Super-tough nylon alloy and preparation method and application thereof

Abstract

The invention relates to the technical field of nylon alloys, in particular to a super-tough nylon alloy and a preparation method and application thereof. The preparation method of the super-tough nylon alloy comprises the following steps: (1) epoxidizing a conjugated diene polymer to obtain an epoxidized conjugated diene polymer; or partially hydrogenating the conjugated diene polymer and then epoxidizing the conjugated diene polymer to obtain a partially hydrogenated epoxidized conjugated diene polymer; and (2) carrying out reaction extrusion on the epoxidized conjugated diene polymer and / or the partially hydrogenated epoxidized conjugated diene polymer and nylon to obtain the super-tough nylon alloy. Wherein in terms of mass, the feeding amount of the nylon is greater than the feeding amount of the epoxidized conjugated diene polymer and / or the partially hydrogenated epoxidized conjugated diene polymer. The super-tough nylon alloy provided by the invention has excellent ductility, high notch impact strength and low-temperature toughness, and is suitable for industrial popularization.

Description

Technical Field

[0001] The invention relates to the field of nylon alloy preparation, and in particular to a super-tough nylon alloy and a preparation method and application thereof. Background Art

[0002] Nylon, also known as polyamide, is a general term for thermoplastic resins containing repeated amide groups ([NHCO]) on the main chain of the molecule. As a widely used engineering plastic, nylon has the characteristics of good wear resistance and high mechanical strength. However, it has defects such as high water absorption, poor dimensional stability, low notched impact strength, and poor ductility, which limit its application in automotive parts, electronic appliances and other fields. Therefore, nylon materials need to be toughened and modified.

[0003] An effective way to improve the impact toughness of nylon is to modify nylon into nylon alloy, that is, to disperse a softer nylon blend that can absorb impact energy in a harder nylon without excessively reducing strength and rigidity. Commonly used nylon blends are generally polyolefins, polyphenylene ethers, polyarylates, rubbers and other substances. Although this method can improve the toughness of nylon to a certain extent, the miscibility between nylon and nylon blends is poor, and phase separation is serious, resulting in poor ductility of nylon alloys, low tensile strength, and low-temperature toughness that still needs to be further improved. Moreover, this method is not suitable for large-scale processing of waste nylon.

[0004] As people's demand for engineering plastics represented by nylon increases, a large amount of waste is inevitably generated during consumption, such as fishing nets used in large quantities in coastal areas, nylon films used in food or industrial packaging, and nylon parts for cars. After long-term use, these materials have various properties, especially impact toughness, significantly reduced due to degradation and other reasons, and become waste nylon. Waste nylon is difficult to degrade in the natural environment. If these wastes are not handled properly, they will cause serious damage to the environment and cause a large amount of waste of resources. Therefore, it is necessary to recycle these waste nylons and give them a new life cycle.

[0005] Traditional methods for recycling waste nylon mainly include energy recovery, physical recovery and chemical recovery. Among them, energy recovery mainly adopts the method of landfill incineration, which causes secondary environmental pollution; physical recovery is to melt the waste materials and then granulate them again, but there is a problem of poor performance of the recycled materials; chemical recovery refers to the decomposition of macromolecular chains into nylon monomers through chemical reactions, but this route usually needs to be carried out under high temperature and high pressure, and there are problems such as high energy consumption, high equipment requirements, large investment, and low monomer recovery rate. Summary of the invention

[0006] The purpose of the present invention is to solve the problem of poor compatibility between nylon and nylon blends and how to use waste nylon to prepare a super-tough nylon alloy with high tensile strength, good ductility and high notched impact strength at low temperature, and to provide a super-tough nylon alloy and its preparation method and application.

[0007] In order to achieve the above object, a first aspect of the present invention provides a method for preparing a super-tough nylon alloy, wherein the method comprises:

[0008] (1) epoxidizing a conjugated diene polymer to obtain an epoxidized conjugated diene polymer; or partially hydrogenating a conjugated diene polymer and then epoxidizing it to obtain a partially hydrogenated epoxidized conjugated diene polymer;

[0009] (2) reacting and extruding the epoxidized conjugated diene polymer and / or the partially hydrogenated epoxidized conjugated diene polymer with nylon to obtain a super-tough nylon alloy;

[0010] The conjugated diene polymer contains a structural unit A represented by formula (1), a structural unit B represented by formula (2), and an optional structural unit C represented by formula (3):

[0011]

[0012] Among them, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 are each independently selected from H, substituted or unsubstituted C 1 -C 7 One or more of alkyl, 2-methyl-2-pentenyl, 2,6-dimethyl-2,6-octadienyl; R 13 is selected from H, substituted or unsubstituted C 1 -C 5 One or more of the alkyl groups;

[0013] Wherein, the feed amount of the nylon is greater than the feed amount of the epoxidized conjugated diene polymer and / or the partially hydrogenated epoxidized conjugated diene polymer in terms of mass.

