Functional thermosetting resin and preparation method thereof

Abstract

The present invention belongs to the field of C08F technology, and more specifically relates to a functional thermosetting resin and a preparation method thereof. A functional thermosetting resin, the raw materials for its preparation include: a polymer containing two or more epoxy groups in its molecule, an alkyl compound containing hydroxyl groups and / or phenyl groups, a compound containing carboxyl groups and carbon-carbon double bonds, and an additive. The functional thermosetting resin prepared by the present invention can ensure that the prepared vinyl resin improves its adhesion to the material when used on the surface of a cement material through the interaction between the diluent and the polymer containing two or more epoxy groups in its molecule. Performance test results show that when used on the surface of a cement substrate, the shear strength is as high as 31MPa or more, further improving its bonding performance with the cement substrate.

Description

Technical Field

[0001] The present invention belongs to the field of C08F technology, and more specifically relates to a functional thermosetting resin and a preparation method thereof. Background Art

[0002] With the advancement and development of technology, some materials with light weight, high strength, large modulus, good corrosion resistance and excellent electrical properties have appeared on the market at this stage. These materials include thermosetting resin-based composite materials.

[0003] Thermosetting resin-based composite materials include materials prepared from vinyl resins, which are mostly made by reacting epoxy resins and unsaturated acids. The Chinese invention patent with application number 202110216776.7 discloses a vinyl resin and its preparation method, and a thickened vinyl resin composition. The disclosed patent discloses that a vinyl resin containing an epoxy group is reacted with an epoxy resin or a double A-type epoxy resin and a dibasic acid in the presence of a unit acid containing a carbon-carbon double bond to prepare a carboxyl-terminated polyepoxy polymer. However, in the disclosed patent, since the type of epoxy resin added is basic epoxy 828, the viscosity of the vinyl resin prepared under this condition, the adhesion of the system, and the shear strength effect cannot be controlled.

[0004] In order to further ensure that the prepared resin has excellent mechanical properties and high shear strength and adhesion, optimizing and improving the preparation raw materials, preparation methods, reaction temperature and reaction time is an important challenge facing researchers at this stage. Summary of the Invention

[0005] In order to solve the above technical problems, the first aspect of the present invention provides a functional thermosetting resin, the preparation raw materials of which include: a polymer containing two or more epoxy groups in the molecule, an alkyl compound containing hydroxyl and / or phenyl groups, a compound containing carboxyl groups and carbon-carbon double bonds, and an auxiliary agent.

[0006] In some preferred embodiments, the polymer containing two or more epoxy groups in the molecule includes a solid polymer and / or a liquid polymer.

[0007] More preferably, the polymer containing two or more epoxy groups in the molecule includes solid polymers and liquid polymers.

[0008] In some preferred embodiments, the epoxy value of the liquid polymer is 0.4-0.6 Eq / 100 g; preferably, the epoxy value of the liquid polymer is 0.41-0.47 Eq / 100 g.

[0009] In some preferred embodiments, the epoxy equivalent of the solid polymer is 450-750 g / Eq.

[0010] Further preferably, the solid polymer includes 901 epoxy resin and / or 902 epoxy resin.

[0011] During the experiment, the applicant discovered that in the process of preparing functional thermosetting resins in this system, the different epoxy values of the polymers containing two or more epoxy groups in the selected molecules have a great influence on the performance of the prepared resin. In particular, when the added resin is a liquid polymer with an epoxy value of 0.4-0.6Eq / 100g and a solid polymer with an epoxy equivalent of 450-750g / Eq, it can ensure further reactivity between the epoxy groups in the system and the carboxyl-containing substances, ensure the presence of reactive groups in the molecular chain segments, and enhance the wetting performance of the resin on the surfaces of other substrates.

[0012] Further preferably, the solid polymer includes 901 epoxy resin or 902 epoxy resin.

[0013] In some preferred embodiments, the compound containing a carboxyl group and a carbon-carbon double bond includes at least one of acrylic acid, methacrylic acid, butenoic acid, pentenoic acid, 5-octenoic acid, and 7-octenoic acid.

[0014] More preferably, the compound containing a carboxyl group and a carbon-carbon double bond includes methacrylic acid.

[0015] In some preferred embodiments, the auxiliary agent includes at least one of a diluent, a stabilizer, an antioxidant, an inhibitor, a catalyst, and an ultraviolet absorber.

[0016] More preferably, the auxiliary agent includes a diluent, an inhibitor, and a catalyst.

