WO2018184601A1 - 铸造用粘结剂组合物及用于制备它的套组 - Google Patents

铸造用粘结剂组合物及用于制备它的套组 Download PDF

Info

Publication number
WO2018184601A1
WO2018184601A1 PCT/CN2018/090079 CN2018090079W WO2018184601A1 WO 2018184601 A1 WO2018184601 A1 WO 2018184601A1 CN 2018090079 W CN2018090079 W CN 2018090079W WO 2018184601 A1 WO2018184601 A1 WO 2018184601A1
Authority
WO
WIPO (PCT)
Prior art keywords
sterol
mol
prepolymer
molecular weight
resin
Prior art date
Application number
PCT/CN2018/090079
Other languages
English (en)
French (fr)
Inventor
祝建勋
白世龙
刘昭荐
周国栋
Original Assignee
济南圣泉集团股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 济南圣泉集团股份有限公司 filed Critical 济南圣泉集团股份有限公司
Publication of WO2018184601A1 publication Critical patent/WO2018184601A1/zh

Links

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
    • 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
    • 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
    • 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
    • B22C1/2246—Condensation polymers of aldehydes and ketones
    • B22C1/2253—Condensation polymers of aldehydes and ketones with phenols
    • 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
    • C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08L61/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
    • C08L61/24—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with urea or thiourea
    • 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
    • C08L61/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08L61/04, C08L61/18 and C08L61/20
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
    • C09J161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C09J161/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
    • C09J161/24—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with urea or thiourea
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
    • C09J161/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C09J161/04, C09J161/18 and C09J161/20

