Fluoroether-silicon-modified polyamide elastomer and preparation method therefor

Abstract

The present invention relates to the field of polymers, and specifically to a fluoroether-silicon-modified polyamide elastomer and a preparation method therefor. The elastomer has a general structural formula represented by formula (I): polyamide segment-linking group-fluoroether silicon polymer segment, wherein in formula (I), the polyamide segment is provided by a polyamide, the fluoroether silicon polymer segment is provided by a fluoroether silicon polymer, and the linking group is formed by reacting an end-capping group A at an end of the polyamide with a reactive group B in the fluoroether silicon polymer; the end-capping group A is selected from at least one of amino, carboxyl, and a group containing terminal alkenyl; and the reactive group B is selected from a group containing at least one of carboxyl, hydroxyl, amino, a silicon hydrogen bond, an isocyanate group, an acyl chloride group, and a cyanuric chloride group. The polyamide elastomer of the present invention exhibits excellent mechanical properties by means of the innovative combination of the polyamide and the ether silicon polymer.

Description

Fluoroether-silicone modified polyamide elastomer and its preparation method

[0001] Cross-reference to related applications

[0002] This application claims the benefit of Chinese Patent Application No. 202411818693.5, filed on December 11, 2024, the contents of which are incorporated herein by reference. Technical Field

[0003] This invention relates to the field of polymers, specifically to a fluoroether-silicone modified polyamide elastomer and its preparation method. Background Technology

[0004] Thermoplastic polyamide elastomer (TPAE), commonly known as nylon elastomer, is a type of multi-block copolymer composed of high-melting-point crystalline polyamide hard segments and low-glass transition-temperature amorphous polyester or polyether soft segments. It possesses properties such as ultra-lightweight, high strength, low-temperature resistance, fatigue resistance, abrasion resistance, organic solvent resistance, and antistatic properties, and is widely used in sporting goods, medical devices, automotive parts, electronics, aerospace, and everyday consumer goods. Currently, commonly used hard segments in TPAE include PA12, PA11, PA6, PA66, PA610, PA1012, PA126, PA1212, PA1211, and PA10T / 10I, while soft segments include polyethylene glycol (PEG), polypropylene glycol (PPG), polybutanediol (PTMG), polycaprolactone (PCL), and polycarbonate (PC).

[0005] Research on TPAE abroad began in the early 1980s. S. Mumcu and others at Hüels in Germany produced the first generation of commercial TPAE using sebacic acid, dodecyl lactam, and polybutanediol as raw materials via melt polymerization. Subsequently, Arkema in France launched a series of elastomers with varying hardnesses based on polyamide 11 and polyamide 12: the XX33 series and the Rnew series. Ube Industries in Japan launched the UBESTA XPA series of polyamide elastomers, using PA12 as the hard segment and polyetheramine as the soft segment. This series includes four varieties: 9044X2, 9055X1, 9055X2, and 9063X1, with Shore hardnesses of 44D, 62D, 54D, and 56D, respectively. In addition, the company also developed four rubber-like TPAE varieties under the trade names PAE600, 601, 1200, and 1201. This series of products has a flexural modulus of elasticity of 49-294 MPa, a tensile strength of 20-29 MPa, a melting point of 150-170℃, a wide operating temperature range, and good wear resistance, cold resistance, and chemical resistance. Domestic research and development of TPAE started relatively late. Only Zhejiang Xinyuan Technology Co., Ltd., Xinyuan Chemical (Shandong) Co., Ltd., and Cangzhou Xuyang Technology Co., Ltd. have achieved industrial-scale production of TPAE, but the product range is relatively limited, and the performance lags behind foreign products. Therefore, further strengthening the design, development, and preparation research of TPAE is of great significance.

[0006] Currently, relevant literature on the preparation of TPAE mainly includes CN 109206613A, CN 110003464A, CN 104910377B, CN 200910200343A, CN 104327266A, CN 105566639B, CN 109970971A, CN 108752581A, CN 106565953A, CN 109705338A, CN 111378124A, CN 111004389A, CN 108841002A, and CN 108794742A. All of the above techniques employ bulk melt polymerization to prepare TPAE, which involves first preparing a polyamide prepolymer with dual carboxyl groups, and then esterifying it with a hydroxyl-terminated polyether to prepare TPAE. However, esterification requires high reaction temperatures, long reaction times, and high vacuum levels in the reaction system. Furthermore, its small equilibrium constant and low efficiency result in elastomers with low molecular weight and poor performance. Excessive reaction temperatures and long reaction times not only increase energy consumption but also lead to numerous side reactions that affect the product's appearance and performance. To address this, Sinopec Baling Petrochemical Co., Ltd. disclosed a method for preparing polyamide elastomers via the reaction of carboxylic acids and esters, including CN 115477753A and CN 115490850A. However, during the polycondensation reaction, because the transesterification rate is higher than the esterification rate, transesterification occurs between hydroxyl-terminated polyesters, resulting in a very low degree of reaction between the polyamide prepolymer and the polyester.

[0007] Furthermore, current TPAE products researched and developed both domestically and internationally all use polyethylene glycol, polypropylene glycol, and polytetrahydrofuran glycol as soft segments. However, these polyether diols have poor acid and alkali resistance and high hygroscopicity, which to some extent affects the performance of the final product. Fluoroether silicone polymers are special high-performance materials containing C-F bonds, Si-O bonds, and C-H bonds. They combine the excellent properties of organofluorine and organosilicon, exhibiting low surface energy, wide temperature range, UV resistance, oxidation resistance, and oleophobic and hydrophobic properties. They are widely used in various fields such as national defense, aerospace, and petrochemicals. CN109642025A discloses a polyamide containing (per)fluoropolyether and poly(organosiloxane) units and its preparation method. The polyamide contains repeating (per)fluoropolyether and poly(organosiloxane) units. An embodiment discloses a preparation method in which diethyl adipic acid, m-xylenediamine, 2AP PDMS, and PFPE alcohol (IIa) are loaded into a high-pressure autoclave, and the polyamide containing (per)fluoropolyether and poly(organosiloxane) units is synthesized by bulk polymerization. This polyamide exhibits excellent water and oil repellency, favorable mechanical properties, and stain resistance. However, this technique involves adding the monomers all at once, resulting in random polymerization. The synthesized substance is a non-segmented block copolymer, lacking designability, and the prepared substance shows indistinct phase separation, limiting the improvement in mechanical properties. Summary of the Invention

[0008] The purpose of this invention is to overcome the shortcomings of existing polyamide elastomers, such as incomplete phase separation and poor mechanical properties, and to provide a fluoroether-silicone modified polyamide elastomer and its preparation method. This polyamide elastomer combines the advantages of both polyamides and organofluorosilicones, significantly improving the product's acid and alkali resistance, flexibility, and oleophobic and hydrophobic properties. It provides new research ideas for the development of high-performance, high-value-added TPAEs, and lays the foundation for further realizing differentiated domestic TPAE varieties, possessing significant practical application value and immeasurable economic benefits.

[0009] To achieve the above objectives, a first aspect of the present invention provides a fluoroether-silicone modified polyamide elastomer, the elastomer having the general structural formula shown in formula (I).

[0010] Polyamide segment-linking group-fluoroether silicone polymer segment formula (I),

[0011] In formula (I), the polyamide segment is provided by polyamide, the fluoroether silicone polymer segment is provided by fluoroether silicone polymer, and the linking group is formed by the reaction of the end capping group A at the end of the polyamide with the reactive group B in the fluoroether silicone polymer; the end capping group A is selected from at least one of amino, carboxyl and alkenyl groups; the reactive group B is selected from at least one of carboxyl, hydroxyl, amino, silane-hydrogen bond, isocyanate group, acyl chloride group and cyanuric chloride group.

[0012] A second aspect of the present invention provides a method for preparing a fluoroether silicone-modified polyamide elastomer, the method comprising: reacting a polyamide with a fluoroether silicone polymer under solution polymerization conditions; wherein the end-capping group A at the end of the polyamide is selected from at least one of amino, carboxyl, and alkenyl groups; the fluoroether silicone polymer contains a reactive group B, the reactive group B being selected from at least one of carboxyl, hydroxyl, amino, silane-hydrogen bond, isocyanate, acyl chloride, and cyanuric chloride groups, and the end-capping group A at the end of the polyamide reacts with the reactive group B in the fluoroether silicone polymer to form a linking group.

[0013] The third aspect of the present invention provides a fluoroether-silicone modified polyamide elastomer prepared by the preparation method described in the second aspect of the present invention.

[0014] Through the above technical solution, the present invention has at least the following beneficial effects:

[0015] 1. The polyamide elastomer in this invention has the dual advantages of polyamide and organofluorosilicone, which significantly improves the product's acid and alkali resistance, flexibility, oleophobicity and hydrophobicity, reduces the product's hygroscopicity, and broadens the product's application range.

[0016] 2. The specific types of linking groups, polyamide segments, and fluoroether silicone polymer segments can be adjusted according to target requirements, which can effectively realize the design and control of elastomer structure, add new product types to polyamide elastomers, avoid the disadvantages of fierce competition and single structure of homogeneous products, realize the differentiated characteristics of products, and further develop its multi-scenario applications.

[0017] 3. The preparation method of the present invention realizes the in-situ copolymerization of polyamide and fluoroether silicone polymer, which has the advantages of mild reaction conditions, simple operation, short process flow, low equipment investment, easy process control and environmental friendliness. Attached Figure Description

[0018] Figure 1 is the infrared spectrum of polyamide 1211 in Example 1;

[0019] Figure 2 is the infrared spectrum of the double-ended perfluoropolyether-b-polysiloxane used in Example 1;

[0020] Figure 3 is the infrared spectrum of the polyamide elastomer in Example 1. Detailed Implementation

[0021] The endpoints and any values ​​of the ranges disclosed herein 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 the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0022] In this invention, a group containing a certain functional group not only includes the functional group itself, but also includes derivative groups of that functional group. For example, a "group containing a silane-hydrogen bond" can not only contain a silane-hydrogen bond, but can also be a group obtained by reacting a silane-hydrogen bond with at least one of an acid containing a carbon-carbon double bond, an amine containing a carbon-carbon double bond, an alcohol containing a carbon-carbon double bond, and cyanuric chloride; or it can be a group obtained by reacting a silane-hydrogen bond with an acid containing a carbon-carbon double bond, followed by an acylation reaction. As another example, a group containing cyanuric chloride can be understood as containing a cyanuric chloride group, or it can be understood as a cyanuric chloride-derived group, such as a "triazine ring group," which is a group derived from the reaction of a cyanuric chloride group with a silane-hydrogen bond.