[0014] The second aspect of the present invention provides a super-tough nylon alloy prepared by the preparation method described in the first aspect of the present invention.

[0015] The third aspect of the present invention provides an application of the super-tough nylon alloy described in the second aspect of the present invention in automotive parts, pipes, and electronic appliances.

[0016] Through the above technical solution, the beneficial technical effects achieved by the present invention are as follows:

[0017] 1) The preparation method of the super-tough nylon alloy provided in the present invention uses epoxidized conjugated diene polymers and / or partially hydrogenated epoxidized conjugated diene polymers as nylon blends, which can significantly improve the compatibility between the nylon blend and nylon, reduce the difficulty of preparing the nylon alloy, and improve the ductility and impact toughness of the nylon alloy;

[0018] 2) The method for preparing the super-tough nylon alloy provided in the present invention can use waste nylon as raw material to prepare a super-tough nylon alloy with good ductility and high notched impact strength, thereby realizing the resource recycling of waste nylon;

[0019] 3) The preparation method of the super-tough nylon alloy provided in the present invention has a simple route, short reaction time, high production efficiency, low production cost, and is suitable for industrial promotion. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 is the conjugated diene polymer SBS before epoxidation in Example 1 1 H-NMR.

[0021] Figure 2 is the epoxidation rate E obtained in Example 1 1 27.93% of epoxidized conjugated diene polymer 1 H-NMR.

[0022] Figure 3 is the epoxidation rate E obtained in Example 4 1 The epoxidized conjugated diene polymer is 45.67% 1 H-NMR. DETAILED DESCRIPTION

[0023] The specific implementation of the present invention is described in detail below in conjunction with the accompanying drawings. It should be understood that the specific implementation described here is only used to illustrate and explain the present invention, and is not used to limit the present invention.

[0024] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0025] A first aspect of the present invention provides a method for preparing a super-tough nylon alloy, wherein the method comprises:

[0026] (1) epoxidizing a conjugated diene polymer to obtain an epoxidized conjugated diene polymer; or partially hydrogenating a conjugated diene polymer and then epoxidizing it to obtain a partially hydrogenated epoxidized conjugated diene polymer;

[0027] (2) reacting and extruding the epoxidized conjugated diene polymer and / or the partially hydrogenated epoxidized conjugated diene polymer with nylon to obtain a super-tough nylon alloy;

[0028] The conjugated diene polymer contains a structural unit A represented by formula (1), a structural unit B represented by formula (2), and an optional structural unit C represented by formula (3):

[0029]

[0030] Among them, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 are each independently selected from H, substituted or unsubstituted C 1 -C 7 One or more of alkyl, 2-methyl-2-pentenyl, 2,6-dimethyl-2,6-octadienyl; R 13 is selected from H, substituted or unsubstituted C 1 -C 5 One or more of the alkyl groups;

[0031] Wherein, the feed amount of the nylon is greater than the feed amount of the epoxidized conjugated diene polymer and / or the partially hydrogenated epoxidized conjugated diene polymer in terms of mass.

[0032] In the present invention, the conjugated diene polymer is epoxidized to convert part of the -C=C- double bond groups in the structural unit A and / or the structural unit B into epoxy groups. The conjugated diene polymer is hydrogenated to hydrogenate a portion of the -C=C- double bonds of the structural unit A and / or the structural unit B to obtain saturated carbon-carbon bonds.

[0033] The inventors of the present invention have found through research that blending a small amount of epoxidized conjugated diene polymers modified by epoxidation, or partially hydrogenated epoxidized conjugated diene polymers modified by partial hydrogenation and epoxidation into nylon can significantly improve the compatibility between the nylon blend and nylon, significantly improve the toughness, ductility and notched impact strength of the nylon alloy, and obtain a super-tough nylon alloy.

