Three-component amine process cold-box binder

Abstract

A three-component amine process cold box binder is disclosed comprising: Component A comprising a phenol-formaldehyde resin; Component B comprising a polyisocyanate; and Component C comprising a compound having the structure shown in Formula (I) and Formula (II); Formula (I) is R 1 -R 2 -R x1 (OR) 2‑x1 Si-(O-Si-R x2 (OR) 2‑x2 ) n -O-SiR x3 (OR) 2‑x3 -R 3 -R 4 , Formula (II) is (OR) m1 (R) 3‑m1 Si-R 5 -R 6 -NH-R 7 -R 8 -Si(R) 3‑m2 (OR) m2 ; wherein R 1 and R 4 are independently selected from alkyl, alkoxy and alkylamino groups having from 1 to 20 carbon atoms, R 2 , R 3 , R 5 , R 6 , R 7 and R 8 are independently selected from alkylene, alkoxyalkylene and alkylaminoalkylene groups having from 1 to 20 carbon atoms, and each R is independently selected from alkyl and aryl groups.

Description

Technical Field

[0001] This application relates to the field of adhesive technology, specifically to a three-component amine-based cold box adhesive. Background Technology

[0002] In existing technologies, the resin binder used in the amine-based cold box process includes phenolic resin components and polyisocyanate components, which is a polyurethane-based casting binder system. A casting mixture is prepared by mixing the binder with casting aggregates, and then hardened using an alkaline catalyst.

[0003] Therefore, binders are typically required to have low viscosity, and both components contain a large amount of aromatic solvents, which may include compounds such as toluene, xylene, 1,2,4-trimethylbenzene, naphthalene, and other aromatic compounds. Generally, the solvent for the phenolic resin component is a mixture of high-boiling polar solvents (such as esters and ketones) and high-boiling aromatics. The solvent for the polyisocyanate component is a high-boiling aromatic. In recent years, the environmental problems caused by the use of aromatic solvents in casting binders have received increasing attention.

[0004] The catalysts used in the amine-based cold box process include triethylamine, dimethylethylamine, and dimethylisopropylamine. Due to its low cost, triethylamine is commonly used as the catalyst. Its advantages include rapid hardening, high core dimensional accuracy, and energy savings, meeting the requirements of high-quality, high-efficiency, and energy-saving casting production. It is suitable for the mass production of complex sand cores and is now widely used in industries such as automobiles, internal combustion engines, locomotives, aircraft, and pump manufacturing, becoming the mainstream of various core-making processes.

[0005] With the increasing demand for large-volume casting production, the core-making unit is becoming more and more streamlined, integrating into a core-making center. This involves using robots to automatically and continuously process various sand cores manufactured by cold box core shooters, performing a series of operations such as core extraction, core assembly, and impregnation coating. The requirements for the performance of casting cores are becoming increasingly stringent, which necessitates the use of amine-based cold box binders with excellent performance.

[0006] CN107624124A discloses a three-component polyurethane adhesive system. The first two components are conventional and used in cold box or self-curing processes. The third component, when used in combination with the first two components, includes at least an alkyl silicate and optionally a bipodial aminosilane. The use of organic adhesive systems provides improved tensile strength for molds, especially under high relative humidity. However, alkyl silicates, particularly tetraethyl silicate, can form a gel in acidic washing solutions used to reduce amine curing gases. The resulting white silica particles can deposit on castings, accumulate in used sand, or be carried in the air. This makes it prone to fracture defects due to insufficient sand core strength when preparing cores with complex shapes, especially during humid seasons, leading to high scrap rates and decreased product quality.

[0007] Application content

[0008] To address the problems of insufficient strength of sand cores and molds, high scrap rates, and declining quality in existing technologies, this application provides an environmentally friendly three-component amine-based cold box binder that significantly improves the strength of sand cores and molds, reduces the amount of binder required, decreases the emission of black smoke and toxic gases during casting, protects the ecological environment, and improves the yield of castings.