[0023] The first aspect of this invention provides a fluoroether-silicone modified polyamide elastomer, said elastomer having the general structural formula shown in formula (I).

[0024] Polyamide segment-linking group-fluoroether silicone polymer segment formula (I),

[0025] In formula (I), the polyamide segment is provided by polyamide, the fluoroether silicone polymer segment is provided by fluoroether silicone polymer, and the linking group is formed by the reaction of the end capping group A at the end of the polyamide with the reactive group B in the fluoroether silicone polymer; the end capping group A is selected from at least one of amino, carboxyl and alkenyl groups; the reactive group B is selected from at least one of carboxyl, hydroxyl, amino, silane-hydrogen bond, isocyanate group, acyl chloride group and cyanuric chloride group.

[0026] The polyamide elastomer of this invention is composed of hard polyamide segments and soft fluoroether silicone polymer segments, combining the advantages of both polyamide and organofluorosilicone. The acid and alkali resistance, flexibility, and oleophobic and hydrophobic properties of the polyamide elastomer are significantly improved. Furthermore, the hard polyamide segments and the soft fluoroether silicone polymer segments are connected by specific linking groups, resulting in a polyamide elastomer with excellent mechanical properties. This invention not only adds a new product category to polyamide elastomers but also improves product performance and broadens the application range of the products.

[0027] Polymers exhibit uncertainty in molecular chain length, meaning that the polymerization reaction during polymer synthesis is often not completely uniform; some chains may be longer while others may be shorter, resulting in a certain degree of "diversity" in polymer composition. For this invention, the polymer not only has uncertainty in molecular chain length but also diversity in linking groups. That is, when the reactive group B in the fluoroether silicone polymer has at least two different groups that can react with the end-capping group A at the end of the polyamide to form a linking group, the final polymer also exhibits diversity in end groups, linking groups, and other structures, and the final polyamide elastomer possesses excellent mechanical properties.

[0028] According to the present invention, the specific end capping group A and reactive group B can be selected from the above-mentioned wide range of combinations that can react to form linking groups.

[0029] In some embodiments, in formula (I), the end-capping group A is an amino group, and the reactive group B is selected from groups containing at least one of carboxyl, hydroxyl, isocyanate, acyl chloride, and cyanuric chloride. For example, in formula (I), the end-capping group A is an amino group, and the reactive group B is a hydroxyl-containing group; in formula (I), the end-capping group A is an amino group, and the reactive group B, as the end-capping group, is an acyl chloride-containing group; in formula (I), the end-capping group A is an amino group, and the reactive group B, as the end-capping group, is an isocyanate-containing group.

[0030] In some embodiments, in formula (I), the end-capping group A is a carboxyl group, and the reactive group B is selected from at least one group selected from hydroxyl, amino, silane-hydrogen bond, isocyanate, acyl chloride, and cyanochlorotrichloro group. For example, the end-capping group A is selected from a carboxyl group, and the reactive group B is selected from a group containing cyanochlorotrichlorotrichloro.

[0031] In some embodiments, in formula (I), the end-capping group A is a group containing a terminal alkenyl group, and the reactive group B is a group containing a silane-hydrogen bond.

[0032] In some embodiments, the terminal alkenyl group in the capping group A is shown in formula (A1) and / or formula (A2).

[0033] In equation (A1), R 11 Selected from C1-C 20 Alkylene or C1-C 20 alkylene-phenylene, R 12 Selected from H, phenyl, C1-C 20 Alkyl or C2-C 20 Terminal alkenyl, R 13 Selected from H or C1-C 20 Alkyl group, n is 0 or 1, * indicates a linking site; in formula (A2), R 21 Selected from C1-C 20Alkylene, R 22 Selected from H or C1-C 20 Alkyl group, m is 0 or 1, * indicates a linking site. It can be understood that the linking sites are located at both ends of the polyamide segment.

[0034] In this invention, "C1-C" 20 "C" refers to a group having 1-20 carbon atoms, where the number of carbon atoms can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20. Similarly, "C2-C" 20 "Refers to a group having 2 to 20 carbon atoms, which can be 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms."

[0035] In this invention, C1-C 20 Alkyl groups refer to branched or branched monovalent groups of saturated aliphatic hydrocarbons having 1-20 carbon atoms. Examples include methyl (1 carbon atom), ethyl (2 carbon atoms), n-propyl and isopropyl (3 carbon atoms), n-butyl, isobutyl, and tert-butyl (4 carbon atoms), n-pentyl, neopentyl, and isopentyl (5 carbon atoms), n-hexyl, isohexyl, and secondary hexyl (6 carbon atoms), n-heptyl and isoheptyl (7 carbon atoms), n-octyl and isooctyl (8 carbon atoms), and n-nonyl (9 carbon atoms). , having 10 carbon atoms: n-decyl, isodeyl, tert-decyl; n-undecyl having 11 carbon atoms; n-dodecyl having 12 carbon atoms; n-tridecyl having 13 carbon atoms; n-tetradecyl having 14 carbon atoms; n-pentadecanyl having 15 carbon atoms; n-hexadecyl having 16 carbon atoms; n-heptadecyl having 17 carbon atoms; n-octadecyl having 18 carbon atoms; n-nonadecanyl having 19 carbon atoms; n-eicosyl having 20 carbon atoms.

[0036] In this invention, C1-C 20 Alkylene refers to a group having a C1-C2 bond structure. 20 Divalent groups with the same structure as alkyl groups, i.e., C1-C 20Alkyl groups formed by losing one hydrogen atom are divalent groups, such as methylene (1 carbon atom), ethylene (2 carbon atom), n-propylene and isopropylene (3 carbon atom), n-butylene, isobutylene, and tert-butylene (4 carbon atom), n-pentylene, neopentylene, and isopentylene (5 carbon atom), n-hexylene, isohexylene, and secondary hexylene (6 carbon atom), n-heptylene and isoheptylene (7 carbon atom), n-octylene and isooctylene (8 carbon atom), n-nonylene (9 carbon atom), and n-nonylene (10 carbon atom). The following are the carbon atoms of n-decylene, isodemylide, tertiary decylene, n-undecylene (11 carbon atoms), n-dodecylene (12 carbon atoms), n-tridecylene (13 carbon atoms), n-tetradecylene (14 carbon atoms), n-pentadecanylene (15 carbon atoms), n-hexadecylene (16 carbon atoms), n-heptadecylene (17 carbon atoms), n-octadecylene (18 carbon atoms), n-nonadecanylene (19 carbon atoms), and n-icosene (20 carbon atoms).

[0037] In this invention, C1-C 20 Alkylene-phenylene refers to C1-C as defined in this invention. 20 A group in which one hydrogen atom of an alkyl group is replaced by a phenylene group, for example, C1 alkylene-phenylene refers to methylene-phenylene (-CH2-(C6H4)-) and C3 alkylene-phenylene refers to propylene-phenylene (-CH2(CH2)2-(C6H4)-).

[0038] In this invention, "terminal alkenyl" refers to a carbon-carbon double bond (alkenyl) group located at the end of the molecular chain (i.e., the end position of the molecular structure).

[0039] In this invention, C2-C 20 Terminal alkenyl groups refer to alkenyl groups with 2-20 carbon atoms, where there is a carbon-carbon double bond between the terminal carbon atom (i.e., the carbon atom bonded to other molecules). For example, C2 terminal alkenyl groups refer to vinyl groups (-CH=CH2 groups), C4 terminal alkenyl groups refer to butenyl groups (-CH2CH2CH=CH2 groups), and C... 10 The terminal alkenyl group refers to the decaenyl (-CH2(CH2)8CH=CH2) group.

[0040] In this invention, R 11 This can be any of the C1-C defined and listed in this invention. 20 Alkylene or C1-C 20 In some embodiments, alkylene-phenylene, in formula (A1), R 11 Selected from C1-C 10 Alkylene or C1-C 10Alkylene-phenylene. In this invention, R is used... 11 The use of methylene or methylene-phenylene as an example is to illustrate the advantages of the invention, but does not represent a limitation of the invention.

[0041] In this invention, R 12 This can be any of the C1-C defined and listed in this invention. 20 Alkyl or C2-C 20 Terminal alkenyl groups, in some embodiments, in formula (A1), R 12 Selected from H, phenyl, C1-C 10 Alkyl or C2-C 10 Terminal alkenyl group. In this invention, R is used. 12 The use of H, phenyl, methyl, or propenyl groups is provided as an example to illustrate the advantages of the invention, but does not constitute a limitation thereof.

[0042] In this invention, R 13 This can be any of the C1-C defined and listed in this invention. 20 Alkyl groups, in some embodiments, where R is an alkyl group of formula (A1). 13 Selected from H or C1-C 10 Alkyl group. In this invention, R is used. 13 The use of H or methyl is illustrative of the advantages of the invention, but does not imply any limitation thereof.

[0043] In this invention, R 21 This can be any of the C1-C defined and listed in this invention. 20 Alkylene, in some embodiments, R in formula (A2) 21 Selected from C1-C 10 Alkylene. In this invention, R is used. 21 The use of methylene, ethylene, or butylene as examples to illustrate the advantages of the invention, but does not represent a limitation thereof.

[0044] In this invention, R 22 This can be any of the C1-C defined and listed in this invention. 20 Alkyl groups, in some embodiments, where R is an alkyl group of formula (A2). 22 Selected from H or C1-C 10 Alkyl group. In this invention, R is used. 22 The use of H or methyl is provided as an example to illustrate the advantages of the invention, but does not represent a limitation thereof.

