Chilled phenolic resin and preparation method thereof

Abstract

The invention discloses a chilled phenolic resin which comprises the following components in percentage by mass: 15%-25% of a phenolic compound, 20%-35% of an aldehyde compound, 2.5%-6% of a basic catalyst, 0.5%-1.5% of a modifier, 0.8%-2% of an aldehyde removal agent, 20%-32% of water, 8%-18% of an alcohol compound, 0.3%-1% of a pH regulator, 0.5%-1% of a silane coupling agent and 0.05%-0.3% of a surfactant, the phenolic compound comprises at least one of phenol, bisphenol A and cardanol; the aldehyde compound is liquid formaldehyde. The chilled phenolic resin disclosed by the invention is relatively low in alkali addition amount, the pH value is alkalescent, the service cycle of 3D printing equipment is prolonged, and the normal-temperature storage period of the resin is prolonged; urotropine, lignin salt and tung oil are added as modifiers, the curing speed and toughness of the phenolic resin are effectively improved, a printing sand mold can be hardened at normal temperature in cooperation with an organic ester curing agent, heating equipment is not needed, and the problem that pungent smell is generated when a phenolic resin sand mold is heated is solved.

Description

Technical Field

[0001] The present invention relates to the technical field of casting auxiliary materials, in particular to a chilled phenolic resin and a preparation method thereof. Background Art

[0002] Binder jetting 3D printing is an industrial-grade additive manufacturing technology that selectively bonds powdered materials by spraying a binder onto a powder bed, creating a three-dimensional object layer by layer. This technology offers advantages such as low equipment cost, fast printing speed, and suitability for large-scale and multi-material printing. Currently, the binders used for sand bonding in casting 3D printing primarily include furan resin, inorganic binders, and phenolic resin. These three types of binders have distinct characteristics and are used in different scenarios.

[0003] Furan resin binders offer advantages such as high strength, rapid room-temperature hardening, and a high sand regeneration rate. However, they produce a strong pungent odor during hardening of the sand mold and have poor high-temperature resistance, making them unsuitable for the production of steel castings. Inorganic silicate binders offer advantages such as a simple production process, no odor, and low VOC emissions, making them particularly advantageous in non-ferrous alloy casting. However, their slow room-temperature hardening, low strength, and poor high-temperature resistance limit their application in the casting field. Phenolic resin binders offer advantages such as good high-temperature resistance, high bond strength, good water solubility, high residual carbon content, low smoke and toxicity, and chemical resistance, and are widely used in numerous industries. However, phenolic resin is brittle and prone to self-polymerization, which increases the resin's viscosity and shortens its shelf life. This can also lead to nozzle clogging and frame dropouts during printing, limiting its application in the 3D casting industry.

[0004] Patent CN104817665A discloses an alkaline phenolic resin for 3D printing and its preparation method. The binder is highly alkaline and will corrode the equipment over a long period of use, reducing the equipment's service life. In addition, the resin easily self-polymerizes during storage, causing the viscosity to increase, thereby clogging the printer nozzle and affecting the use effect. The binder has a short shelf life when stored at room temperature. Summary of the Invention

[0005] Based on this, in order to solve the technical problems that alkaline phenolic resins are prone to corroding 3D printing equipment, clogging print heads, and have a short storage period, the present invention provides a cold-hardening phenolic resin for 3D printing that is weakly alkaline, has a long shelf life when stored at room temperature, does not clog print heads, and can be hardened at room temperature.

[0006] In order to solve the above technical problems, the present invention adopts the following technical solutions:

[0007] A cold-hard phenolic resin comprises, by weight percentage, 15% to 25% of a phenolic compound, 20% to 35% of an aldehyde compound, 2.5% to 6% of an alkaline catalyst, 0.5% to 1.5% of a modifier, 0.8% to 2% of an aldehyde scavenger, 20% to 32% of water, 8% to 18% of an alcohol compound, 0.3% to 1% of a pH regulator, 0.5% to 1% of a silane coupling agent, and 0.05% to 0.3% of a surfactant; the phenolic compound comprises at least one of phenol, bisphenol A, and cardanol; and the aldehyde compound is liquid formaldehyde.

