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

Abstract

The application relates to the fields of high polymer materials and oil and gas exploitation, and discloses a bisphenol phenolic resin, a preparation method and application thereof, a curing agent composition, an epoxy resin composition and application, and an epoxy resin and application. The bisphenol phenolic resin comprises structural unit A shown in formula I and structural unit B shown in formula II; Q is wherein R1 and R2 are each independently H, CH3, CF3 or CH2CH3; the content of the structural unit A is 0-100 wt% and the content of the structural unit B is 0-100 wt% based on the total weight of the bisphenol phenolic resin. The molecular chain of the bisphenol phenolic resin has a certain rigidity, and when the bisphenol phenolic resin is used as a curing agent to cure an epoxy resin, the compression strength and flow guiding capacity of the epoxy resin product after curing can be remarkably improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of high molecular materials and oil and gas exploitation, and in particular to a bisphenol phenolic resin, a preparation method and application thereof, a curing agent composition and application, an epoxy resin product and a preparation method and application thereof. BACKGROUND

[0002] Epoxy thermosetting resins are widely used in coatings, paints, adhesives and engineering fields due to their excellent mechanical properties and cementing properties, such as wind turbine blades, aerospace pressure components, sucker rods, etc. However, water-based epoxy resins are required in some special working conditions, such as underwater engineering component bonding, underwater plugging, oil and gas well plugging, oil and gas well fracturing, and oil and gas well sand control. Commonly used water-based epoxy resins are obtained by emulsification. According to different emulsification methods, they can be divided into external emulsification and internal emulsification. External emulsification is to disperse epoxy resin in water by adding an emulsifier to form a stable emulsion. Internal emulsification is to introduce a certain hydrophilic group into the molecular chain of epoxy resin, so that the modified epoxy resin has a certain emulsifying capacity and can be stably dispersed in water. In addition, there is a less common water-soluble epoxy resin-water solution epoxy resin, which is to enhance the hydrophilicity of epoxy resin to form a solution in water. Because water is the cheapest solvent, this type of epoxy resin can be applied to large-scale application fields such as oil and gas exploitation. Regardless of which type of epoxy resin, a curing agent needs to be added to achieve curing in order to demonstrate its mechanical properties, cementing properties, etc., and achieve practical purposes.

[0003] Because of the hydrolysis problem of epoxy groups in aqueous solution, if the activity or water solubility of the curing agent is not enough, the reaction rate of the curing agent reaction group with the epoxy group is not as high as the hydrolysis rate of the epoxy group when the curing reaction occurs at high temperature, resulting in the phenomenon of insufficient strength or no curing. For water-soluble epoxy thermosetting resin, polyethylene polyamine can meet both conditions, but its activity is too high, and curing reaction occurs immediately after addition, which increases the viscosity of the system instantaneously, which is not conducive to the application in many working conditions, such as oil and gas well fracturing, which requires a certain flowability to facilitate pumping and movement in the fracture.

[0004] Therefore, there is an urgent need to provide a high molecular curing agent that can cause epoxy resin to cure in an aqueous solution and does not occur curing reaction at room temperature. SUMMARY

[0005] The present application aims to overcome the problem that the curing agent is difficult to cure the epoxy resin in situ and easy to cure at room temperature in the prior art, and provides a bisphenol phenolic resin and a preparation method and application thereof, a curing agent composition and application thereof, an epoxy resin product and a preparation method and application thereof. The molecular chain of the bisphenol phenolic resin has a certain rigidity, and when the bisphenol phenolic resin is used as a curing agent to cure the epoxy resin, the compressive strength and flow conductivity of the epoxy resin product after curing can be significantly improved.

[0006] In order to achieve the above-mentioned purpose, the present application provides a bisphenol phenolic resin in a first aspect, wherein the bisphenol phenolic resin comprises structural unit A shown in formula I and structural unit B shown in formula II.

[0007]

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

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

[0010] The present application provides a preparation method of a bisphenol phenolic resin in a second aspect, wherein the preparation method comprises the following steps.

