WO2019001382A1 - 一种3d打印用粘结剂及其制备方法和应用 - Google Patents

一种3d打印用粘结剂及其制备方法和应用 Download PDF

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Publication number
WO2019001382A1
WO2019001382A1 PCT/CN2018/092586 CN2018092586W WO2019001382A1 WO 2019001382 A1 WO2019001382 A1 WO 2019001382A1 CN 2018092586 W CN2018092586 W CN 2018092586W WO 2019001382 A1 WO2019001382 A1 WO 2019001382A1
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WIPO (PCT)
Prior art keywords
printing
binder
parts
resin
reaction
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PCT/CN2018/092586
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English (en)
French (fr)
Inventor
祝建勋
白世龙
周国栋
Original Assignee
济南圣泉集团股份有限公司
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Priority to EP18824476.8A priority Critical patent/EP3646965A4/en
Publication of WO2019001382A1 publication Critical patent/WO2019001382A1/zh

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
    • B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
    • B22C1/22—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins
    • B22C1/2233—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • B22C1/224—Furan polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
    • B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C9/00—Moulds or cores; Moulding processes
    • B22C9/02—Sand moulds or like moulds for shaped castings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28—Chemically modified polycondensates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C08L61/14—Modified phenol-aldehyde condensates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G16/00—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00
    • C08G16/02—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes
    • C08G16/025—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with heterocyclic organic compounds
    • C08G16/0256—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with heterocyclic organic compounds containing oxygen in the ring
    • C08G16/0262—Furfuryl alcohol
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
    • C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol

Definitions

  • the present application relates to the field of 3D printed materials, and in particular to a binder for 3D printing, a preparation method and application thereof.
  • 3D printing technology has been receiving much attention since its birth more than 30 years ago. Some foreign companies that have made great achievements in 3D printing technology, including EXONE, Voxeljet and 3D Stratsys, have played a certain role in promoting 3D printing technology. With the advent of the third industrial revolution, it has become increasingly popular in the eyes of the general public.
  • the 3D printing scientific name is additive manufacturing technology. The principle is to decompose the three-dimensional model designed by the computer into several layers of planar slices, and then superimpose the "printing" materials layer by layer, and finally "stack" into a complete object.
  • 3D printing is used in the field of casting for inkjet printing technology to prepare cores and cores. At present, some industrial grade 3D printers have been used in casting production services, mainly for rapid prototyping of castings, remanufacturing molds, printing molds, Sand core, etc.
  • the publication No. 104086734A discloses a preparation method for a binder for 3D printing, which is simple in preparation, introduces a modifier and a coupling agent, and is prepared. The resin satisfies the requirements for use of the 3D printing apparatus, but does not improve the performance of the resin sand including the mechanical strength of the resin sand, the curing speed, and the sand falling.
  • the first object of the present application is to provide a binder for 3D printing, which has a very low room temperature viscosity and a viscosity of less than 10 mPa.s at 20 ° C, which satisfies the resin requirements of the print head in a 3D printing device.
  • the printing nozzle is not easy to block, easy to clean and clean, and plays a vital role in the maintenance and maintenance of the machine; the binder has good sand wrapping performance during the sanding process, and the printed sand type has high mechanical strength.
  • the curing speed is fast; the 3D printing adhesive is easy to operate in the sand falling sand, and the use performance is improved.
  • a second object of the present application is to provide a method for preparing the above-mentioned binder for 3D printing, which is simple and easy, and the obtained binder for 3D printing is excellent in overall performance and stable in performance.
  • a third object of the present application is to provide the use of the 3D printing adhesive in the preparation of a foundry sand mold for a 3D ink jet printing apparatus.
  • a binder for 3D printing comprising the following components: 15-60 parts by weight of furan resin, 42-68 parts of decyl alcohol, 1-12 parts of accelerator, 0.1-5 parts of additive; The phenolic resin is reacted with decyl alcohol to obtain.
  • the adhesive for 3D printing provided by the application has the synergistic cooperation between the components, and the viscosity at room temperature is extremely low, and the viscosity is lower than 10 mPa.s at 20 ° C, which satisfies the requirements of the printing nozzle on the resin in the 3D printing device.
  • the printing nozzle is not easy to block, easy to clean and clean, which plays a vital role in the maintenance and maintenance of the machine; the sand wrapping performance is good during the sanding process, the printed sand type has higher mechanical strength, and the curing speed is higher. Fast; easy to operate in sand and sand cleaning, improving the performance.
  • the mass ratio of the phenolic resin to the decyl alcohol is from 1:1 to 2.5.
  • the furan resin has a weight average molecular weight of from 200 to 350 g/mol.
  • the phenolic resin has a weight average molecular weight of from 150 to 250 g/mol.
  • the accelerator comprises one or more of resorcinol, catechol, bisphenol A, 2,5-dihydroxysterol.
  • the additive comprises one or more of polysorbate, sodium dioctylsuccinate, sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium laurate, sodium stearatekind.
  • the phenolic resin is polymerized from xylenol and formaldehyde;
  • the xylenol is 3,5-dimethylphenol.
  • the present application also provides a method for preparing a binder for 3D printing, comprising the following steps:
  • the preparation method of the 3D printing adhesive provided by the present application has the advantages of simple preparation steps, and the obtained 3D printing adhesive has low viscosity, high tensile strength, fast curing speed, excellent comprehensive performance and stable performance.
  • the phenolic resin is polymerized by polycondensation reaction of xylenol and formaldehyde.
  • the xylenol is 3,5-dimethylphenol.
  • the molar ratio of the 3,5-dimethylphenol to the formaldehyde is from 1:1 to 1.8.
  • the formaldehyde participates in the reaction in the form of an aqueous formaldehyde solution having a formaldehyde content of 35% to 48% by mass.
  • the step of dehydrating is further included after the polycondensation reaction.
  • step (a) the polycondensation reaction is carried out under the action of a catalyst.
  • the catalyst is triethylamine.
  • the catalyst is added in an amount of from 0.5% to 2.0% by weight based on the weight of the 3,5-dimethylphenol.
  • the polycondensation reaction is carried out at a pH of from 8.0 to 8.5.
  • the polycondensation reaction is: firstly reacting at a temperature of 80 ⁇ 2° C. for 0.5-1 h, and then heating to a temperature of 85 ⁇ 2° C. for 0.5-1 h.