[0008] Furthermore, the alkaline catalyst includes at least one of sodium hydroxide, potassium hydroxide, ammonia water, and triethylamine.

[0009] Furthermore, the modifier is a mixture of hexamethylenetetramine, sodium lignin sulfonate and tung oil, wherein the ratio of the added amounts of hexamethylenetetramine, sodium lignin sulfonate and tung oil is preferably 3:2:5.

[0010] Furthermore, the formaldehyde remover includes at least one of urea, hydroxylamine hydrochloride, sodium sulfite, and melamine.

[0011] Furthermore, the alcohol compound includes a high-boiling point alcohol compound and a low-boiling point alcohol compound; the ratio of the added amount of the high-boiling point alcohol compound to the low-boiling point alcohol compound is 1 to 4:1.

[0012] Wherein, the high-boiling-point alcohol compound includes at least one of ethylene glycol and propylene glycol; the low-boiling-point alcohol compound includes at least one of isopropanol, methanol and ethanol.

[0013] Furthermore, the pH adjuster includes at least one of formic acid, acetic acid, citric acid, and salicylic acid.

[0014] Furthermore, the surfactant includes at least one of a phosphate compound, an acetylene glycol compound, a polyether-modified alcohol compound, and an alkyl sulfate compound.

[0015] Furthermore, the silane coupling agent includes at least one of KH-560, KH-602, A-151, and KH-792.

[0016] In a second aspect, the present application further provides a preparation method, which is applied to any of the above-mentioned cold-hard phenolic resins, and the preparation method comprises the following steps:

[0017] S1, adding the phenolic compound into the reactor, stirring and heating, raising the temperature to 40°C to 50°C; adding the alkaline catalyst into the reactor, stirring for 10min to 20min;

[0018] S2. Add the aldehyde compound into the reaction kettle, raise the temperature to 70°C to 80°C, and stir for 90min to 150min;

[0019] S3, adding the alkaline catalyst and the modifier into the reactor, heating to 80°C to 90°C, and stirring for 90min to 150min;

[0020] S4, add the formaldehyde removal agent into the reactor and stir for 20min to 40min;

[0021] S5, cooling to 55°C to 65°C, adding the water and the alcohol compound into the reactor, and stirring for 20min to 40min;

[0022] S6. Add the pH regulator into the reactor to adjust the pH to 8-9, and stir for 20-40 minutes;

[0023] S7. Cooling to below 40° C., adding the silane coupling agent and the surfactant, and stirring for 20 to 40 minutes.

[0024] Compared with the prior art, the method of the present invention has the following beneficial effects:

[0025] The cold-hardening phenolic resin disclosed in the present invention has a low alkali addition amount and a weakly alkaline pH value. It is more friendly to the pipes, nozzles and other parts of the 3D printing equipment that directly contact the resin, has low corrosiveness, and extends the service life of the equipment. The weak alkalinity of the resin can also delay the resin's own polycondensation, reduce the viscosity growth trend of the resin during storage, and increase the storage time of the resin; the alcohol solvent of the bonding system adopts a mixed form of a high-boiling point solvent and a low-boiling point solvent to ensure that the resin has a stable low viscosity and extend the shelf life of the resin at room temperature to 3-6 months. When the cold-hardening phenolic resin of the present invention is stored at 20°C for 30 days, the resin viscosity growth rate is controlled at 3% to 7%.