[0045] In some embodiments, the reactive group B is located at both ends of the fluoroether silicone polymer and / or in the chain of the fluoroether silicone polymer. Wherein, "reactive group B at both ends of the fluoroether silicone polymer" means that the fluoroether silicone polymer uses reactive group B as an end cap, and "reactive group B in the chain of the fluoroether silicone polymer" means that reactive group B is present in the chain segment of the fluoroether silicone polymer. It will be understood by those skilled in the art that the fluoroether silicone polymer is a polymer having perfluoropolyether segments or perfluoropolyether segment derivative segments and polysiloxane segments, wherein the reactive group B is specifically attached to a silicon atom on the polysiloxane segment.

[0046] In some embodiments, the reactive group B contains a silane-hydrogen bond. Using the aforementioned embodiments, the silane-hydrogen bond can undergo a silane-hydrogen reaction with a polyamide end-capped with an alkenyl group to obtain a polyamide elastomer with high molecular weight and excellent mechanical properties.

[0047] In some embodiments, the reactive group B contains a group obtained by reacting a silicon-hydrogen bond with at least one of an acid containing a carbon-carbon double bond, an amine containing a carbon-carbon double bond, an alcohol containing a carbon-carbon double bond, and cyanuric chloride. The polyamide elastomers of the foregoing embodiments have high molecular weight and excellent mechanical properties.

[0048] In some embodiments, the reactive group B contains a group obtained by reacting a silicon-hydrogen bond with an acid containing a carbon-carbon double bond, followed by an acyl chloride reaction. The aforementioned embodiments result in the final polyamide having an acyl chloride group, and the resulting polyamide elastomer exhibits high molecular weight and excellent mechanical properties.

[0049] In some embodiments, the reactive group B contains a group as shown in formula (B1):

[0050] In equation (B1), R 31 Selected from H or C1-C 20 Alkyl, R 32 Selected from C1-C 20 Alkylene or C1-C 20 alkylene-phenylene-C1-C 10 Alkylene, where X is a carboxyl, amino, or acyl chloride group, and * indicates a linkage site. It can be understood that the * linkage site is attached to either end of a polysiloxane segment or to a silicon atom within the chain.

[0051] In this invention, R 31 This can be any of the C1-C defined and listed in this invention. 20 Alkyl, in some embodiments, R 31 Selected from H or C1-C 20 Alkyl groups, preferably selected from H or C1-C 10 Alkyl group. In this invention, R... 31The advantages of the present invention are illustrated by using H, ethyl, octyl and other groups as examples, but this does not imply any limitation on the present invention.

[0052] In this invention, R 32 This can be any of the C1-C defined and listed in this invention. 20 Alkylene, C1-C 20 alkylene-phenylene-C1-C 10 C1-C in alkylene 20 Alkylene can be any C1-C alkylene defined and listed in this invention. 20 Alkylene, similarly, C1-C 10 Alkylenes can be any specific alkylene group consisting of 1 to 10 carbon atoms, and can be listed as C1-C1. 20 alkylene-phenylene-C1-C 10 Alkylenes include C1 alkylene-phenylene-C1 alkylene, which refers to methylene-phenylene-methylene (-CH2-(C6H4)-CH2-), C2 alkylene-phenylene-C1 alkylene, which refers to ethylene-phenylene-methylene (-CH2CH2-(C6H4)-CH2-), and C4 alkylene-phenylene-C2 alkylene, which refers to butylene-phenylene-ethylene (-CH2CH2CH2CH2-(C6H4)-CH2-), etc. In this invention, methylene-phenylene-methylene is used as an example to illustrate the advantages of the invention, but it does not represent a limitation of the invention.

[0053] In some embodiments, the reactive group B contains a group as shown in formula (B2).

[0054] In equation (B2), R 41 Selected from H or C1-C 20 Alkyl, R 42 Selected from C1-C with or without substituents 20 alkylene hydroxyl, C1-C 20 Alkylene-C1-C 20 hydroxyalkylene ester group or C2-C containing ether bond 20 alkylene hydroxyl, wherein the substituent is selected from -R 43 -*、C1-C 20 Alkyl or C1-C 20 alkylene hydroxyl, R 43 Selected from C1-C 20 alkylene ester group -C2-C 20 Alkylene, * indicates a linking site. It can be understood that the * linking site is attached to either end of a polysiloxane segment or to a silicon atom within the chain.

[0055] In this invention, R 41This can be any of the C1-C defined and listed in this invention. 20 Alkyl groups, in some embodiments, where R is an alkyl group of formula (B2). 41 Selected from H or C1-C 10 Alkyl group. In this invention, R 41 H is used as an example to illustrate the advantages of the present invention, but it does not represent a limitation of the present invention.

[0056] In this invention, C1-C 20 Alkyl hydroxyl refers to the C1-C hydroxyl group as defined in this invention. 20 A group in which one hydrogen atom on an alkyl group is replaced by a hydroxyl group can be listed in C1-C2. 20 Alkyl hydroxyl groups include, but are not limited to, C1 alkyl hydroxyl groups (-CH2-OH), C2 alkyl hydroxyl groups (-CH2CH2-OH), C3 alkyl hydroxyl groups (-CH2CH2CH2-OH), and C7 alkyl hydroxyl groups (-CH2(CH2)6-OH).

[0057] In this invention, C1-C 20 Alkylene-C1-C 20 C1-C in hydroxyalkylene ester group 20 Hydroxyalkylene esters refer to alkylene groups where there is a 1-20 carbon atom distance between the ester functional group and the OH group. Examples include C1-C... 20 Alkylene-C1-C 20 Hydroxyalkylene ester groups include, but are not limited to, C1-C1 hydroxyalkylene ester groups (methylene-hydroxymethylene ester group -CH2-(COO)-CH2OH), and C1-C2 hydroxyalkylene ester groups (methylene-hydroxyethylene ester group -CH2-(COO)-CH2CH2OH), etc., preferably C1-C 10 Alkylene-C1-C 10 Hydroxyalkylene ester group

[0058] In this invention, C2-C containing ether bonds 20 alkylene hydroxyl refers to C2-C 20 An oxygen atom is inserted into an alkylene hydroxyl group to form an ether bond. Examples of C2-C structures containing ether bonds can be listed. 20 Alkylhydroxyl groups include, but are not limited to, C2 alkylhydroxyl groups containing ether bonds (-CH2-O-CH2OH), and are preferably C2-C alkylhydroxyl groups containing ether bonds. 10 Alkyl hydroxyl group.

[0059] In this invention, C1-C containing substituents 20 alkylene hydroxyl, C1-C 20 Alkylene-C1-C 20 hydroxyalkylene ester group or C2-C containing ether bond20 alkylene hydroxyl refers to C1-C 20 alkylene hydroxyl, C1-C 20 Alkylene-C1-C 20 hydroxyalkylene ester group or C2-C containing ether bond 20 Any one or more, preferably one or two H atoms on the alkylene hydroxyl group, are substituted by a substituent. When the substituent is selected from -R 43 -* indicates that at least two sites in the group shown in formula (B2) are connected to the main chain of the fluoroether silicone polymer, which is a branched structure.

[0060] In some embodiments, the reactive group B contains a group obtained by reacting a group of formula (B2) with a diisocyanate. Using the aforementioned embodiments, fluoroether silicone polymers containing isocyanate groups can be obtained, resulting in polyamide elastomers with high molecular weight and excellent mechanical properties.

[0061] According to the present invention, the diisocyanate is a compound containing two isocyanate groups. As long as the purpose of the present invention can be achieved, the diisocyanate can be any diisocyanate in the art. In one embodiment, the diisocyanate includes at least one of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and lysine diisocyanate.

[0062] In some embodiments, the reactive group B contains a group as shown in formula (B3).

[0063] In equation (B3), * denotes a linkage site. It can be understood that the * linkage site is attached to either end of a polysiloxane segment or to a silicon atom within the chain.

[0064] In this invention, the polyamide elastomer obtained by connecting polyamide segments with fluoroether silicone polymer segments through the above-mentioned linking groups has a variety of controllable structures, and the final elastomer can have a variety of structures such as star-shaped and linear.

[0065] According to the present invention, polyamide is a general term for polymers whose macromolecular backbone contains repeating structural unit amide groups (-NHCO-). The polyamide in the present invention can be any polyamide in the art. In one embodiment, the polyamide is selected from C 2- C 20 Dicarboxylic acids and C2-C 20 Polymers obtained by diamine polycondensation or their derivatives; in one embodiment, the polyamide is selected from C4-C64. 10 Polymers or their derivatives obtained by ring-opening polymerization of lactams.

[0066] Fluoroether silicone polymers have excellent resistance to acids and alkalis, hydrolysis, low temperature, heat, UV, and ozone aging. The polyamide elastomer obtained by introducing fluoroether silicone polymers as soft segments in the polyamide elastomer of this invention not only has excellent low temperature flexibility, solvent resistance, and oil resistance, but also has excellent mechanical properties.

[0067] In this invention, the fluoroether silicone polymer is a type of polymer having fluorinated hydrocarbon segments (fluoroether chains) and siloxane segments (silane or siloxane groups). In some embodiments, the structure of the fluoroether silicone polymer is R. f -bR, where R f R is a perfluoropolyether segment or a derivative segment, where R is a polysiloxane segment. The perfluoropolyether segment or its derivative segment can be selected from a wide range, preferably at least one of K-type, D-type, Y-type, and Z-type perfluoropolyether segments. Examples of perfluoropolyether derivative segments include, but are not limited to, perfluoropolyether vinyl ether segments, perfluoropolyether carboxylic acid segments, and perfluoropolyether methyl ester segments. The K-type perfluoropolyether segment is used as an example to illustrate the advantages of the invention, but this does not constitute a limitation on the invention.

[0068] The polysiloxane segment in this invention can be any type of polysiloxane segment in the art. The segment contains a reactive group B, and its main segment can be a hydrogen-containing polysiloxane segment, an olefin polysiloxane segment, an amino polysiloxane segment, or a mercapto polysiloxane segment, etc.

[0069] According to the present invention, R f There are no special restrictions on the content of R, but the content of R is preferred. f The molar ratio of R is 1:20-10:1, for example, it can be 1:20, 1:10, 1:5, 1:3, 1:2, 1:1, 2:1, 3:1, 5:1, 8:1 or 10:1, or any range of two of the above values.

