A polymer alloy and a method for preparing the same

Abstract

The application discloses a kind of polymer alloy materials, which is generated by radical polymerization and epoxy ring-opening polymerization reaction from polar polymer monomer containing carbon-carbon double bond, epoxy resin and epoxy curing agent.The specific preparation method is that polar polymer monomer containing carbon-carbon double bond is mixed with free radical initiator, under nitrogen protection, and stirred under reflux at 70-90 DEG C for 15-20 min, then rapidly cooled to 45-65 DEG C;Epoxy resin, curing agent and antioxidant are added, and the temperature is stirred to reaction system is completely gelled;After heat preservation, heat to 100-120 DEG C, continue heat preservation, and the polymer alloy material can be obtained.The application uses step polymerization process, and the polymer alloy material with excellent performance is generated by radical polymerization and epoxy ring-opening polymerization reaction, which has partial crosslinking structure, can reduce the activity of polar polymer segment, and the glass transition temperature is obviously higher than that of polar polymer monomer containing carbon-carbon double bond.

Description

Technical Field

[0001] This invention relates to the field of composite materials, and more specifically, to a polymer alloy and its preparation method. Background Technology

[0002] Polymer alloys, also known as polymer blends, are a class of seemingly homogeneous, multi-component polymer materials containing two or more different structures. In recent years, many polymer blends that are mutually compatible or partially mutually compatible under certain conditions have been discovered. These include blends composed of two different amorphous polymers, blends composed of amorphous and crystalline polymers, isomorphic polymer blends, and blends composed of two polymers that can form complexes, etc.

[0003] With the continuous advancement of technology and manufacturing processes, thermosetting-thermoplastic composites have been extensively studied. These materials can complement each other's advantages and disadvantages, and their formulations and synthesis processes can be adjusted flexibly according to molding requirements.

[0004] Epoxy resin is the most widely used thermosetting material and a key material for research on thermosetting-thermoplastic composites. Patent CN201280006307 describes a thermosetting epoxy resin composite material. This material is a thermosetting-thermoplastic composite that retains the transparency of epoxy resin while improving its crack resistance, making it a high-performance sealing material. However, this composite material is limited by thermosetting molding processes, making it impossible to produce dimensionally stable and highly precise products. Summary of the Invention

[0005] To address the above problems, the present invention provides a thermoplastic polymer alloy containing an epoxy resin component.

[0006] The technical solution of the present invention is as follows:

[0007] A polymer alloy material is generated by free radical polymerization and epoxy ring-opening polymerization of a polar polymer monomer containing carbon-carbon double bonds, an epoxy resin, and an epoxy curing agent.

[0008] In a further embodiment, the polymer alloy material is prepared from the following components in parts by weight:

[0009]

[0010] In a further embodiment, the polar polymer monomer containing carbon-carbon double bonds includes, but is not limited to, the following substances: (meth)acrylic acid, butenoic acid, isobutenoic acid, and other fatty acid vinyl monomers; or (meth)acrylates of straight-chain alkyl alcohols such as (meth)acrylate, (meth)acrylate, (meth)acrylate n-butyl acrylate, (meth)acrylate isobutyl acrylate, (meth)acrylate tert-butyl acrylate, (meth)acrylate hexyl acrylate, (meth)acrylate-2-ethylhexyl acrylate, (meth)acrylate octyl acrylate; or monomers containing sulfonic acid groups such as allyl sulfonic acid; or (meth)acrylates containing carbonyl groups such as acetoacetic acid ethyl meth)acrylate; or at least one of the following vinyl monomers containing cycloalkyl groups such as cyclohexyl acrylate, cyclohexyl methacrylate, dicyclopentyl acrylate, dicyclopentyl methacrylate, tricyclodecyl acrylate, tricyclodecyl methacrylate, isobornyl acrylate, and adamantane acrylate.

[0011] These monomers can be used alone or in combination. Among the monomers mentioned above, methyl methacrylate is preferred as the polymerization monomer.

[0012] In a further embodiment, the epoxy resin includes, but is not limited to, the following substances: bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, alicyclic epoxy resin, triglycidyl isocyanate, aliphatic epoxy resin, etc. These resins can be used individually or in combination. From the perspective of operability and reducing side reactions, bisphenol A type epoxy resin and aliphatic epoxy resin are preferred.

