A polymeric elastomer and preparation method thereof

Abstract

The present invention relates to the technical field of polymer elastomers, and in particular to a polymer elastomer and a preparation method thereof. The mechanical properties of polymer elastomers produced by conventional methods are poor. In view of the above problems, the present invention provides a polymer elastomer, wherein a cross-linking agent is added during the polymerization reaction of polyethylene glycol and dicarboxylic acid. The cross-linking agent is an aminosiloxane containing two amino groups, which can participate in the polymerization reaction of polyethylene glycol and dicarboxylic acid. The amino groups in the cross-linking agent undergo amidation reaction with the carboxyl groups in the reaction system, thereby being introduced into the molecular structure of the elastomer in the form of chemical bonds. The aminopropyldimethylsilyl-terminated polydimethylsiloxane has better flexibility than other aminosiloxanes. The introduction of its molecular structure will further improve the overall flexibility and mechanical strength of the polymer elastomer, so that the polymer elastomer has better tolerance under high strain conditions.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer elastomers, and in particular to a polymer elastomer and a preparation method thereof. Background Art

[0002] Polymeric elastomers synthesized with polyethylene glycol (PEG) as raw material have good biocompatibility and low toxicity and immunogenicity, and are suitable for biomedical fields such as drug delivery and tissue engineering.

[0003] Polymer elastomers obtained simply by reacting dicarboxylic acids with diols exhibit low tensile strength, tear strength and wear resistance, which limits their use in certain high-demand applications. Summary of the Invention

[0004] The problem in the prior art is that the mechanical properties of polymeric elastomers produced by conventional methods are poor. To address the above problem, the present invention provides a polymeric elastomer, the preparation method of which comprises the following steps:

[0005] Under nitrogen protection, dicarboxylic acid, polyethylene glycol, crosslinking agent, and catalyst are mixed and stirred uniformly, the temperature of the reaction system is raised to 160-180°C, and the reaction is stirred for 2 hours under normal pressure, and then stirred for 3 hours under negative pressure. During the reaction, the hydroxyl groups in the reaction system react with the carboxyl groups to form ester bonds, and the carboxyl groups react with the amino groups to form amide bonds. After the reaction is completed, a polymerized elastomer is obtained;

[0006] The crosslinking agent is aminosiloxane containing two amino groups.

[0007] Preferably, the catalyst is a mixture of stannous oxalate and a super strong solid acid.

[0008] Preferably, the mass ratio of stannous oxalate to super solid acid is 1:2.

[0009] Preferably, the super strong solid acid is aluminum silicate or lithium fluorozirconate.

[0010] Preferably, the catalyst is a mixture of stannous oxalate and an activated carbon-supported catalyst.

[0011] Preferably, the mass ratio of stannous oxalate to the activated carbon-supported catalyst is 1:1.

[0012] Preferably, the activated carbon-supported catalyst is palladium-supported activated carbon.

[0013] Preferably, the dicarboxylic acid includes one or a combination of two or more of 1,4-cyclohexanedicarboxylic acid, 1,1′-di(cyclohexyl)-4,4′-dicarboxylic acid, and decahydronaphthalene-2,6-dicarboxylic acid.

[0014] Preferably, the polyethylene glycol is PEG4000 or PEG6000.

[0015] Preferably, the aminosiloxane includes at least one of 1,3-bis(4-aminobutyl)tetramethyldisiloxane or aminopropyldimethylsilyl-terminated polydimethylsiloxane (CAS: 97917-34-5).

[0016] The present invention has the following beneficial effects:

[0017] (1) The present invention adds a cross-linking agent during the polymerization reaction between polyethylene glycol and dicarboxylic acid. The cross-linking agent is an aminosiloxane containing two amino groups, which can participate in the polymerization reaction between polyethylene glycol and dicarboxylic acid. The amino groups in the cross-linking agent undergo an amidation reaction with the carboxyl groups in the reaction system, thereby being introduced into the molecular structure of the elastomer in the form of a chemical bond. The aminopropyldimethylsilyl-terminated polydimethylsiloxane has better flexibility than other aminosiloxanes. The introduction of its molecular structure will further improve the overall flexibility and mechanical strength of the polymerized elastomer, so that the polymerized elastomer has better tolerance under high strain conditions;

[0018] (2) In the molecular structure of the polymeric elastomer obtained by the present invention, abundant Si-O-Si chemical bonds are introduced through the crosslinking agent. The presence of Si-O-Si chemical bonds can also significantly improve the wear resistance of the obtained polymeric elastomer. DETAILED DESCRIPTION

[0019] The present invention will be described in detail below with reference to the following examples. However, it should be understood that the following examples are merely illustrative of the embodiments of the present invention and are not intended to limit the scope of the present invention.