[0026] The chilled phenolic resin disclosed in the present invention incorporates methenamine, lignin salt, and tung oil as modifiers, effectively increasing the curing speed and toughness of the phenolic resin, improving the surface quality of printed products, and increasing the tensile strength of printed products by 5%-10%. The chilled phenolic resin, when combined with an organic ester curing agent, can be cured at room temperature when used to print sand molds, eliminating the need for heating equipment. This avoids the irritating odor generated by heating phenolic resin sand molds, improves the working environment, reduces energy consumption, and lowers production costs by 10%-20%. The chilled phenolic resin disclosed in the present invention has a simple preparation process, a short production period, and is easy to operate. DETAILED DESCRIPTION

[0027] To facilitate understanding of the present invention, the present invention will be described more fully below with reference to the relevant examples. Preferred embodiments of the present invention are provided in the examples. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to provide a more thorough and comprehensive understanding of the disclosure of the present invention.

[0028] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this invention pertains. The terms used herein in the specification of the present invention are for the purpose of describing specific embodiments only and are not intended to limit the present invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0029] One of the purposes of the present invention is to disclose a cold-hard phenolic resin, which comprises, by weight percentage, 15% to 25% of a phenolic compound, 20% to 35% of an aldehyde compound, 2.5% to 6% of a basic catalyst, 0.5% to 1.5% of a modifier, 0.8% to 2% of a formaldehyde scavenger, 20% to 32% of water, 8% to 18% of an alcohol compound, 0.3% to 1% of a pH regulator, 0.5% to 1% of a silane coupling agent and 0.05% to 0.3% of a surfactant.

[0030] The phenolic compound may be at least one of phenol, bisphenol A, and cardanol. The aldehyde compound may be liquid formaldehyde. The alkaline catalyst may be at least one of sodium hydroxide, potassium hydroxide, aqueous ammonia, and triethylamine. The modifier may be a mixture of urotropine, sodium lignin sulfonate, and tung oil, preferably with the ratio of urotropine: sodium lignin sulfonate: tung oil being 3:2:5. The addition of urotropine, lignin salt, and tung oil as modifiers during the synthesis of the phenolic resin product can improve the curing speed and toughness of the phenolic resin, making its sand mold strength comparable to, or even superior to, that of ordinary alkaline phenolic resin.

[0031] The formaldehyde scavenger can be at least one of urea, hydroxylamine hydrochloride, sodium sulfite, and melamine. Adding the formaldehyde scavenger reduces the free formaldehyde content to below 0.1%, significantly reducing the pungent odor of the phenolic resin and improving the 3D printing working environment. Alcohol compounds include high-boiling point alcohol compounds and low-boiling point alcohol compounds, with the ratio of the two added being 1 to 4:1, preferably 1 to 2.5:1. A mixture of high-boiling point and low-boiling point solvents ensures that the phenolic resin has a usable and stable low viscosity, good storage stability, and a shelf life of 3-6 months at room temperature. The high-boiling point alcohol compound can be at least one of ethylene glycol and propylene glycol; the low-boiling point alcohol compound can be at least one of isopropyl alcohol, methanol, and ethanol. The pH adjuster can be at least one of formic acid, acetic acid, citric acid, and salicylic acid.

[0032] The present invention requires only 2.5% to 6% of the alkaline catalyst, and a pH adjuster is added to adjust the pH to 8 to 9. The weakly alkaline environment slows down the self-polymerization of the phenolic resin, making the resin more stable. It is also more friendly to the nozzle and equipment, extending the equipment lifecycle. The surfactant can be at least one of a phosphate ester compound, an acetylenic diol compound, a polyether-modified alcohol compound, and an alkyl sulfate compound. The silane coupling agent can be at least one of KH-560, KH-602, A-151, and KH-792.

[0033] A second object of the present invention is to disclose a method for preparing any of the above-mentioned cold-hard phenolic resins, which may include the following steps:

[0034] S1. Add 15% to 25% of phenolic compound into a reactor, start stirring and heating, and raise the temperature to 40°C to 50°C; add 1% to 3% of alkaline catalyst into the reactor and stir for 10min to 20min;

[0035] S2. Add 20% to 35% of aldehyde compound into the reactor, heat to 70°C to 80°C, and stir for 90min to 150min;

[0036] S3. Add 1.5% to 3% of alkaline catalyst and 0.5% to 1.5% of modifier into the reactor, heat to 80°C to 90°C, and stir for 90min to 150min;