  • step (a) is specifically:
  • the first mixture is adjusted to be acidic and reacted to form a furan resin.
  • the first mixture is adjusted to acidity using one or more of hydrochloric acid, formic acid, and phosphoric acid.
  • the acidic first mixture has a pH of from 3.5 to 5.5.
  • the reaction is carried out at 85-110 ° C for 1-2 hours.
  • the mass ratio of the phenolic resin to the decyl alcohol is from 1:1 to 2.5.
  • step (b) 15-60 parts of the furan resin, 42-68 parts of the decyl alcohol, 1-12 parts of the accelerator, and 0.1-5 parts of the additive are added in parts by weight.
  • the accelerator comprises one or more of resorcinol, catechol, bisphenol A, 2,5-dihydroxysterol.
  • the additive comprises one or more of polysorbate, sodium dioctylsuccinate, sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium laurate, sodium stearatekind.
  • the present application also provides the use of the above-described 3D printing adhesive in the preparation of a foundry sand mold by a 3D inkjet printing apparatus.
  • the prepared 3D printing adhesive has a very low room temperature viscosity, and the viscosity is lower than 10 mPa.s at 20 ° C, which satisfies the printing in the 3D printing device.
  • the requirements of the nozzle for the resin, the print nozzle is not easy to block, easy to clean and clean, and plays a vital role in the maintenance and maintenance of the machine.
  • the prepared 3D printing adhesive has good sand wrapping performance in the sand laying process, and the printed sand type has high mechanical strength and curing speed. Faster.
  • the method for preparing a 3D printing adhesive provided by the present application the prepared 3D printing adhesive is easy to handle in the sand falling sand, and the use performance is improved.
  • One aspect of the present application relates to a binder for 3D printing comprising the following components: 15-60 parts by weight of furan resin, 42-68 parts of decyl alcohol, 1-12 parts of accelerator, 0.1-5 parts of additive;
  • the furan resin is prepared by reacting a phenol resin with decyl alcohol.
  • the furan resin has a weight average molecular weight of 200 to 350 g/mol.
  • the furan resin in the present application is a mixture having a weight average molecular weight in the range of 200 to 350 g/mol.
  • the furan resin has a weight average molecular weight of from 200 to 300 g/mol; in some embodiments, the furan resin has a weight average molecular weight of from 200 to 250 g/mol; in some embodiments, the weight of the furan resin The average molecular weight is from 300 to 350 g/mol; in some embodiments, the furan resin has a weight average molecular weight of from 280 to 300 g/mol;
  • a furan resin is obtained by reacting a phenol resin with decyl alcohol.
  • the mass ratio of the phenolic resin to the decyl alcohol is from 1:1 to 2.5.
  • the mass ratio of phenolic resin to decyl alcohol may be 1:1, 1:1.5, 1:2, 1:2.5, and the like.
  • the phenolic resin has a weight average molecular weight of from 150 to 250 g/mol.
  • the phenolic resin in the present application is a mixture having a weight average molecular weight ranging from 150 to 250 g/mol.
  • the furan resin has a weight average molecular weight of from 150 to 200 g/mol; in some embodiments, the furan resin has a weight average molecular weight of from 180 to 250 g/mol; in some embodiments, the weight of the furan resin The average molecular weight is from 150 to 220 g/mol; in some embodiments, the furan resin has a weight average molecular weight of from 180 to 250 g/mol;
  • the phenolic resin is polymerized from xylenol and formaldehyde.
  • This step is a polycondensation reaction of xylenol and formaldehyde, and polymerization is carried out to obtain a phenol resin.
  • the xylenol is 3,5-dimethylphenol.
  • the phenolic resin obtained by the reaction of 3,5-dimethylphenol with formaldehyde is not easily entangled.
  • the molar ratio of the 3,5-dimethylphenol to the formaldehyde is from 1:1 to 1.8.
  • the molar ratio of 3,5-dimethylphenol to formaldehyde may be 1:1, 1:1.2, 1:1.5, 1:1.6, 1:1.7, 1:1.8, and the like.
  • the formaldehyde participates in the reaction in the form of an aqueous formaldehyde solution having a formaldehyde content of 35% to 48% by mass.
  • the mass percentage of formaldehyde in the aqueous formaldehyde solution may be 35%, 37%, 38%, 40%, 45%, 48%, and the like.
  • the step of dehydration after the polycondensation reaction in the step (a) further includes a step of dehydration.
  • the polycondensation reaction is carried out under the action of a catalyst.
  • the catalyst is triethylamine.
  • the catalyst is added in an amount of from 0.5% to 2.0% by weight based on the weight of the 3,5-dimethylphenol.
  • the amount of the catalyst added may be 0.5%, 0.8%, 1.0%, 1.2%, 1.5%, 1.8%, 2.0%, or the like by weight of the 3,5-dimethylphenol.
  • the solution is alkaline, that is, the polycondensation reaction in the step (a) is carried out under basic conditions.
  • the polycondensation reaction is carried out at a pH of from 8.0 to 8.5.
  • the pH of the polycondensation reaction in the step (a) may be 8.0, 8.2, 8.3, 8.4, 8.5 or the like.
  • the polycondensation reaction is: firstly reacting at a temperature of 80 ⁇ 2° C. for 0.5-1 h, and then heating to a temperature of 85 ⁇ 2° C. for 0.5-1 h.
  • the 3,5-dimethylphenol is more fully reacted with formaldehyde by gradually heating the reaction.
  • the phenol resin obtained after the reaction is a mixture, and the phenol resin has a weight average molecular weight of 150 to 250.
  • the accelerator comprises one or more of resorcinol, catechol, bisphenol A, 2,5-dihydroxysterol.
  • the additive comprises one of polysorbate, sodium dioctylsuccinate, sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium laurate, sodium stearate or A variety.
  • the 3D printing adhesive provided by the present application has enhanced synergy between the components, and has a very low viscosity at room temperature, and the viscosity is lower than 10 mPa.s at 20 ° C, which satisfies the printing nozzle in the 3D printing device.
  • the printing nozzle is not easy to block, easy to clean and clean, which plays a vital role in the maintenance and maintenance of the machine; the sand wrapping performance is good in the sanding process, and the printed sand type has high mechanical strength.
  • the curing speed is faster; it is easy to operate in sand falling sand and improves the performance.