[0011] The first monomer, the second monomer and water are mixed under alkaline conditions, and then a polymerization reaction is carried out to obtain the bisphenol phenolic resin.

[0012] The alkaline conditions make n(OH) - is 1.4mol / L-3mol / L.

[0013] The first monomer is selected from formaldehyde and / or polyformaldehyde.

[0014] The second monomer comprises monomer A shown in formula III and / or monomer B shown in formula IV.

[0015]

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

[0017] The present application provides a bisphenol phenolic resin prepared by the preparation method of the second aspect in a third aspect.

[0018] The present application provides the application of the bisphenol phenolic resin of the first aspect or the third aspect as a curing agent, preferably as a curing agent in the epoxy resin.

[0019] The fifth aspect of the present application 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 novolac resin of the first aspect or the third aspect.

[0021] The sixth aspect of the present application provides a preparation method of an epoxy resin product, wherein the preparation method comprises:

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

[0023] The component A comprises an epoxy resin; and the curing agent is the bisphenol novolac resin of the first aspect or the third aspect.

[0024] The seventh aspect of the present application provides an epoxy resin product, wherein the epoxy resin product is prepared by the preparation method of the epoxy resin product of the sixth aspect.

[0025] The eighth aspect of the present application provides the 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 solutions, the bisphenol novolac resin and the preparation method and application thereof, the curing agent composition and the application thereof, and the epoxy resin product and the preparation method and application thereof provided by the present application have the following beneficial effects:

[0027] The bisphenol novolac resin provided by the present application contains specific structural unit I and structural unit II, which can cause the molecular chain of the bisphenol novolac resin to have a micro-crosslinking structure, form a phenolic resin with a micro-network structure, and finally make the molecular chain of the bisphenol novolac resin have a certain rigidity. When the bisphenol novolac resin is used as a curing agent for curing an epoxy resin, the compressive strength and flow conductivity of the epoxy resin can be significantly improved.

[0028] In the present application, the curing agent composition contains the bisphenol novolac resin with a specific structure provided by the present application, has high apparent viscosity (100-400 mPa·s), high flowability and excellent storage stability (less increase in apparent viscosity at room temperature for 180 days), and can significantly improve the compressive strength and flow conductivity of the epoxy resin when used as a curing agent for curing the epoxy resin. BRIEF DESCRIPTION OF DRAWINGS

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

[0030] The endpoints of the ranges and any values disclosed herein are not limited to the precise values recited as the exact dimensions are not critical to the invention. Any numeric range recited is intended to include all values from the lower value to the upper value, inclusive of both values, and to also include any value approximately or about the value. For numeric ranges, the endpoints are included in the ranges, are included between the endpoints of the ranges, and the individual points are combinable to form one or more new numeric ranges, which are to be considered as specifically disclosed herein.

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

[0032]

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

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

[0035] In the present application, 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 application, the bisphenol phenolic resin comprises specific structural unit I and structural unit II, which can make the molecular chain of the bisphenol phenolic resin produce a micro-crosslinking structure, form a phenolic resin with a micro-network, and make the molecular chain of the bisphenol phenolic resin have a certain rigidity. When the bisphenol phenolic 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.

[0037] In the present application, the flow conductivity of the epoxy resin product is characterized by the permeability of the epoxy resin product under 40MPa, that is, the higher the permeability of the epoxy resin product under 40MPa, the higher the flow conductivity of the epoxy resin product.

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

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

[0040] In the present application, when the content of the structural unit A and the structural unit B in the bisphenol novolac resin satisfies the above specific content, the content of the sulfonic acid group contained in the bisphenol novolac resin is appropriate, and the hydrophilicity of the bisphenol novolac resin can be improved, so that the epoxy resin product obtained by curing the same still maintains a high compressive strength under high-temperature and water-containing conditions.

