Bisphenol phenolic resin and preparation method and application thereof, curing agent composition and application thereof, epoxy resin product and preparation method and application thereof

Abstract

The invention relates to the field of high polymer materials and oil and gas exploitation, and discloses bisphenol phenolic resin and a preparation method and application thereof, a curing agent composition, an epoxy resin composition and application thereof, and epoxy resin and application thereof. The bisphenol phenolic resin comprises a structural unit A as shown in a formula I and a structural unit B as shown in a formula II, # imgabs 0 # Q is # imgabs 1 #, wherein R1 and R2 are respectively and independently H, CH3, CF3 or CH2CH3; on the basis of the total weight of the bisphenol phenolic resin, the content of the structural unit A is 0-100 wt%, and the content of the structural unit B is 0-100 wt%. The molecular chain of the bisphenol phenolic resin has certain rigidity, and when the bisphenol phenolic resin is used as a curing agent for curing epoxy resin, the compressive strength and the flow conductivity of a cured epoxy resin product can be remarkably improved.

Description

Technical Field

[0001] The present invention relates to the field of polymer materials and oil and gas exploitation, and in particular to a bisphenol-formaldehyde resin and a preparation method and application thereof, a curing agent composition and application thereof, and an epoxy resin product and a preparation method and application thereof. Background Art

[0002] Epoxy thermosetting resins are widely used in coatings, paints, adhesives and engineering fields due to their excellent mechanical properties and bonding properties. For example, epoxy thermosetting resins can be found in wind turbine blades, pressure-bearing parts of aerospace, and sucker rods. However, water-based epoxy resins are required under some special working conditions, such as bonding of underwater engineering parts, underwater plugging, plugging of oil and gas wells in oil and gas production, oil and gas well fracturing, and sand control of oil and gas wells. Commonly used water-based epoxy resins are obtained by emulsification. According to the different emulsification methods, they can be divided into external emulsification and internal emulsification. External emulsification is to disperse the epoxy resin in water by adding an emulsifier to form a stable emulsion; internal emulsification is to introduce certain hydrophilic groups into the epoxy resin molecular chain. The modified epoxy resin itself has a certain emulsification ability, so it can be stably dispersed in water. In addition, there is a relatively rare type of water-soluble epoxy resin - aqueous solution epoxy resin, which is to enhance the hydrophilicity of epoxy resin to be able to dissolve in water to form a solution. Because water is the lowest cost solvent, this type of epoxy resin can be applied to large-scale applications such as oil and gas extraction. Regardless of the type of epoxy resin, a curing agent must be added to achieve curing in order to reflect its mechanical properties, bonding properties, etc., to achieve practical purposes.

[0003] Because epoxy groups have the problem of hydrolysis in aqueous solution, if the curing agent is not active or water-soluble enough, the reaction rate between the reactive groups of the curing agent and the epoxy groups is not as high as the hydrolysis rate of the epoxy groups when the curing reaction occurs at high temperature, resulting in the phenomenon of insufficient strength or non-curing. For water-soluble epoxy thermosetting resins, polyethylene polyamine can meet these two conditions at the same time, but its activity is too high. After adding, the curing reaction will occur immediately, causing the viscosity of the system to increase instantly, which is not conducive to the application in many working conditions, such as oil and gas well fracturing, which needs to maintain fluidity for a certain period of time to facilitate pumping and movement in the cracks.

[0004] Therefore, there is an urgent need to provide a polymer curing agent that can cure epoxy resin in aqueous solution and does not undergo a curing reaction at room temperature. Summary of the invention

[0005] The purpose of the present invention is to overcome the problem that the curing agent in the prior art is difficult to cure the epoxy resin in situ and is easy to cure at room temperature, and to provide a bisphenol phenolic resin and its preparation method and application, a curing agent composition and application, an epoxy resin product and its preparation method and application. The molecular chain of the bisphenol phenolic resin has a certain rigidity. When it is used as a curing agent for curing epoxy resin, it can significantly improve the compressive strength and flow conductivity of the cured epoxy resin product.

[0006] In order to achieve the above object, the first aspect of the present invention provides a bisphenol novolac resin, wherein the bisphenol novolac resin comprises a structural unit A shown in formula I and a structural unit B shown in formula II;

[0007]

[0008] Q is Wherein, R1 and R2 are each independently H, CH3, CF3 or CH2CH3;

[0009] Based on the total weight of the bisphenol-formaldehyde resin, the content of the structural unit A is 0-100wt%, and the content of the structural unit B is 0-100wt%.