  • Another aspect of the present application is also directed to a method of preparing the 3D printing adhesive, comprising the steps of:
  • the phenolic resin is polymerized by polycondensation reaction of xylenol and formaldehyde.
  • the xylenol is 3,5-dimethylphenol.
  • the phenolic resin obtained by the reaction of 3,5-dimethylphenol with formaldehyde is not easily entangled.
  • the molar ratio of the 3,5-dimethylphenol to the formaldehyde is from 1:1 to 1.8.
  • the molar ratio of 3,5-dimethylphenol to formaldehyde may be 1:1, 1:1.2, 1:1.5, 1:1.6, 1:1.7, 1:1.8, and the like.
  • the formaldehyde participates in the reaction in the form of an aqueous formaldehyde solution having a formaldehyde content of 35% to 48% by mass.
  • the mass percentage of formaldehyde in the aqueous formaldehyde solution may be 35%, 37%, 38%, 40%, 45%, 48%, and the like.
  • the step of dehydration after the polycondensation reaction in the step (a) further includes a step of dehydration.
  • the polycondensation reaction is carried out under the action of a catalyst.
  • the catalyst is triethylamine.
  • the addition of the catalyst promotes the progress of the polycondensation reaction of xylenol and formaldehyde.
  • the catalyst is added in an amount of from 0.5% to 2.0% by weight based on the weight of the 3,5-dimethylphenol.
  • the amount of the catalyst added may be 0.5%, 0.8%, 1.0%, 1.2%, 1.5%, 1.8%, 2.0%, or the like by weight of the 3,5-dimethylphenol.
  • the solution is alkaline, that is, the polycondensation reaction in the step (a) is carried out under basic conditions.
  • the polycondensation reaction is carried out at a pH of from 8.0 to 8.5.
  • the pH of the polycondensation reaction in the step (a) may be 8.0, 8.2, 8.3, 8.4, 8.5 or the like.
  • the polycondensation reaction is: firstly reacting at a temperature of 80 ⁇ 2° C. for 0.5-1 h, and then heating to a temperature of 85 ⁇ 2° C. for 0.5-1 h.
  • the 3,5-dimethylphenol is more fully reacted with formaldehyde by gradually heating the reaction.
  • the phenol resin obtained after the reaction is a mixture, and the phenol resin has a weight average molecular weight of 150 to 250.
  • step (a) is specifically:
  • the first mixture is adjusted to be acidic and reacted to form a furan resin.
  • the phenolic resin and the decyl alcohol are reacted under acidic conditions, and the reaction is a polycondensation reaction, and the reaction is sufficiently carried out sufficiently, and the obtained furan resin has small viscosity, high strength, and short curing time.
  • the mass ratio of the phenolic resin to the decyl alcohol is from 1:1 to 2.5, and the phenolic resin in this ratio is reacted with decyl alcohol to obtain a furan resin.
  • the mass ratio of phenolic resin to decyl alcohol may be 1:1.5, 1:1.8, 1:2, 1:2.2, 1:2.5, and the like.
  • the first mixture is adjusted to acidity using one or more of hydrochloric acid, formic acid, and phosphoric acid.
  • the acidic first mixture has a pH of from 3.5 to 5.5.
  • the pH may be 3.5, 4.0, 4.5, 5.0, 5.3, 5.5, and the like.
  • the reaction is carried out at 85-110 ° C for 1-2 hours.
  • the temperature of the polycondensation reaction may be 85 ° C, 90 ° C, 95 ° C, 98 ° C, 100 ° C, 102 ° C, 105 ° C, 110 ° C, etc.
  • the reaction time may be 60 min, 80 min, 90 min, 100 min, 120 min, and the like.
  • step (b) 15-60 parts of the furan resin, 42-68 parts of the decyl alcohol, 1-12 parts of the accelerator, and 0.1-5 parts of the additive are added in parts by weight.
  • the raw materials used in each step are synergistically combined, and the reaction is more fully and effectively obtained, and the obtained 3D printing adhesive has excellent comprehensive performance and stable and reliable performance.
  • the raw materials are mutually matched to further increase the overall performance of the obtained binder for 3D printing.
  • the accelerator comprises one or more of resorcinol, catechol, bisphenol A, 2,5-dihydroxysterol.
  • the additive comprises one or more of polysorbate, sodium dioctylsuccinate, sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium laurate, sodium stearatekind.
  • the present application also provides the 3D printing adhesive prepared by the above preparation method, the furan resin has a viscosity of less than 10 mPa.s at 20 ° C, which satisfies the requirements of the printing head on the resin in the 3D printing device; the furan resin is The sand wrapping performance is good in the sand laying process, the printed sand type has higher mechanical strength, and the curing speed is faster; the furan resin is easy to operate in the sand falling sand cleaning, and the use performance is improved. That is, the 3D printing adhesive prepared by the present application has superior comprehensive performance, and the defects of the 3D printing adhesive in the related art are well solved.
  • the present application also provides the use of the above-described 3D printing adhesive in the preparation of a foundry sand mold by a 3D inkjet printing apparatus.
  • the binder for 3D printing is prepared by the following steps:
  • the binder for 3D printing is prepared by the following steps:
  • Sterol 815Kg 3,5-dimethylphenol 122Kg, formalin (37wt%) 121.5Kg, resorcinol 30Kg, sodium dioctyl succinate 0.15Kg;
  • the reaction vessel was charged with 122 kg of 3,5-dimethylphenol and 121.5 kg of formalin.
  • the pH was adjusted to 8.4 with a triethylamine solution, stirring was started, and the temperature was slowly raised to 80 ° C, and then reacted for 1 hour, and then heated to 85 ° C. End the reaction in 1 hour;
  • Sterol 823Kg 3,5-dimethylphenol 61Kg, formalin (37%) 55Kg, bisphenol A 80Kg, sodium laurate 0.5Kg;
  • Sterol 885Kg 3,5-dimethylphenol 73.2Kg, formalin (37%) 58.3Kg, 2,5-dihydroxynonanol 25Kg, polysorbate 0.2Kg;
  • ⁇ lol 450Kg 3,5-dimethylphenol 30Kg, formalin (37%) 35Kg, resorcinol 20Kg, bisphenol A10Kg, polysorbate 0.3Kg;
  • the temperature is dehydrated by 20.25 Kg at 60 ° C, 100 Kg of decyl alcohol is added, then the solution is adjusted to pH 5.2-5.5 with formic acid (50 wt%), and the reaction is started by heating to 100-102 ° C for 1 h;
  • the binder for 3D printing is prepared by the following reaction steps:
  • the binder for 3,5-dimethylphenol 3D printing is prepared by the following reaction steps:
  • the binder for 3D printing is prepared by the following reaction steps:
  • composition of the raw materials is the same as that of the first embodiment, and the reaction steps are different, specifically:
  • the catechol and polysorbate were sequentially added, and the mixture was stirred for 10 minutes to sufficiently dissolve the above materials, and the binder for 3D printing was discharged at 40 ° C.