[0009] The specific technical solution of this application is as follows:

[0010] 1. A three-component amine-based cold box adhesive, wherein it comprises:

[0011] Component A includes phenolic resin;

[0012] Component B, which includes polyisocyanate; and

[0013] Component C, comprising compounds with structures shown in formula (I) and / or formula (II) below;

[0014] R 1 -R 2 -R x1 (OR) 2-x1 Si-O-Si-R x2 (OR) 2-x2 n -O-SiR x3 (OR) 2-x3 -R 3 -R 4 Formula (I),

[0015] (OR) m1 (R) 3-m1 Si-R 5 -R 6 -NH-R 7 -R 8 -Si(R) 3-m2 (OR) m2 Equation (II);

[0016] Among them, R 1 and R 4 Independently selected from alkyl, alkoxy, and alkylamino groups having 1 to 20 carbon atoms, R 2 R 3 R 5 R 6 R 7 and R 8 Each R is independently selected from alkylene, alkoxyene, and alkylamino groups having 1 to 20 carbon atoms, and each R is independently selected from alkyl and aryl groups.

[0017] 2. The cold box adhesive according to item 1, wherein R 1 and R 4 They are independently selected from alkyl, alkoxy, and alkylamino groups having 1 to 10 carbon atoms;

[0018] Preferably, R 1 and R 4 They are independently selected from alkyl, alkoxy, and alkylamino groups having 1 to 4 carbon atoms;

[0019] Preferably, R 1 and R 4 They are independently selected from ethylamino and propanamino.

[0020] 3. The cold box adhesive according to item 1 or 2, wherein R 2 R 3 R 5 R 6 R 7 and R 8 They are independently selected from alkylene, alkoxyene, and alkylaminoenes having 1 to 10 carbon atoms;

[0021] Preferably, R 2 R 3 R 5 R 6 R 7 and R 8 They are independently selected from alkylene, alkeneoxy, and alkyleneamino groups having 1 to 4 carbon atoms;

[0022] Preferably, R 2 R 3 R 5 R 6 R 7 and R 8 They are independently selected from ethyleneamino and propyleneamino.

[0023] 4. The cold box adhesive according to any one of items 1 to 3, wherein each R is independently selected from alkyl groups having 1 to 10 carbon atoms;

[0024] Preferably, each R is independently selected from alkyl groups having 1 to 6 carbon atoms;

[0025] Preferably, each R is independently selected from methyl and ethyl.

[0026] 5. The cold box adhesive according to any one of items 1 to 4, wherein x1, x2, and x3 are independently selected from 0 and 1;

[0027] Preferably, n is an integer from 1 to 100, more preferably an integer from 1 to 50, and even more preferably an integer from 2 to 40;

[0028] Preferably, m1 and m2 are 1, 2, or 3 independently of each other;

[0029] Preferably, m1 and m2 are 2 or 3 independently.

[0030] 6. The cold box adhesive according to any one of claims 1 to 5, wherein, based on the total weight of the cold box adhesive, the cold box adhesive comprises: 40% to 64% of component A, 35% to 60% of component B, and 0.1% to 8% of component C;

[0031] Preferably, based on the total weight of the cold box adhesive, the cold box adhesive comprises: 45% to 59% of component A, 40% to 55% of component B, and 0.5% to 5% of component C;

[0032] Preferably, based on the total weight of component A, component A comprises: 55%–70% phenolic resin, 10–20% ester solvent, and 5–25% aromatic solvent;

[0033] Preferably, based on the total weight of component A, component A comprises: 60%–67% phenolic resin, 10%–15% ester solvent, and 6%–20% aromatic solvent;

[0034] Preferably, based on the total weight of component B, component B comprises: 65-94% polyisocyanate, 5-20% aromatic solvent, and 0-15% ester solvent;

[0035] Preferably, based on the total weight of component B, component B comprises: 70%–90% polyisocyanate, 5%–15% aromatic solvent, and 0%–10% ester solvent.

[0036] 7. The cold box adhesive according to any one of items 1 to 6, wherein the phenolic resin is a benzyl ether phenolic resin, preferably a high-ortho-benzyl ether phenolic resin;

[0037] Preferably, the benzyl ether phenolic resin has a weight-average molecular weight of 500-2000, more preferably 600-1200.

[0038] 8. The cold box adhesive according to any one of items 1 to 7, wherein the polyisocyanate is selected from any one, two, or three of diphenylmethane-4,4'-diisocyanate, crude diphenylmethane-4,4'-diisocyanate, and polymethylene polyphenyl polyisocyanate.

[0039] 9. The cold box adhesive according to item 8, wherein the ester solvent is selected from any one or more of dibutyl phthalate, dioctyl phthalate, diisobutyl phthalate, diisooctyl phthalate, dioctyl adipate, dimethyl adipate, dimethyl succinate, and dimethyl glutarate.