[0034] In a preferred embodiment, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 are each independently selected from H, substituted or unsubstituted C 1 -C 4 One or more of alkyl, 2-methyl-2-pentenyl, and 2,6-dimethyl-2,6-octadienyl.

[0035] Among them, in the present invention, C 1 -C 4 The alkyl group may be methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, or tert-butyl. 1 -C 4 The substituent in may be halogen, such as F, Cl, Br and I, and the present invention is for C 1 -C 4 The substitution position and substitution amount of the substituent are not particularly limited.

[0036] In a preferred embodiment, R 1 , R 2 , R 6 , R 7 , R 8 , R 9 , R 12 Both H, R 3 , R 4 , R 5 , R 10, R 11 are each independently selected from H, substituted or unsubstituted C 1 -C 4 One or more of alkyl, 2-methyl-2-pentenyl, and 2,6-dimethyl-2,6-octadienyl.

[0037] In a preferred embodiment, R 1 , R 2 , R 6 , R 7 , R 8 , R 9 , R 12 Both H, R 3 , R 4 , R 5 , R 10 , R 11 Each is independently selected from one or more of H, methyl, 2-methyl-2-pentenyl, and 2,6-dimethyl-2,6-octadienyl.

[0038] In a preferred embodiment, the structural unit A is selected from -CH 2 -CH=CH-CH 2 -、 One or more of, preferably -CH 2 -CH=CH-CH 2 - and / or

[0039] In a preferred embodiment, the structural unit B is selected from One or more of, preferably and / or

[0040] In a preferred embodiment, in the structural unit A and the structural unit B, The total mass content of the structural units does not exceed 30% of the total mass of the conjugated diene polymer.

[0041] Among them, in the present invention, the conjugated diene polymer may contain one or more of the above-mentioned four structural units. The present invention does not specifically limit the mixing ratio of these four structural units. However, the inventors have found through research that when the total mass content of these four structural units does not exceed 30% of the total mass of the conjugated diene polymer, the performance of the prepared super-tough nylon alloy is better.

[0042] In a preferred embodiment, R 13 is selected from H, substituted or unsubstituted C1 -C 4 Preferably, the R 13 The number of them on the benzene ring is 1, and the position is selected from one of the ortho position, para position, and meta position.

[0043] In a preferred embodiment, the structural unit C is selected from One or more of, preferably and / or

[0044] In a preferred embodiment, the conjugated diene polymer does not contain the structural unit C represented by formula (3), and includes the structural unit A represented by formula (1) and the structural unit B represented by formula (2); in a further preferred embodiment, R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 9 , R 11 , R 12 All are hydrogen, R 4 and R 10 Each is independently selected from hydrogen or methyl.

[0045] In a preferred embodiment, the conjugated diene polymer comprises a structural unit A represented by formula (1), a structural unit B represented by formula (2) and a structural unit C represented by formula (3).

[0046] In a preferred embodiment, the structural unit A is -CH 2 -CH=CH-CH 2 - and / or The structural unit B is and / or The structural unit C is

[0047] In a preferred embodiment, the number average molecular weight of the conjugated diene polymer is 30,000-300,000 g / mol, preferably 50,000-100,000 g / mol.

[0048] Among them, in the present invention, when the number average molecular weight of the conjugated diene polymer is between 50,000 and 100,000 g / mol, the toughness of the prepared super-tough nylon alloy is better.

[0049] In a preferred embodiment, based on the total mass of the conjugated diene polymer, the mass content of the structural unit C is 0-40%, preferably 5-40%, and more preferably 8-30%.

[0050] In a preferred embodiment, based on the total mass of the conjugated diene polymer, the sum of the mass of the structural unit A and the mass of the structural unit B is 60-100%, preferably 60-95%, and more preferably 70-92%.

[0051] In a preferred embodiment, the molar ratio of the structural unit A to the structural unit B is 30-93:7-70, preferably 60-65:35-40.

[0052] In a preferred embodiment, the epoxidation rate E of the epoxidized conjugated diene polymer is 1 5-60%, preferably 10-40%. In the present invention, the epoxidation rate E 1 It refers to the percentage of the molar amount of epoxy groups in the epoxidized conjugated diene polymer to the molar amount of double bonds contained in the conjugated diene polymer.

[0053] In a preferred embodiment, the degree of hydrogenation of the partially hydrogenated epoxidized conjugated diene polymer is not more than 95%, preferably 60%-90%; the epoxidation rate E 2 5-98%.