[0070] In this invention, the average molecular weight of the polyamide can be selected within a wide range. The following range is for illustrative purposes only and does not represent a limitation of this invention. In some embodiments, the average molecular weight of the polyamide is 400-20000 g / mol, such as 400 g / mol, 1000 g / mol, 2000 g / mol, 4000 g / mol, 6000 g / mol, 8000 g / mol, 10000 g / mol, 12000 g / mol, 14000 g / mol, 16000 g / mol, 1800 g / mol, or 2000 g / mol, or any combination of two of the above values.

[0071] In this invention, the average molecular weight of the fluoroether silicone polymer can be selected within a wide range. The following range is for illustrative purposes only and does not represent a limitation of this invention. In some embodiments, the average molecular weight of the fluoroether silicone polymer is 400-50000 g / mol, for example, it can be 400 g / mol, 1000 g / mol, 5000 g / mol, 10000 g / mol, 15000 g / mol, 20000 g / mol, 25000 g / mol, 30000 g / mol, 35000 g / mol, 40000 g / mol, 45000 g / mol, or 50000 g / mol, or any combination of two of the above values.

[0072] In this invention, unless otherwise specified, "average molecular weight" refers to exponential average molecular weight, with units of g / mol, and its testing method is as follows: 1 H NMR testing: [The text abruptly ends here, likely due to an incomplete sentence or a missing section.] 1 1H NMR analysis was performed using CDCl3 as the deuteration reagent and tetramethylsilane (TMS) as the internal standard.

[0073] In this invention, the content of polyamide segments and fluoroether silicone polymer segments in the elastomer can be selected within a wide range. The following ranges are for illustrative purposes only and do not represent a limitation of this invention. In some embodiments, the mass ratio of the polyamide segments to the fluoroether silicone polymer segments is 10-90:90-10, such as 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, or 90:10, or any two of the above values.

[0074] In this invention, the elastomer has a molecular weight that enables differentiated properties and can achieve a high molecular weight. The following ranges are provided as examples and do not represent limitations on this invention. In some embodiments, the average molecular weight of the elastomer is 3000-60000 g / mol, for example, 3000 g / mol, 33851 g / mol, 37151 g / mol, 39520 g / mol, 40150 g / mol, 42100 g / mol or 60000 g / mol, or any combination of two of the above values.

[0075] The elastomer of the present invention has excellent mechanical properties. In some embodiments, the tensile strength of the elastomer is 22-40 MPa, for example, 22 MPa, 23 MPa, 24 MPa, 25 MPa, 26 MPa, 27 MPa, 28 MPa, 30 MPa or 40 MPa; in some embodiments, the elongation at break of the elastomer is 450-650%, for example, 450%, 490%, 510%, 535%, 550%, 600% or 650%, or any combination of two of the above values.

[0076] The tensile strength and elongation at break of the elastomer were tested using a CMT4104 electronic universal testing machine, following the method in GB / T1040.1-2006, with a tensile rate of 20 mm / min.

[0077] A second aspect of the present invention provides a method for preparing a fluoroether silicone-modified polyamide elastomer, the method comprising: reacting a polyamide with a fluoroether silicone polymer under solution polymerization conditions; wherein the end-capping group A at the end of the polyamide is selected from at least one of amino, carboxyl, and alkenyl groups; the fluoroether silicone polymer contains a reactive group B, the reactive group B being selected from at least one of carboxyl, hydroxyl, amino, silane-hydrogen bond, isocyanate, acyl chloride, and cyanuric chloride groups, and the end-capping group A at the end of the polyamide reacts with the reactive group B in the fluoroether silicone polymer to form a linking group.

[0078] This invention employs a solution method to prepare polyamide elastomers. Compared to bulk melt polymerization, the solution method offers milder reaction conditions and lower viscosity of the reaction system. Furthermore, the in-situ copolymerization of polyamide with specific groups in the fluoroether silicone polymer in this invention effectively increases collisions between reactive groups. This method boasts advantages such as mild reaction conditions, simple operation, short process flow, low equipment investment, easy process control, and environmental friendliness. This preparation method adds new product types to polyamide elastomers, improves product performance, avoids oversupply of homogeneous products, and broadens its application fields, possessing immeasurable economic value and social benefits.

[0079] In some embodiments, the terminal alkenyl group in the capping group A is shown in formula (A1) and / or formula (A2).

[0080] In equation (A1), R 11 Selected from C1-C 20 Alkylene or C1-C 20 alkylene-phenylene, R 12 Selected from H, phenyl, C1-C 20 Alkyl or C2-C 20 Terminal alkenyl, R 13 Selected from H or C1-C20 Alkyl group, n is 0 or 1, * indicates a linking site; in formula (A2), R 21 Selected from C1-C 20 Alkylene, R 22 Selected from H or C1-C 20 Alkyl group, m is 0 or 1, * indicates a linking site.

[0081] The polyamide in this invention is the same as any of the polyamides described in the first aspect of this invention, that is, in one embodiment, the polyamide is selected from: polymers obtained by condensation polymerization of a diacid and a diamine or their derivatives; in one embodiment, the polyamide is selected from: polymers obtained by ring-opening polymerization of a lactam or their derivatives; in one embodiment, the polyamide may also simultaneously contain polymers obtained by condensation polymerization of a diacid and a diamine or their derivatives and polymers obtained by ring-opening polymerization of a lactam or their derivatives, preferably the diacid is C. 2- C 20 Dicarboxylic acid, preferably a diamine with C2-C 20 Diamines, preferably lactams, are C4-C. 10 Lactam.

[0082] The polyamide in this invention can be obtained commercially or by conventional preparation methods in the art. The preparation method of polyamide includes: carrying out a polymerization reaction containing a reactive monomer, water, a solvent, optionally a capping agent, optionally an antioxidant, and optionally a polymerization inhibitor; wherein the reactive monomer is a diacid and a diamine, or a lactam, or a mixture of lactam, diacid, and diamine.

[0083] According to the present invention, in the preparation of polyamide, the optional end-capping agent refers to adding or not adding an end-capping agent as needed. Those skilled in the art will understand that when the reactant monomer contains a diacid and a diamine, the type of end-capping group is controlled by controlling the amount of diacid and diamine. When the diacid is in excess, the end-capping group is a carboxyl group, and when the diamine is in excess, the end-capping group is an amino group. That is, the diacid or diamine itself can play the role of end-capping so that the end-capping group of the polyamide is a carboxyl group or an amino group. In this case, no additional end-capping agent needs to be added.

[0084] When the reactive monomer is only lactam, in order to obtain polyamide elastomers with amino or carboxyl end-capping groups, diamino or carboxyl end-capping agents can be added accordingly. Diamine or diacid can be used as end-capping agents. Generally, the number of carbon atoms in the diamine or diacid end-capping agent is chosen to be the same as the number of carbon atoms in the lactam. The amount of end-capping agent used is only enough to end one or both ends of the polyamide.

[0085] According to the present invention, in order to obtain polyamides with end-capping groups containing terminal alkenyl groups, compounds of formula (A1-1) and / or formula (A2-1) can be added as end-capping agents.

[0086] In equation (A1-1), R 11 R 12 R 13 The definitions of and n are the same as those in equation (A1), and the definitions of R21, R22, and m in equation (A2-1) are the same as those in equation (A2).

[0087] According to the present invention, compounds of formula (A1-1) may include, but are not limited to, allylamines and vinylamines. Specifically, allylamines may include, but are not limited to, 2-methylallylamine, N-allylaniline, diallylamine, N-methylallylamine, etc.; vinylamines may include, but are not limited to, 4-vinylbenzylamine.

[0088] According to the present invention, the compounds of formula (A2-1) that can be listed include, but are not limited to, allyl acids and vinyl acids. Specifically, the allyl acids that can be listed include, but are not limited to, butenoic acid, and the vinyl acids that can be listed include, but are not limited to, acrylic acid, methacrylic acid, 4-pentenoic acid, vinyldecanoic acid, etc.

[0089] According to the present invention, in the preparation of polyamide, the antioxidant optionally refers to an antioxidant that can be added or not added as needed. The purpose of adding an antioxidant during the polymerization process is mainly to improve the antioxidant capacity of the polymer. Preferably, the antioxidant is added during the polymerization reaction. Based on the total mass of the polymerization reaction system, the amount of antioxidant added is 0.01-8 wt%, for example, it can be 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, or 8 wt%, or any two of the above values. The type of antioxidant can be a conventional type in the art, such as at least one of antioxidant 1010, antioxidant 1076, antioxidant 1024, antioxidant 1098, and antioxidant 1216.

[0090] According to the present invention, when preparing polyamide, a polymerization inhibitor is added to suppress unwanted side reactions that may occur during the polymerization reaction. Optionally, the polymerization inhibitor refers to the agent that can be added or not added as needed. The type of polymerization inhibitor can be a type conventional in the art, such as sodium nitrite, nitrosophenyl hydroxylamine, p-benzoquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine nitroxide radical, etc. Generally, the amount of polymerization inhibitor used is 0.01-5 wt% of the total mass of the reaction system, for example, it can be 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, or 5 wt%, or any two of the above values.

[0091] According to the present invention, in the preparation of polyamide, the role of water mainly includes promoting the forward shift of the polymerization reaction. The amount of water used is only required to maximize the promotion of the polymerization reaction. The amount of water used is generally 0.5-10 wt% of the mass of the reactant monomer, for example, it can be 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, or 10 wt%, or any two of the above values.

[0092] According to the present invention, it is understood in the art that polyamides are generally prepared through a condensation reaction of a diacid and a diamine or a ring-opening reaction of a lactam. That is, when preparing polyamides, specific polymerization reaction conditions can be selected according to actual needs. Specifically, the reaction can be carried out first at 100-350°C for 1-48 hours at a pressure of 0.1-5 MPa; then a vacuum is applied at a vacuum degree of 5 Pa-10000 Pa for 0.5-12 hours. More specifically, the reaction can be carried out first at 100-230°C for 1-24 hours, then at 230-350°C for 1-24 hours, finally at a vacuum degree of 5 Pa-10000 Pa for 0.5-12 hours. The pressure in the reaction system before vacuuming is the pressure of each individual reaction system.