[0040] 10. The cold box binder according to item 8, wherein the aromatic solvent is selected from any one or more of kerosene, benzene, toluene, xylene, ethylbenzene, and liquid petroleum aromatic fractions with a distillation range of 150–290°C.

[0041] The effects of the invention

[0042] The amine-based cold core box binder of this application simultaneously contains phenolic resin, polyisocyanate, and compounds of formula (I) and formula (II). The combined use of these components, especially the compounds with structures shown in formula (I) and formula (II), reacts with the phenolic resin, significantly improving the curing speed and strength of the sand core, particularly its moisture resistance. At the same time, it reduces the amount of binder added, saving costs and reducing the emission of black smoke and harmful gases during casting. It also reduces the addition of aromatic solvents, which is beneficial to environmental protection. Detailed Implementation

[0043] The following specific embodiments illustrate and explain the implementation of this application in detail, but the following content should not be construed as limiting this application in any way.

[0044] Unless otherwise defined, technical and scientific terms used in this specification have the same meaning as commonly understood by one of ordinary skill in the art. While similar or identical methods and materials may be applied in experimental or practical applications, materials and methods are described herein. In case of conflict, the definitions included herein shall prevail. Furthermore, materials, methods, and examples are for illustrative purposes only and are not intended to be limiting. The present application is further described below with reference to specific embodiments, but is not intended to limit the scope of the application.

[0045] This application provides a three-component amine-based cold box adhesive, wherein it comprises:

[0046] Component A includes phenolic resin;

[0047] Component B, which includes polyisocyanate; and

[0048] Component C includes compounds with structures shown in formulas (I) and (II) below;

[0049] R 1 -R 2 -R x1 (OR) 2-x1Si-O-Si-R x2 (OR) 2-x2 nO-SiR x3 (OR) 2-x3 -R 3 -R 4 Formula (I),

[0050] (OR) m1 (R) 3-m1 Si-R 5 -R 6 -NH-R 7 -R 8 -Si(R) 3-m2 (OR) m2 Equation (II);

[0051] Among them, R 1 and R 4 Independently selected from alkyl, alkoxy, and alkylamino groups having 1 to 20 carbon atoms, R 2 R 3 R 5 R 6 R 7 and R 8 Each R is independently selected from alkylene, alkoxyene, and alkylamino groups having 1 to 20 carbon atoms, and each R is independently selected from alkyl and aryl groups.

[0052] The alkyl group having 1 to 20 carbon atoms can be substituted or unsubstituted, straight-chain or branched, and examples include: methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, eicosyl, etc., preferably alkyl groups having 1 to 10 carbon atoms, and more preferably alkyl groups having 1 to 4 carbon atoms.

[0053] Alkoxy groups with 1 to 20 carbon atoms can be substituted or unsubstituted, straight-chain or branched, and include: methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy, 2-methylbutoxy, 3-methylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1-propylbutoxy, pentoxy, isopentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1-ethylpentoxy, 2-ethylpentoxy, 3-ethylpentoxy, hexyl... The alkoxy group includes alkoxy groups such as isohexoxy, 2-methylhexoxy, 3-methylhexoxy, 4-methylhexoxy, 5-methylhexoxy, 2-ethylhexoxy, heptoxy, isohexoxy, octoxy, isooctoxy, nonoxy, decoxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecanyloxy, octadecyloxy, nonadecanyloxy, and eicosyloxy, preferably alkoxy groups with 1 to 10 carbon atoms, and more preferably alkoxy groups with 1 to 4 carbon atoms.

[0054] The hydrogen atom in an amino group (-NH2) is partially or completely replaced by an alkyl group to form an alkylamino group. The alkylamino group having 1 to 20 carbon atoms can be substituted or unsubstituted, straight-chain or branched, and examples include: methylamino (-NHCH3), dimethylamino (-N(CH3)2), ethylamino, diethylamino, methylethylamino, propylamino, isopropylamino, butylamino, sec-butylamino, tert-butylamino, pentylamino, isopentylamino, neopentylamino, 2,3-dimethylpropylamino, 1-ethylpropylamino, 1-methylbutylamino, hexylamino, isohexylamino, 1,1,2-trimethylpropylamino, heptylamino, octylamino, nonylamino, decylamino, undecylamino, dodecylamino, tridecylamino, tetradecylamino, pentadecylamino, hexadecylamino, heptadecanylamino, octadecylamino, nonadecanylamino, eicosylamino, etc., preferably alkylamino groups having 1 to 10 carbon atoms, more preferably alkylamino groups having 1 to 4 carbon atoms.