[0010] A second aspect of the present invention provides a method for preparing a bisphenol novolac resin, wherein the preparation method comprises the following steps:

[0011] Under alkaline conditions, the first monomer, the second monomer and water are mixed and polymerized to obtain the bisphenol novolac resin;

[0012] Wherein, the alkaline condition makes n(OH) - 1.4mol / L-3mol / L;

[0013] The first monomer is selected from formaldehyde and / or paraformaldehyde;

[0014] The second monomer includes a monomer A shown in formula III and / or a monomer B shown in formula IV:

[0015]

[0016] Among them, Q is Wherein, R1 and R2 are each independently H, CH3, CF3 or CH2CH3.

[0017] The third aspect of the present invention provides a bisphenol novolac resin prepared by the preparation method of the second aspect.

[0018] The fourth aspect of the present invention provides that the bisphenol-formaldehyde resin of the first aspect or the third aspect is used as a curing agent, preferably as a curing agent in epoxy resin.

[0019] A fifth aspect of the present invention provides a curing agent composition, wherein the curing agent composition comprises a curing agent, an emulsifier and water;

[0020] The curing agent is the bisphenol-formaldehyde resin of the first aspect or the third aspect.

[0021] A sixth aspect of the present invention provides a method for preparing an epoxy resin product, wherein the preparation method comprises:

[0022] Mixing component A with a curing agent and curing to obtain the epoxy resin product;

[0023] Wherein, the component A comprises epoxy resin; and the curing agent is the bisphenol-formaldehyde resin of the first aspect or the third aspect of the present invention.

[0024] A seventh aspect of the present invention provides an epoxy resin product, wherein the epoxy resin product is prepared by the preparation method of the epoxy resin product according to the sixth aspect.

[0025] An eighth aspect of the present invention provides use of the curing agent composition of the fifth aspect or the epoxy resin product of the seventh aspect in a fracturing fluid.

[0026] Through the above technical scheme, the bisphenol-formaldehyde resin and its preparation method and application, curing agent composition and application, epoxy resin product and its preparation method and application provided by the present invention achieve the following beneficial effects:

[0027] The bisphenol phenol-formaldehyde resin provided by the present invention comprises specific structural units I and II, which can make the molecular chain of the bisphenol phenol-formaldehyde resin produce a micro-crosslinked structure, form a phenolic resin with a micro-network, and finally make the molecular chain of the bisphenol phenol-formaldehyde resin have a certain rigidity. When the bisphenol phenol-formaldehyde resin is used as a curing agent for curing epoxy resin, the compressive strength and flow conductivity of the epoxy resin can be significantly improved.

[0028] In the present invention, the curing agent composition comprises the bisphenol novolac resin with a specific structure described in the present invention, exhibits high apparent viscosity (100-400 mPa·s), high fluidity and excellent storage stability (the apparent viscosity increases slightly at room temperature for 180 days). When it is used as a curing agent for epoxy resin curing, it can significantly improve the compressive strength and flow conductivity of the epoxy resin. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 This is an environmental scanning electron microscope (ESEM) image of the bisphenol-formaldehyde resin of Example 1. DETAILED DESCRIPTION

[0030] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0031] A first aspect of the present invention provides a bisphenol novolac resin, wherein the bisphenol novolac resin comprises a structural unit A shown in formula I and a structural unit B shown in formula II;

[0032]

[0033] Q is Wherein, R1 and R2 are each independently H, CH3, CF3 or CH2CH3;

[0034] Based on the total weight of the bisphenol-formaldehyde resin, the content of the structural unit A is 0-100wt%, and the content of the structural unit B is 0-100wt%.

[0035] In the present invention, the content of the structural unit A and the content of the structural unit B are not both 0, and the sum of the content of the structural unit A and the content of the structural unit B is 100%.

[0036] In the present invention, the bisphenol novolac resin contains specific structural units I and II, which can make the molecular chain of the bisphenol novolac resin produce a micro-crosslinked structure to form a phenolic resin with a micro-network, so that the molecular chain of the bisphenol novolac resin has a certain rigidity. When it is used as a curing agent for curing epoxy resin, it can significantly improve the compressive strength and flow conductivity of the epoxy resin.