[0017] In some preferred embodiments, the catalyst is selected from at least one of lithium chloride, tin chloride, N,N-dimethylbenzylamine, tri-n-butylamine, ammonium chloride, and ammonium bromide.

[0018] In some preferred embodiments, the polymerization inhibitor is selected from at least one of hydroquinone, methylhydroquinone, and p-tert-butylcatechol.

[0019] In some preferred embodiments, the weight ratio of the diluent to the polymer containing two or more epoxy groups in the molecule is 1:(0.8-1.8).

[0020] Further preferably, the weight ratio of the diluent to the polymer containing two or more epoxy groups in the molecule is 1:1.5.

[0021] In some preferred embodiments, the diluent is selected from at least one of styrene, hydroxypropyl methacrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, isooctyl acrylate, and vinyltoluene.

[0022] Further preferably, the diluent includes styrene and hydroxypropyl methacrylate.

[0023] During the experimental process, after extensive experimental research, the applicant found that the diluents added in the present application are styrene and hydroxypropyl methacrylate. During the reaction process, further cross-linking can occur between the polymer containing two or more epoxy groups in the molecule and the compound methacrylic acid containing a carboxyl group and a carbon-carbon double bond. In particular, when the weight ratio of the diluent to the polymer containing two or more epoxy groups in the molecule is 1: (0.8-1.8), it can ensure that the prepared vinyl resin has improved adhesion to the material when used on the surface of the cement material. Performance test results show that when used on the surface of the cement substrate, the shear strength is as high as 31 MPa or more, further improving its bonding performance with the cement substrate. The applicant speculates that the reason for this phenomenon may be that the presence of a certain number of benzene ring structures in the system will cause the electron cloud density in the system to shift, thereby improving the strength of the interaction between the active hydroxyl, epoxy, carboxyl and other groups contained in the system. When the functional thermosetting resin used for the cement substrate is subjected to external force, the strong intermolecular interaction will lead to an enhanced ability to dissipate the external force, thereby improving its adhesion to the cement surface while improving the tensile strength and flexural strength of the material.

[0024] In some preferred embodiments, the weight of the compound containing a carboxyl group and a carbon-carbon double bond accounts for 10-20 wt % of the total weight of the raw materials.

[0025] In some preferred embodiments, a functional thermosetting resin is prepared by raw materials, which include, by weight:

[0026] Liquid polymer: 30-55 parts

[0027] Solid polymer: 3-10 parts

[0028] Alkyl compounds containing hydroxyl groups and phenyl groups: 8 to 25 parts

[0029] Compounds containing carboxyl groups and carbon-carbon double bonds: 18-32 parts

[0030] Catalyst: 0.3-1.5 parts

[0031] Inhibitor: 0.05-0.25 parts

[0032] Diluent: 30-45 parts.

[0033] A second aspect of the present invention provides a method for preparing a functional thermosetting resin, comprising the following steps:

[0034] 1) Calculate the weight of each raw material in the formula, add the liquid polymer, the alkyl compound containing hydroxyl and phenyl groups, and 1 / 4 of the catalyst to the reactor in sequence, raise the temperature to 110°C, gradually increase the reactor temperature, and keep the temperature at 160±2°C. Sampling and measuring the epoxy equivalent of the resin every 1 hour, when the epoxy equivalent reaches 350-380g / eq, immediately cool to 104°C;

[0035] 2) Add solid polymer to the reactor and, after dissolving, add 2 / 3 of the polymerization inhibitor, the remaining catalyst, and methacrylic acid. Control the reaction temperature at 95±2°C and keep it warm for 30 minutes. Then, sample the resin every 1.5 hours to determine the acid value and epoxy equivalent of the resin. When the acid value and epoxy equivalent of the resin reach 4500-6500 g / eq, immediately cool down.

[0036] 3) Cooling to 105° C., adding diluent and remaining polymerization inhibitor to the reactor respectively, stirring evenly, cooling to 50-55° C., and filtering to obtain a functional thermosetting resin.

[0037] Beneficial effects: The functional thermosetting resin prepared by the present invention has the following advantages:

[0038] 1. The functional thermosetting resin prepared by the present invention comprises a liquid polymer having an epoxy value of 0.4-0.6 Eq / 100 g and a solid polymer having an epoxy equivalent of 450-750 g / Eq, which can ensure further reactivity between epoxy groups and carboxyl-containing substances in the system, ensure the presence of reactive groups in the molecular chain segments, and enhance the resin's wettability on other substrate surfaces.