[0055] The alkylene groups having 1 to 20 carbon atoms can be substituted or unsubstituted, straight-chain or branched, and examples include: methylene, ethylene, propylene, isopropylene, butylene, sec-butylene, isobutylene, tert-butylene, pentamethyleneene, neopentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecanylene, octadecylene, nonadecanylene, eicosylene, etc., preferably alkylene groups having 1 to 10 carbon atoms, and more preferably alkylene groups having 1 to 4 carbon atoms.

[0056] The alkoxides having 1 to 20 carbon atoms can be substituted or unsubstituted, straight-chain or branched, and examples include: methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy, pentaoxy, isopentoxy, hexoxy, isohexoxy, heptoxy, isohexoxy, octoxy, isooctoxy, nonoxy, decoxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecanoxy, octadecyloxy, nonadecanoxy, eicosyloxy, etc., preferably alkoxides having 1 to 10 carbon atoms, and more preferably alkoxides having 1 to 4 carbon atoms.

[0057] The alkylamino group having 1 to 20 carbon atoms can be substituted or unsubstituted, straight-chain or branched, and examples include: methylamino (NHCH2), ethylamino (NHC2H4), propylamino (NHC3H6), butylamino, pentyloamino, isopentylamino, hexylamino, heptaylamino, octylamino, nonylamino, decylamino, undecylamino, dodecylamino, tridecylamino, tetradecylamino, pentadecylamino, hexadecylamino, heptadecanylamino, octadecylamino, nonadecanylamino, eicosylamino, etc., preferably an alkylamino group having 1 to 10 carbon atoms, more preferably an alkylamino group having 1 to 4 carbon atoms.

[0058] "Aryl" refers to a monovalent cyclic aromatic hydrocarbon moiety composed of a monocyclic, bicyclic, or tricyclic aromatic ring. The aryl group may be optionally substituted or not substituted. Examples of aryl groups include, but are not limited to: phenyl, naphthyl, phenanthryl, fluorenyl, indene, chamomilecycloyl, oxadiphenyl, biphenyl, methylenediphenyl, aminodiphenyl, diphenylsulfonyl, diphenylisopropylidene, benzodioxane, benzofuranyl, benzopyranyl, benzooxazinyl, benzooxazinoneyl, benzopiperidinyl, benzopiperazinyl, benzopyrrolidinyl, benzomorpholinyl, methylenedioxyphenyl, ethylenedioxyphenyl, and their partially hydrogenated derivatives; preferred aryl groups are phenyl, naphthyl, phenanthryl, fluorenyl, indene, chamomilecycloyl, and biphenyl; more preferably, phenyl or naphthyl, and particularly preferably phenyl.

[0059] In one specific embodiment, each R is independently selected from alkyl groups having 1 to 10 carbon atoms, specifically methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl; preferably methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl; more preferably methyl or ethyl.

[0060] In a preferred embodiment, R 1and R 4 Selected independently from ethylamino and propanamino, R 2 R 3 R 5 R 6 R 7 and R 8 Each of the Rs is independently selected from ethyleneamino and propyleneamino, and each R is independently selected from methyl and ethyl.

[0061] In one specific embodiment, x1, x2, and x3 are independently selected from 0 and 1, and n is an integer from 1 to 100, such as 1, 2, 4, 6, 8, 10, 12, 14, 18, 20, 22, 25, 28, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, etc., preferably an integer from 1 to 50, and more preferably an integer from 2 to 40.

[0062] In one specific implementation, m1 and m2 are independently 1, 2 or 3, preferably 2 or 3.

[0063] In one specific embodiment, based on the total weight of the cold box adhesive, the cold box adhesive comprises: 40%–64% component A, 35%–60% component B, and 0.1%–8% component C. For example, it may include 40%, 42%, 44%, 45%, 46%, 48%, 50%, 52%, 54%, 56%, 58%, 60%, 62%, 64%, etc., of component A, and 35%, 36%, etc., of component B, B, C, etc. Component B, with concentrations of 38%, 40%, 42%, 44%, 46%, 48%, 50%, 52%, 54%, 55%, 56%, 58%, and 60%, and component C, with concentrations of 0.1%, 0.5%, 0.7%, 1%, 1.2%, 1.4%, 1.6%, 18%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, and 8%.