[0037] In the present invention, the permeability of the epoxy resin product at 40 MPa is used to characterize the flow conductivity of the epoxy resin product, that is, the higher the permeability of the epoxy resin product at 40 MPa, the higher the flow conductivity of the epoxy resin product.

[0038] According to the present invention, Q is Wherein, R1 and R2 are each independently H or CH3, preferably CH3.

[0039] In the present invention, in order to further improve the water solubility and storage stability of the bisphenol novolac resin, preferably, the bisphenol novolac resin comprises both the structural unit A shown in formula I and the structural unit B shown in formula II. Specifically, based on the total weight of the bisphenol novolac resin, the content of the structural unit A is 70wt%-80wt%, and the content of the structural unit B is 20wt%-30wt%.

[0040] In the present invention, when the contents of structural unit A and structural unit B in the bisphenol novolac resin meet the above-mentioned specific contents, the sulfonic acid group content in the bisphenol novolac resin is appropriate, which can ensure that the hydrophilicity of the bisphenol novolac resin is improved, thereby allowing the epoxy resin product obtained by curing it to maintain a high compressive strength under high temperature and water conditions.

[0041] Furthermore, based on the total weight of the bisphenol-formaldehyde resin, the content of the structural unit A is 72wt%-77wt%, and the content of the structural unit B is 23wt%-28wt%.

[0042] According to the present invention, the weight average molecular weight of the bisphenol novolac resin is 2000 g / mol-10000 g / mol, preferably 3000 g / mol-5000 g / mol.

[0043] A second aspect of the present invention provides a method for preparing a bisphenol novolac resin, wherein the preparation method comprises the following steps:

[0044] Under alkaline conditions, the first monomer, the second monomer and water are mixed and polymerized to obtain the bisphenol novolac resin;

[0045] Wherein, the alkaline condition makes n(OH) - 1.4mol / L-3mol / L;

[0046] The first monomer is selected from formaldehyde and / or paraformaldehyde;

[0047] The second monomer includes a monomer A shown in formula III and / or a monomer B shown in formula IV:

[0048]

[0049] Among them, Q is Wherein, R1 and R2 are each independently H, CH3, CF3 or CH2CH3.

[0050] In the present invention, under alkaline conditions, formaldehyde and / or paraformaldehyde are polymerized with a second monomer having a specific structure, in particular, by controlling n(OH) - By meeting the above range, the bisphenol novolac resin containing specific structural units as described in the first aspect of the present invention can be obtained. The bisphenol novolac resin is used as a curing agent for curing epoxy resin, which can significantly improve the compressive strength and flow conductivity of the epoxy resin.

[0051] In the present invention, conventional methods in the art can be used to achieve the n(OH) -Adjustments can be made, such as adding alkaline substances such as NaOH.

[0052] In a specific embodiment of the present invention, the first monomer is paraformaldehyde, which can slowly release formaldehyde in the system to achieve precise control of the polymerization reaction rate and polymerization degree.

[0053] Furthermore, Q is Wherein, R1 and R2 are each independently H or CH3, preferably CH3.

[0054] In one embodiment of the present invention, monomer A is bisphenol A, that is, as shown in formula III, Q is And R1 and R2 are CH3.

[0055] In one embodiment of the present invention, monomer A is bisphenol AF, that is, as shown in formula III, Q is And R1 and R2 are CF3.

[0056] In one embodiment of the present invention, monomer A is bisphenol B, that is, as shown in formula III, Q is And R1 is CH3 and R2 is CH2CH3.

[0057] In one embodiment of the present invention, monomer A is bisphenol F, that is, as shown in formula III, Q is And R1 and R2 are H.

[0058] In one embodiment of the present invention, monomer A is bisphenol S, that is, as shown in formula III, Q is

[0059] According to the present invention, based on the total weight of the first monomer and the second monomer, the amount of the first monomer is 10-40 wt %, and the amount of the second monomer is 60-90 wt %.

[0060] Furthermore, based on the total weight of the first monomer and the second monomer, the amount of the first monomer is 20-35 wt %, and the amount of the second monomer is 65-80 wt %.

[0061] According to the present invention, the second monomer A and the monomer B, wherein the mass ratio of the monomer A to the monomer B is 1:0.25-0.43.