  • the 3D printing adhesive prepared by the preparation method provided by the present application has a viscosity of less than 10 mPa.s at 20 ° C, which satisfies the requirements of the printing head on the resin in the 3D printing device; the furan resin is sanded.
  • the sand wrapping performance is good, the printed sand type has high mechanical strength, and the curing speed is fast; the furan resin is easy to operate in the sand falling sand cleaning, and the use performance is improved. That is, the 3D printing adhesive prepared by the present application has superior comprehensive performance, and the defects of the 3D printing adhesive in the related art are well solved.

Abstract

一种3D打印用粘结剂，包括以下组分：按重量份计，呋喃树脂15‑60份，糠醇42‑68份，促进剂1‑12份，添加剂0.1‑5份；所述呋喃树脂由酚醛树脂和糠醇反应制得。还公开了一种3D打印用粘结剂的制备方法和应用。上述3D打印用粘结剂，在常温粘度极低，在20℃下粘度低于10mPa.s，满足了3D打印设备中打印喷头对树脂的要求，打印喷头不易堵塞，对机器的维护和保养起到至关重要的作用；在铺砂过程中对砂子包裹性能好，打印出的砂型有较高的力学强度，同时固化速度较快；在落砂清砂方面容易操作，提高了使用性能。

Description

一种3D打印用粘结剂及其制备方法和应用 技术领域
本申请涉及3D打印材料领域，具体而言，涉及一种3D打印用粘结剂及其制备方法和应用。
背景技术
3D打印技术自诞生30多年以来一直备受关注，国外一些在3D打印技术方面取得较大成果的公司包括EXONE、Voxeljet以及3D Stratsys对3D打印技术的推动起到了一定的作用。随着第三次工业革命的提出，在普通大众眼中也日渐火爆。3D打印学名叫增材制造技术，原理是将计算机设计出的三维模型分解成若干层平面切片，然后把“打印”材料按切片图形逐层叠加，最终“堆积”成完整的物体。3D打印应用于铸造领域为喷墨打印技术来制备型芯和砂芯，目前，已有部分工业级3D打印机应用于铸造生产服务，主要用于铸件的快速原型、翻制模具、打印模壳、砂芯等。
目前，我国3D铸造打印技术处于起步阶段，有些厂家已经用3D打印机做一些模具的使用，粘结剂树脂一般采用国外进口，成本价格大大提高。一些树脂厂家也对3D打印树脂进行了开发研究，比如公开号104086734A公开了一篇关于3D打印用粘结剂的制备方法，该树脂制备方法简单，引入改性剂和偶联剂，所制备的树脂满足3D打印设备的使用要求，但是对于打印出树脂砂的一些性能包括树脂砂力学性能强度、固化速度以及落砂清砂等性能没有得到改善。
鉴于3D打印设备的高要求，制备一款力学性能强度高、固化速度快、落砂清砂容易以及常温粘度低的呋喃树脂是现在3D打印设备所需要的。
有鉴于此，特提出本申请。
发明内容
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。
本申请的第一目的在于提供一种3D打印用粘结剂，该粘结剂常温粘度极低，在20℃下粘度低于10mPa.s，满足了3D打印设备中打印喷头对树脂的要求，打印喷头就不易堵塞，容易清理打扫，对机器的维护和保养起到至关重要的作用；该粘结剂在铺砂过程中对砂子包裹性能好，打印出的砂型有较高的力学强度，同时固化速度较快；该3D打印用粘结剂在落砂清砂方面容易操作，提高了使用性能。
本申请的第二目的在于提供上述的3D打印用粘结剂的制备方法，该方法简便易行，制得的3D打印用粘结剂综合性能优良，并且性能稳定。
本申请的第三目的在于提供所述的3D打印用粘结剂在用于3D喷墨打印设备制备铸造砂型中的应用。
为了实现本申请的上述目的，特采用以下技术方案：
一种3D打印用粘结剂，包括以下组分：按重量份计，呋喃树脂15-60份，糠醇42-68份，促进剂1-12份，添加剂0.1-5份；所述呋喃树脂由酚醛树脂和糠醇反应制得。
本申请提供的3D打印用粘结剂，各组分之间协同配合增强，在常温粘度极低，在20℃下粘度低于10mPa.s，满足了3D打印设备中打印喷头对树脂的要求，打印喷头就不易堵塞，容易清理打扫，对机器的维护和保养起到至关重要的作用；在铺砂过程中对砂子包裹性能好，打印出的砂型有较高的力学强度，同时固化速度较快；在落砂清砂方面容易操作，提高了使用性能。
优选地，所述呋喃树脂制备中，酚醛树脂与糠醇的质量比为1∶1-2.5。
优选地，所述呋喃树脂的重均分子量为200-350g/mol。
优选的，所述酚醛树脂的重均分子量为150-250g/mol。
优选的，所述促进剂包括间苯二酚、邻苯二酚、双酚A、2，5-二羟基糠醇中的一种或多种。