[0013] In a further embodiment, the epoxy curing agent includes, but is not limited to, the following substances: various hydrogenated phthalic anhydrides such as hexahydrophthalic anhydride, tetrahydrophthalic anhydride, and methylhexahydrophthalic anhydride; various aliphatic and alicyclic anhydrides such as acetic anhydride, hexanoic anhydride, succinic anhydride, and cyclohexanecarboxylic acid; and aromatic amines such as aniline and m-phenylenediamine. Hydrogenated phthalic anhydride curing agents are preferred in this invention.

[0014] In a further embodiment, antioxidants are obtained by compounding the following types of substances: hindered phenolic antioxidants (such as 1010, 1076, 1098, 1024), phosphite antioxidants (such as V76-P, 168), and thioester antioxidants (such as DSTDP, DLTDP).

[0015] From the perspective of resin type and production process, the preferred antioxidants are: a compound system of four antioxidants, namely 1076, V76-P, 168, and DSTDP, mixed in a mass ratio of 1:1:1:1.

[0016] Further options, as free radical initiators, include, but are not limited to, the following substances: organic peroxide initiators (benzoyl peroxide, lauroyl peroxide, tert-butyl peroxypentanoate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, tert-butyl hydroperoxide, cumene hydroperoxide, acetylcyclohexanesulfonyl peroxide), azo initiators (azobisisobutyronitrile, azobisisoheptanenitrile, dimethyl azobisisobutyrate, azobisisobutyramidine hydrochloride, azobisisobutyramidine hydrochloride, azobisisobutyramidine cyanoformamide), and inorganic peroxide initiators (potassium persulfate, ammonium persulfate).

[0017] From a production process perspective, azobisisobutyronitrile (AIBN) is the preferred initiator for the aforementioned free radical initiators.

[0018] The second objective of this invention is to provide a method for preparing a polymer alloy material, the method of which is as follows:

[0019] (1) After mixing the polar polymer monomer containing carbon-carbon double bonds with the free radical initiator, under nitrogen protection, stir and reflux at 70-90℃ for 15-20 min, and then quickly cool down to 45-65℃.

[0020] (2) Add epoxy resin, curing agent and antioxidant, and stir the reaction while maintaining the temperature until the reaction system is completely gelled;

[0021] (3) After heat preservation, the temperature is raised to 100-120℃ and heat preservation is continued to obtain polymer alloy material.

[0022] The heat preservation process involves transferring the reactants to an oven at 45-65℃ and keeping them at that temperature for 7-10 hours, then raising the temperature to 100-120℃ and keeping them at that temperature for another 2-6 hours.

[0023] Compared with the prior art, the present invention has the following advantages:

[0024] This invention is based on the characteristics of epoxy ring-opening polymerization and free polymerization of polar free radical monomers. By adopting a stepwise polymerization process and optimizing the epoxy resin curing system, the bulk polymerization catalytic system of polar free radical monomers, and the reaction conditions, a thermoplastic polymer alloy material with excellent performance is prepared.

[0025] The polymer alloy material prepared by this invention has a partially cross-linked structure, which can reduce the chain segment mobility of polar polymers and has a more significant increase in glass transition temperature compared to polar polymer monomers containing carbon-carbon double bonds.

[0026] The polymer alloy material prepared by this invention can be used to manufacture injection molded or molded parts with high dimensional accuracy requirements, and its application prospects are very broad. Detailed Implementation

[0027] The invention is further described below with reference to specific implementation examples (but not limited to the examples given):

[0028] The polar polymer monomers containing carbon-carbon double bonds in the following examples were purchased from Aladdin Biochemical Technology, and were dehydrated and redistilled before use;

[0029] Both the epoxy resin and epoxy curing agent are commercially available products, purchased from Shanghai Huayi Resin, and used directly.

[0030] The free radical initiator described in this invention is a commercially available product from Aladdin Biochemical Technology, which is recrystallized from anhydrous ethanol and thoroughly dried before use.

[0031] In the following examples, the antioxidants are a mixture of 1076, V76-P, 168 and DSTDP in a mass ratio of 1:1:1:1; where 1076, V76-P, 168 and DSTDP are all commonly used commercial products that can be used directly.

[0032] Example 1

[0033] 30 parts of 2-ethylhexyl acrylate and 0.2 parts of potassium persulfate free radical initiator were mixed, stirred and refluxed at 70°C for 15 min under nitrogen protection, and then rapidly cooled to 45°C.

[0034] Add 35 parts of bisphenol F epoxy resin, 35 parts of epoxy curing agent hexahydrophthalic anhydride and 0.5 parts of antioxidant, and stir the reaction at 45°C until the system is completely gelled;

[0035] Then, transfer it to a 45°C oven and keep it at that temperature for 7 hours. After that, raise the temperature to 100°C and keep it at that temperature for another 2 hours to obtain the polymer alloy material.

