, granulation, and homogenization treatment to obtain the elastomer grafting compatibilizer.

19. The method of claim 18, wherein: The process parameters of the double screw extrusion device include: the temperature of the first zone is 130-150℃, the temperature of the second zone is 140-160℃, the temperature of the third zone is 160-180℃, the temperature of the fourth zone is 170-190℃, the temperature of the fifth zone is 170-190℃, the temperature of the sixth zone is 175-195℃, the temperature of the seventh zone is 175-195℃, the temperature of the eighth zone is 170-190℃, the temperature of the ninth zone is 170-190℃, the temperature of the tenth zone is 170-185℃, the temperature of the eleventh zone is 170-185℃, the temperature of the twelfth zone is 165-185℃, the length-diameter ratio of the screw is 42:1-52:1, the rotation speed of the main screw is 200-400rpm, and the rotation speed of the feeding screw is 20-40rpm.

Images