[0054] In the present invention, the degree of hydrogenation of the partially hydrogenated epoxidized conjugated diene polymer refers to the percentage of the molar amount of double bonds reduced after the conjugated diene polymer is partially hydrogenated to the molar amount of double bonds contained in the conjugated diene polymer. 2 It refers to the percentage of the molar amount of epoxy groups contained in the partially hydrogenated epoxidized conjugated diene polymer to the molar amount of double bonds contained in the hydrogenated epoxidized conjugated diene polymer before epoxidation. 1 and epoxidation rate E 2 Can be used 1 H-NMR spectrum was calculated.

[0055] In the present invention, partial hydrogenation can reduce the number of double bonds remaining in the product and improve the aging resistance of the product during long-term use. However, if the hydrogenation is too high, the number of subsequent epoxy groups is too low, and they cannot effectively react with nylon to form chemical bonds, resulting in phase separation of the product, which ultimately leads to poor material performance.

[0056] In a preferred embodiment, the epoxidation rate E 2It can be 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, and any number in between.

[0057] In a preferred embodiment, in the partially hydrogenated epoxidized conjugated diene polymer, the molar content of epoxy groups accounts for 10-40% of the molar content of double bonds in the conjugated diene polymer.

[0058] Wherein, in the present invention, if the number of epoxy groups contained in the epoxidized conjugated diene polymer and / or the partially hydrogenated epoxidized conjugated diene polymer is too low, the epoxidized conjugated diene polymer and / or the partially hydrogenated epoxidized conjugated diene polymer cannot effectively react with nylon to form a chemical bond, thereby causing the product to have a phase separation phenomenon, ultimately resulting in poor material performance. If the number of epoxy groups in the epoxidized conjugated diene polymer and / or the partially hydrogenated epoxidized conjugated diene polymer is too high, similar epoxy groups are easily reunited with each other after ring opening, resulting in a cross-linking phenomenon, loss of reactivity, and similarly making the epoxidized conjugated diene polymer and / or the partially hydrogenated epoxidized conjugated diene polymer unable to effectively react with nylon to form a chemical bond, ultimately resulting in poor material performance.

[0059] In a preferred embodiment, the present invention does not specifically limit the epoxidation or hydrogenation method in step (1) (i.e., the synthesis method of epoxidized conjugated diene polymers and partially hydrogenated epoxidized conjugated diene polymers), and the polymers can be prepared according to conventional methods known in the art.

[0060] For example, for partial hydrogenation of conjugated diene polymers, first, the conjugated diene polymer glue is pressed into a hydrogenation kettle by nitrogen. If a metallocene catalyst is used for hydrogenation, only the butadiene structural units can be hydrogenated under the metallocene catalyst. The hydrogenation degree of the final product is controlled by adjusting the ratio of the butadiene structural units to the isoprene structural units in the polymer. For example, if the ratio of the butadiene structural units to the isoprene structural units is controlled to 7:3, a partially hydrogenated conjugated diene polymer with a hydrogenation degree of 70% can be obtained. Alternatively, the hydrogenation degree of the product can be controlled by controlling the cumulative flow rate of hydrogen introduced. For example, if the double bond content of the butadiene structural unit is 4 mol and the cumulative amount of hydrogen introduced is 1 mol, the hydrogenation degree of the butadiene structural unit is about 25%, and the process parameters can be carried out according to patent CN02139784.8. If a nickel-based hydrogenation catalyst is used for the hydrogenation reaction, for example, a nickel-based hydrogenation catalyst Ni / Al catalyst is used, and the catalyst uses nickel cyclohexaneate and triisobutylaluminum, the butadiene structural units and the isoprene structural units can be hydrogenated at the same time. According to patent ZL201711193760.9, the conjugated dienes are hydrogenated and the degree of hydrogenation of the product can be controlled by controlling the cumulative flow rate of hydrogen. The principle is the same as above.

[0061] In the present invention, epoxidation is carried out under the action of methyl trioctyl phosphotungstate quaternary ammonium salt, and the epoxidation rate can be adjusted by controlling the amount, concentration, reaction time, reaction temperature, etc. of hydrogen peroxide. The preparation of methyl trioctyl phosphotungstate quaternary ammonium salt and the specific epoxidation operation can be referred to the embodiments of the present invention.