[0037] S4. Add 0.8% to 2% formaldehyde remover into the reactor and stir for 20 to 40 minutes;

[0038] S5. Cool down to 55-65°C, add 20%-32% water and 8%-18% alcohol compound into the reactor, and stir for 20-40 minutes;

[0039] S6. Add 0.3% to 1% pH regulator to the reactor, adjust the pH to 8 to 9, and stir for 20 to 40 minutes;

[0040] S7. Cooling to below 40° C., adding 0.5% to 1% of a silane coupling agent and 0.05% to 0.3% of a surfactant, and stirring for 20 to 40 minutes to obtain the cold-hard phenolic resin of the present invention.

[0041] In the embodiments disclosed in the present invention, the cold-hard phenolic resin may further include 0.5% to 1% of a polymerization inhibitor, which may be hydroquinone. Adding hydroquinone as a polymerization inhibitor can consume free radicals in the system, slowing down the polymerization rate of the resin. In combination with the weak alkalinity of the resin, it can also slow down the condensation of the resin itself. The two together effectively reduce the viscosity growth trend of the resin during storage, further extending the shelf life of the resin. Hydroquinone contains two phenolic hydroxyl groups, which can combine with active free radicals in the resin bonding system to form a quinone structure, terminate the free radical chain reaction, and slow down the polymerization rate. Hydroquinone can remove oxygen from the system, preventing cross-linking reactions initiated by oxygen, making the phenolic resin reaction more controllable. Hydroquinone can also regulate reaction activity. During the condensation reaction, hydroquinone can consume a portion of formaldehyde or intermediate free radicals to control the reaction rate. In addition, hydroquinone has good thermal stability and can maintain the stability of the bonding system under high temperature conditions.

[0042] It should be noted that, during the preparation of the cold-hard phenolic resin, hydroquinone should be added to the reactor together with the phenolic compound in step S1.

[0043] The cold-hardening phenolic resin of the present invention is used in combination with an organic ester curing agent for binder jetting 3D printing casting sand molds. The cold-hardening phenolic resin can self-harden at room temperature without the need for heating equipment, thereby reducing production costs by 10% to 20%. In addition, the phenolic resin product has a long storage period and is free of print head corrosion and clogging.

[0044] Example 1

[0045] A cold-hard phenolic resin comprises, by weight percentage, 19.6% phenol, 1% hydroquinone, 26% liquid formaldehyde, 1% sodium hydroxide, 1.5% potassium hydroxide, 0.18% hexamethylenetetramine, 0.12% sodium lignin sulfonate, 0.3% tung oil, 0.9% urea, 30% water, 10.8% ethylene glycol, 7.2% methanol, 0.6% acetic acid, 0.7% silane coupling agent (KH-560) and 0.1% acetylenic diol compound.

[0046] The preparation method of the chilled phenolic resin may include the following steps:

[0047] S1. Add 19.6% phenol and 1% hydroquinone into a reactor, start stirring and heating, and raise the temperature to 40°C to 50°C; add 0.4% sodium hydroxide and 0.6% potassium hydroxide into the reactor and stir for 10min to 20min;

[0048] S2. Add 26% liquid formaldehyde into the reactor, heat to 70-80°C, and stir for 90-150 minutes;

[0049] S3. Add 0.6% sodium hydroxide, 0.9% potassium hydroxide, 0.18% hexamethylenetetramine, 0.12% sodium lignin sulfonate and 0.3% tung oil into the reactor, heat to 80-90°C, and stir for 90-150 minutes;

[0050] S4. Add 0.9% urea into the reactor and stir for 20 to 40 minutes;

[0051] S5. Cool down to 55-65°C, add 30% water, 10.8% ethylene glycol and 7.2% methanol into the reactor, and stir for 20-40 minutes;

[0052] S6. Add 0.6% acetic acid to the reactor, adjust the pH to 8-9, and stir for 20-40 minutes;

[0053] S7. Cool the mixture to below 40° C., add 0.7% KH-560 and 0.1% acetylene glycol compound, and stir for 20 to 40 minutes to obtain the cold-hard phenolic resin of this embodiment.