[0062] In the present invention, when monomer A and monomer B are selected as the second monomer at the same time and the mass ratio of the two structures is controlled to meet the above range, the content of SO3H in the final bisphenol novolac resin can be controlled, so that the prepared bisphenol novolac resin not only has good water solubility but also maintains high fluidity. At the same time, the bisphenol novolac resin can maintain a viscosity that is substantially not increased during long-term storage.

[0063] Furthermore, the mass ratio of monomer A to monomer B is 1:0.3-0.38.

[0064] In the present invention, the monomer B can be purchased commercially. Preferably, the monomer B is prepared according to the following method:

[0065] In the presence of a first catalyst and water, a bisphenol compound is contacted with a sulfonating agent to carry out a sulfonation reaction to obtain a monomer B;

[0066] The molar ratio of the bisphenol compound to the sulfonating agent is 1:0.1-1.

[0067] In the present invention, by adopting the above method and controlling the molar ratio of the bisphenol compound to the sulfonating agent to satisfy the above range, the monomer B having formula IV of the present invention, i.e., containing a monosulfonated bisphenol compound, can be obtained.

[0068] Furthermore, the molar ratio of the bisphenol compound to the sulfonating agent is 1:0.7-1.

[0069] In the present invention, the bisphenol compound is at least one selected from bisphenol A, bisphenol S, bisphenol B, bisphenol F and bisphenol AF.

[0070] In the present invention, the sulfonating agent is selected from at least one of concentrated sulfuric acid, chlorosulfonic acid and aminosulfonic acid.

[0071] In the present invention, the first catalyst is Lewis acid.

[0072] In the present invention, the Lewis acid can be a Lewis acid commonly used in the art, such as titanium tetrachloride, ferric chloride, ferric oxide, zirconium oxychloride, aluminum oxide, aluminum chloride, hydrated tin tetrachloride, and the like.

[0073] In the present invention, the mass ratio of the bisphenol compound to the first catalyst is 1:0.0001-0.0006.

[0074] In the present invention, the mass ratio of the bisphenol compound to the first catalyst satisfies the above range, which can reduce the reaction temperature by 20° C.-30° C. and make the reaction conditions milder.

[0075] Furthermore, the mass ratio of the bisphenol compound to the first catalyst is 1:0.00015-0.00045.

[0076] According to the present invention, the alkaline conditions make n(OH) - It is 1.6-2.5 mol / L, preferably 1.8-2 mol / L.

[0077] According to the present invention, the conditions of the polymerization reaction include: a polymerization temperature of 30-80° C. and a polymerization time of 1-6 h.

[0078] In the present invention, the polymerization reaction is carried out under the above-mentioned polymerization reaction conditions, and the polymerization reaction can be completed under relatively mild conditions, and substantially no side reaction products are generated.

[0079] Furthermore, the conditions of the polymerization reaction include: a polymerization temperature of 50-70° C. and a polymerization time of 2-4 h.

[0080] The third aspect of the present invention provides a bisphenol novolac resin prepared by the preparation method of the second aspect.

[0081] The fourth aspect of the present invention provides that the bisphenol-formaldehyde resin of the first aspect or the third aspect is used as a curing agent, preferably as a curing agent in epoxy resin.

[0082] A fifth aspect of the present invention provides a curing agent composition, wherein the curing agent composition comprises a curing agent, an emulsifier and water;

[0083] The curing agent is the bisphenol-formaldehyde resin of the first aspect or the third aspect.

[0084] In the present invention, the curing agent composition comprises a bisphenol novolac resin with a specific structure, exhibiting high apparent viscosity (100 mPa·s-400 mPa·s), high fluidity and excellent storage stability (the apparent viscosity increases slightly at room temperature for 180 days). When the curing agent is used as a curing agent for epoxy resin curing, the compressive strength and flow conductivity of the epoxy resin can be significantly improved.

[0085] According to the present invention, based on the total weight of the curing agent composition, the content of the bisphenol-formaldehyde resin is 40-60wt%, the content of the emulsifier is 2-6wt%, and the content of water is 34-58wt%.

[0086] In the present invention, by controlling the amount of each component in the curing agent composition to meet the above range, it can be ensured that the curing agent composition contains sufficient reactive sites while ensuring that the curing agent composition has suitable viscosity and good fluidity. When the curing agent composition is used for epoxy resin curing, it has good compatibility with the epoxy resin, thereby improving the curing uniformity of the epoxy resin.