Definitions

  • the present invention relates to an organic binder for casting molding cores, and more particularly to a casting binder composition comprising a polyvinyl alcohol modified urea formaldehyde furan resin and a kit for preparing the same.
  • Furan resin is a general term for a class of resins containing a furan ring and a sterol and furfural as raw materials.
  • the self-hardening furan resin for casting is usually a thermosetting resin prepared from decyl alcohol, formaldehyde, urea, phenol and other modified substances, and is usually a pale yellow to dark brown transparent or translucent homogeneous liquid.
  • the self-hardening furan resin can harden the sand type (sand core) by an acid catalyst at room temperature, and is currently the most widely used organic binder in the foundry industry.
  • the superior properties of furan resin include fast curing, high strength, low gas generation and good collapsibility. Its use in the foundry industry is increasing year by year.
  • casting is one of the most polluting industries in the mechanical manufacturing industry, in which the binder for molding core is the main source of pollution.
  • the free sterol content in the furan resin for sale in the market is high
  • the free sterol content in the low decyl furan resin is above 45%
  • the free sterol content in most furan resins is 60-80%.
  • the furan resin has a high free sterol content, which causes a dioxin effect during casting, which adversely affects the casting environment.
  • a furan resin having a free sterol content of less than 25% is classified as an environmentally friendly resin, and it is considered that such a furan resin having a free sterol content of less than 25% has a small adverse effect on the environment.
  • the mechanical strength of the furan resin is lowered, and the prepared sand core or sand type cannot meet the casting requirements or greatly increase the production cost of the casting.
  • an object of the present invention is to provide a furan resin-based binder composition for casting having a low free sterol content and good mechanical strength, and for preparing the casting binder.
  • the composition and its kit are provided.
  • the present inventors conducted intensive studies to solve the above technical problems, and as a result, found that by adding a specific sterol prepolymer, the casting binder can be made in a case where the content of free sterol in the binder composition for casting is lowered. The composition still maintains good mechanical strength, thereby completing the present invention.
  • the present invention includes:
  • a binder composition for casting comprising:
  • the resin is one or two selected from the group consisting of urea formaldehyde furan resin and phenol urea formaldehyde furan resin.
  • the sterol prepolymer has a number average molecular weight of 650 g/mol or less.
  • the sterol prepolymer having a molecular weight of 401-650 g/mol accounts for 20 mol% or more
  • the sterol prepolymer having a molecular weight of 301-400 g/mol accounts for 10 mol% or more
  • the molecular weight is 150-300 g.
  • the /mol sterol prepolymer accounts for 10 mol% or more.
  • the total weight of the binder composition was taken as 100% by weight.
  • Component A which is a resin mother liquor comprising a resin selected from one or both of a urea-formaldehyde resin and a phenol urea-formaldehyde resin;
  • Component B which is a sterol prepolymer liquid, the sterol prepolymer liquid comprising a sterol prepolymer;
  • the sterol prepolymer has a number average molecular weight of 650 g / mol or less;
  • the sterol prepolymer having a molecular weight of 401-650 g/mol accounts for 20 mol% or more
  • the sterol prepolymer having a molecular weight of 301-400 g/mol accounts for 10 mol% or more
  • the molecular weight is 150-300 g. /mol of sterol prepolymer accounts for more than 10% by mole;
  • the component A and the component B are packaged separately.
  • urea-formaldehyde resin is an alcohol-modified urea-formaldehyde furan resin.
  • the kit of claim 11 wherein the alcohol is selected from the group consisting of polyvinyl alcohol, polypropylene alcohol, ethylene glycol, and glycerol.
  • the component A is a resin mother liquid comprising a resin which is one or both selected from the group consisting of urea formaldehyde furan resin and phenol urea formaldehyde furan resin;
  • the component B is a sterol prepolymer liquid, and the sterol prepolymer liquid comprises a sterol prepolymer, and the sterol prepolymer has a number average molecular weight of 650 g/mol or less;
  • the sterol prepolymer having a molecular weight of 401-650 g/mol accounts for 20 mol% or more
  • the sterol prepolymer having a molecular weight of 301-400 g/mol accounts for 10 mol% or more
  • the molecular weight is 150-300 g.
  • the /mol sterol prepolymer accounts for 10 mol% or more.
  • component A further comprises a medium.
  • urea formaldehyde furan resin is an alcohol modified urea formaldehyde furan resin.
  • the alcohol is selected from the group consisting of polyvinyl alcohol, polypropylene alcohol, ethylene glycol, and glycerol.