[0093] According to the present invention, in order to avoid the influence of oxygen-containing gas on the polymerization reaction during the preparation of polyamide, the air in the reaction system can be replaced with an inert gas (such as argon or nitrogen) before the polymerization reaction.

[0094] According to the present invention, when preparing polyamide, the crude polyamide product obtained after the polymerization reaction may contain oligomers and other impurities. The crude polyamide product can be purified after the polymerization reaction. Generally, solvent extraction is used to remove the oligomers and impurities and then drying is used to obtain polyamide. Preferably, the solvent used for extraction is at least one of water, ethanol, methanol, ethyl acetate, acetone, N,N-dimethylformamide, tetrahydrofuran, acetonitrile, chloroform and dimethyl sulfoxide.

[0095] According to the present invention, fluoroether silicone polymers are a class of polymers having fluorinated hydrocarbon segments (fluoroether chains) and siloxane segments (siloxane alkyl groups). In some embodiments, the structure of the fluoroether silicone polymer is R. f -bR, where R f R is a segment of perfluoropolyether or its derivative, and R is a segment of polysiloxane.

[0096] In some embodiments, the fluoroether silicone polymer is selected from double-terminated perfluoropolyether-b-polysiloxane and / or perfluoropolyether-b-polysiloxane containing perfluoropolyether-b-polysiloxane in the chain.

[0097] According to the present invention, in order to achieve the purpose of the present invention, the fluoroether silicone polymer is end-capped and modified. The polyamide can be directly polymerized with the modified fluoroether silicone polymer to obtain a polyamide elastomer. Alternatively, the modified fluoroether silicone polymer can be first modified with a third monomer to obtain a fluoroether silicone polymer modified with a third monomer, and then polymerized with polyamide to obtain a polyamide elastomer.

[0098] In some embodiments, the preparation method of the fluoroether silicone polymer includes: a modification reaction of a bipolar perfluoropolyether-b-polysiloxane and / or a perfluoropolyether-b-polysiloxane containing a silane in the chain, in the presence of a modifier and a catalyst; optionally, a third monomer modification reaction is carried out in the presence of a third monomer; wherein the modifier is selected from at least one of an acid containing a carbon-carbon double bond, an amine containing a carbon-carbon double bond, an alcohol containing a carbon-carbon double bond, and cyanuric chloride; and the third monomer is selected from diisocyanate and / or acyl chloride.

[0099] In some embodiments, the modifier contains a compound as shown in formula (B11) and / or a compound as shown in formula (B12).

[0100] In equation (B11), R 311 Selected from H or C1-C 20 Alkyl, R 321 Selected from C1-C 20 Mesenyl or C1-C 20 Phenylidene-phenylene-C1-C 10 Alkylene, where X1 is a carboxyl or amino group;

[0101] In equation (B21), R 411 Selected from H or C1-C 20 Alkyl, R 421 Selected from C1-C with or without substituents 20 Phenyl alkyl hydroxyl, C1-C 20 Phenyl-C1-C 20 hydroxyalkylene ester group or C2-C containing ether bond 20 The substituent is selected from -R. 433R 433 Selected from C1-C 20 alkylene ester group -C2~C 20 Terminal alkenyl group.

[0102] In this invention, C1-C 20 Phenylene refers to C1-C as defined in this invention. 20 An alkylene group is formed by losing one hydrogen atom.

[0103] According to the present invention, the specific types of modifiers that can be listed include, but are not limited to, butenoic acid, allyl alcohol, oleylamine, oleic acid, pentaerythritol triacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, trimethylolpropane allyl ether, etc.

[0104] In some embodiments, the diisocyanate includes at least one selected from toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and lysine diisocyanate.

[0105] In some embodiments, the acyl chloride includes at least one of dichloroacetyl chloride, carbamate chloride, oxaloyl chloride, terephthaloyl chloride, isophthaloyl chloride, adipicoyl chloride, chloroacetyl chloride, trichloroacetyl chloride, acryloyl chloride, and methacryloyl chloride.

[0106] In some embodiments, the preparation method of the fluoroether silicone polymer includes: a modification reaction of a double-terminated perfluorosilane-b-polysiloxane and / or a perfluorosilane-b-polysiloxane containing a silane in the chain, in the presence of a modifier and a catalyst; and a third monomer modification reaction in the presence of a third monomer; wherein the modifier is selected from an acid containing a carbon-carbon double bond; and the third monomer is selected from an acyl chloride.

[0107] In some embodiments, the preparation method of the fluoroether silicone polymer includes: a modification reaction of a double-terminated perfluorosilane-b-polysiloxane and / or a perfluorosilane-b-polysiloxane containing a silane in the chain, in the presence of a modifier and a catalyst; and a third monomer modification reaction in the presence of a third monomer; wherein the modifier is selected from an alcohol containing a carbon-carbon double bond; and the third monomer is selected from a diisocyanate.

[0108] In some embodiments, the double-terminated perfluoropolyether-b-polysiloxane and the perfluoropolyether segments in the perfluoropolyether-b-polysiloxane chain are each independently selected from at least one of K-type perfluoropolyether segments, D-type perfluoropolyether segments, Y-type perfluoropolyether segments, Z-type perfluoropolyether segments, perfluoropolyether vinyl ether segments, perfluoropolyether carboxylic acid segments, and perfluoropolyether methyl ester segments.

[0109] In some embodiments, the molar ratio of the perfluoropolyether-b-polysiloxane and the perfluoropolyether-b-polysiloxane containing perfluoropolyether to polysiloxane segments in the chain is 1:20-10:1, for example, it can be 1:20, 1:10, 1:5, 1:3, 1:2, 1:1, 2:1, 3:1, 5:1, 8:1 or 10:1, or any two of the above values.

[0110] According to the present invention, the catalyst can be selected from a wide range of options, as long as it can promote the modification reaction. In some embodiments, the catalyst is selected from at least one of Speier catalyst, Karstedt catalyst, benzoyl peroxide and di-tert-butyl peroxide.

[0111] The amount of catalyst added is not particularly limited as long as the purpose of this invention can be achieved. In some embodiments, the mass of the catalyst is 0.01wt%-10wt% of the mass of terminal silane-perfluoropolyether-b-polysiloxane and / or silane-perfluoropolyether-b-polysiloxane in the chain, for example, it can be 0.01wt%, 0.05wt%, 0.1wt%, 0.5wt%, 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, or 10wt%.

[0112] According to the present invention, there is no particular limitation on the amount of the double-ended perfluorosilane-b-polysiloxane and / or the perfluorosilane-b-polysiloxane in the chain containing silane and the modifier, as long as all or part of the silane-hydrogen bonds in the double-ended perfluorosilane-b-polysiloxane and / or the perfluorosilane-b-polysiloxane in the chain can be modified as needed. In one embodiment, the molar ratio of the double-ended perfluorosilane-b-polysiloxane and / or the perfluorosilane-b-polysiloxane in the chain to the modifier is 1:1.05-5, for example, it can be 1:1.05, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5 or 1:5, or any two of the above values.

[0113] According to the present invention, optionally carrying out the third monomer modification reaction in the presence of the third monomer means carrying out the third monomer modification reaction or not carrying out it as needed. When carrying out the third monomer modification reaction, the amount of the third monomer can be selected as needed. In one embodiment, the molar ratio of the double-terminated perfluorosilane-b-polysiloxane and / or the perfluorosilane-b-polysiloxane-b-polysiloxane in the chain to the third monomer is 1:1.05-5, for example, it can be 1:1.05, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5 or 1:5, or any two of the above values.

[0114] In order to induce free radical polymerization or other side reactions during the modification reaction and the third monomer modification reaction in this invention, polymerization inhibitors may be added as needed.

[0115] According to the present invention, in order to promote the modification reaction, the modification reaction is carried out in the presence of a solvent, preferably the solvent includes at least one of perfluorocyclic ethers, hydrofluoroethers and 1,3-bis(trifluoromethyl)benzene, and the amount of solvent is not particularly limited, generally 0.8-4 times the mass of the di-terminated perfluorosilane-b-polysiloxane and / or the perfluorosilane-b-polysiloxane containing perfluorosilane-b-polysiloxane in the chain.

[0116] According to the present invention, in order to promote the modification reaction of the third monomer, the modification reaction can be carried out in the presence of a solvent, preferably selected from at least one of acetonitrile, n-hexane, pentane, n-heptane, benzonitrile, acetone, toluene, tetrahydrofuran, and chloroform. The amount of solvent used is sufficient to dissolve or uniformly disperse the third monomer.

[0117] According to the present invention, any modification reaction can be carried out under conditions that allow for modification of the silane-hydrogen bonds of the fluoroether silicone polymer. Preferably, the modification reaction conditions include: a reaction temperature of 25-200°C, more preferably 40-120°C, and the reaction time during modification can be adjusted according to the selected temperature, preferably 0.5-72h, more preferably 5-48h.

[0118] According to the present invention, as long as the conditions of the third monomer modification reaction are sufficient to modify the modified fluoroether silicone polymer with a third monomer, the modification reaction with a third monomer is preferred. The third monomer modification reaction includes a reaction temperature of 10-100°C, preferably 50-80°C, and the reaction time during modification can be adjusted according to the selected temperature. The reaction time is preferably 0.5-72h, preferably 8-48h.

[0119] According to the present invention, in order to obtain the final modified double-terminated perfluorosilane-b-polysiloxane and / or perfluorosilane-b-polysiloxane containing perfluorosilane in the chain, purification can be carried out after the modification reaction or the third monomer modification reaction. The target product is generally obtained by conventional means such as standing and separating (generally, the current product is the lower layer of the standing and separating liquid).

[0120] In this invention, before modifying the double-terminated perfluorosilane-b-polysiloxane and / or the perfluorosilane-b-polysiloxane containing silane in the chain, if the double-terminated perfluorosilane-b-polysiloxane and / or the perfluorosilane-b-polysiloxane containing silane in the chain contains moisture, the moisture can be removed by conventional methods for removing moisture from polymers in the art. Preferably, the moisture is removed by vacuuming for 0.5-5 hours at 60-200°C and a vacuum degree of 20Pa-50000 Pa.