[0054] Example 2

[0055] A cold-hard phenolic resin comprises, by weight percentage, 20% phenol, 5% bisphenol A, 27.5% liquid formaldehyde, 1.5% potassium hydroxide, 1.5% triethylamine, 0.3% hexamethylenetetramine, 0.2% sodium lignin sulfonate, 0.5% tung oil, 2% hydroxylamine hydrochloride, 24% water, 11.5% propylene glycol, 4.9% ethanol, 0.3% salicylic acid, 0.64% silane coupling agent (KH-602) and 0.16% phosphate compound.

[0056] The preparation method of the chilled phenolic resin may include the following steps:

[0057] S1. Add 20% phenol and 5% bisphenol A into a reactor, start stirring and heating, and raise the temperature to 40°C to 50°C; add 1.0% potassium hydroxide and 0.5% triethylamine into the reactor and stir for 10min to 20min;

[0058] S2. Add 27.5% liquid formaldehyde into the reactor, heat to 70-80°C, and stir for 90-150 minutes;

[0059] S3. Add 0.5% potassium hydroxide, 1.0% triethylamine, 0.3% hexamethylenetetramine, 0.2% sodium lignin sulfonate and 0.5% tung oil into the reactor, heat to 80-90°C, and stir for 90-150 minutes;

[0060] S4. Add 2% hydroxylamine hydrochloride into the reaction kettle and stir for 20 to 40 minutes;

[0061] S5. Cool down to 55-65°C, add 24% water, 11.5% propylene glycol and 4.9% ethanol into the reactor, and stir for 20-40 minutes;

[0062] S6. Add 0.3% salicylic acid to the reactor, adjust the pH to 8-9, and stir for 20-40 minutes;

[0063] S7. Cool the mixture to below 40° C., add 0.64% KH-602 and 0.16% phosphate compound, and stir for 20 to 40 minutes to obtain the cold-hard phenolic resin of this embodiment.

[0064] Example 3

[0065] A cold-hard phenolic resin comprises, by weight percentage, 0.9% hydroquinone, 17.1% cardanol, 32.1% liquid formaldehyde, 1.5% ammonia water, 4.5% potassium hydroxide, 0.24% hexamethylenetetramine, 0.16% sodium lignin sulfonate, 0.4% tung oil, 0.4% sodium sulfite, 0.4% urea, 25% water, 7.7% ethylene glycol, 7.7% isopropyl alcohol, 0.7% citric acid, 1% silane coupling agent (A-151), and 0.2% alkyl sulfate compound.

[0066] The preparation method of the chilled phenolic resin may include the following steps:

[0067] S1. Add 0.9% hydroquinone and 17.1% cardanol into a reactor, start stirring and heating, and raise the temperature to 40°C to 50°C; add 0.75% ammonia water and 2.25% potassium hydroxide into the reactor and stir for 10min to 20min;

[0068] S2. Add 32.1% liquid formaldehyde into the reactor, heat to 70-80°C, and stir for 90-150 minutes;

[0069] S3. Add 0.75% ammonia water, 2.25% potassium hydroxide, 0.24% hexamethylenetetramine, 0.16% sodium lignin sulfonate and 0.4% tung oil into the reactor, heat to 80-90°C, and stir for 90-150 minutes;

[0070] S4. Add 0.4% sodium sulfite and 0.4% urea into the reactor and stir for 20 to 40 minutes;

[0071] S5. Cool down to 55-65°C, add 25% water, 7.7% ethylene glycol and 7.7% isopropyl alcohol into the reactor, and stir for 20-40 minutes;

[0072] S6. Add 0.7% citric acid to the reactor, adjust the pH to 8-9, and stir for 20-40 minutes;

[0073] S7. Cool the mixture to below 40° C., add 1% A-151 and 0.2% alkyl sulfate compound, and stir for 20 to 40 minutes to obtain the cold-hard phenolic resin of this embodiment.