优选地，所述添加剂包括聚山梨酯、二辛基琥珀酸磺酸钠、十二烷基苯磺酸钠、十二烷基硫酸钠、月桂酸钠、硬脂酸钠中的一种或多种。
优选地，所述酚醛树脂由二甲酚和甲醛聚合而成；
优选地，所述二甲酚为3，5-二甲基苯酚。
本申请还提供了一种3D打印用粘结剂的制备方法，包括以下步骤：
(a)酚醛树脂与糠醇反应生成呋喃树脂；
(b)所述呋喃树脂用糠醇稀释后，加入促进剂和添加剂，混合即可。
本申请提供的3D打印用粘结剂的制备方法，制备步骤简便，制得的3D打印用粘结剂粘度低、抗拉强度高以及固化速度快，综合性能优良，并且性能稳定。
优选地，步骤(a)中，所述酚醛树脂由二甲酚和甲醛经缩聚反应聚合而成。
优选地，所述二甲酚为3，5-二甲基苯酚。
优选地，所述3，5-二甲基苯酚与所述甲醛的摩尔数比例为1∶1-1.8。
可选地，所述甲醛以甲醛水溶液的形式参与反应，所述甲醛水溶液中的甲醛的质量百分含量为35％-48％。
可选地，缩聚反应后还包括脱水的步骤。
优选地，步骤(a)中，所述缩聚反应在催化剂的作用下进行。
优选地，所述催化剂为三乙胺。
优选地，所述催化剂的添加量为所述3，5-二甲基苯酚重量的0.5％-2.0％。
优选地，所述缩聚反应在pH为8.0-8.5条件下进行。
优选地，所述缩聚反应为：先在温度80±2℃条件下反应0.5-1h，再升温至85±2℃条件下反应0.5-1h。
优选地，步骤(a)具体为：
酚醛树脂和糠醇混合，得到第一混合物；
调整所述第一混合物至酸性，进行反应，生成呋喃树脂。
优选地，采用盐酸、甲酸以及磷酸中的一种或者多种调整所述第一混合物至酸性。
优选地，所述酸性的第一混合物的pH为3.5-5.5。
优选地，所述反应为85-110℃下反应1-2个小时。
优选地，步骤(a)中，酚醛树脂与糠醇的质量比为1∶1-2.5。
优选地，步骤(b)中，按重量份计，呋喃树脂15-60份，糠醇42-68份，促进剂1-12份，添加剂0.1-5份。
优选地，所述促进剂包括间苯二酚、邻苯二酚、双酚A、2，5-二羟基糠醇中的一种或多种。
优选地，所述添加剂包括聚山梨酯、二辛基琥珀酸磺酸钠、十二烷基苯磺酸钠、十二烷基硫酸钠、月桂酸钠、硬脂酸钠中的一种或多种。
本申请还提供了上述的3D打印用粘结剂在3D喷墨打印设备制备铸造砂型中的应用。
与相关技术相比，本申请的有益效果为：
(1)本申请提供的3D打印用粘结剂的制备方法，制备的3D打印用粘结剂常温粘度极低，在20℃下粘度低于10mPa.s，有利的满足了3D打印 设备中打印喷头对树脂的要求，打印喷头就不易堵塞，容易清理打扫，对机器的维护和保养起到至关重要的作用。
(2)本申请提供的3D打印用粘结剂的制备方法，制备的3D打印用粘结剂在铺砂过程中对砂子包裹性能好，打印出的砂型有较高的力学强度，同时固化速度较快。
(3)本申请提供的3D打印用粘结剂的制备方法，制备的3D打印用粘结剂在落砂清砂方面容易操作，提高了使用性能。
在阅读并理解了详细描述后，可以明白其他方面。
具体实施方式
本申请一方面涉及一种3D打印用粘结剂，包括以下组分：按重量份计，呋喃树脂15-60份，糠醇42-68份，促进剂1-12份，添加剂0.1-5份；所述呋喃树脂由酚醛树脂和糠醇反应制得。
其中，所述呋喃树脂的重均分子量为200-350g/mol。本申请中呋喃树脂是一个混合物，重均分子量的范围为200-350g/mol。如，在一些实施例中，呋喃树脂的重均分子量为200-300g/mol；在一些实施例中，呋喃树脂的重均分子量为200-250g/mol；在一些实施例中，呋喃树脂的重均分子量为300-350g/mol；在一些实施例中，呋喃树脂的重均分子量为280-300g/mol；等等。
具体地，呋喃树脂由酚醛树脂和糠醇反应制得。其中，酚醛树脂与糠醇的质量比为1∶1-2.5。在不同的实施例中，酚醛树脂与糠醇的质量比可以为1∶1、1∶1.5、1∶2、1∶2.5等等。
可选地，所述酚醛树脂的重均分子量为150-250g/mol。本申请中酚醛树脂是一个混合物，重均分子量的范围为150-250g/mol。如，在一些实施例中，呋喃树脂的重均分子量为150-200g/mol；在一些实施例中，呋喃树 脂的重均分子量为180-250g/mol；在一些实施例中，呋喃树脂的重均分子量为150-220g/mol；在一些实施例中，呋喃树脂的重均分子量为180-250g/mol；等等。
可选地，酚醛树脂由二甲酚和甲醛聚合而成。该步骤是二甲酚和甲醛发生缩聚反应，聚合得到酚醛树脂。
优选地，所述二甲酚为3，5-二甲基苯酚。3，5-二甲基苯酚与甲醛反应得到的酚醛树脂不易缠连。
为了使3，5-二甲基苯酚与甲醛更充分的反应，优选地，所述3，5-二甲基苯酚与所述甲醛的摩尔数比例为1∶1-1.8。如3，5-二甲基苯酚与甲醛的摩尔数比例可以为1∶1、1∶1.2、1∶1.5、1∶1.6、1∶1.7、1∶1.8等等。
可选地，所述甲醛以甲醛水溶液的形式参与反应，所述甲醛水溶液中的甲醛的质量百分含量为35％-48％。如甲醛水溶液中的甲醛的质量百分含量可以为35％、37％、38％、40％、45％、48％等等。
由于甲醛水溶液中含有大量的水，并且缩聚反应还产生部分水，为了便于得到的产物与糠醇的反应，可选地，步骤(a)中缩聚反应后还包括脱水的步骤。
可选地，步骤(a)中，所述缩聚反应在催化剂的作用下进行。
优选地，所述催化剂为三乙胺。
优选地，所述催化剂的添加量为所述3，5-二甲基苯酚重量的0.5％-2.0％。如催化剂的添加量可以为3，5-二甲基苯酚重量的0.5％、0.8％、1.0％、1.2％、1.5％、1.8％、2.0％等等。
3，5-二甲基苯酚、甲醛与催化剂混合后，溶液呈碱性，即步骤(a)中的缩聚反应在碱性条件下反应。