[0062] In a preferred embodiment, the nylon in the present invention can be a commercially available nylon product, a product synthesized according to a known method, or waste nylon. The present invention does not specifically limit nylon, and all polyamide resins known in the art can be used in the present invention, for example, including but not limited to nylon 6, nylon 66, nylon 6 / 66, nylon 610, nylon 612, nylon 6 / 612, nylon 11, nylon 12, nylon 1010, etc. When the nylon is waste nylon, the waste nylon needs to be re-melted and granulated and then reacted and extruded with the epoxidized conjugated diene polymer and / or the partially hydrogenated epoxidized conjugated diene polymer.

[0063] In a preferred embodiment, the mass ratio of the nylon to the epoxidized conjugated diene polymer and / or the partially hydrogenated epoxidized conjugated diene polymer is 60-90:10-40, preferably 70-85:15-30.

[0064] In the present invention, if the amount of nylon is too little, the rigidity of the super-tough nylon alloy is insufficient; if the amount of nylon is too much, the toughness of the super-tough nylon alloy is insufficient. When the mass ratio of nylon to epoxidized conjugated diene polymer and / or partially hydrogenated epoxidized conjugated diene polymer is between 70-85:15-30, the comprehensive mechanical properties of the super-tough nylon alloy are optimal.

[0065] In a preferred embodiment, the reactive extrusion is achieved by a twin-screw extruder; wherein the temperature of each zone of the twin-screw extruder is independently selected from 100-270°C, and the head temperature is 150-265°C.

[0066] The second aspect of the present invention provides a super-tough nylon alloy prepared by the preparation method described in the first aspect of the present invention.

[0067] In a preferred embodiment, the tensile strength of the super-tough nylon alloy is 30-45 MPa, the elongation at break is 200-300%, and the notched impact strength at room temperature is 80-160 KJ / m 2 , low temperature (-40℃) notched impact strength is 10-30KJ / m 2 The normal temperature in the present invention is room temperature, which has a well-known meaning.

[0068] The third aspect of the present invention provides an application of the super-tough nylon alloy described in the second aspect of the present invention in automotive parts, pipes, and electronic appliances.

[0069] The super-tough nylon alloy provided in the present invention has a tensile strength of 30-45MPa, an elongation at break of 200-300%, and good ductility. In addition, the super-tough nylon alloy provided in the present invention has a room temperature notched impact strength of 80-160KJ / m 2 , low temperature (-40℃) notched impact strength is 10-30KJ / m 2 , and has excellent room temperature and low temperature toughness. Therefore, the super-tough nylon alloy provided in the present invention can be widely used in the fields of automotive parts, pipes, electronic appliances, etc.

[0070] The present invention will be described in detail below by way of examples. In the following examples and comparative examples, the preparation of the epoxidation catalyst is as follows:

[0071] In a 250 mL three-necked round-bottom flask equipped with a thermometer, condenser, and constant pressure dropping funnel, 3.3 g of tungstic acid and 22 mL of 30 wt% H 2 O 2, stirring and heating to 60°C, reacting for 60 minutes until the reaction liquid becomes colorless and transparent; then adding 0.64g of phosphoric acid (98wt%) to the solution, diluting with 20mL of distilled water and continuing to stir for 30min; then dissolving 5.05g of methyl trioctyl ammonium chloride in 50mL of chloroform, and slowly dropping it into the above solution, the dropping time is controlled at 30-45min, and after the dropping is completed, stirring is continued for 1h before stopping the reaction; the reaction solution is allowed to stand and separate, and the lower yellow organic phase is taken out and the solvent is removed by rotary evaporation at 55°C, and then vacuum dried at 60°C to obtain a yellow viscous liquid methyl trioctyl phosphotungstate quaternary ammonium salt (cat2).

[0072] Nylon-6, purchased from Sinopec Hunan Petrochemical Co., Ltd., product model BL3240. Nylon 6 / 66, purchased from Sinopec Hunan Petrochemical Co., Ltd., product model BL2330. Nylon 12, purchased from Suzhou Buffett Engineering Plastics Co., Ltd., Wanhua Nylon P12 L2000. Waste nylon is nylon fishing net yarn recycled material, purchased from Zhejiang Jubao Nylon Technology Co., Ltd., made by re-melting and granulating waste nylon fishing net yarn.