[0064] In a preferred embodiment, the cold box adhesive comprises, based on the total weight of the cold box adhesive, 45% to 59% of component A, 40% to 55% of component B, and 0.5% to 5% of component C.

[0065] In most cases, a diluent (solvent) needs to be introduced into the cold box binder to reduce the viscosity of the components, making the binder suitable for uniform mixing with the molding sand. Solvents that can be used include ester solvents and aromatic solvents.

[0066] In one specific embodiment, based on the total weight of component A, component A comprises: 55%–70% phenolic resin, 10%–20% ester solvent, and 5%–25% aromatic solvent; for example, it may include 55%, 57%, 59%, 60%, 62%, 64%, 66%, 68%, 70% of phenolic resin, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 18%, 20% of ester solvent, and 5%, 7%, 8%, 10%, 12%, 14%, 16%, 18%, 20%, 22%, 25% of aromatic solvent. In a preferred embodiment, based on the total weight of component A, component A comprises: 60%–67% phenolic resin, 10%–15% ester solvent, and 6%–20% aromatic solvent.

[0067] In one specific embodiment, based on the total weight of component B, component B comprises: 65% to 94% polyisocyanate, 5% to 20% aromatic solvent, and 0% to 15% ester solvent, such as 65%, 67%, 69%, 70%, 72%, 74%, 76%, 78%, 80%, 82%, 84%, 86%, 88%, 90%, 92%, 94% of polyisocyanate, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20% of aromatic solvent, and 0%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15% of ester solvent. In a preferred embodiment, based on the total weight of component B, component B comprises: 70% to 90% polyisocyanate, 5% to 15% aromatic solvent, and 0% to 10% ester solvent.

[0068] In one specific embodiment, based on the total weight of the cold box adhesive, the cold box adhesive consists of 40% to 64% component A, 35% to 60% component B, and 0.1% to 8% component C.

[0069] In one specific embodiment, based on the total weight of the cold box adhesive, the cold box adhesive consists of 45% to 59% component A, 40% to 55% component B, and 0.5% to 5% component C.

[0070] In one specific embodiment, based on the total weight of component A, component A is composed of 55%–70% phenolic resin, 10%–20% ester solvent, and 5%–25% aromatic solvent; based on the total weight of component B, component B is composed of 65%–94% polyisocyanate, 5%–20% aromatic solvent, and 0%–15% ester solvent; and in component C, the total mass of compounds with the structures shown in formulas (I) and (II) accounts for more than 90% of the mass of component C, for example, it can be 90%, 92%, 94%, 96%, 98%, 100%, etc.

[0071] In one specific embodiment, based on the total weight of component A, component A is composed of 60%–67% phenolic resin, 10%–15% ester solvent, and 6%–20% aromatic solvent. Based on the total weight of component B, component B is composed of 70%–90% polyisocyanate, 5%–15% aromatic solvent, and 0%–10% ester solvent. In component C, the total mass of compounds with the structures shown in formulas (I) and (II) accounts for more than 90% of the mass of component C, for example, it can be 90%, 92%, 94%, 96%, 98%, 100%, etc.

[0072] In a preferred embodiment, in the adhesive, the mass percentage of component A is not less than the mass percentage of component B; and in component C, the mass of the compound with the structure shown in formula (I) is greater than the mass of the compound with the structure shown in formula (II).

[0073] In a preferred embodiment, the molar ratio of the compound with the structure shown in formula (I) to the compound with the structure shown in formula (I) in component C is 1:0.1 to 0.25.

[0074] In one embodiment, component A may contain additives. In one embodiment, component B may contain additives.

[0075] In this application, the phenolic resin is typically a benzyl ether type phenolic resin, preferably a high-ortho-benzyl ether phenolic resin. In this application, the weight-average molecular weight of the benzyl ether phenolic resin is preferably between 500 and 2000, more preferably between 600 and 1200. An example of the preparation of this benzyl ether phenolic resin is disclosed in the applicant's Chinese patent CN200710188114.3. The benzyl ether phenolic resin used in the examples below is also this resin.