[0087] Furthermore, based on the total weight of the curing agent composition, the content of the bisphenol-formaldehyde resin is 45-60wt%, the content of the emulsifier is 3-5wt%, and the content of water is 35-52wt%.

[0088] Furthermore, based on the total weight of the curing agent composition, the content of the bisphenol-formaldehyde resin is 45-50wt%, the content of the emulsifier is 4-5wt%, and the content of the water is 45-51wt%.

[0089] According to the present invention, the emulsifier is selected from at least one of sodium maleic anhydride monohexadecyl carboxylate (HEC16), sodium maleic anhydride monomethacrylate hydroxyethyl carboxylate (MAME), octadecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, dodecyl trimethyl ammonium chloride, dihexadecyl dimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium chloride, sodium dodecyl sulfonate, sodium dodecyl carboxylate and alkylphenol polyoxyethylene ether, and is preferably a mixture of sodium maleic anhydride monohexadecyl carboxylate, sodium maleic anhydride monomethacrylate hydroxyethyl carboxylate and alkylphenol polyoxyethylene ether.

[0090] In the present invention, the alkylphenol polyoxyethylene ether may be nonylphenol polyoxyethylene ether (OP-10, OP-15, etc.).

[0091] According to the present invention, at 25° C., the apparent viscosity of the curing agent composition is 100 mPa·s-400 mPa·s, preferably 200 mPa·s-300 mPa·s.

[0092] In the present invention, the apparent viscosity of the curing agent composition is measured at room temperature using a six-speed rotational viscometer.

[0093] In the present invention, the curing agent composition also includes conventional auxiliary agents in the art, such as a curing accelerator. There is no particular limitation on the type and amount of the curing accelerator. Conventional curing accelerators in the art can be used and added in conventional amounts in the art.

[0094] In the present invention, there is no particular limitation on the preparation method of the curing agent composition, and the bisphenol-formaldehyde resin of the present invention can be directly mixed with an emulsifier and water. There is no particular limitation on the mixing conditions, as long as the bisphenol-formaldehyde resin, the emulsifier and the water can be fully mixed and uniform.

[0095] A sixth aspect of the present invention provides a method for preparing an epoxy resin product, wherein the preparation method comprises: mixing component A with a curing agent, and curing to obtain the epoxy resin product;

[0096] Wherein, the component A comprises epoxy resin, and the curing agent is the curing agent composition of the fifth aspect.

[0097] In the present invention, the curing agent composition provided by the present invention is used for curing epoxy resin, so that the cured epoxy resin product has better compressive strength and flow conductivity under high temperature conditions, so that the epoxy resin product can be used in high temperature and high pressure environments such as oil and gas fracturing.

[0098] According to the present invention, relative to 100 parts by weight of component A, the content of the curing agent is 40-80 parts by weight.

[0099] Furthermore, relative to 100 parts by weight of component A, the content of the curing agent is 60-80 parts by weight.

[0100] In the present invention, the epoxy resin is a water-soluble epoxy resin and / or a solvent-based epoxy resin, wherein the water-soluble epoxy resin is preferably a water-soluble bisphenol epoxy resin.

[0101] In the present invention, the first component also includes conventional auxiliary agents in the art such as emulsifiers. The type and amount of the emulsifier are not particularly limited and are added in the conventional amount in the art.

[0102] In the present invention, conventional equipment in the art may be used to mix the first component including the epoxy resin with the components in the curing agent composition, such as a twin-screw extruder or a mixer.

[0103] In the present invention, the curing conditions include: a curing temperature of 30-80° C., a curing time of 1-6 hours, and a curing pressure of 20-40 MPa.

[0104] The seventh aspect of the present invention provides an epoxy resin product produced by the preparation method of the epoxy resin product of the sixth aspect.

[0105] An eighth aspect of the present invention provides the curing agent composition of the fifth aspect or the epoxy resin product of the seventh aspect.

[0106] The present invention will be described in detail below by way of examples. In the following examples and comparative examples,

[0107] The content of each structural unit in bisphenol-formaldehyde resin is measured by feed ratio calculation method.

[0108] The weight average molecular weight of the bisphenol-formaldehyde resin was measured by GPC.

[0109] The apparent viscosity of the curing agent composition is measured by a six-speed rotation viscometer.

[0110] The microstructure of bisphenol-formaldehyde resin was measured by environmental scanning electron microscopy (ESEM).