[0020] Example 1

[0021] A polymeric elastomer, prepared as follows:

[0022] Under nitrogen protection, 1,4-cyclohexanedicarboxylic acid, 1,1'-di(cyclohexyl)-4,4'-dicarboxylic acid, PEG-4000, a crosslinker, and a catalyst were mixed and stirred uniformly. The temperature of the reaction system was raised to 160°C, and the mixture was stirred and reacted at normal pressure for 2 hours, and then stirred and reacted at -0.07 MPa for 3 hours. After the reaction was completed, a polymerized elastomer was obtained.

[0023] The molar ratio of PEG-4000 to 1,4-cyclohexanedicarboxylic acid, 1,1'-di(cyclohexyl)]-4,4'-dicarboxylic acid, and cross-linking agent is 1:0.8:0.2:0.1;

[0024] The crosslinking agent is aminopropyldimethylsilyl-terminated polydimethylsiloxane (CAS: 97917-34-5);

[0025] The catalyst is a mixture of stannous oxalate and aluminum silicate in a mass ratio of 0.5:2;

[0026] Example 2

[0027] A polymeric elastomer, prepared as follows:

[0028] Under nitrogen protection, 1,4-cyclohexanedicarboxylic acid, 1,1'-di(cyclohexyl)-4,4'-dicarboxylic acid, PEG-4000, a crosslinker, and a catalyst were mixed and stirred uniformly. The temperature of the reaction system was raised to 170°C, and the mixture was stirred and reacted at normal pressure for 2 hours, and then stirred and reacted at -0.09 MPa for 3 hours. After the reaction was completed, a polymerized elastomer was obtained.

[0029] The molar ratio of PEG-4000 to 1,4-cyclohexanedicarboxylic acid, 1,1'-di(cyclohexyl)]-4,4'-dicarboxylic acid, and cross-linking agent is 1:0.9:0.2:0.1;

[0030] The crosslinking agent is aminopropyldimethylsilyl-terminated polydimethylsiloxane (CAS: 97917-34-5);

[0031] The catalyst is a mixture of stannous oxalate and aluminum silicate in a mass ratio of 1:1;

[0032] Example 3

[0033] A polymeric elastomer, prepared as follows:

[0034] Under nitrogen protection, 1,4-cyclohexanedicarboxylic acid, 1,1'-di(cyclohexyl)-4,4'-dicarboxylic acid, PEG-4000, a crosslinker, and a catalyst were mixed and stirred uniformly. The temperature of the reaction system was raised to 180°C, and the mixture was stirred and reacted at normal pressure for 2 hours, and then stirred and reacted at -0.09 MPa for 3 hours. After the reaction was completed, a polymerized elastomer was obtained.

[0035] The molar ratio of PEG-4000 to 1,4-cyclohexanedicarboxylic acid, 1,1'-di(cyclohexyl)]-4,4'-dicarboxylic acid, and cross-linking agent is 1:0.7:0.3:0.1;

[0036] The cross-linking agent is aminopolydimethylsiloxane;

[0037] The catalyst is a mixture of stannous oxalate and aluminum silicate in a mass ratio of 2:1;

[0038] Example 4

[0039] A polymeric elastomer, prepared as follows:

[0040] Under nitrogen protection, 1,4-cyclohexanedicarboxylic acid, decahydronaphthalene-2,6-dicarboxylic acid, PEG-4000, a crosslinking agent, and a catalyst were mixed and stirred uniformly. The temperature of the reaction system was raised to 170°C, and the mixture was stirred and reacted at normal pressure for 2 hours, and then stirred and reacted at -0.08 MPa for 3 hours. After the reaction was completed, a polymerized elastomer was obtained.

[0041] The molar ratio of PEG-4000 to 1,4-cyclohexanedicarboxylic acid, decahydronaphthalene-2,6-dicarboxylic acid, and cross-linking agent is 1:0.8:0.3:0.1;

[0042] The crosslinking agent is aminopropyldimethylsilyl-terminated polydimethylsiloxane (CAS: 97917-34-5);

[0043] The catalyst is a mixture of stannous oxalate and aluminum silicate in a mass ratio of 1:2;

[0044] Example 5

[0045] A polymeric elastomer, prepared as follows:

[0046] Under nitrogen protection, 1,4-cyclohexanedicarboxylic acid, decahydronaphthalene-2,6-dicarboxylic acid, PEG-6000, a crosslinking agent, and a catalyst were mixed and stirred uniformly. The temperature of the reaction system was raised to 170°C, and the mixture was stirred and reacted at normal pressure for 2 hours, and then stirred and reacted at -0.08 MPa for 3 hours. After the reaction was completed, a polymerized elastomer was obtained.