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

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

[0043] The second aspect of the present application provides a preparation method of a bisphenol novolac resin, wherein the preparation method comprises the following steps:

[0044] After mixing the first monomer, the second monomer and water under alkaline conditions, a polymerization reaction is carried out to obtain the bisphenol novolac resin;

[0045] The alkaline conditions make n(OH) - 1.4mol / L-3mol / L;

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

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

[0048]

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

[0050] In the present application, formaldehyde and / or polyformaldehyde is polymerized with the second monomer having a specific structure under alkaline conditions, and in particular, by controlling n(OH) - satisfying the above range, the bisphenol novolac resin containing the specific structural unit according to the first aspect of the present application can be obtained, and the compressive strength and the flow conductivity of the epoxy resin can be significantly improved when the bisphenol novolac resin is used as a curing agent for the curing of the epoxy resin.

[0051] In the present application, the method for controlling n(OH) -adjustment, such as adding alkali such as NaOH.

[0052] In one embodiment of the present application, the first monomer is paraformaldehyde, which can slowly release formaldehyde in the system, so as to precisely control the polymerization rate and the polymerization degree.

[0053] Further, Q is wherein R1, R2 are each independently H or CH3, preferably CH3.

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

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

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

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

[0058] In one embodiment of the present application, the monomer A is bisphenol S, i.e. as shown in formula III, Q is

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

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

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

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

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

[0064] In the present application, the monomer B can be commercially available, preferably, the monomer B is prepared according to the following method:

[0065] The bisphenol compound is contacted with a sulfonating agent in the presence of a first catalyst and water to perform a sulfonation reaction, thereby obtaining the monomer B;

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

[0067] In the present application, by using the above method and controlling the mass ratio of the bisphenol compound and the sulfonating agent to meet the above range, the monomer B with formula IV, i.e. containing a monosulfonated bisphenol compound, can be prepared.

[0068] Further, the mass ratio of the bisphenol compound and the sulfonating agent is 1:0.7-1.

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

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

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

[0072] In the present application, the Lewis acid can be a Lewis acid commonly used in the art, such as titanium tetrachloride, ferric trichloride, diiron trioxide, zirconium oxychloride, aluminum trioxide, aluminum trichloride, hydrated tin tetrachloride, etc.

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

[0074] In the present application, the mass ratio of the bisphenol compound and the first catalyst meets the above range, which can reduce the reaction temperature by 20-30℃, and make the reaction condition more mild.

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

[0076] According to the present application, the alkaline condition is such that n(OH) - is 1.6-2.5 mol / L, preferably 1.8-2 mol / L.

[0077] According to the present application, the polymerization conditions include that the polymerization temperature is 30-80℃ and the polymerization time is 1-6h.

[0078] In the present application, the polymerization reaction is carried out under the above polymerization conditions, and the polymerization reaction can be completed under relatively mild conditions and without by-products.

[0079] Further, the polymerization conditions include that the polymerization temperature is 50-70℃ and the polymerization time is 2-4h.

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

[0081] The fourth aspect of the present application provides the bisphenol novolac resin of the first aspect or the third aspect as a curing agent, preferably as a curing agent in an epoxy resin.

[0082] The fifth aspect of the present application 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 novolac resin of the first aspect or the third aspect.

[0084] In the present application, the curing agent composition contains the bisphenol novolac resin with a specific structure, which has high apparent viscosity (100mPa·s-400mPa·s), high flowability and excellent storage stability (less increase in apparent viscosity at room temperature for 180 days), and when used as a curing agent for an epoxy resin, can significantly improve the compressive strength and flow conductivity of the epoxy resin.

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

[0086] In the present application, by controlling the amount of each component in the curing agent composition to meet the above range, the curing agent composition can ensure that it contains sufficient reactive sites while ensuring that it has appropriate viscosity and good flowability, and when used for curing an epoxy resin, it has good compatibility with the epoxy resin and improves the curing uniformity of the epoxy resin.