[0111] The bisphenol-formaldehyde resin aqueous solution (40-50 wt%) was freeze-dried at -40°C under vacuum and then tested.

[0112] Monomer A1-bisphenol A;

[0113] Monomer A2-bisphenol S;

[0114] Other raw materials used in the examples and comparative examples are all commercially available.

[0115] Preparation Example - Preparation of Monomer B

[0116] Preparation Example 1

[0117] 57g of bisphenol A, 0.03g of ferric chloride and 25g of concentrated sulfuric acid (98wt%) were contacted for sulfonation reaction at a reaction temperature of 130°C for a reaction time of 4h, wherein the molar ratio of bisphenol A to concentrated sulfuric acid was 1:1, and the mass ratio of bisphenol A to ferric chloride was 1:0.0005. After purification, monosulfonated bisphenol A monomer B1 was obtained.

[0118] Preparation Example 2

[0119] The monosulfonated bisphenol compound S2 was prepared according to the preparation method of Preparation Example 1, except that 62.5 g of bisphenol S was used to replace 57 g of bisphenol A, wherein the molar ratio of bisphenol S to concentrated sulfuric acid was 1:1, and the mass ratio of bisphenol S to ferric chloride was 1:0.0005, to obtain monosulfonated bisphenol S-monomer B2.

[0120] Comparative Preparation Example

[0121] Trisulfonated bisphenol A was prepared according to the preparation method of Preparation Example 1, except that the amount of concentrated sulfuric acid used was 75 g, wherein the molar ratio of bisphenol A to concentrated sulfuric acid was 1:3, to obtain trisulfonated bisphenol A.

[0122] Example I - Preparation of bisphenol phenolic resin

[0123] Example 1

[0124] Under stirring conditions, 60 parts by weight of the second monomer A (bisphenol A) and 21 parts by weight of the monomer B1 (monosulfonated bisphenol compound S1) were mixed with 30 parts by weight of the first monomer (polyformaldehyde) in deionized water, and NaOH was added to make n(OH) - The concentration of the first monomer is 2 mol / L, and the polymerization is carried out at 50° C. for 4 h to obtain a bisphenol novolac resin I1. The first monomer is used in an amount of 27 wt %, the second monomer is used in an amount of 73 wt %, and the mass ratio of the monomer A to the monomer B is 1:0.35, based on the total weight of the monomers.

[0125] Examples and Comparative Examples

[0126] The bisphenol novolac resin was prepared according to the method of Example 1, except that the types of monomer A and monomer B and the mass ratio thereof were different from those in Example 1, as shown in Table 1.

[0127] Table 1

[0128] Monomer A Monomer A: Monomer B Monomer A: Monomer B Example 1 A1 A1:B1=1:0.35 1:0.35 Example 2 A1 A1:B2=1:0.35 1:0.35 Example 3 A2 A2:B1=1:0.35 1:0.35 Example 4 A1 A1:B1=1:0.25 1:0.25 Example 5 A1 / 1:0 Example 6 / B1 0:1

[0129] Example 7

[0130] The bisphenol phenolic resin was prepared according to the method of Example 1, except that an equal amount of formaldehyde was used to replace paraformaldehyde.

[0131] Example 8

[0132] The bisphenol phenolic resin was prepared according to the method of Example 1, except that NaOH was added to make n(OH) in the system - It is 2.5mol / L.

[0133] Example 9

[0134] The bisphenol phenolic resin was prepared according to the method of Example 1, except that NaOH was added to make n(OH) in the system - It is 3mol / L.

[0135] Example 10

[0136] The bisphenol phenolic resin was prepared according to the method of Example 1, except that the amounts of monomer A and monomer B were different from those in Example 1. Specifically, the amounts of monomer A and monomer B were such that A1:B1=1:0.43.

[0137] Embodiment 11

[0138] The bisphenol phenolic resin was prepared according to the method of Example 1, except that the amounts of monomer A and monomer B were different from those in Example 1. Specifically, the amounts of monomer A and monomer B were such that A1:B1=1:1.

[0139] Comparative Example 1

[0140] The bisphenol phenolic resin was prepared according to the method of Example 1, except that NaOH was added to make n(OH) in the system - It is 4mol / L.

[0141] Comparative Example 2

[0142] A bisphenol-type phenolic resin was prepared according to the method of Example 1, except that an equal mass of trisulfonyl bisphenol A was used to replace bisphenol A.