优选地，步骤(a)中，所述缩聚反应在pH为8.0-8.5条件下进行。 如骤(a)中的缩聚反应的pH可以为8.0、8.2、8.3、8.4、8.5等等。
优选地，步骤(a)中，所述缩聚反应为：先在温度80±2℃条件下反应0.5-1h，再升温至85±2℃条件下反应0.5-1h。通过逐步加温反应，使得3，5-二甲基苯酚与甲醛更充分的反应。该反应后得到的酚醛树脂是一种混合物，酚醛树脂的重均分子量在150-250。
可选地，所述促进剂包括间苯二酚、邻苯二酚、双酚A、2，5-二羟基糠醇中的一种或多种。
可选地，所述添加剂包括聚山梨酯、二辛基琥珀酸磺酸钠、十二烷基苯磺酸钠、十二烷基硫酸钠、月桂酸钠、硬脂酸钠中的一种或多种。
经大量试验发现，本申请提供的3D打印用粘结剂，各组分之间协同配合增强，在常温粘度极低，在20℃下粘度低于10mPa.s，满足了3D打印设备中打印喷头对树脂的要求，打印喷头就不易堵塞，容易清理打扫，对机器的维护和保养起到至关重要的作用；在铺砂过程中对砂子包裹性能好，打印出的砂型有较高的力学强度，同时固化速度较快；在落砂清砂方面容易操作，提高了使用性能。
本申请的另一方面还涉及所述的3D打印用粘结剂的制备方法，包括以下步骤：
(a)酚醛树脂与糠醇反应生成呋喃树脂；
(b)所述呋喃树脂用糠醇稀释后，加入促进剂和添加剂，混合即可。
其中，步骤(a)中，所述酚醛树脂由二甲酚和甲醛经缩聚反应聚合而成。
优选地，所述二甲酚为3，5-二甲基苯酚。3，5-二甲基苯酚与甲醛反应得到的酚醛树脂不易缠连。
为了使3，5-二甲基苯酚与甲醛更充分的反应，优选地，所述3，5-二 甲基苯酚与所述甲醛的摩尔数比例为1∶1-1.8。如3，5-二甲基苯酚与甲醛的摩尔数比例可以为1∶1、1∶1.2、1∶1.5、1∶1.6、1∶1.7、1∶1.8等等。
可选地，所述甲醛以甲醛水溶液的形式参与反应，所述甲醛水溶液中的甲醛的质量百分含量为35％-48％。如甲醛水溶液中的甲醛的质量百分含量可以为35％、37％、38％、40％、45％、48％等等。
由于甲醛水溶液中含有大量的水，并且缩聚反应还产生部分水，为了便于得到的产物与糠醇的反应，可选地，步骤(a)中缩聚反应后还包括脱水的步骤。
可选地，所述缩聚反应在催化剂的作用下进行。
优选地，所述催化剂为三乙胺。通过加入催化剂，更好的促进二甲酚和甲醛的缩聚反应的进行。
优选地，所述催化剂的添加量为所述3，5-二甲基苯酚重量的0.5％-2.0％。如催化剂的添加量可以为3，5-二甲基苯酚重量的0.5％、0.8％、1.0％、1.2％、1.5％、1.8％、2.0％等等。
3，5-二甲基苯酚、甲醛与催化剂混合后，溶液呈碱性，即步骤(a)中的缩聚反应在碱性条件下反应。
优选地，所述缩聚反应在pH为8.0-8.5条件下进行。如骤(a)中的缩聚反应的pH可以为8.0、8.2、8.3、8.4、8.5等等。
优选地，所述缩聚反应为：先在温度80±2℃条件下反应0.5-1h，再升温至85±2℃条件下反应0.5-1h。通过逐步加温反应，使得3，5-二甲基苯酚与甲醛更充分的反应。该反应后得到的酚醛树脂是一种混合物，酚醛树脂的重均分子量在150-250。
可选地，步骤(a)具体为：
酚醛树脂和糠醇混合，得到第一混合物；
调整所述第一混合物至酸性，进行反应，生成呋喃树脂。
酚醛树脂和糠醇在酸性条件下进行反应，该反应为缩聚反应，有效的充分的进行反应，得到的呋喃树脂粘性小，强度较高，固化时间短。
可选地，酚醛树脂与糠醇的质量比为1∶1-2.5，该比例的酚醛树脂与糠醇反应，得到呋喃树脂。在不同的实施例中，酚醛树脂与糠醇的质量比可以为1∶1.5、1∶1.8、1∶2、1∶2.2、1∶2.5等等。
优选地，采用盐酸、甲酸以及磷酸中的一种或者多种调整所述第一混合物至酸性。
优选地，所述酸性的第一混合物的pH为3.5-5.5。如pH可以为3.5、4.0、4.5、5.0、5.3、5.5等等。
为了使得酚醛树脂和糠醇更充分的反应，优选地，所述反应为85-110℃下反应1-2个小时。如缩聚反应的温度可以为85℃、90℃、95℃、98℃、100℃、102℃、105℃、110℃等等，反应的时间可以为60min、80min、90min、100min、120min等等。
可选地，步骤(b)中，按重量份计，呋喃树脂15-60份，糠醇42-68份，促进剂1-12份，添加剂0.1-5份。
各步骤所用的原料协同配合，更充分有效的反应，得到的3D打印用粘结剂综合性能优良，并且性能稳定可靠。
通过加入特定种类的促进剂、添加剂，使得各原料之间相互配合，进一步增加制得的3D打印用粘结剂的综合性能。
可选地，所述促进剂包括间苯二酚、邻苯二酚、双酚A、2，5-二羟基糠醇中的一种或多种。
优选地，所述添加剂包括聚山梨酯、二辛基琥珀酸磺酸钠、十二烷基苯磺酸钠、十二烷基硫酸钠、月桂酸钠、硬脂酸钠中的一种或多种。
本申请还提供了上述的制备方法制得的3D打印用粘结剂，该呋喃树脂在20℃下粘度低于10mPa.s，满足了3D打印设备中打印喷头对树脂的要求；该呋喃树脂在铺砂过程中对砂子包裹性能好，打印出的砂型有较高的力学强度，同时固化速度较快；该呋喃树脂在落砂清砂方面容易操作，提高了使用性能。即本申请制得的3D打印用粘结剂综合性能优越，很好的解决了相关技术中的3D打印用粘结剂的缺陷。
本申请还提供了上述的3D打印用粘结剂在3D喷墨打印设备制备铸造砂型中的应用。
下面将结合实施例对本申请的实施方案进行详细描述，但是本领域技术人员将会理解，下列实施例仅用于说明本申请，而不应视为限制本申请的范围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