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

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

[0089] According to the present application, the emulsifier is at least one selected from sodium maleic anhydride monohexadecyl carboxylate (HEC16), sodium maleic anhydride monohydroxyethyl methacrylate carboxylate (MAME), octadecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, dodecyl trimethyl ammonium chloride, bis-hexadecyl dimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium chloride, sodium dodecyl sulfonate, sodium dodecyl carboxylate, and alkyl phenol polyoxyethylene ether, preferably a mixture of sodium maleic anhydride monohexadecyl carboxylate, sodium maleic anhydride monohydroxyethyl methacrylate carboxylate, and alkyl phenol polyoxyethylene ether.

[0090] In the present application, the alkyl phenol polyoxyethylene ether can be nonyl phenol polyoxyethylene ether (OP-10, OP-15, etc.).

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

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

[0093] In the present application, the curing agent composition further comprises an auxiliary agent which is conventional in the art, such as a curing accelerator, and the type and amount of the curing accelerator are not particularly limited, and a conventional curing accelerator in the art can be used and added in a conventional amount in the art.

[0094] In the present application, the method for preparing the curing agent composition is not particularly limited, and the bisphenol novolac resin, the emulsifier, and the water can be directly mixed. The mixing conditions are not particularly limited, as long as the bisphenol novolac resin, the emulsifier, and the water can be sufficiently and uniformly mixed.

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

[0096] The component A comprises an epoxy resin, and the curing agent is the curing agent composition of the fifth aspect described above.

[0097] In the present application, the curing agent composition provided by the present application is used for curing of the epoxy resin, so that the cured epoxy resin product has more excellent compressive strength and flow conductivity under high temperature conditions, and 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 application, the content of the curing agent is 40-80 parts by weight relative to 100 parts by weight of component A.

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

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

[0101] In the present application, the first component further comprises an emulsifier and other conventional auxiliaries in the art, and the type and amount of the emulsifier are not particularly limited and are added according to the conventional amount in the art.

[0102] In the present application, conventional equipment in the art can be used to mix the first component containing the epoxy resin with the components in the curing agent composition, such as a double screw extruder or a stirrer.

[0103] In the present application, the curing conditions include a curing temperature of 30-80℃, a curing time of 1-6h, and a curing pressure of 20-40MPa.

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

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

[0106] The present application will be described in detail below through examples. In the following examples and comparative examples,

[0107] The content of each structural unit in the bisphenol phenolic resin is measured by a feeding ratio calculation method.

[0108] The weight average molecular weight of the bisphenol phenolic resin is measured by GPC.

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

[0110] The microstructure of the bisphenol phenolic resin is measured by an environmental scanning electron microscope (ESEM).

[0111] The aqueous solution of bisphenol novolac resin (40-50wt%) was tested after freeze-drying under vacuum at minus 40°C.

[0112] Monomer A1 - Bisphenol A;

[0113] Monomer A2 - Bisphenol S;

[0114] The other raw materials used in the examples and comparative examples are 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 a sulfonation reaction, the reaction temperature was 130°C, and the reaction time was 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] Monosulfonated bisphenol compound S2 was prepared according to the preparation method of Preparation Example 1, except that 62.5g of bisphenol S was used instead of 57g 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 was 75g, 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 Novolac Resin

[0123] Example 1

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

[0125] Examples and Comparative Examples

[0126] The bisphenol novolac resin was prepared according to the method of Example 1, except that the types and mass ratio of monomer A and monomer B were different from those of Example 1, and were specifically 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 novolac resin was prepared according to the method of Example 1, except that equal mass of formaldehyde was used to replace the paraformaldehyde.

[0131] Example 8

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

[0133] Example 9

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

[0135] Example 10

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

[0137] Example 11

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

[0139] Comparative Example 1

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

[0141] Comparative Example 2

[0142] The bisphenol novolac resin was prepared according to the method of Example 1, except that equal mass of trisulfone bisphenol A was used to replace the bisphenol A.

[0143] Comparative Example 3

[0144] The bisphenol novolac resin was prepared according to the method of Example 1, except that equal mass of acetaldehyde was used instead of paraformaldehyde.