[0073] Example 1

[0074] (1) Add 10 g of conjugated diene polymer SBS (H-NMR as Figure 1 As shown in FIG. 1 ), 100 mL of toluene were added to prepare a 10 wt% SBS solution, and then a catalyst (cat2, 2 mmol / L) was added. The water bath temperature was set to 60° C. After the temperature stabilized, 5 mL of 30% H 2 O 2 The reaction mixture was cooled and poured into 300 mL of ethanol to obtain a white solid, which was then washed with a small amount of ethanol and dried in an oven at 60°C to obtain an epoxidation rate of E 1 The epoxidized conjugated diene polymer is 27.93%, and its H-NMR is as follows Figure 2 As shown;

[0075] Among them, the epoxidation rate E of the epoxidized conjugated diene polymer is 1 The results were determined by nuclear magnetic resonance (1H-NMR) with CDCl as solvent. 3 , the temperature is 25℃.

[0076] Figure 2 and Figure 1 In comparison, two proton peaks appeared at about δ 2.7 after epoxidation of polybutadiene 1,4 structure. The different displacements are due to the cis and trans structures, and the cis form has a larger peak area.

[0077] The number of moles of butadiene is: (2×1.6016+0.3412) / 4=0.8861

[0078] The number of moles of epoxidized butadiene is: 0.6869 / 2 = 0.34345

[0079] Epoxidation rate E 1 :0.34345 / (0.34345+0.8861)×100%=27.93%

[0080] Among them, the number average molecular weight of SBS is 100,000 g / mol, and the structural unit C is The mass content is 30%, and the structural unit A is -CH 2 -CH=CH-CH 2 -, structural unit B is The total mass content of the structural unit A and the structural unit B is 70%, and the molar ratio of the structural unit A to the structural unit B is 62:38.

[0081] (2) 30 g of the above-mentioned epoxidized conjugated diene polymer and 70 g of nylon-6 were fully mixed and added into a twin-screw extruder for reaction extrusion. The extruder head temperature was 120° C. and the temperature of other sections was set to 245° C. to obtain a super-tough nylon alloy.

[0082] Example 2

[0083] (1) 100 g of conjugated diene polymer SBS (same as in Example 1) was dissolved in cyclohexane to prepare 1 L of glue solution, which was then pressurized into a 3 L hydrogenation reactor by nitrogen gas, and a tetrahydrofuran solution (15 g / 1000 mL) of a main catalyst of dicyclopentadiene titanium dichloride was added, the amount of the main catalyst of dicyclopentadiene titanium dichloride being calculated as 0.13 mmol / 100 g SBS, and a co-catalyst of dimethyl phthalate being added, the amount of the co-catalyst being calculated as 0.7 mmol / 100 g SBS, and the reaction temperature being controlled at 80° C. 0.8178 mol (calculated by the formula PV=nRT) of hydrogen is introduced through the cumulative flow meter to make the initial system pressure reach 1.2 MPa, and the system reaction temperature and pressure are maintained. When the hydrogen consumption in the system accumulates to 0.9057 mol, the flow meter is used to observe that when the hydrogen consumption in the system reaches 0.9057 mol, the hydrogen introduction is stopped and the pressure in the system is released. The system is replaced with nitrogen and the system temperature is lowered to room temperature to obtain a partially hydrogenated conjugated diene polymer with a hydrogenation degree of 70%.

[0084] The above partially hydrogenated conjugated diene polymer was subjected to epoxidation treatment. The epoxidation method was the same as that in Example 1, except that “5 mL 30% H 2 O 2 Reaction 110min" was changed to "10mL30%H 2 O 2 After 120 min of reaction, the degree of hydrogenation was 70% and the epoxidation rate was E 2The partially hydrogenated epoxidized conjugated diene polymer is 40%, wherein the molar content of epoxy groups in the partially hydrogenated epoxidized conjugated diene polymer accounts for 12% of the molar content of double bonds in the conjugated diene polymer SBS.

[0085] (2) 15 g of partially hydrogenated epoxidized conjugated diene polymer and 85 g of nylon 6 / 66 were fully mixed and added into a twin-screw extruder for reaction extrusion. The extruder head temperature was 120° C. and the temperatures of other sections were set to 245° C. to obtain a super-tough nylon alloy.