[0074] Example 4

[0075] A cold-hard phenolic resin comprises, by weight percentage, 11.1% phenol, 7.4% cardanol, 35% liquid formaldehyde, 2% sodium hydroxide, 3.5% potassium hydroxide, 0.45% hexamethylenetetramine, 0.3% sodium lignin sulfonate, 0.75% tung oil, 0.8% melamine, 0.8% urea, 22.8% water, 8.22% propylene glycol, 5.48% methanol, 0.63% formic acid, 0.5% silane coupling agent (KH-792) and 0.27% polyether-modified alcohol compound.

[0076] The preparation method of the chilled phenolic resin may include the following steps:

[0077] S1. Add 11.1% phenol and 7.4% cardanol into a reactor, start stirring and heating, and raise the temperature to 40°C to 50°C; add 1% sodium hydroxide and 2% potassium hydroxide into the reactor and stir for 10min to 20min;

[0078] S2. Add 35% liquid formaldehyde into the reactor, heat to 70°C to 80°C, and stir for 90min to 150min;

[0079] S3. Add 1% sodium hydroxide, 1.5% potassium hydroxide, 0.45% hexamethylenetetramine, 0.3% sodium lignin sulfonate and 0.75% tung oil into the reactor, heat to 80-90°C, and stir for 90-150 minutes;

[0080] S4. Add 0.8% melamine and 0.8% urea into the reactor and stir for 20 to 40 minutes;

[0081] S5. Cool the temperature to 55-65°C, add 22.8% water, 8.22% propylene glycol and 5.48% methanol into the reactor, and stir for 20-40 minutes;

[0082] S6. Add 0.63% formic acid into the reactor, adjust the pH to 8-9, and stir for 20-40 minutes;

[0083] S7. Cool the mixture to below 40° C., add 0.5% KH-792 and 0.27% polyether-modified alcohol compound, and stir for 20 to 40 minutes to obtain the chilled phenolic resin of this embodiment.

[0084] Example 5

[0085] A cold-hard phenolic resin comprises, by weight percentage, 19.5% phenol, 0.8% hydroquinone, 29.35% liquid formaldehyde, 1.8% sodium hydroxide, 2.7% triethylamine, 0.225% hexamethylenetetramine, 0.15% sodium lignin sulfonate, 0.375% tung oil, 0.7% hydroxylamine hydrochloride, 0.7% sodium sulfite, 32% water, 7.35% ethylene glycol, 3.15% ethanol, 0.35% acetic acid, 0.55% silane coupling agent (KH-560) and 0.3% acetylenic diol compound.

[0086] The preparation method of the chilled phenolic resin may include the following steps:

[0087] S1. Add 19.5% phenol and 0.8% hydroquinone into a reactor, start stirring and heating, and raise the temperature to 40°C to 50°C; add 1% sodium hydroxide and 1.5% triethylamine into the reactor and stir for 10min to 20min;

[0088] S2. Add 29.35% liquid formaldehyde into the reactor, heat to 70°C to 80°C, and stir for 90min to 150min;

[0089] S3. Add 0.8% sodium hydroxide, 1.2% triethylamine, 0.225% hexamethylenetetramine, 0.15% sodium lignin sulfonate and 0.375% tung oil into the reactor, heat to 80-90°C, and stir for 90-150 minutes.

[0090] S4. Add 0.7% hydroxylamine hydrochloride and 0.7% sodium sulfite into the reactor and stir for 20 to 40 minutes;

[0091] S5. Cool down to 55-65°C, add 32% water, 7.35% ethylene glycol and 3.15% ethanol into the reactor, and stir for 20-40 minutes;

[0092] S6. Add 0.35% acetic acid to the reactor, adjust the pH to 8-9, and stir for 20-40 minutes;

[0093] S7. Cool the mixture to below 40° C., add 0.55% KH-560 and 0.3% acetylene glycol compound, and stir for 20 to 40 minutes to obtain the cold-hard phenolic resin of this embodiment.