  • a furan resin-based binder composition for casting having a low free sterol content and good mechanical strength
  • a kit for preparing the binder composition for casting is provided.
  • the present invention also achieves the following beneficial effects:
  • the prepared low decyl furan resin has good environmental performance, reduces the release of monomers including sterol, formaldehyde, phenol and other small molecules during the casting process, and does not produce dioxin effect on the atmosphere; no other expensive modification is added to the resin. Sex agent, production costs are greatly reduced;
  • the resin is modified with alcohol to slow down the tensile strength of the resin sand, and the mechanical properties meet the market requirements.
  • the present invention provides a binder composition for casting (composition of the present invention) comprising: a resin and a sterol prepolymer; wherein the resin is selected from the group consisting of urea-formaldehyde furan resin and phenol urea-formaldehyde furan One or both of the resins, the sterol prepolymer having a number average molecular weight of 650 g/mol or less (the lower molecular weight may be 150 g/mol), and the sterol prepolymer having a molecular weight of 401 to 650 g/mol.
  • the sterol prepolymer accounts for 20% by mole or more, the sterol prepolymer having a molecular weight of 301 to 400 g/mol accounts for 10% by mole or more, and the sterol prepolymer having a molecular weight of 150-300 g/mol accounts for 10% by mole or more.
  • the composition of the present invention maintains good mechanical strength even in the case where the content of free sterols therein is lowered (meaning that the adverse effects on the environment are reduced).
  • the content of the free sterol in the composition of the present invention is 25% by weight or less (100% by weight based on the total weight of the binder composition for casting), the mechanical strength thereof is not significantly lowered.
  • the urea formaldehyde furan resin is an alcohol modified urea formaldehyde furan resin.
  • the alcohol may be selected from the group consisting of polyvinyl alcohol, polypropylene alcohol, ethylene glycol, and glycerol.
  • the viscosity of the composition of the present invention may be 80 mPa ⁇ s (20 ° C) or less, which greatly improves the usability.
  • the weight ratio of the resin to the sterol prepolymer may be from 1:4 to 1:2.
  • the composition of the present invention can be prepared by mixing a resin mother liquor with a decyl alcohol prepolymer solution.
  • the present invention provides a kit (the kit of the present invention) for preparing a composition of the present invention, comprising: component A, which is a resin mother liquor comprising a resin, The resin is one or both selected from the group consisting of urea formaldehyde furan resin and phenol urea formaldehyde furan resin; and component B, which is a sterol prepolymer liquid, the sterol prepolymer liquid comprising a sterol prepolymer;
  • the number average molecular weight of the sterol prepolymer is 650 g/mol or less; in the sterol prepolymer, the sterol prepolymer having a molecular weight of 401-650 g/mol accounts for 20 mol% or more, and the sterol has a molecular weight of 301-400 g/mol.
  • the polymer accounts for
  • the component A may also comprise a medium, preferably water.
  • the component A can be prepared, for example, by adding formaldehyde (for example, 15 to 25 parts by weight) to the reaction vessel, adjusting the pH to be weakly basic (7.5 to 8.5), and adding an alcohol for modification (for example, poly) as needed.
  • Vinyl alcohol, PVA) for example, 0.1-5 parts by weight
  • start stirring and heating for a period of time heating to, for example, 60 ° C to 70 ° C
  • part of urea for example, 15-30 parts by weight
  • dissolution and temperature increase for example
  • the reaction is carried out for a period of time, and then the pH of the material system is adjusted to be acidic (for example, 3.0 to 40) to
  • the formaldehyde may be liquid formaldehyde or solid formaldehyde.
  • the base used for adjusting the pH to alkaline may be sodium hydroxide, potassium hydroxide, aqueous ammonia, sodium carbonate, potassium carbonate, barium hydroxide or the like.
  • the acid used to adjust the pH to acid may be formic acid, acetic acid, sulfonic acid, hydrochloric acid, sulfuric acid or the like.
  • the base or acid is most preferably the same base or the same acid.
  • the component B can be prepared, for example, by adding decyl alcohol (for example, 100 parts by weight) and water (for example, 1 to 10 parts by weight) to the reaction vessel, and adding an acid (for example, 0.1 to 5 parts by weight) dropwise to start stirring and raising the temperature. (heating to, for example, 60 ° C to 70 ° C) for 0.1 to 1 hour, and then raising the temperature (heating to, for example, 90 ° C to 99 ° C) for 0.5 to 8 hours; after the reaction is finished, the temperature is lowered, dehydrated, and the decyl alcohol prepolymer solution is discharged.