[0036] Example 2

[0037] 40 parts of n-butyl acrylate and 0.3 parts of free radical initiator benzoyl peroxide were mixed, and the mixture was stirred and refluxed at 75°C for 15 min under nitrogen protection, and then rapidly cooled to 50°C.

[0038] Add 30 parts of triglycidyl isocyanurate, 30 parts of epoxy curing agent aniline, and 0.8 parts of antioxidant, and stir the reaction at 45°C until the system is completely gelled;

[0039] Then, transfer it to a 45℃ oven and keep it at that temperature for 8 hours, then raise the temperature to 105℃ and keep it at that temperature for another 3 hours to obtain the polymer alloy material.

[0040] Example 3

[0041] 50 parts of methyl methacrylate were mixed with 0.4 parts of free radical initiator azobisisobutyronitrile, and stirred and refluxed at 80°C for 18 min under nitrogen protection, and then rapidly cooled to 55°C.

[0042] Add 25 parts of bisphenol A type epoxy resin, 25 parts of epoxy curing agent tetrahydrophthalic anhydride and 1 part of antioxidant, and stir the reaction at 55°C until the system is completely gelled.

[0043] Then, after transferring it to a 55℃ oven and keeping it at that temperature for 9 hours, the temperature is raised to 110℃ and kept at that temperature for another 4 hours to obtain the polymer alloy material.

[0044] Example 4

[0045] 70 parts of dicyclopentyl acrylate and 0.5 parts of dimethyl azobisisobutyrate, a free radical initiator, were mixed and stirred under nitrogen protection at 90°C for 20 minutes, and then rapidly cooled to 65°C.

[0046] Add 15 parts aliphatic epoxy resin, 15 parts epoxy curing agent acetic anhydride and 0.5 parts antioxidant, and stir at 65°C until the system is completely gelled;

[0047] Then, transfer it to a 65℃ oven and keep it at that temperature for 10 hours, then raise the temperature to 120℃ and keep it at that temperature for another 6 hours to obtain the polymer alloy material.

[0048] Example 5

[0049] 80 parts of dicyclopentyl acrylate and 0.8 parts of free radical initiator azobisisobutyronitrile were mixed, and the mixture was stirred and refluxed at 80°C for 15 min under nitrogen protection, and then rapidly cooled to 65°C.

[0050] Add 10 parts aliphatic epoxy resin, 10 parts epoxy curing agent hexahydrophthalic anhydride and 0.5 parts antioxidant, and stir at 65°C until the system is completely gelled;

[0051] Then, transfer it to a 50℃ oven and keep it at that temperature for 9 hours, then raise the temperature to 120℃ and keep it at that temperature for another 3 hours to obtain the polymer alloy material.

[0052] Comparative Example 1

[0053] Mix 100 parts of methyl methacrylate with 0.4 parts of free radical initiator azobisisobutyronitrile (AIBN). Under nitrogen protection, stir and reflux at 80°C for 18 min. Then, rapidly cool to 55°C and maintain the temperature at 55°C while stirring until the system is completely gelled. Transfer the mixture to a 55°C oven and keep it at that temperature for 9 h. Then, raise the temperature to 110°C and keep it at that temperature for another 4 h to obtain the polymer alloy material.

[0054] Comparative Example 2

[0055] After mixing 50 parts of methyl methacrylate with 0.4 parts of free radical initiator azobisisobutyronitrile, the mixture was stirred and refluxed at 80°C for 18 minutes under nitrogen protection, and then rapidly cooled to 55°C.

[0056] By adding 25 parts of bisphenol A type epoxy resin, 25 parts of curing agent tetrahydrophthalic anhydride and 1 part of antioxidant, and heating to 110℃ and holding for 4 hours, a polymer alloy material can be obtained.

[0057] Comparative Example 3

[0058] After thoroughly mixing 50 parts of bisphenol A epoxy resin, 50 parts of curing agent tetrahydrophthalic anhydride, and 1 part of antioxidant, the mixture was cured at 110°C for 12 hours to obtain a polymer alloy material.

[0059] Before insulation, the various materials of the examples and comparative examples are poured into the mold of the standard specimens and then insulated to obtain the corresponding standard specimens. The specimens are then subjected to standardized tests, and the performance data of the examples and comparative examples are shown in Table 1.