[0076] The polyisocyanate has two or more, preferably from two to five, functionalities. It can be aliphatic, alicyclic, or aromatic, or a mixture of these polyisocyanates. These polyisocyanates can also be protected polyisocyanates, polyisocyanate prepolymers, and polyisocyanate quasi-prepolymers. The polyisocyanates used in this application include, but are not limited to, diphenylmethane-4,4'-diisocyanate (hereinafter “MDI”), crude diphenylmethane-4,4'-diisocyanate (hereinafter “crude” MDI), or polymethylene polyphenyl polyisocyanate (hereinafter “PAPI”).

[0077] In one specific embodiment, the ester solvent is selected from any one or more of dibutyl phthalate, dioctyl phthalate, diisobutyl phthalate, diisooctyl phthalate, dioctyl adipate, dimethyl adipate, dimethyl succinate, and dimethyl glutarate; the aromatic solvent is selected from any one or more of kerosene, benzene, toluene, xylene, ethylbenzene, and liquid petroleum aromatic fractions with a distillation range of 150–290°C.

[0078] Example

[0079] In the following specific examples and comparative examples, component C was provided by Jinan Shengquan Group Co., Ltd. The model of component C in Examples 1 to 4 is CBR-III-616-A, and the models of component C in Examples 5 and 6 are CBR-III-616-B and CBR-III-616-C, respectively. The high-ortho-benzyl ether phenolic resin was prepared according to Example 1 in patent CN200710188114.3. The polyisocyanate model is CBR-II-816, which is from Jinan Shengquan Group Co., Ltd. Unless otherwise specified, all other materials and reagents are commercially available.

[0080] Example 1

[0081] (1) In a mixing vessel, add 6.5 kg of high ortho-benzyl ether phenolic resin with a weight average molecular weight of 800-1200, 1.5 kg of dioctyl phthalate, and 2 kg of aromatic hydrocarbon Solvesso 150, and stir for 2 h to obtain component A;

[0082] (2) In a mixing vessel, add 8 kg of polyisocyanate, 1.94 kg of aromatic Solvesso 150, and 0.06 kg of phosphorus oxychloride, and stir for 2 h to obtain component B;

[0083] (3) Component C consists of compounds of formula (I) and formula (II). The total mass of component C is 0.03 kg, and the molar ratio of compounds of formula (I) to (II) is 1:0.1–0.15.

[0084] Equation (I) is:

[0085] C2H5NH-CH2CH2NH-CH3(OCH3)Si-O-Si-CH3(OCH3) 40 -O-CH3(OCH3)Si-NHCH2CH2-NHC2H5;

[0086] Equation (II) is:

[0087] (OCH3)(CH3)2Si-CH2CH2NH-CH2CH2NH-NH-CH2CH2NH-CH2CH2NH-Si(CH3)2(OCH3);

[0088] (4) Package the above components A, B and C separately in three containers to obtain the high-performance amine-based cold box adhesive of this application. When it is ready for use, the three components are mixed together.

[0089] Example 2

[0090] (1) In a mixing vessel, add 7.15 kg of high ortho-benzyl ether phenolic resin with a weight average molecular weight of 800-1200, 1.65 kg of dioctyl phthalate, and 2.2 kg of aromatic hydrocarbon Solvesso 150, and stir for 2 h to obtain component A;

[0091] (2) In a mixing vessel, add 7.2 kg of polyisocyanate, 1.746 kg of aromatic Solvesso 150, and 0.054 kg of phosphorus oxychloride, and stir for 2 h to obtain component B;

[0092] (3) Component C is composed of compound (I) and compound (II). The total mass of component C is 0.03 kg. The molar ratio of compound (I) and compound (II) is 1:0.1 to 0.14. The chemical formulas of compound (I) and compound (II) are the same as those in Example 1.

[0093] (4) Package the above components A, B and C separately in three containers to obtain the high-performance amine-based cold box adhesive of this application. When it is ready for use, the three components are mixed together.

[0094] Example 3

[0095] The difference between this embodiment and Embodiment 2 is that the total mass of component C is 0.105 kg.

[0096] Example 4

[0097] The difference between this embodiment and Embodiment 2 is that the total mass of component C is 1.05 kg.

[0098] Example 5

[0099] The difference between this embodiment and Example 2 is that the molar ratio of compound (I) to compound (II) is 1:0.15 to 0.2.