[0086] Example 3

[0087] The same as Example 1, except that the hydrogen at the meta position of the benzene ring in the structural unit C is replaced by a tert-butyl group, that is, the structural unit C is composed of becomes

[0088] Example 4

[0089] The same as Example 1, except that the number average molecular weight of the conjugated diene polymer SBS is 60,000 g / mol, the mass content of the structural unit C is 8%; the epoxidation "5 mL 30% H 2 O 2 The operating conditions of "reaction 110 min" were changed to "7.8 mL 30% H 2 O 2 Reaction time: 135 min, the epoxidation rate of the prepared epoxidized conjugated diene polymer is E 1 is 45.67%, wherein the H-NMR of the epoxidized conjugated diene polymer is as follows Figure 3 As shown, an equal amount of nylon-6 is replaced with waste nylon.

[0090] Example 5

[0091] The same as Example 1, except that the number average molecular weight of the conjugated diene polymer SBS is 280,000, the mass content of the structural unit C is 40%, and the molar ratio of the structural unit A to the structural unit B is 32:58; the epoxidation "5mL 30% H 2 O 2 The operating conditions of "reaction 110 min" were changed to "8 mL 10% H 2 O 2 The epoxidation rate of the prepared epoxidized conjugated diene polymer was E 1 is 5%.

[0092] Example 6

[0093] The same as Example 1, except that in the conjugated diene polymer, the structural unit A includes -CH2 -CH=CH-CH 2 - Structural units and Structural unit, structural unit B includes Structural units and Structural unit, structural unit C is Structural unit; wherein the number average molecular weight of the conjugated diene polymer is 100,000 g / mol, the mass proportion of structural unit C is 40%, the molar ratio of structural unit A to structural unit B is 60:40; and in structural unit A Structural unit with -CH 2 -CH=CH-CH 2 -The molar ratio of the structural units is 1:4, and the structural unit B and The molar ratio of the structural units is 1:4.

[0094] Place the epoxidation solution in 5 mL of 30% HO 2 O 2 The operating conditions of "reaction 110 min" were changed to "12.5 mL 30% H 2 O 2 The epoxidation rate of the obtained epoxidized conjugated diene polymer was E 1 is 60%; nylon 6 is replaced by a mixture of nylon 6 and waste nylon; among them, 56g of waste nylon and 12g of nylon.

[0095] Example 7

[0096] The same as Example 1, except that in the conjugated diene polymer, the structural unit A includes -CH 2 -CH=CH-CH 2 -Structural unit A1, Structural unit A2, Structural unit A3, structural unit B includes Structural unit B1, Structural unit B2, Structural unit B3; Structural unit C is Structural unit; wherein the number average molecular weight of the conjugated diene polymer is 290,000 g / mol, the mass proportion of structural unit C is 8%, and the molar ratio of structural unit A to structural unit B is 32:68; wherein the molar ratio of A1:A2:A3 in structural unit A is approximately 2:2:1, and the molar ratio of B1:B2:B3 in structural unit B is approximately 2:2:1.

[0097] Place the epoxidation solution in 5 mL of 30% HO 2 O 2 The operating conditions of "reaction 110 min" were changed to "15 mL 20% H2 O 2 The epoxidation rate of the obtained epoxidized conjugated diene polymer was E 1 is 15%; nylon 6 is replaced by a mixture of nylon 12 and waste nylon, wherein the waste nylon is 66.5g and the nylon 12 is 3.5g.

[0098] Example 8

[0099] The same as Example 7, except that the content of structural unit C is 0.

[0100] Comparative Example 1

[0101] Same as Example 1, except that no epoxidation was performed.

[0102] Comparative Example 2

[0103] Same as Example 2, except that the epoxidation rate E 2 is 3%.

[0104] Comparative Example 3

[0105] Same as Example 7, except that the epoxidation rate E 1 is 75%.

[0106] Test Case

[0107] The super-tough nylon alloys prepared in Examples 1-8 and Comparative Examples 1-3 were subjected to performance tests, wherein the tensile properties were measured according to ISO527-2, and the notched impact properties were measured according to ISO180 / 1A. The results are shown in Table 1:

[0108] Table 1

[0109]

[0110] By comparing Example 1 and Comparative Example 1, it can be seen that epoxidation of the conjugated diene polymer improves the ductility and toughness of the super-tough nylon alloy.

[0111] By comparing Example 2 and Comparative Example 2, as well as Example 7 and Comparative Example 3, it can be seen that an epoxidation rate that is too large or too small is detrimental to the ductility and toughness of the super-tough nylon alloy.