实施例1
3D打印用粘结剂，通过以下步骤制备：
一、原材料组成
糠醇850kg，3，5-二甲基苯酚122Kg，甲醛水(37wt％)121.5Kg，邻苯二酚20Kg，聚山梨酯2Kg；
二、反应步骤
向反应釜中投入3，5-二甲基苯酚122Kg和甲醛水121.5Kg，用三乙胺溶液调节pH值为8.3，启动搅拌，缓慢升温至80℃后反应1小时，再升温至85℃反应1小时结束反应；
降温至60℃，真空脱水85.25Kg，加入糠醇170Kg，然后用甲酸(50wt％)溶液调pH为5.2-5.5，升温至100-102℃下反应1h结束反应，降温至65℃， 真空脱水10.25Kg；加入糠醇680Kg，依次加入邻苯二酚20Kg，聚山梨酯2Kg，混合搅拌10分钟使上述物质充分溶解，40℃下放料得3D打印用粘结剂。
实施例2
3D打印用粘结剂，通过以下步骤制备：
一、原材料组成
糠醇815Kg，3，5-二甲基苯酚122Kg，甲醛水(37wt％)121.5Kg，间苯二酚30Kg，二辛基琥珀酸磺酸钠0.15Kg；
二、反应步骤
向反应釜中投入3，5-二甲基苯酚122Kg和甲醛水121.5Kg，用三乙胺溶液调节pH值为8.4，启动搅拌，缓慢升温至80℃后反应1小时，再升温至85℃反应1小时结束反应；
降温至60℃，真空脱水85.25Kg，加入糠醇165Kg，然后用甲酸(50wt％)溶液调pH＝5.2-5.5，升温至100-102℃下反应1h结束反应；
在65℃下真空脱水10.25Kg，加入糠醇650Kg，依次加入间苯二酚30Kg，二辛基琥珀酸磺酸钠1.5Kg，混合搅拌10分钟使上述物质充分溶解，40℃下放料得3D打印用粘结剂。
实施例3
一、原材料组成
糠醇823Kg，3，5-二甲基苯酚61Kg，甲醛水(37％)55Kg，双酚A 80Kg，月桂酸钠0.5Kg；
二、反应步骤
向反应釜中投入3，5-二甲基苯酚61Kg和甲醛水55Kg，用三乙胺溶液调节pH值为8.5，启动搅拌，缓慢升温至80℃后反应1个小时，再升温至 85℃反应1小时结束反应；
降温后60℃下真空脱水41.25Kg，加入糠醇187Kg，然后用甲酸(50wt％)溶液调pH＝5.2-5.5，升温至100-102℃下反应1h结束反应；
65℃下真空脱水8.25Kg，加入糠醇636Kg，依次加入双酚A 80Kg，月桂酸钠0.5Kg，混合搅拌10分钟使上述物质充分溶解，40℃下放料得3D打印用粘结剂。
实施例4
一、原材料组成
糠醇885Kg，3，5-二甲基苯酚73.2Kg，甲醛水(37％)58.3Kg，2，5-二羟基糠醇25Kg，聚山梨酯0.2Kg；
二、反应步骤
向反应釜中投入3，5-二甲基苯酚73.2Kg和甲醛水58.3Kg，用三乙胺溶液调节pH值为8.4，启动搅拌，缓慢升温至80℃后反应1小时，再升温至85℃反应1小时结束反应；
降温后60℃下真空脱水36.5Kg，加入糠醇185Kg，然后用甲酸(50wt％)溶液调pH＝5.2-5.5，升温至100-102℃下反应1h结束反应；
65℃下真空脱水8.25Kg，加入糠醇700Kg，依次加入2，5-二羟基糠醇25Kg，聚山梨酯2Kg，混合搅拌10分钟使上述物质充分溶解，40℃下放料得3D打印用粘结剂。
实施例5
一、原材料组成
糠醇450Kg，3，5-二甲基苯酚30Kg，甲醛水(37％)35Kg，间苯二酚20Kg，双酚A10Kg，聚山梨酯0.3Kg；
二、反应步骤
向反应釜中投入3，5-二甲基苯酚30Kg和甲醛水35Kg，用三乙胺溶液调节pH值为8.3，启动搅拌，缓慢升温至80℃后反应1小时，再升温至85℃反应1小时结束反应；
降温后60℃下真空脱水20.25Kg，加入糠醇100Kg，然后用甲酸(50wt％)溶液pH＝5.2-5.5，升温至100-102℃下反应1h结束反应；
65℃下真空脱水11.25Kg，加入糠醇350Kg，依次加入间苯二酚20Kg，双酚A 10Kg，聚山梨酯3Kg，混合搅拌10分钟使上述物质充分溶解，40℃下放料得3D打印用粘结剂。
实施例6
3D打印用粘结剂通过以下反应步骤制备：
向反应釜中投入80kg 3，5-二甲基苯酚和56kg甲醛水(35％)，用三乙胺溶液调节pH值为8.0，启动搅拌，缓慢升温至80℃后反应0.5小时，再升温至85℃反应0.5小时结束反应；
降温后60℃下真空脱水，得到酚醛树脂，按酚醛树脂的2倍质量加入糠醇，然后用盐酸溶液pH＝5.0，升温至100℃下反应1h结束反应，65℃下真空脱水，得到呋喃树脂；
取呋喃树脂180kg，加入204kg糠醇，依次加入邻苯二酚10kg、双酚A 10kg、2，5-二羟基糠醇16kg、十二烷基苯磺酸钠15kg，混合搅拌10分钟使上述物质充分溶解，40℃下放料得3D打印用粘结剂。
实施例7
3，5-二甲基苯酚3D打印用粘结剂通过以下反应步骤制备：
向反应釜中投入50Kg 3，5-二甲基苯酚和53Kg甲醛水(40％)，用三乙胺溶液调节pH值为8.2，启动搅拌，缓慢升温至80℃后反应1小时，再升温至85℃反应0.5小时结束反应；
降温后60℃下真空脱水，得到酚醛树脂，按酚醛树脂的1倍质量加入糠醇，然后用磷酸溶液5.1，升温至95℃下反应2h结束反应，65℃下真空脱水，得到呋喃树脂；
取呋喃树脂150kg，加入420kg糠醇，依次加入邻苯二酚5kg、双酚A 3kg、2，5-二羟基糠醇2kg、十二烷基硫酸钠1kg，混合搅拌10分钟使上述物质充分溶解，40℃下放料得3D打印用粘结剂。
实施例8
3D打印用粘结剂通过以下反应步骤制备：