[0145] The content of each structural unit in the bisphenol novolac resin prepared in the examples and comparative examples and the weight average molecular weight of the novolac resin 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 novolac resin prepared in Example I, 4 g of the emulsifier sodium maleic anhydride monohexadecyl ester 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 composition at 25°C and the apparent viscosity of the curing agent composition 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 (mPa-s) after 180 days 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] As can be seen from the results in Table 3, the curing agent compositions C1-C9 containing the bisphenol novolac resin of the present application have a specific apparent viscosity, and the apparent viscosity increases less after storage at room temperature for 180 days, compared to comparative examples DC1-DC3, indicating that the curing agent composition containing the bisphenol novolac resin of the present application 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 high sulfonation degree, and the curing agent composition DC1 has high apparent viscosity due to the emulsification of the emulsifier.

[0154] Test example - epoxy resin product

[0155] 65 parts by weight of the curing agent composition of Example II and 100 parts of epoxy resin (E51 grade) were uniformly mixed and placed in a high-temperature reaction kettle, and cured at 30 MPa and 80°C for 6 h. After removal, the curing was complete, and epoxy resin products P1-P11 and DP1-DP3 were obtained. The flow conductivity and compressive strength of the epoxy resin product were tested, and the results are shown in Table 4.

[0156] The test method of the flow conductivity is as follows: the epoxy resin product is tested for the permeability at 40 MPa by using a high-pressure displacement device, and the test is performed according to the Enterprise Standard Q / SH1020 of Shengli Oilfield Administration Bureau, i.e., "Method for Determining Permeability of High-Permeability Consolidated Core".

[0157] The test method of the compressive strength is as follows: the compressive strength of the epoxy resin product is tested at 130°C by using a universal weight loading machine.

[0158] Table 4

[0159]

[0160]

[0161] As can be seen from the results in Table 4, compared with PD1-PD3, the epoxy resin product cured by using the curing agent composition containing the bisphenol novolac resin provided by the application as the curing agent has more excellent flow conductivity and compressive strength.

[0162] Figure 1 The ESEM image of the bisphenol novolac resin prepared for Example 1 shows that the bisphenol novolac resin provided by the application has a micro-network structure, which is obtained due to the micro-crosslinking structure of the molecular chain of the bisphenol novolac resin. The molecular chain of the bisphenol novolac resin has a certain rigidity, and when the bisphenol novolac resin is used as a curing agent to cure the epoxy resin, the compressive strength and flow conductivity of the epoxy resin can be significantly improved.

[0163] The above describes the preferred embodiments of the application in detail, but the application is not limited thereto. Within the technical concept of the application, various simple modifications can be made to the technical solutions of the application, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as the disclosed content of the application and belong to the protection scope of the application.

Claims

1. A bisphenol novolac resin characterized by, The bisphenol novolac resin comprises structural unit A shown in Formula I and structural unit B shown in Formula II. Formula I; Formula II; Q is or wherein R1, R2 are each independently H, CH3, CF3, or CH2CH3; The content of the structural unit A is 70-80 wt% and the content of the structural unit B is 20-30 wt% based on the total weight of the bisphenol novolac resin.

2. The bisphenol novolac resin of claim 1, wherein, Q is wherein R1, R2 are each independently H or CH3.

3. The bisphenol novolac resin of claim 1, wherein, R1, R2 are each independently CH3.

4. The bisphenol novolac resin according to claim 1 or 2, wherein, The weight average molecular weight of the bisphenol novolac resin is 2000-10000 g / mol.

5. The bisphenol novolac resin of claim 4, wherein, The weight average molecular weight of the bisphenol novolac resin is 3000-5000 g / mol.

6. A process for producing the bisphenol novolac resin according to any one of claims 1 to 5, characterized by, The preparation method comprises the following steps: The first monomer, the second monomer and water are mixed under alkaline conditions, and then a polymerization reaction is performed to obtain the bisphenol novolac resin. wherein the basic conditions are such that n(OH) - 1.4 mol / L - 3 mol / L; The first monomer is selected from formaldehyde and / or polyformaldehyde. The second monomer comprises monomer A shown in Formula III and monomer B shown in Formula IV: Formula III; Formula IV; wherein Q is or wherein R1, R2are each independently H, CH3, CF3, or CH2CH3.