[0100] Example 6

[0101] The difference between this embodiment and Example 2 is that the molar ratio of compound (I) to compound (II) is 1:0.21 to 0.25.

[0102] Comparative Example 1

[0103] The difference between this comparative example and Example 1 is that it does not contain component C.

[0104] Comparative Example 2

[0105] This comparative example uses commercially available cold box adhesives GP201SC / GP202SC (including components I and II), provided by Jinan Shengquan Group Co., Ltd.

[0106] The key parameters of each embodiment and comparative example are summarized in Table 1 below.

[0107] Table 1

[0108]

[0109] Test case

[0110] To demonstrate the positive effects of the three-component amine-based cold box binder containing siloxane of the present invention, the flexural strength performance of the resin sand was tested in accordance with GB2684 / T-2009 "Test Methods for Raw Sand and Mixtures for Foundry".

[0111] The binders from Examples 1-6 were mixed with the Dahlin standard sand at a mass ratio of 100:0.6 to Dahlin standard sand to form resin sand. Specifically, components A and C were first added and mixed with the Dahlin standard sand for 1 minute, then component B was added and mixed for 2 minutes. The resulting resin sand was then blown and pressed into flexural test blocks of Examples 1-6 using an MLA1 core-making machine.

[0112] Following a mass ratio of 100:0.6 between Dahlin standard sand and component A, component A of the binder in Comparative Example 1 was mixed with Dahlin standard sand for 1 minute, followed by the addition of component B and mixing for 2 minutes. The resulting resin sand was then pressurized using an MLA1 core-making machine to form the bending test block of Comparative Example 1. Similarly, following a mass ratio of 100:0.6 between Dahlin standard sand and component I, component I of the binder in Comparative Example 2 was mixed with Dahlin standard sand for 1 minute, followed by the addition of component II and mixing for 2 minutes. The resulting resin sand was then pressurized using an MLA1 core-making machine to form the bending test block of Comparative Example 2.

[0113] The core-making process parameters for each embodiment and comparative example are as follows: sand injection pressure 0.4 MPa, amine blowing pressure 0.2 MPa, washing pressure 0.2 MPa, amine quantity 0.4 mL, and amine blowing and purification time 8 s.

[0114] The initial strength at 5s, strength at 1h, strength at 3h, high dry strength at 24h, and high wet strength at 24h (humidity ≥95%) of the figure-eight tensile test blocks were measured respectively, and the results are shown in Table 2.

[0115] Table 2. Flexural strength (MPa) of cold-box resin sand molds at room temperature (23℃)

[0116]

[0117] As can be seen from Table 2 above, the cold core box adhesive of this application has a fast curing speed and high initial strength, which significantly improves the strength of the sand core, extends the storage time of the sand core, reduces the scrap rate of the sand core and sand mold, and improves the quality of the casting.

[0118] The principles and implementation methods of this application have been described above with reference to specific embodiments. The description of the embodiments above is only for the purpose of helping to understand the method and core ideas of this application. For those skilled in the art, various modifications and variations to certain details of the above content do not require creative effort. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application should be included within the protection scope of this application.

Claims

1. A three-component amine-based cold box adhesive, wherein, It includes: Component A includes phenolic resin; Component B, which includes polyisocyanate; and Component C includes compounds with structures shown in formulas (I) and (II) below; R 1 -R 2 -R x1 (OR) 2-x1 Si-[O-Si-R x2 (OR) 2-x2 n -O-SiR x3 (OR) 2-x3 -R 3 -R 4 Formula (I)​ (OR) m1 (R) 3-m1 Si-R 5 -R 6 -NH-R 7 -R 8 -Si(R) 3-m2 (OR) m2 Formula (II); Among them, R 1 and R 4 Independently selected from alkyl, alkoxy, and alkylamino groups having 1 to 20 carbon atoms, R 2 R 3 R 5 R 6 R 7 and R 8 Each R is independently selected from alkylene, alkoxyene, and alkylamino groups having 1 to 20 carbon atoms, and each R is independently selected from alkyl and aryl groups.

2. The cold box adhesive according to claim 1, wherein, R 1 and R 4 They are independently selected from alkyl, alkoxy, and alkylamino groups having 1 to 10 carbon atoms.