向反应釜中投入30Kg 3，5-二甲基苯酚和25Kg甲醛水(48％)，用三乙胺溶液调节pH值为8.3，启动搅拌，缓慢升温至80℃后反应1小时，再升温至83℃反应1小时结束反应；
降温后60℃下真空脱水，得到酚醛树脂，按酚醛树脂的1.5倍质量加入糠醇，然后用甲酸(50wt％)溶液5.3，升温至100℃下反应1h结束反应，65℃下真空脱水，得到呋喃树脂；
取呋喃树脂60kg，加入150kg糠醇，依次加入邻苯二酚7kg、双酚A 8kg、硬脂酸钠3kg，混合搅拌10分钟使上述物质充分溶解，40℃下放料得3D打印用粘结剂。
对比例1
与实施例1不同的是，第一次添加糠醇的时候全部加入。
对比例2
与实施例5不同的是，第一次添加糠醇的时候全部加入。
对比例3
原料组成同实施例1，反应步骤不同，具体为：
向反应釜中投入3，5-二甲基苯酚、甲醛水和糠醇，启动搅拌，在85℃ 条件下反应2h，脱水；
依次加入邻苯二酚、聚山梨酯，混合搅拌10分钟使上述物质充分溶解，40℃下放料得3D打印用粘结剂。
检测实施例1-8制得的3D打印用粘结剂的理化指标，其中游离甲醛和强度的分析方法按照JB/T7526-1994《铸造用自硬呋喃树脂》进行。具体结果如表1所示。
表1 3D打印用粘结剂的理化指标
Figure PCTCN2018092586-appb-000001
综上可见，本申请提供的制备方法制得的3D打印用粘结剂，在20℃下粘度低于10mPa.s，满足了3D打印设备中打印喷头对树脂的要求；该呋喃树脂在铺砂过程中对砂子包裹性能好，打印出的砂型有较高的力学强度，同时固化速度较快；该呋喃树脂在落砂清砂方面容易操作，提高了使用性能。即本申请制得的3D打印用粘结剂综合性能优越，很好的解决了相关技术中的3D打印用粘结剂的缺陷。
尽管已用具体实施例来说明和描述了本申请，然而应意识到，在不背离本申请的精神和范围的情况下可以作出许多其它的更改和修改。因此， 这意味着在所附权利要求中包括属于本申请范围内的所有这些变化和修改。

Claims (11)

  1. 一种3D打印用粘结剂，其包括以下组分：按重量份计，呋喃树脂15-60份，糠醇42-68份，促进剂1-12份，添加剂0.1-5份；所述呋喃树脂由酚醛树脂和糠醇反应制得。
  2. 根据权利要求1所述的3D打印用粘结剂，其中，所述呋喃树脂制备中，酚醛树脂与糠醇的质量比为1∶1-2.5。
  3. 根据权利要求1或2所述的3D打印用粘结剂，其中，
    所述呋喃树脂的重均分子量为200-350g/mol；
    所述酚醛树脂的重均分子量为150-250g/mol；
    所述促进剂包括间苯二酚、邻苯二酚、双酚A、2，5-二羟基糠醇中的一种或多种；
    所述添加剂包括聚山梨酯、二辛基琥珀酸磺酸钠、十二烷基苯磺酸钠、十二烷基硫酸钠、月桂酸钠、硬脂酸钠中的一种或多种。
  4. 根据权利要求1至3中任一项所述的3D打印用粘结剂，其中，所述酚醛树脂由二甲酚和甲醛聚合而成；
    优选地，所述二甲酚为3，5-二甲基苯酚。
  5. 一种3D打印用粘结剂的制备方法，其包括以下步骤：
    (a)酚醛树脂与糠醇反应生成呋喃树脂；
    (b)所述呋喃树脂用糠醇稀释后，加入促进剂和添加剂，混合即可。
  6. 根据权利要求5所述的3D打印用粘结剂的制备方法，其中，步骤(a)中，所述酚醛树脂由二甲酚和甲醛经缩聚反应聚合而成；
    优选地，所述二甲酚为3，5-二甲基苯酚；
    优选地，所述3，5-二甲基苯酚与所述甲醛的摩尔数比例为1∶1-1.8；
    可选地，所述甲醛以甲醛水溶液的形式参与反应，所述甲醛水溶液中的甲醛的质量百分含量为35％-48％；
    可选地，缩聚反应后还包括脱水的步骤。
  7. 根据权利要求6所述的3D打印用粘结剂的制备方法，其中，步骤(a)中，所述缩聚反应在催化剂的作用下进行；
    优选地，所述催化剂为三乙胺；
    优选地，所述催化剂的添加量为所述3，5-二甲基苯酚重量的0.5％-2.0％；
    优选地，所述缩聚反应在pH为8.0-8.5条件下进行；
    优选地，所述缩聚反应为：先在温度80±2℃条件下反应0.5-1h，再升温至85±2℃条件下反应0.5-1h。
  8. 根据权利要求5所述的3D打印用粘结剂的制备方法，其中，步骤(a)具体为：
    酚醛树脂和糠醇混合，得到第一混合物；
    调整所述第一混合物至酸性，进行反应，生成呋喃树脂；
    优选地，采用盐酸、甲酸以及磷酸中的一种或者多种调整所述第一混合物至酸性；
    优选地，所述酸性的第一混合物的pH为3.5-5.5；
    优选地，所述反应为85-110℃下反应1-2个小时。
  9. 根据权利要求5-8任一项所述的3D打印用粘结剂的制备方法，其中，步骤(a)中，酚醛树脂与糠醇的质量比为1∶1-2.5；
    优选地，步骤(b)中，按重量份计，呋喃树脂15-60份，糠醇42-68份，促进剂1-12份，添加剂0.1-5份。
  10. 根据权利要求5-8任一项所述的3D打印用粘结剂的制备方法，其中，所述促进剂包括间苯二酚、邻苯二酚、双酚A、2，5-二羟基糠醇中的一种或多种；
    优选地，所述添加剂包括聚山梨酯、二辛基琥珀酸磺酸钠、十二烷基苯磺酸钠、十二烷基硫酸钠、月桂酸钠、硬脂酸钠中的一种或多种。
  11. 权利要求1-4任一项所述的3D打印用粘结剂或权利要求5-10任一项所述的制备方法制备的3D打印用粘结剂在3D喷墨打印设备制备铸造砂型中的应用。
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