[0039] 2. The functional thermosetting resin prepared by the present invention can improve its adhesion to cement materials when used on cement surfaces through the interaction between the diluent and the polymer containing two or more epoxy groups in the molecule. Performance testing results show that when used on cement substrates, the shear strength is as high as 31 MPa or more, further improving the bonding performance between the functional thermosetting resin and the cement substrate.

[0040] 3. The preparation method of the functional thermosetting resin provided by the present invention can ensure that the occurrence of side reactions during the reaction process is reduced to the greatest extent possible by further optimizing the conditions, thereby saving energy and reducing energy consumption while improving product quality. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 This is a picture of the functional thermosetting resin product prepared in Example 1 of this application. DETAILED DESCRIPTION

[0042] Example

[0043] Example 1

[0044] A functional thermosetting resin, wherein the raw materials for preparing the resin are calculated by weight and include:

[0045] Liquid polymer: 50 parts

[0046] Solid polymer: 4 parts

[0047] Alkyl compounds containing hydroxyl groups and phenyl groups: 15 parts

[0048] Compounds containing carboxyl groups and carbon-carbon double bonds: 30 parts

[0049] Catalyst: 0.5 parts

[0050] Inhibitor: 0.1 part

[0051] Diluent: 36 parts.

[0052] The liquid polymer has an epoxy value of 0.4-0.6 Eq / 100 g, model CYD-128, and was purchased from Baling Petrochemical;

[0053] The solid polymer, epoxy equivalent weight 600-650g / Eq, model NPES-902, was purchased from Shanghai Kaiyin Chemical;

[0054] The alkyl compound containing hydroxyl and phenyl is bisphenol A;

[0055] The compound containing a carboxyl group and a carbon-carbon double bond is methacrylic acid;

[0056] The catalyst is tri-n-butylamine;

[0057] The polymerization inhibitor is hydroquinone.

[0058] The diluent is styrene and hydroxypropyl methacrylate in a weight ratio of 8:1;

[0059] A method for preparing a functional thermosetting resin comprises the following steps:

[0060] 1) Calculate the weight of each raw material in the formula, add the liquid polymer, the alkyl compound containing hydroxyl and phenyl groups, and 1 / 4 of the weight of the catalyst to the reactor in sequence, raise the temperature to 110°C, gradually increase the reactor temperature, and keep the temperature at 160±2°C. Sampling and measuring the epoxy equivalent of the resin every 1 hour, when the epoxy equivalent reaches 350-380g / eq, immediately cool to 104°C;

[0061] 2) Add solid polymer to the reactor and, after dissolution, add 2 / 3 of the weight of polymerization inhibitor, remaining catalyst, and methacrylic acid. Control the reaction temperature at 95±2°C and keep warm for 30 minutes. Then, sample the resin every 1.5 hours to determine the acid value and epoxy equivalent weight. When the acid value and epoxy equivalent weight of the resin reach 4500-6500 g / eq, immediately cool down.

[0062] 3) Cooling to 105° C., adding diluent and remaining polymerization inhibitor to the reactor respectively, stirring evenly, cooling to 50° C., and filtering to obtain a functional thermosetting resin.

[0063] Comparative Example 1

[0064] A vinyl ester resin, the raw materials for preparation thereof, calculated by weight, include:

[0065] Liquid polymer: 50 parts

[0066] Alkyl compounds containing hydroxyl groups and phenyl groups: 15 parts

[0067] Compounds containing carboxyl groups and carbon-carbon double bonds: 30 parts

[0068] Catalyst: 0.5 parts

[0069] Inhibitor: 0.1 part

[0070] Diluent: 36 parts.

[0071] The liquid polymer has an epoxy value of 0.4-0.6 Eq / 100 g, model CYD-128, and was purchased from Baling Petrochemical;

[0072] The alkyl compound containing hydroxyl and phenyl is bisphenol A;

[0073] The compound containing a carboxyl group and a carbon-carbon double bond is methacrylic acid;

[0074] The catalyst is tri-n-butylamine;

[0075] The polymerization inhibitor is hydroquinone.