[0112] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A method for preparing a super-tough nylon alloy, characterized in that: The method comprises: (1) epoxidizing a conjugated diene polymer to obtain an epoxidized conjugated diene polymer; or partially hydrogenating a conjugated diene polymer and then epoxidizing it to obtain a partially hydrogenated epoxidized conjugated diene polymer; (2) reacting and extruding the epoxidized conjugated diene polymer and / or the partially hydrogenated epoxidized conjugated diene polymer with nylon to obtain a super-tough nylon alloy; The conjugated diene polymer contains a structural unit A represented by formula (1), a structural unit B represented by formula (2), and an optional structural unit C represented by formula (3): Among them, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 Each is independently selected from one or more of H, substituted or unsubstituted C1-C7 alkyl, 2-methyl-2-pentenyl, 2,6-dimethyl-2,6-octadienyl; R 13 One or more selected from H, substituted or unsubstituted C1-C5 alkyl; Wherein, the feed amount of the nylon is greater than the feed amount of the epoxidized conjugated diene polymer and / or the partially hydrogenated epoxidized conjugated diene polymer in terms of mass.

2. The preparation method according to claim 1, wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 Each is independently selected from one or more of H, substituted or unsubstituted C1-C4 alkyl, 2-methyl-2-pentenyl, and 2,6-dimethyl-2,6-octadienyl; Preferably, R1, R2, R6, R7, R8, R9, R 12 All are H, R3, R4, R5, R 10 , R 11 Each is independently selected from one or more of H, substituted or unsubstituted C1-C4 alkyl, 2-methyl-2-pentenyl, and 2,6-dimethyl-2,6-octadienyl; Preferably, R 13 One or more selected from H, substituted or unsubstituted C1-C4 alkyl; Preferably, R 13 The number of the benzene ring is 1, and the position is selected from one of the ortho position, para position, and meta position; Preferably, the C1-C4 alkyl group is selected from one or more of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl and tert-butyl; and the substituent in the C1-C4 alkyl group is selected from halogen.

3. The preparation method according to claim 1 or 2, wherein The structural unit A is selected from -CH2-CH=CH-CH2-, One or more of, preferably -CH2-CH=CH-CH2- and / or Preferably, the structural unit B is selected from One or more of, preferably and / or Preferably, the structural unit C is selected from One or more of, preferably and / or 4. The preparation method according to any one of claims 1 to 3, wherein The conjugated diene polymer comprises the structural unit A and the structural unit B.

5. The preparation method according to any one of claims 1 to 3, wherein: The conjugated diene polymer comprises the structural unit A, the structural unit B and the structural unit C; Wherein, the structural unit A is -CH2-CH=CH-CH2- and / or The structural unit B is and / or The structural unit C is 6. The preparation method according to any one of claims 1 to 5, wherein: The number average molecular weight of the conjugated diene polymer is 30,000-300,000 g / mol, preferably 50,000-100,000 g / mol; Preferably, based on the total mass of the conjugated diene polymer, the mass content of the structural unit C is 0-40%, preferably 5-40%, and more preferably 8-30%; Preferably, based on the total mass of the conjugated diene polymer, the sum of the mass of the structural unit A and the structural unit B is 60-100%, preferably 60-95%, and more preferably 70-92%; Preferably, in the conjugated diene polymer, the molar ratio of the structural unit A to the structural unit B is 30-93:7-70, preferably 60-65:35-40.

7. The preparation method according to any one of claims 1 to 6, wherein: The epoxidation rate E1 of the epoxidized conjugated diene polymer is 5-60%, preferably 10-40%.

8. The preparation method according to any one of claims 1 to 7, wherein: The degree of hydrogenation of the partially hydrogenated epoxidized conjugated diene polymer is not more than 95%, preferably 60%-90%; the epoxidation rate E2 is 5-98%; Preferably, in the partially hydrogenated epoxidized conjugated diene polymer, the content of epoxy groups accounts for 10-40% of the double bond content in the conjugated diene polymer.

9. The preparation method according to any one of claims 1 to 8, wherein: The mass ratio of the nylon to the epoxidized conjugated diene polymer and / or the partially hydrogenated epoxidized conjugated diene polymer is 60-90:10-40, preferably 70-85:15-30; Preferably, the reactive extrusion is achieved by a twin-screw extruder; wherein the temperature of each zone of the twin-screw extruder is independently selected from 100-270°C, and the head temperature is 150-265°C.

10. A super-tough nylon alloy prepared by the method according to any one of claims 1 to 9.

11. Application of the super-tough nylon alloy according to claim 10 in automotive parts, pipes, and electronic appliances.

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