[0121] In this invention, the average molecular weight of the fluoroether silicone polymer can be selected within a wide range. In some embodiments, the average molecular weight of the fluoroether silicone polymer is 400-50000 g / mol.

[0122] In this invention, the average molecular weight of the polyamide can be selected within a wide range. In some embodiments, the average molecular weight of the polyamide is 400-20000 g / mol.

[0123] In this invention, the amounts of fluoroether silicone polymer and polyamide can be selected within a wide range. In some embodiments, the mass ratio of the fluoroether silicone polymer to polyamide is 10-90:90-10, such as 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20 or 90:10, or any two of the above values.

[0124] According to the present invention, solution polymerization is carried out in the presence of a solvent. The solvent used in the solution polymerization is not particularly limited as long as it achieves the objectives of the present invention. Preferably, the solvent is selected from at least one of sulfolane, N,N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, and acetone. Specifically, the polyamide can be dissolved in a solvent at a temperature of 25-300°C, and then a fluoroether silicone polymer is added for solution polymerization. In solution polymerization, the amount of solvent is only required to ensure smooth polymerization, generally 2-8 times the mass of the polyamide.

[0125] In some embodiments, the conditions for solution polymerization include: a reaction temperature of 50-300°C, preferably 100-180°C, and a solution polymerization time that can be adjusted according to the specific temperature selection, preferably 0.5-48h, and more preferably 6-48h.

[0126] In order to allow free radical polymerization or other side reactions to occur during the solution polymerization process of this invention, polymerization inhibitors may be added as needed.

[0127] The third aspect of the present invention provides a fluoroether-silicone modified polyamide elastomer prepared by the preparation method described in the second aspect of the present invention.

[0128] The preparation method of this invention can prepare different types of fluoroether-silicone modified polyamide elastomers, achieving an innovative combination of polyamide and fluoroether-silicone polymers. At the same time, the fluoroether-silicone modified polyamide elastomers prepared in the molecular chain structure have excellent mechanical properties.

[0129] The elastomers prepared by the method of the present invention have a wide range of molecular weights, and in particular, elastomers with higher molecular weights can be obtained. In some embodiments, the average molecular weight of the elastomer is 3000-60000 g / mol.

[0130] The elastomer prepared in this invention has excellent mechanical properties. In some embodiments, the tensile strength of the elastomer is 22-40 MPa; in some embodiments, the elongation at break of the elastomer is 450-650%.

[0131] The present invention will be described in detail below through embodiments.

[0132] In the following examples, the evaluation and analysis method is as follows: the tensile properties of the sample to be tested are tested using a CMT4104 electronic universal testing machine, and the test is performed in accordance with the method of GB / T 1040.1-2006, with a tensile rate of 20 mm / min.

[0133] Example 1

[0134] First, 25.7g of undecanoic acid, 22.8g of dodecanoic acid diamine, 2.13g of deionized water, and 0.26g of antioxidant 1010 were added to a reactor. The reactor was purged with argon gas to replace the air, and then the temperature was raised. The reaction was carried out at 160℃ for 3 hours, then at 250℃ and 2.5MPa for 2 hours, and finally under a vacuum of 50Pa for 1.5 hours. After the reaction, the material was cooled to 120℃ and discharged to obtain crude polyamide. The crude product was extracted with ethanol to remove oligomers and impurities, and then dried to obtain carboxyl-terminated polyamide 1211 (average molecular weight 3707g / mol) for later use.

[0135] Take 15.8g of double-terminated perfluorosilane-b-polysiloxane with an average molecular weight of 6000g / mol (its general structural formula is: Among them, R f R1 and R2 are polysiloxane segments (K-type perfluoropolyether segments, R1 and R2 are polysiloxane segments, with a molar ratio of K-type perfluoropolyether segments to total polysiloxane segments of 1:2). These segments are added to 35.8 g of perfluorocyclic ether, followed by 0.02 g of Speier catalyst and 3.2 g of 2-methylallylamine. The reaction is carried out at 100 °C for 5 h. After the reaction, the mixture is allowed to stand and separated. The lower layer is collected for later use, yielding amino-modified perfluorosilane-b-polysiloxane (average molecular weight 6106 g / mol). One structure of amino-modified perfluorosilane-b-polysiloxane is as follows:

[0136] 23.6 g of the above-mentioned carboxyl-terminated polyamide 1211 was dissolved in 100 g of N,N-dimethylformamide at 120 °C. Then, 14.9 g of the above-mentioned amino-modified perfluorosilane-b-polysiloxane and 0.21 g of sodium nitrite were added, and the mixture was reacted at 130 °C for 6 h. After the reaction was completed, the solvent was removed to obtain the polyamide elastomer product. An exemplary structure of the polyamide elastomer product is as follows:

[0137] The infrared spectra of polyamide 1211 (PA1211) with carboxyl-terminated ends are shown in Figure 1; the infrared spectra of perfluoropolyether-b-polysiloxane with silane-hydrogen end are shown in Figure 2; and the infrared spectrum of the polyamide elastomer is shown in Figure 3.

[0138] In Figure 1, at a wavelength of 3310 cm⁻¹ -1 and 673cm -1 1640cm -1 and 583cm -1 And 1544cm -1 The characteristic infrared absorption of the amide group was detected at 2127 cm⁻¹; in Figure 2, 2127 cm⁻¹ -1 The characteristic absorption peak at point 1 is that of the Si-H bond. In Figure 3, both the characteristic peaks of the amide group and the characteristic absorption peaks of the Si-H bond were detected, indicating that the copolymer was successfully prepared through chemical grafting.

[0139] The molecular weight and mechanical properties of polyamide elastomers are shown in Table 1.

[0140] Example 2

[0141] First, 21.3g of sebacic acid, 23.3g of hexamethylenediamine, 1.95g of deionized water, and 0.33g of antioxidant 1076 were added to a reactor. The reactor was purged with argon gas to replace the air, and then the temperature was raised. The reaction was carried out at 110℃ for 8 hours, then at 270℃ and 1.2MPa for 8 hours, and finally under a vacuum of 2000Pa for 3 hours. After the reaction, the material was cooled to 160℃ and discharged to obtain crude polyamide. The crude product was extracted with acetone to remove oligomers and impurities, and then dried to obtain amino-terminated polyamide 610 (average molecular weight 5709g / mol) for later use.

[0142] Take 16.2g of a perfluoropolyether-b-polysiloxane containing silane in its chain, with an average molecular weight of 8000g / mol (its general structural formula is: Among them, R fA K-type perfluoropolyether segment (where n represents the degree of polymerization, and the molar ratio of the K-type perfluoropolyether segment to the silane-polysiloxane segment in the chain is 1:1) was added to 20.1 g of 1,3-bis(trifluoromethyl)benzene, followed by 0.25 g of benzoyl peroxide and 2.8 g of oleic acid. The mixture was reacted at 150 °C for 20 h. After the reaction, the mixture was allowed to stand and separated, and the lower layer was collected for later use. 2.3 g of terephthaloyl chloride was dissolved in acetonitrile, and then added to the lower layer. The mixture was reacted at 60 °C for 8 h. After the reaction, acyl chloride-modified perfluoropolyether-b-polysiloxane (average molecular weight 9133 g / mol) was obtained for later use.

[0143] 20.7 g of amino-terminated polyamide 610 was dissolved in 80 g of dimethyl sulfoxide at 180 °C, and then 12.1 g of the above-mentioned acyl chloride-modified perfluoropolyether-b-polysiloxane was added, and the mixture was reacted at 160 °C for 24 h. After the reaction was completed, the solvent was removed to obtain the polyamide elastomer product.

[0144] An exemplary structure of the polyamide elastomer product is as follows:

[0145] The molecular weight and mechanical properties of polyamide elastomers are shown in Table 1.

[0146] Example 3

[0147] First, 30.7 g of caprolactam, 2.2 g of N-allyl aniline, 3.2 g of deionized water, 0.33 g of p-benzoquinone, and 0.28 g of antioxidant 1216 were added to a reactor. The reactor was purged with argon gas to replace the air, and then the temperature was raised. The reaction was carried out at 200°C for 2 hours, then at 300°C and 3.8 MPa for 1 hour, and finally under a vacuum of 700 Pa for 0.5 hours. After the reaction, the material was cooled to 190°C and discharged to obtain crude polyamide. The crude product was extracted with ethyl acetate to remove oligomers and impurities, and then dried to obtain di-terminated alkenyl-terminated polyamide 6 (average molecular weight 4552 g / mol) for later use.

[0148] Take 20.7g of double-terminated perfluorosilane-b-polysiloxane with an average molecular weight of 12000g / mol (its general structural formula is: Among them, R f R1 and R2 are polysiloxane segments (K-type perfluoropolyether segments, with a molar ratio of K-type perfluoropolyether segments to total polysiloxane segments of 1:2). These segments are dissolved in 10.3 g of hydrofluoroether, and then 4.7 g of cyanuric chloride is added. The mixture is reacted at 40 °C for 12 h. After the reaction is complete, the mixture is allowed to stand and separated. The lower layer is collected for later use, yielding triazine ring-terminated perfluoropolyether-b-polysiloxane (average molecular weight 12108 g / mol).

[0149] 15.9 g of di- and alkenyl-terminated polyamide 6 was dissolved in 50 g of N,N-dimethylformamide at 130 °C. Then, 13.8 g of triazine ring-terminated perfluoropolyether-b-polysiloxane and 0.45 g of di-tert-butyl peroxide were added, and the mixture was reacted at 140 °C for 24 h. After the reaction was completed, the solvent was removed to obtain the polyamide elastomer product.

[0150] Two exemplary structures of the polyamide elastomer product are as follows:

[0151] The molecular weight and mechanical properties of polyamide elastomers are shown in Table 1.

[0152] Example 4

[0153] First, 22.7g of dodecanoic acid, 23.9g of decanediamine, 1.7g of deionized water, and 0.11g of antioxidant 1010 were added to a reactor. The reactor was purged with argon gas to replace the air, and then the temperature was raised. The reaction was carried out at 130℃ for 12 hours, then at 230℃ and 1.3MPa for 6 hours, and finally under a vacuum of 5000Pa for another 6 hours. After the reaction was completed, the material was cooled to 140℃ and discharged to obtain crude polyamide. The crude product was extracted with chloroform to remove oligomers and impurities, and then dried to obtain amino-terminated polyamide 1012 (average molecular weight 6356g / mol) for later use.