[0060] Table 1

[0061]

[0062]

[0063] Note 1. Tensile test conditions: A1 type spline, tensile speed: 50mm / min;

[0064] 2. Cantilever beam notched impact strength test conditions: machined V-notch, temperature: 23℃;

[0065] 3. Glass transition temperature test: Heating rate: 20℃ / min.

[0066] As can be seen from the test data of Example 3 and Comparative Examples 1-3, the polymer alloy material prepared by this invention effectively compensates for the deficiencies of epoxy resin in terms of toughness and ductility without affecting the rigidity of the material, and the tensile strength and cantilever beam notched impact strength are significantly improved. In addition, the glass transition temperature of the polymer alloy material prepared by this invention is significantly improved, thereby increasing the upper limit of the material's service temperature.

[0067] The above description of the embodiments is provided to enable those skilled in the art to understand and apply the present invention. It will be apparent to those skilled in the art that various modifications can be easily made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, the present invention is not limited to the embodiments described herein, and any improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the invention should be within the protection scope of the present invention.

Claims

1. A polymer alloy material, characterized in that: It is produced by free radical polymerization and epoxy ring-opening polymerization of polar polymer monomers containing carbon-carbon double bonds, epoxy resin and epoxy curing agent.

2. The polymer alloy material according to claim 1, characterized in that: It is prepared from the following components in parts by weight: 30-80 parts of polar polymer monomers containing carbon-carbon double bonds 10-35 parts epoxy resin 10-35 parts of epoxy curing agent 0.2-0.8 parts of free radical initiator Antioxidant 0.5-1 part.

3. A polymer alloy material according to claim 1 or 2, characterized in that: The polar polymer monomers containing carbon-carbon double bonds include at least one of acrylic acid, methacrylic acid, butyl acrylate, isobutyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, hexyl acrylate, hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, octyl acrylate, octyl methacrylate, allyl sulfonic acid, ethyl acetoacetate, ethyl acetoacetate, cyclohexyl acrylate, cyclohexyl methacrylate, dicyclopentyl acrylate, dicyclopentyl methacrylate, tricyclodecyl acrylate, tricyclodecyl methacrylate, isobornyl acrylate, isobornyl methacrylate, adamantane acrylate, and adamantane methacrylate.

4. A polymer alloy material according to claim 1 or 2, characterized in that: The epoxy resin includes at least one of bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, alicyclic epoxy resin, triglycidyl isocyanate, and aliphatic epoxy resin.

5. The polymer alloy material according to claim 4, characterized in that: The epoxy resin is a mixture of bisphenol A type epoxy resin and aliphatic epoxy resin.

6. A polymer alloy material according to claim 1 or 2, characterized in that: The epoxy curing agent includes at least one of hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, acetic anhydride, hexanoic anhydride, succinic anhydride, cyclohexanecarboxylic acid, aniline, and m-phenylenediamine.

7. The polymer alloy material according to claim 2, characterized in that: The antioxidants include hindered phenolic antioxidants, phosphite antioxidants, and thioester antioxidants; The free radical initiator includes at least one of organic peroxide initiators, azo initiators, and inorganic peroxide initiators.

8. The polymer alloy material according to claim 7, characterized in that: The antioxidant is a mixture of 1076, V76-P, 168 and DSTDP in a mass ratio of 1:1:1:1; The organic peroxide initiators include benzoyl peroxide, lauroyl peroxide, tert-butyl peroxypentanoate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, tert-butyl hydroperoxide, cumene hydroperoxide, or acetylcyclohexanesulfonyl peroxide. The azo initiators include azobisisobutyronitrile, azobisisoheptanenitrile, dimethyl azobisisobutyrate, azobisisobutyramidoline hydrochloride, azobisisobutyramidine hydrochloride, or azobisisobutyronitrile cyanoformamide; The inorganic peroxide initiator includes potassium persulfate or ammonium persulfate.

9. A method for preparing a polymer alloy material as described in claim 2, characterized in that: Includes the following steps: (1) Mix the polar polymer monomer containing carbon-carbon double bonds with a free radical initiator, stir and reflux at 70-90℃ for 15-20 min under nitrogen protection, and then quickly cool down to 45-65℃. (2) Add epoxy resin, curing agent and antioxidant, and stir the reaction while maintaining the temperature until the reaction system is completely gelled; (3) After heat preservation, the temperature is raised to 100-120℃ and heat preservation is continued to obtain polymer alloy material.

10. The preparation method according to claim 9, characterized in that: In step (3), heat preservation refers to transferring the reactants to an oven at 45-65℃ and keeping them warm for 7-10 hours, then raising the temperature to 100-120℃ and keeping them warm for another 2-6 hours.

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