[0076] The diluent is styrene and hydroxypropyl methacrylate in a weight ratio of 8:1;

[0077] A method for preparing a functional thermosetting resin comprises the following steps:

[0078] 1) Calculate the weight of each raw material in the formula, add the liquid polymer, the alkyl compound containing hydroxyl and phenyl groups, and 1 / 4 of the weight of the catalyst to the reactor in sequence, raise the temperature to 110°C, gradually increase the reactor temperature, and keep the temperature at 160±2°C. Sampling and measuring the epoxy equivalent of the resin every 1 hour, when the epoxy equivalent reaches 350-380g / eq, immediately cool to 104°C;

[0079] 2) Add solid polymer to the reactor and, after dissolution, add 2 / 3 of the weight of polymerization inhibitor, remaining catalyst, and methacrylic acid. Control the reaction temperature at 95±2°C and keep warm for 30 minutes. Then, sample the resin every 1.5 hours to determine the acid value and epoxy equivalent weight. When the acid value and epoxy equivalent weight of the resin reach 4500-6500 g / eq, immediately cool down.

[0080] 3) Cooling to 105° C., adding diluent and remaining polymerization inhibitor to the reactor respectively, stirring evenly, cooling to 50° C., and filtering to obtain a functional thermosetting resin.

[0081] Performance Testing

[0082] The vinyl resin prepared in Example 1 was subjected to the following performance tests:

[0083]

[0084]

[0085] The resins prepared in Example 1 and Comparative Example 1 of the present application were subjected to the following performance tests, and the results are recorded in the following table:

[0086] Performance Testing Example 1 Comparative Example 1 Test standards tensile strength 90MPa 88MPa ISO 527-2 Tensile modulus 3400MPa 3150MPa ISO 527-2 Bending strength 130MPa 127MPa ISO 178 flexural modulus 3400MPa 3200MPa ISO 178 Impact strength <![CDATA[13KJ / m 2 ]]> <![CDATA[21KJ / m 2 ]]> ISO 179 Shear strength 31MPa 26MPa GB / T 30396-2014

Claims

1. A functional thermosetting resin, characterized in that: The preparation raw materials include: polymers containing two or more epoxy groups in the molecule, bisphenol A, methacrylic acid, and additives; The polymer containing two or more epoxy groups in the molecule includes solid polymers and liquid polymers; The epoxy value of the liquid polymer is 0.4-0.6Eq / 100g; model CYD-128, purchased from Baling Petrochemical; the solid polymer has an epoxy equivalent of 600-650g / Eq, model NPES-902, purchased from Shanghai Kaiyin Chemical; The auxiliary agents include diluents, inhibitors and catalysts; The raw materials for preparing the functional thermosetting resin include, by weight: Liquid polymer: 30-55 parts Solid polymer: 3-10 parts Bisphenol A: 8-25 parts Methacrylic acid: 18-32 parts Catalyst: 0.3-1.5 parts Inhibitor: 0.05-0.25 parts Diluent: 30-45 parts.

2. The functional thermosetting resin according to claim 1, characterized in that The weight ratio of the diluent to the polymer containing two or more epoxy groups in the molecule is 1:(0.8-1.8).

3. The functional thermosetting resin according to claim 1, characterized in that The diluent is selected from at least one of styrene, hydroxypropyl methacrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, isooctyl acrylate and vinyltoluene.

4. The functional thermosetting resin according to claim 1, characterized in that The weight of the methacrylic acid accounts for 10-20wt% of the total weight of the raw materials.

5. A method for preparing a functional thermosetting resin according to any one of claims 2 to 4, characterized in that: The following steps are involved: 1) Calculate the weight of each raw material in the formula and add the liquid polymer, alkyl compound containing hydroxyl and phenyl groups, and 1 / 4 catalyst to the reactor in sequence. Raise the temperature to 110°C. Gradually increase the reactor temperature while maintaining a constant temperature of 160±2°C. Sample the resin every hour to determine its epoxy equivalent. When the epoxy equivalent reaches 350-380 g / eq, immediately lower the temperature to 104°C. 2) Add solid polymer to the reactor and wait for it to dissolve. Then add 2 / 3 of the polymerization inhibitor, the remaining catalyst, and methacrylic acid. Control the reaction temperature at 95±2°C and keep it warm for 30 minutes. Then, take samples every 1.5 hours to measure the acid value and epoxy equivalent of the resin. When the acid value and epoxy equivalent of the resin reach 4500-6500g / eq, immediately reduce the temperature. 3) Cool to 105°C, add diluent and remaining inhibitor to the reactor respectively, stir evenly, cool to 50-55°C, and filter to obtain functional thermosetting resin.

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