3. The cold box adhesive according to claim 1, wherein, R 1 and R 4 They are independently selected from alkyl, alkoxy, and alkylamino groups having 1 to 4 carbon atoms.

4. The cold box adhesive according to claim 1, wherein, R 1 and R 4 They are independently selected from ethylamino and propanamino.

5. The cold box adhesive according to claim 1, wherein, R 2 R 3 R 5 R 6 R 7 and R 8 They are independently selected from alkylene, alkoxyene, and alkylaminoenes having 1 to 10 carbon atoms.

6. The cold box adhesive according to claim 1, wherein, R 2 R 3 R 5 R 6 R 7 and R 8 They are independently selected from alkylene, alkoxy, and alkylamino groups having 1 to 4 carbon atoms.

7. The cold box adhesive according to claim 1, wherein, R 2 R 3 R 5 R 6 R 7 and R 8 They are independently selected from ethyleneamino and propyleneamino.

8. The cold box adhesive according to claim 1, wherein, Each R is independently selected from alkyl groups having 1 to 10 carbon atoms.

9. The cold box adhesive according to claim 1, wherein, Each R is independently selected from alkyl groups having 1 to 6 carbon atoms.

10. The cold box adhesive according to claim 1, wherein, Each R is independently selected from methyl and ethyl.

11. The cold box adhesive according to claim 1, wherein, x1, x2, and x3 are independently selected from 0 and 1.

12. The cold box adhesive according to claim 1, wherein, n is an integer from 1 to 100.

13. The cold box adhesive according to claim 1, wherein, n is an integer from 1 to 50.

14. The cold box adhesive according to claim 1, wherein, n is an integer from 2 to 40.

15. The cold box adhesive according to claim 1, wherein, m1 and m2 are independently 1, 2 or 3.

16. The cold box adhesive according to claim 1, wherein, m1 and m2 are either 2 or 3.

17. The cold box adhesive according to claim 1, wherein, Based on the total weight of the cold box adhesive, the cold box adhesive comprises: 40% to 64% component A, 35% to 58% component B, and 0.1% to 8% component C.

18. The cold box adhesive according to claim 1, wherein, Based on the total weight of the cold box adhesive, the cold box adhesive comprises: 45% to 59% component A, 40% to 54% component B, and 0.5% to 5% component C.

19. The cold box adhesive according to claim 1, wherein, Based on the total weight of component A, component A includes: 55%–70% phenolic resin, 10%–20% ester solvent, and 10%–25% aromatic solvent.

20. The cold box adhesive according to claim 1, wherein, Based on the total weight of component A, component A includes: 60%–67% phenolic resin, 13%–15% ester solvent, and 6%–20% aromatic solvent.

21. The cold box adhesive according to claim 1, wherein, Based on the total weight of component B, component B comprises: 65%–94% polyisocyanate, 5%–20% aromatic solvent, and 0%–15% ester solvent.

22. The cold box adhesive according to claim 1, wherein, Based on the total weight of component B, component B comprises: 76%–90% polyisocyanate, 5%–15% aromatic solvent, and 0%–10% ester solvent.

23. The cold box adhesive according to claim 1, wherein, The phenolic resin is benzyl ether phenolic resin.

24. The cold box adhesive according to claim 23, wherein, The phenolic resin is a high-ortho-benzyl ether phenolic resin.

25. The cold box adhesive according to claim 23, wherein, The weight-average molecular weight of the benzyl ether phenolic resin is 500–2000.

26. The cold box adhesive according to claim 23, wherein, The weight-average molecular weight of the benzyl ether phenolic resin is 600–1200.

27. The cold box adhesive according to any one of claims 1 to 26, wherein, The polyisocyanate is selected from any one, two, or three of diphenylmethane-4,4'-diisocyanate, crude diphenylmethane-4,4'-diisocyanate, and polymethylene polyphenyl polyisocyanate.

28. The cold box adhesive according to any one of claims 19 to 22, wherein, The ester solvent is selected from any one or more of dibutyl phthalate, dioctyl phthalate, diisobutyl phthalate, diisooctyl phthalate, dioctyl adipate, dimethyl adipate, dimethyl succinate, and dimethyl glutarate.

29. The cold box adhesive according to any one of claims 19 to 22, wherein, The aromatic solvent is selected from any one or more of kerosene, benzene, toluene, xylene, ethylbenzene, and liquid petroleum aromatic fractions with a distillation range of 150–290°C.

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