[0047] The molar ratio of PEG-4000 to 1,4-cyclohexanedicarboxylic acid, decahydronaphthalene-2,6-dicarboxylic acid, and cross-linking agent is 1:0.9:0.3:0.1;

[0048] The crosslinking agent is aminopropyldimethylsilyl-terminated polydimethylsiloxane (CAS: 97917-34-5);

[0049] The catalyst is a mixture of stannous oxalate and aluminum silicate in a mass ratio of 1:2;

[0050] Comparative Example 1 is the same as Example 1, except that the crosslinking agent in Comparative Example 1 is 1,3-bis(4-aminobutyl)tetramethyldisiloxane.

[0051] Comparative Example 2 is the same as Example 5, except that the crosslinking agent in Comparative Example 2 is 1,3-bis(4-aminobutyl)tetramethyldisiloxane.

[0052] Comparative Example 3 is the same as Example 1, except that Comparative Example 3 does not contain 1,1'-di(cyclohexyl)-4,4'-dicarboxylic acid, and the molar ratio of PEG-4000 to 1,4-cyclohexanedicarboxylic acid and the crosslinking agent is 1:1:0.1.

[0053] Comparative Example 4 is the same as Example 5, except that decahydronaphthalene-2,6-dicarboxylic acid is not contained in Comparative Example 4, and the molar ratio of PEG-4000 to 1,4-cyclohexanedicarboxylic acid and the cross-linking agent is 1:1.2:0.1.

[0054] Comparative Example 5 is the same as Example 1, except that the PEG-4000 in Example 1 is replaced by PEG-2000 in an equal molar amount.

[0055] Comparative Example 6 is the same as Example 5, except that the PEG-4000 in Example 5 is replaced by PEG-2000 in an equal molar amount.

[0056] Performance Testing

[0057] The polymerized elastomers obtained in Examples 1-5 of the present invention and Comparative Examples 1-6 were respectively subjected to relevant performance tests, and the specific test results are shown in Table 1.

[0058] Tensile strength: According to GB / T 1040-2006, the test was carried out using an INSTRON-1185 universal tensile testing machine. The test samples were made into standard dumbbell-shaped specimens and the tensile speed was 20 mm / min.

[0059] Elongation at break: measured in accordance with GB / T 1040-2006 using an INSTRON-1185 universal tensile testing machine. The test samples were made into standard dumbbell-shaped specimens at a tensile speed of 20 mm / min.

[0060] Recovery rate: According to GB / T 1040-2006, the recovery rate was measured using an INSTRON-1185 universal tensile testing machine. The test samples were made into standard dumbbell-shaped specimens.

[0061] Table 1

[0062] Test items Tensile strength (MPa) Elongation at break (%) Recovery rate (%) Example 1 27.3 965.34 86.43 Example 2 25.45 987.21 86.29 Example 3 38.35 996.64 87.63 Example 4 29.38 841.42 81.23 Example 5 30.23 832.35 80.98 Comparative Example 1 25.34 921.33 79.61 Comparative Example 2 23.12 813.15 73.23 Comparative Example 3 22.44 820.24 71.33 Comparative Example 4 27.65 854.33 82.34 Comparative Example 5 22.11 993.45 88.64 Comparative Example 6 23.61 873.41 83.22

[0063] With the above-described preferred embodiments of the present invention as a guide, and with reference to the above description, relevant personnel are fully capable of making various changes and modifications without departing from the technical scope of this invention. The technical scope of this invention is not limited to the contents of the specification and must be determined according to the scope of the claims.

Claims

1. A polymeric elastomer, characterized in that The preparation method comprises the following steps: Under nitrogen protection, dicarboxylic acid, polyethylene glycol, crosslinking agent, and catalyst are mixed and stirred uniformly, the temperature of the reaction system is raised to 160-180°C, and the reaction is stirred for 2 hours under normal pressure, and then stirred for 3 hours under negative pressure. During the reaction, the hydroxyl groups in the reaction system react with the carboxyl groups to form ester bonds, and the carboxyl groups react with the amino groups to form amide bonds. After the reaction is completed, a polymerized elastomer is obtained; The dicarboxylic acid is a composition formed by 1,4-cyclohexanedicarboxylic acid and 1,1'-di(cyclohexyl)-4,4'-dicarboxylic acid or a composition formed by 1,4-cyclohexanedicarboxylic acid and decahydronaphthalene-2,6-dicarboxylic acid; The polyethylene glycol is PEG4000; The cross-linking agent is aminopropyldimethylsilyl-terminated polydimethylsiloxane; The catalyst is a mixture of stannous oxalate and aluminum silicate.