[0094] The initial viscosities of the resin samples of Examples 1-5 of the present application and the comparative (existing alkaline phenolic resin) were all adjusted to 10 mPa·s and tested. The test results are shown in Table 1. It should be noted that the initial viscosity of each resin sample was adjusted by adding a solvent, and the solvent used for adjusting each resin sample should be the same as the solvent used in its preparation process.

[0095] Table 1 Test results

[0096]

[0097] The above-described embodiments merely illustrate several implementations of the present invention, and while their descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the patent. It should be noted that a person skilled in the art would be able to make numerous variations and improvements without departing from the spirit of the present invention, all of which fall within the scope of protection of the present invention. Therefore, the scope of protection of the patent for this invention shall be determined by the appended claims.

Claims

1. A cold-hard phenolic resin, characterized in that Calculated by mass percentage, it includes: 15% to 25% phenolic compounds, 20% to 35% aldehyde compounds, 2.5% to 6% alkaline catalysts, 0.5% to 1.5% modifiers, 0.8% to 2% formaldehyde removers, 20% to 32% water, 8% to 18% alcohol compounds, 0.3% to 1% pH regulators, 0.5% to 1% silane coupling agents, and 0.05% to 0.3% surfactants; The phenolic compound includes at least one of phenol, bisphenol A, and cardanol; The aldehyde compound is liquid formaldehyde.

2. The cold-hardening phenolic resin according to claim 1, wherein The alkaline catalyst includes at least one of sodium hydroxide, potassium hydroxide, ammonia water, and triethylamine.

3. The cold-hardening phenolic resin according to claim 1, wherein The modifier is a mixture of hexamethylenetetramine, sodium lignin sulfonate and tung oil.

4. The cold-hardening phenolic resin according to claim 1, wherein The formaldehyde remover includes at least one of urea, hydroxylamine hydrochloride, sodium sulfite and melamine.

5. The chilled phenolic resin according to claim 1, wherein The alcohol compound comprises a high-boiling-point alcohol compound and a low-boiling-point alcohol compound; the ratio of the added amount of the high-boiling-point alcohol compound to the low-boiling-point alcohol compound is 1 to 4:

1.

6. The chilled phenolic resin according to claim 5, characterized in that The high-boiling-point alcohol compound includes at least one of ethylene glycol and propylene glycol; the low-boiling-point alcohol compound includes at least one of isopropanol, methanol, and ethanol.

7. The chilled phenolic resin according to claim 1, wherein The pH adjuster includes at least one of formic acid, acetic acid, citric acid, and salicylic acid.

8. The chilled phenolic resin according to claim 1, wherein The surfactant includes at least one of a phosphate compound, an acetylene glycol compound, a polyether-modified alcohol compound, and an alkyl sulfate compound.

9. The chilled phenolic resin according to claim 1, wherein The silane coupling agent includes at least one of KH-560, KH-602, A-151, and KH-792.

10. A preparation method for the chilled phenolic resin according to any one of claims 1 to 9, characterized in that: The steps include: S1, adding the phenolic compound into the reactor, stirring and heating, raising the temperature to 40°C to 50°C; adding the alkaline catalyst into the reactor, stirring for 10min to 20min; S2. Add the aldehyde compound into the reaction kettle, raise the temperature to 70°C to 80°C, and stir for 90min to 150min; S3, adding the alkaline catalyst and the modifier into the reactor, heating to 80°C to 90°C, and stirring for 90min to 150min; S4, add the formaldehyde removal agent into the reactor and stir for 20min to 40min; S5, cooling to 55°C to 65°C, adding the water and the alcohol compound into the reactor, and stirring for 20min to 40min; S6. Add the pH regulator into the reactor to adjust the pH to 8-9, and stir for 20-40 minutes; S7. Cooling to below 40° C., adding the silane coupling agent and the surfactant, and stirring for 20 to 40 minutes.

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