[0154] 15.6 g of double-terminated perfluorosilane-b-polysiloxane with an average molecular weight of 4000 g / mol (its general structural formula is: Among them, R f R1 and R2 are polysiloxane segments (K-type perfluoropolyether segments, with a molar ratio of K-type perfluoropolyether segments to total polysiloxane segments of 1:2). These segments were dissolved in 25.7 g of 1,3-bis(trifluoromethyl)benzene, followed by the addition of 2.4 g of allyl alcohol and 0.54 g of Karstedt catalyst. The reaction was carried out at 70 °C for 24 h. After the reaction, the mixture was allowed to stand and separated, and the lower layer was collected for later use. Then, 3.7 g of hexamethylene diisocyanate was dissolved in toluene, and the lower layer was added. The mixture was then reacted at 60 °C for 48 h. After the reaction, the mixture was allowed to stand and separated, and the lower layer was collected to obtain isocyanate-terminated perfluoropolyether-b-polysiloxane.

[0155] 26.1 g of amino-terminated polyamide 1012 was dissolved in 60 g of sulfolane at 200 °C, and then 15.7 g of isocyanate-terminated perfluoropolyether-b-polysiloxane (average molecular weight 4127 g / mol) was added and reacted at 120 °C for 48 h. After the reaction was completed, the solvent was removed to obtain the polyamide elastomer product.

[0156] An exemplary structure of the polyamide elastomer product is as follows:

[0157] The molecular weight and mechanical properties of polyamide elastomers are shown in Table 1.

[0158] Example 5

[0159] First, 13.1g of adipic acid, 11.4g of hexamethylenediamine, 1.7g of 4-vinylbenzylamine, 1.9g of deionized water, and 0.27g of antioxidant 1024 were added to a reactor. The reactor was purged with argon gas to replace the air, and then the temperature was raised. The reaction was carried out at 170℃ for 48 hours, then at 270℃ and 1.2MPa for 10 hours, and finally at a vacuum of 3000Pa for another 3 hours. After the reaction, the material was cooled to 160℃ and discharged to obtain crude polyamide. The crude product was extracted with water to remove oligomers and impurities, and then dried to obtain amino-terminated polyamide 66 (average molecular weight 5591g / mol) for later use.

[0160] 14.7 g of a perfluoropolyether-b-polysiloxane containing silane in its chain, with an average molecular weight of 2000 g / mol (its general structural formula is: Among them, R f The K-type perfluoropolyether segment (where n is the degree of polymerization, and the molar ratio of the K-type perfluoropolyether segment to the silane-polysiloxane segment in the chain is 1:1) was dissolved in 30.2g of hydrofluoroether. Then, 1.7g of 4-pentenoic acid and 0.61g of di-tert-butyl peroxide were added, and the mixture was reacted at 40℃ for 48h. After the reaction was completed, the mixture was allowed to stand and separated, and the lower layer was taken for later use. Then, 12.7g of the lower layer was taken, and 20.1g of 1,3-bis(trifluoromethyl)benzene was added. After stirring for 10min, 4.2g of oxaloyl chloride was added, and the mixture was reacted at 80℃ for 20h. After the reaction was completed, the mixture was allowed to stand and separated, and the lower layer (containing acyl chloride-modified perfluoropolyether-b-polysiloxane) was taken for later use.

[0161] 19.7 g of amino-terminated polyamide 66 was dissolved in 65 g of N-methylpyrrolidone at 130 °C, and then the lower layer of the above solution was added and reacted at 130 °C for 12 h. After the reaction was completed, the solvent was removed to obtain the polyamide elastomer product.

[0162] An exemplary structure of the polyamide elastomer product is as follows:

[0163] The molecular weight and mechanical properties of polyamide elastomers are shown in Table 1.

[0164] Example 6

[0165] First, 13.3g of adipic acid, 16.2g of dodecanediamine, 3.4g of acrylic acid, 0.33g of sodium nitrite, 3.15g of deionized water, and 0.37g of antioxidant 1010 were added to a reactor. The reactor was purged with argon gas to replace the air, and then the temperature was raised. The reaction was carried out at 110℃ for 3 hours, then at 240℃ and 3.1MPa for 1 hour, and finally at a vacuum of 4000Pa for another 4 hours. After the reaction, the material was cooled to 150℃ and discharged to obtain crude polyamide. The crude product was extracted with acetonitrile to remove oligomers and impurities, and then dried to obtain vinyl-terminated polyamide 126 (average molecular weight 3015g / mol) for later use.

[0166] 25.7g of double-ended perfluorosilane-b-polysiloxane with an average molecular weight of 5000g / mol (its general structural formula is: Among them, R f R1 and R2 are polysiloxane segments (K-type perfluoropolyether segments, R1 and R2 are polysiloxane segments, with a molar ratio of K-type perfluoropolyether segments to total polysiloxane segments of 1:2). The mixture was dissolved in 40.3 g of 1,3-bis(trifluoromethyl)benzene, and then 2.3 g of 4-vinylbenzylamine and 0.31 g of Speier catalyst were added. The mixture was reacted at 65 °C for 24 h. After the reaction was completed, the mixture was allowed to stand and separated. The lower layer (containing amino-terminated perfluoropolyether-b-polysiloxane) was collected for later use.

[0167] 20.1 g of divinyl-terminated polyamide 126 was dissolved in 55 g of N,N-dimethylformamide at 130 °C, and then the lower layer of the above solution was added and reacted at 130 °C for 48 h. After the reaction was completed, the solvent was removed to obtain the polyamide elastomer product.

[0168] An exemplary structure of the polyamide elastomer product is as follows:

[0169] The molecular weight and mechanical properties of polyamide elastomers are shown in Table 1.

[0170] Comparative Example 1

[0171] Compared to Example 1, the soft segment in this comparative example is conventional polytetrahydrofuran diol.

[0172] First, 25.7g of undecanoic acid, 22.8g of dodecanoic acid diamine, 2.13g of deionized water, and 0.26g of antioxidant 1010 were added to a reactor. The reactor was purged with argon gas to replace the air, and then the temperature was raised. The reaction was carried out at 160℃ for 3 hours, then at 250℃ and 2.5MPa for 2 hours, and finally under a vacuum of 50Pa for 1.5 hours. After the reaction, the material was cooled to 120℃ and discharged to obtain crude polyamide. The crude product was extracted with ethanol to remove oligomers and impurities, and then dried to obtain carboxyl-terminated polyamide 1211 (average molecular weight 3707g / mol) for later use.

[0173] 23.6 g of carboxyl-terminated polyamide 1211 was dissolved in 100 g of N,N-dimethylformamide at 120 °C, and then 14.9 g of amine-terminated polytetrahydrofuran with an average molecular weight of 6000 g / mol was added and the reaction was carried out at 130 °C for 6 h. After the reaction was completed, the solvent was removed to obtain the product.

[0174] The molecular weight and mechanical properties of polyamide elastomers are shown in Table 1.

[0175] Comparative Example 2

[0176] Compared to Example 2, the soft segment in this comparative example is conventional polyethylene glycol.

[0177] First, 21.3g of sebacic acid, 23.3g of hexamethylenediamine, 1.95g of deionized water, and 0.33g of antioxidant 1076 were added to a reactor. The reactor was purged with argon gas to replace the air, and then the temperature was raised. The reaction was carried out at 110℃ for 8 hours, then at 270℃ and 1.2MPa for 8 hours, and finally under a vacuum of 2000Pa for 3 hours. After the reaction, the material was cooled to 160℃ and discharged to obtain crude polyamide. The crude product was extracted with acetone to remove oligomers and impurities, and then dried to obtain amino-terminated polyamide 610 (average molecular weight 5709g / mol) for later use.

[0178] 2.3 g of terephthaloyl chloride was dissolved in 80 g of acetonitrile, and then 16.2 g of polyethylene glycol with an average molecular weight of 8000 g / mol was added. The mixture was reacted at 60 °C for 8 h. After the reaction was completed, polyethylene glycol with acyl chloride end-capped was obtained and set aside for later use.

[0179] 20.7 g of polyamide was dissolved in dimethyl sulfoxide at 180 °C, and then 12.1 g of polyethylene glycol with an average molecular weight of 8000 g / mol and terminally capped with acyl chloride was added, and the mixture was reacted at 160 °C for 24 h. After the reaction was completed, the solvent was removed to obtain the product.

[0180] The molecular weight and mechanical properties of polyamide elastomers are shown in Table 1.

[0181] Table 1

[0182] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A fluoroether-silicone modified polyamide elastomer, characterized in that, The elastomer has the general structural formula shown in formula (I). Polyamide segment-linking group-fluoroether silicone polymer segment formula (I), In formula (I), the polyamide segment is provided by polyamide, the fluoroether silicone polymer segment is provided by fluoroether silicone polymer, and the linking group is formed by the reaction of the end capping group A at the end of the polyamide with the reactive group B in the fluoroether silicone polymer; the end capping group A is selected from at least one of amino, carboxyl and alkenyl groups; the reactive group B is selected from at least one of carboxyl, hydroxyl, amino, silane-hydrogen bond, isocyanate group, acyl chloride group and cyanuric chloride group.

2. The elastomer according to claim 1, characterized in that, In the terminator A, the group containing the terminal alkenyl group is shown as shown in formula (A1) and / or as shown in formula (A2). In equation (A1), R 11 Selected from C1-C 20 Alkylene or C1-C 20 alkylene-phenylene, R 12 Selected from H, phenyl, C1-C 20 Alkyl or C2-C 20 Terminal alkenyl, R 13 Selected from H or C1-C 20 Alkyl group, n is 0 or 1, * indicates a linking site; In equation (A2), R 21 Selected from C1-C 20 Alkylene, R 22 Selected from H or C1-C 20 Alkyl group, m is 0 or 1, * indicates a linking site.