7. The production method according to claim 6, wherein The amount of the first monomer is 10-40 wt% and the amount of the second monomer is 60-90 wt% based on the total weight of the first monomer and the second monomer.

8. The production method according to claim 7, wherein The amount of the first monomer is 20-35 wt% and the amount of the second monomer is 65-80 wt% based on the total weight of the first monomer and the second monomer.

9. The production method according to claim 6 or 7, wherein The mass ratio of the monomer A to the monomer B is 1:0.25-0.

43.

10. The production method according to claim 6 or 7, wherein The basic conditions are such that n(OH) - 1.6-2.5 mol / L.

11. The production method according to claim 10, wherein The basic conditions are such that n(OH) - 1.8-2 mol / L.

12. The production method according to claim 6 or 7, wherein The polymerization temperature is 30-80℃ and the polymerization time is 1-6 h.

13. The method of making according to claim 12, wherein, The polymerization temperature is 50-70℃ and the polymerization time is 2-4 h.

14. The bisphenol novolac resin prepared by the preparation method of any one of claims 6-13.

15. The bisphenol novolac resin of any one of claims 1-5 and 14 as a curing agent.

16. The bisphenol novolac resin of any one of claims 1-5 and 14 as a curing agent in an epoxy resin.

17. A curing agent composition characterized by comprising: The curing agent composition comprises a curing agent, an emulsifier and water; The curing agent is the bisphenol novolac resin of any one of claims 1-5 and 14.

18. The curative composition of claim 17, wherein, The content of the bisphenol novolac resin is 40-60 wt%, the content of the emulsifier is 2-6 wt% and the content of the water is 34-58 wt% based on the total weight of the curing agent composition.

19. The curative composition of claim 18, wherein, The content of the bisphenol novolac resin is 45-60 wt%, the content of the emulsifier is 3-5 wt% and the content of the water is 35-52 wt% based on the total weight of the curing agent composition.

20. The curative composition of claim 19, wherein, The content of the bisphenol novolac resin is 45-50 wt%, the content of the emulsifier is 4-5 wt% and the content of the water is 45-51 wt% based on the total weight of the curing agent composition.

21. The curative composition of claim 17, wherein, The emulsifier is at least one selected from sodium maleic anhydride monohexadecyl carboxylate, sodium maleic anhydride monohydroxyethyl methacrylate carboxylate, octadecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, dodecyl trimethyl ammonium chloride, dimethyl bis-hexadecyl ammonium chloride, dodecyl dimethyl benzyl ammonium chloride, sodium dodecyl sulfonate, sodium dodecyl carboxylate and alkyl phenol polyoxyethylene ether.

22. The curative composition of claim 21, wherein, The emulsifier is a mixture of sodium maleic anhydride monohexadecyl ester carboxylate, sodium maleic anhydride monohydroxyethyl methacrylate carboxylate and alkyl phenol polyoxyethylene ether.

23. The curative composition of claim 17, wherein, The apparent viscosity of the curing agent composition is 100-400 mPa·s at 25℃.

24. The curative composition of claim 23, wherein, The apparent viscosity of the curing agent composition is 200-300 mPa·s at 25℃.

25. A method of making an epoxy resin article, characterized by, The preparation method comprises: mixing component A with a curing agent, and curing to obtain the epoxy resin product; The component A comprises an epoxy resin; the curing agent is the curing agent composition according to any one of claims 17-24; the content of the curing agent is 40-80 parts by weight relative to 100 parts by weight of the component A.

26. An epoxy resin product prepared by the preparation method of claim 25.

27. Use of the curing agent composition according to any one of claims 17-24 or the epoxy resin product of claim 26 in a fracturing fluid. ​

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