[0143] Comparative Example 3

[0144] The bisphenol phenolic resin was prepared according to the method of Example 1, except that an equal amount of acetaldehyde was used to replace paraformaldehyde.

[0145] The content of each structural unit in the bisphenol phenolic resins prepared in the examples and comparative examples and the weight average molecular weight of the phenolic resins were tested, and the results are shown in Table 2.

[0146] Table 2

[0147]

[0148]

[0149] Example II - Curing Agent Composition

[0150] 50 g of the bisphenol-formaldehyde resin prepared in Example 1, 4 g of an emulsifier sodium maleic anhydride monohexadecyl carboxylate (HEC16) and 46 g of water were mixed to obtain curing agent compositions C1-C9 and comparative examples DC1-DC3. The apparent viscosity of the curing agent compositions at 25° C. and the apparent viscosity of the curing agent compositions after storage at 25° C. for 180 days were tested, and the results are shown in Table 3.

[0151] Table 3

[0152] Apparent viscosity (mPa·s) Apparent viscosity after 180 days (mPa·s) C1 264 318 C2 255 306 C3 231 279 C4 183 219 C5 192 239 C6 186 225 C7 201 240 C8 303 363 C9 379 456 C10 237 285 C11 207 267 DC1 861 1032 DC2 93 462 DC3 672 1344

[0153] From the results in Table 3, it can be seen that the curing agent composition examples C1-C9 containing the bisphenol novolac resin of the present invention have a specific apparent viscosity compared to the comparative examples DC1-DC3, and the apparent viscosity increases less after being stored at room temperature for 180 days, indicating that the curing agent composition containing the bisphenol novolac resin of the present invention has excellent storage stability. Among them, the bisphenol novolac resin prepared in comparative example 1 is insoluble in water due to the use of bisphenol A with a high degree of sulfonation, while the high apparent viscosity of the curing agent composition DC1 is due to the emulsification effect of the emulsifier.

[0154] Test example-epoxy resin products

[0155] 65 parts by weight of the curing agent composition of Example II and 100 parts of epoxy resin (E51 brand) were mixed evenly and placed in a high temperature reactor at 30 MPa and 80°C for 6 hours. After being taken out, they were completely cured to obtain epoxy resin products P1-P11 and DP1-DP3. The flow conductivity and compressive strength of the epoxy resin products were tested, and the results are shown in Table 4.

[0156] Test method for conductivity: At 40MPa, the permeability of epoxy resin products is tested using a high-pressure displacement device in accordance with Sinopec Shengli Oilfield Administration Enterprise Standard Q / SH1020 "Method for Determination of Permeability of High Permeability Consolidated Cores".

[0157] Compressive strength test method: At 130°C, a universal weight loading machine is used to test the compressive strength of epoxy resin products.

[0158] Table 4

[0159]

[0160]

[0161] It can be seen from the results in Table 4 that, compared with PD1-PD3, the epoxy resin product obtained by curing with the curing agent composition comprising the bisphenol-formaldehyde resin provided by the present invention as a curing agent has better flow conductivity and compressive strength.

[0162] Figure 1 This is an ESEM image of the bisphenol novolac resin prepared in Example 1. As can be seen from the white frame in the figure, the bisphenol novolac resin provided by the present invention has a micro-network structure, which is obtained because the molecular chains of the bisphenol novolac resin produce a micro-cross-linked structure, which makes the molecular chains of the bisphenol novolac resin have a certain rigidity. When it is used as a curing agent for curing epoxy resin, it can significantly improve the compressive strength and flow conductivity of the epoxy resin.

[0163] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A bisphenol novolac resin, characterized in that The bisphenol novolac resin comprises a structural unit A shown in formula I and a structural unit B shown in formula II; Q is Wherein, R1 and R2 are each independently H, CH3, CF3 or CH2CH3; Based on the total weight of the bisphenol-formaldehyde resin, the content of the structural unit A is 0-100wt%, and the content of the structural unit B is 0-100wt%.

2. The bisphenol novolac resin according to claim 1, wherein Q is Wherein, R1 and R2 are each independently H or CH3, preferably CH3.

3. The bisphenol novolac resin according to claim 1 or 2, wherein Based on the total weight of the bisphenol-formaldehyde resin, the content of the structural unit A is 70wt%-80wt%, and the content of the structural unit B is 20wt%-30wt%.