3. The elastomer according to claim 2, characterized in that, In equation (A1), R 11 Selected from C1-C 10 Alkylene or C1-C 10 alkylene-phenylene, R 12 Selected from H, phenyl, C1-C 10 Alkyl or C2-C 10 Terminal alkenyl, R 13 Selected from H or C1-C 10 Alkyl groups; and / or In equation (A2), R 21 Selected from C1-C 10 Alkylene, R 22 Selected from H or C1-C 10 alkyl.

4. The elastomer according to any one of claims 1-3, characterized in that, The reactive group B is located at both ends of the fluoroether silicone polymer and / or in the chain of the fluoroether silicone polymer.

5. The elastomer according to any one of claims 1-4, characterized in that, The reactive group B contains a silane-hydrogen bond; and / or The reactive group B contains a group obtained by reacting a silicon-hydrogen bond with at least one of an acid containing a carbon-carbon double bond, an amine containing a carbon-carbon double bond, an alcohol containing a carbon-carbon double bond, and cyanuric chloride; and / or The reactive group B contains a group obtained by reacting a silicon-hydrogen bond with an acid containing a carbon-carbon double bond, followed by an acyl chloride reaction.

6. The elastomer according to any one of claims 1-5, characterized in that, The reactive group B contains a group as shown in formula (B1): In equation (B1), R 31 Selected from H or C1-C 20 Alkyl, R 32 Selected from C1-C 20 Alkylene or C1-C 20 alkylene-phenylene-C1-C 10 Alkylene, where X is a carboxyl, amino, or acyl chloride group, and * indicates a linking site.

7. The elastomer according to any one of claims 1-5, characterized in that, The reactive group B contains a group as shown in formula (B2) and / or contains a group obtained by reacting a group as shown in formula (B2) with a diisocyanate. In equation (B2), R 41 Selected from H or C1-C 20 Alkyl, R 42 Selected from C1-C with or without substituents 20 alkylene hydroxyl, C1-C 20 Alkylene-C1-C 20 hydroxyalkylene ester group or C2-C containing ether bond 20 alkylene hydroxyl, wherein the substituent is selected from -R 43 -*、C1-C 20 Alkyl or C1-C 20 alkylene hydroxyl, R 43 Selected from C1-C 20 alkylene ester group -C2-C 20 Alkylene, * indicates a linking site.

8. The elastomer according to claim 7, characterized in that, The diisocyanate includes at least one of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and lysine diisocyanate.

9. The elastomer according to any one of claims 1-8, characterized in that, The reactive group B contains a group as shown in formula (B3). In equation (B3), * represents the connection site.

10. The elastomer according to any one of claims 1-9, characterized in that, The polyamide is selected from: C 2- C 20 Dicarboxylic acids and C2-C 20 Polymers or their derivatives obtained by diamine polycondensation, and / or polymers derived from C4-C4 polymers. 10 Polymers or their derivatives obtained by ring-opening polymerization of lactams; and / or The structure of the fluoroether silicone polymer is R f -bR, where R f R is a perfluoropolyether segment or a derivative segment, and R is a polysiloxane segment.

11. The elastomer according to claim 10, characterized in that, The perfluoropolyether segment is selected from at least one of K-type perfluoropolyether segments, D-type perfluoropolyether segments, Y-type perfluoropolyether segments, and Z-type perfluoropolyether segments; and / or The perfluoropolyether derivative segment is selected from at least one of perfluoropolyether vinyl ether segments, perfluoropolyether carboxylic acid segments, and perfluoropolyether methyl ester segments; and / or The R f The molar ratio of R to R is 1:20-10:

1.

12. The elastomer according to any one of claims 1-11, characterized in that, The polyamide has an average molecular weight of 400-20000 g / mol; and / or The average molecular weight of the fluoroether silicone polymer is 400-50000 g / mol; and / or The mass ratio of the polyamide segment to the fluoroether silicone polymer segment is 10-90:90-10; and / or The elastomer has an average molecular weight of 3000-60000 g / mol; and / or The tensile strength of the elastomer is 22-40 MPa; and / or The elongation at break of the elastomer is 450-650%.

13. A method for preparing a fluoroether-silicone modified polyamide elastomer, characterized in that, The preparation method includes: reacting polyamide with a fluoroether silicone polymer under solution polymerization conditions; wherein the end-capping group A of the polyamide is selected from at least one of amino, carboxyl, and alkenyl groups; the fluoroether silicone polymer contains a reactive group B, which is selected from at least one of carboxyl, hydroxyl, amino, silane-hydrogen bond, isocyanate, acyl chloride, and cyanuric chloride groups, and the end-capping group A reacts with the corresponding reactive group B to form a linking group.

14. The preparation method according to claim 13, characterized in that, In the terminator A, the group containing the terminal alkenyl group is shown as shown in formula (A1) and / or as shown in formula (A2). In equation (A1), R 11 Selected from C1-C 20 Alkylene or C1-C 20 alkylene-phenylene, R 12 Selected from H, phenyl, C1-C 20 Alkyl or C2-C 20 Terminal alkenyl, R 13 Selected from H or C1-C 20 Alkyl group, n is 0 or 1, * indicates a linking site; In equation (A2), R 21 Selected from C1-C 20 Alkylene, R 22 Selected from H or C1-C 20 Alkyl group, m is 0 or 1, * indicates a linking site.

15. The preparation method according to claim 13 or 14, characterized in that, The polyamide is selected from: By C 2- C 20 Dicarboxylic acids and C2-C 20 Polymers or their derivatives obtained by diamine polycondensation; and / or From C4-C 10 Polymers or their derivatives obtained by ring-opening polymerization of lactams; and / or The structure of the fluoroether silicone polymer is R f -bR, where R f R is a segment of perfluoropolyether or its derivative, and R is a segment of polysiloxane.

16. The preparation method according to any one of claims 13-15, characterized in that, The fluoroether silicone polymer is selected from biterminated perfluoropolyether-b-polysiloxane and / or perfluoropolyether-b-polysiloxane containing perfluoropolyether-b-polysiloxane in the chain; and / or The method for preparing the fluoroether silicone polymer includes: in the presence of a modifier and a catalyst, a modification reaction is carried out on a double-terminated silane-b-polysiloxane and / or a silane-b-polysiloxane containing silane in the chain; optionally, a third monomer modification reaction is carried out in the presence of a third monomer; wherein the modifier is selected from at least one of an acid containing a carbon-carbon double bond, an amine containing a carbon-carbon double bond, an alcohol containing a carbon-carbon double bond, and cyanuric chloride; and the third monomer is selected from diisocyanate and / or acyl chloride.

17. The preparation method according to claim 16, characterized in that, The modifier contains a compound as shown in formula (B11) and / or a compound as shown in formula (B12). In equation (B11), R 311 Selected from H or C1-C 20 Alkyl, R 321 Selected from C1-C 20 Mesenyl or C1-C 20 Phenylidene-phenylene-C1-C 10 Alkylene, where X1 is a carboxyl or amino group; In equation (B21), R 411 Selected from H or C1-C 20 Alkyl, R 421 Selected from C1-C with or without substituents 20 Phenyl alkyl hydroxyl, C1-C 20 Phenyl-C1-C 20 hydroxyalkylene ester group or C2-C containing ether bond 20 The substituent is selected from -R. 433 R 433 Selected from C1-C 20 alkylene ester group -C2~C 20 Terminal alkenyl group.

18. The preparation method according to claim 16 or 17, characterized in that, The diisocyanate comprises at least one selected from toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and lysine diisocyanate; and / or The acyl chloride includes at least one of dichloroacetyl chloride, carbamate chloride, oxaloyl chloride, terephthaloyl chloride, isophthaloyl chloride, adipicoyl chloride, chloroacetyl chloride, trichloroacetyl chloride, acryloyl chloride, and methacryloyl chloride.

19. The preparation method according to any one of claims 16-18, characterized in that, The double-ended perfluorosilane-b-polysiloxane and the perfluoroether segments in the perfluorosilane-b-polysiloxane chain are each independently selected from at least one of K-type perfluoroether segments, D-type perfluoroether segments, Y-type perfluoroether segments, Z-type perfluoroether segments, perfluoroether vinyl ether segments, perfluoroether carboxylic acid segments, and perfluoroether methyl ester segments; and / or The molar ratio of the perfluoropolyether segment to the polysiloxane segment in the double-ended perfluoropolyether-b-polysiloxane and the perfluoropolyether-b-polysiloxane containing perfluoropolyether-b-polysiloxane is 1:20-10:

1.

20. The preparation method according to any one of claims 16-19, characterized in that, The catalyst is selected from at least one of Speier catalyst, Karstedt catalyst, benzoyl peroxide, and di-tert-butyl peroxide; and / or The catalyst is present in a mass of 0.01 wt% to 10 wt% of terminal silane-perfluoropolyether-b-polysiloxane and / or silane-perfluoropolyether-b-polysiloxane contained in the chain; and / or The molar ratio of the double-ended perfluorosilane-b-polysiloxane and / or the perfluorosilane-b-polysiloxane in the chain to the modifier is 1:1.05-5; and / or The molar ratio of the double-ended perfluorosilane-b-polysiloxane and / or the perfluorosilane-b-polysiloxane in the chain to the third monomer is 1:1.05-5.

21. The preparation method according to any one of claims 16-20, characterized in that, The conditions for the modification reaction include: a reaction temperature of 25-200℃ and / or a reaction time of 0.5-72 h; and / or The conditions for the modification reaction of the third monomer include: a reaction temperature of 10-100℃ and / or a reaction time of 0.5-72h.

22. The preparation method according to any one of claims 16-21, characterized in that, The average molecular weight of the fluoroether silicone polymer is 400-50000 g / mol; and / or The polyamide has an average molecular weight of 400-20000 g / mol; and / or The mass ratio of the fluoroether silicone polymer to the polyamide is 10-90:90-10; and / or The conditions for solution polymerization include a reaction temperature of 50-300℃ and / or a reaction time of 0.5-48h.

23. The fluoroether-silicone modified polyamide elastomer prepared by the preparation method according to any one of claims 13-22.

24. The fluoroether-silicone modified polyamide elastomer according to claim 23, characterized in that, The elastomer has an average molecular weight of 3000-60000 g / mol; and / or The tensile strength of the elastomer is 22-40 MPa; and / or The elongation at break of the elastomer is 450-650%.

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