4. The bisphenol-formaldehyde resin according to any one of claims 1 to 3, wherein The weight average molecular weight of the bisphenol novolac resin is 2000 g / mol-10000 g / mol, preferably 3000 g / mol-5000 g / mol.

5. A method for preparing a bisphenol novolac resin, characterized in that: The preparation method comprises the following steps: Under alkaline conditions, the first monomer, the second monomer and water are mixed and polymerized to obtain the bisphenol novolac resin; Wherein, the alkaline condition makes n(OH) - 1.4mol / L-3mol / L; The first monomer is selected from formaldehyde and / or paraformaldehyde; The second monomer includes a monomer A shown in formula III and / or a monomer B shown in formula IV: Among them, Q is Wherein, R1 and R2 are each independently H, CH3, CF3 or CH2CH3.

6. The preparation method according to claim 5, wherein: Based on the total weight of the first monomer and the second monomer, the amount of the first monomer is 10-40wt%, and the amount of the second monomer is 60-90wt%; Preferably, based on the total weight of the first monomer and the second monomer, the amount of the first monomer is 20-35 wt %, and the amount of the second monomer is 65-80 wt %.

7. The preparation method according to claim 5 or 6, wherein: The first monomer includes monomer A and monomer B; Wherein, the mass ratio of the monomer A to the monomer B is 1:0.25-0.

43.

8. The preparation method according to any one of claims 5 to 7, wherein: The alkaline conditions make the n(OH) - It is 1.6-2.5 mol / L, preferably 1.8-2 mol / L.

9. The preparation method according to any one of claims 5 to 8, wherein: The polymerization reaction conditions include: polymerization temperature of 30-80° C., polymerization time of 1-6 h; Preferably, the polymerization reaction conditions include: polymerization temperature of 50-70° C., and polymerization time of 2-4 h.

10. A bisphenol novolac resin prepared by the preparation method described in any one of claims 5 to 9.

11. Use of the bisphenol-formaldehyde resin according to any one of claims 1 to 4 and 10 as a curing agent, preferably as a curing agent in epoxy resin.

12. A curing agent composition, characterized in that: The curing agent composition comprises a curing agent, an emulsifier and water; The curing agent is the bisphenol-formaldehyde resin according to any one of claims 1 to 4 and 10.

13. The curing agent composition according to claim 12, wherein Based on the total weight of the curing agent composition, the content of the bisphenol-formaldehyde resin is 40-60wt%, the content of the emulsifier is 2-6wt%, and the content of water is 34-58wt%; Preferably, based on the total weight of the curing agent composition, the content of the bisphenol-formaldehyde resin is 45-60wt%, the content of the emulsifier is 3-5wt%, and the content of water is 35-52wt%; More preferably, based on the total weight of the curing agent composition, the content of the bisphenol-formaldehyde resin is 45-50 wt %, the content of the emulsifier is 4-5 wt %, and the content of water is 45-51 wt %.

14. The curing agent composition according to claim 12 or 13, wherein The emulsifier is selected from at least one of sodium maleic anhydride monohexadecyl carboxylate, sodium maleic anhydride monomethacrylate hydroxyethyl carboxylate, octadecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, dodecyl trimethyl ammonium chloride, dimethyl dihexadecyl ammonium chloride, dodecyl dimethyl benzyl ammonium chloride, sodium dodecyl sulfonate, sodium dodecyl carboxylate and alkylphenol polyoxyethylene ether, and is preferably a mixture of sodium maleic anhydride monohexadecyl carboxylate, sodium maleic anhydride monomethacrylate hydroxyethyl carboxylate and alkylphenol polyoxyethylene ether.

15. The curing agent composition according to any one of claims 12 to 14, wherein At 25° C., the apparent viscosity of the curing agent composition is 100 mPa·s-400 mPa·s, preferably 200 mPa·s-300 mPa·s.

16. A method for preparing an epoxy resin product, characterized in that: The preparation method comprises: Mixing component A with a curing agent and curing to obtain the epoxy resin product; Wherein, the component A comprises epoxy resin; the curing agent is the curing agent composition according to any one of claims 12 to 15; Preferably, relative to 100 parts by weight of component A, the content of the curing agent is 40-80 parts by weight.

17. An epoxy resin product obtained by the preparation method according to claim 16.

18. Use of the curing agent composition according to any one of claims 12 to 15 or the epoxy resin product according to claim 17 in fracturing fluid.

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