  • decyl alcohol for example, 100 parts by weight
  • water for example, 1 to 10 parts by weight
  • an acid for example, 0.1 to 5 parts by weight
  • the component of the present invention can be obtained by mixing the component A and the component B.
  • Formaldehyde (concentration 37%): 283.7Kg, urea: 120Kg, sterol: 270Kg, PVA: 6Kg ammonia: 8Kg
  • the number average molecular weight was 520 g/mol by gel permeation chromatography, and the sterol prepolymer having a molecular weight of 401-650 g/mol accounted for 23.5 mol%, and the sterol prepolymer having a molecular weight of 301-400 g/mol accounted for 11.1 mol% or more.
  • the sterol prepolymer having a molecular weight of 150 to 300 g/mol or more accounts for 14 mol%.
  • Formaldehyde (concentration 37%): 567.4Kg, phenol: 50Kg, urea: 180Kg, sterol: 510Kg, PVA: 8Kg, ammonia: 15Kg
  • the reaction was carried out at a temperature of 95 ° C for 1.5 hours; 20 Kg of two-step urea was added, stirred and dissolved to lower the temperature of the system; 20 Kg was dehydrated under vacuum, 15 kg of ammonia water was added and stirred uniformly, and the product (B) was about 1068 Kg.
  • Sterol 500Kg, water: 15Kg, formic acid (50%): 10Kg
  • the number average molecular weight of the gel permeation chromatography was 580 g/mol, and the sterol prepolymer having a number average molecular weight of 401-650 g/mol accounted for 25.5 mol%, and the sterol prepolymer having a molecular weight of 301-400 g/mol accounted for 12.1 mol%. Above, the sterol prepolymer having a molecular weight of 150 to 300 g/mol or more accounts for 15 mol%.
  • Formaldehyde (concentration 37%): 283.7Kg, urea: 140Kg, decyl alcohol: 245Kg, polypropylene alcohol: 4Kg ammonia water: 6Kg
  • the number average molecular weight of the gel permeation chromatography was 620 g/mol, and the sterol prepolymer having a number average molecular weight of 401-650 g/mol accounted for 20.5 mol%, and the sterol prepolymer having a molecular weight of 301-400 g/mol accounted for 10.1 mol%. Above, the sterol prepolymer having a molecular weight of 150 to 300 g/mol or more accounts for 10 mol%.
  • Formaldehyde (concentration 37%): 851Kg, urea: 400Kg, sterol: 750Kg, ethylene glycol: 4Kg ammonia: 20Kg
  • Step urea 50Kg stir to dissolve, reduce the system temperature; dehydrate 55Kg under vacuum conditions, add 20Kg of ammonia water to stir evenly, and release the product (A) about 1550Kg.
  • the number average molecular weight of the gel permeation chromatography was 420 g/mol, and the sterol prepolymer having a number average molecular weight of 401-650 g/mol accounted for 28.5 mol%, and the sterol prepolymer having a molecular weight of 301-400 g/mol accounted for 15.1 mol%. Above, the sterol prepolymer having a molecular weight of 150 to 300 g/mol or more accounts for 18 mol%.
  • Formaldehyde (concentration 37%): 425; Kg, urea: 200Kg, sterol: 375Kg, PVA: 6Kg ammonia: 6Kg
  • the temperature is further raised to 85 ° C for 1 hour; after the end of the reaction, the temperature is lowered, 200 Kg is dehydrated, 375 Kg of sterol component is added for further reaction for 1 hour; the pH of the material system is adjusted to 3.3-3.5, and the reaction temperature is 95 ° C for 1.5 hours; 20Kg of urea, stir and dissolve, reduce the temperature of the system; dehydrate 28Kg under vacuum conditions, add 9Kg of ammonia water to stir evenly, and release the product (A) about 790Kg.
  • the number average molecular weight of the gel permeation chromatography was 320 g/mol, and the sterol prepolymer having a number average molecular weight of 401-650 g/mol accounted for 24.5 mol%, and the sterol prepolymer having a molecular weight of 301-400 g/mol accounted for 12.1 mol%. Above, the sterol prepolymer having a molecular weight of 150 to 300 g/mol or more accounts for 13 mol%.
  • Formaldehyde (concentration 37%): 283.7Kg, urea: 120Kg, sterol: 270Kg, ammonia: 8Kg
  • the above product (A) was diluted with a 1:3 ratio of decyl alcohol to prepare a binder composition for casting of Comparative Example 1.
  • Formaldehyde (concentration 37%): 567.4Kg, phenol: 50Kg, urea: 180Kg, sterol: 510Kg, ammonia: 15Kg
  • the above product (A) was diluted with a 1:4 ratio of decyl alcohol to prepare a binder composition for casting of Comparative Example 2.
  • Formaldehyde (concentration 37%): 283.7Kg, urea: 140Kg, decyl alcohol: 245Kg, polypropylene alcohol: 4Kg ammonia water: 6Kg
  • the number average molecular weight of the gel permeation chromatography was 1020 g/mol, and the sterol prepolymer having a number average molecular weight of 900-1020 g/mol accounted for 30.5 mol%, and the sterol prepolymer having a molecular weight of 782-900 g/mol accounted for 10.1 mol%. Above, the sterol prepolymer having a molecular weight of 650 to 782 g/mol or more accounts for 10 mol%.
  • Formaldehyde (concentration 37%): 851Kg, urea: 400Kg, sterol: 750Kg, ethylene glycol: 4Kg ammonia: 20Kg
  • Step urea 50Kg stir to dissolve, reduce the system temperature; dehydrate 55Kg under vacuum conditions, add 20Kg of ammonia water to stir evenly, and release the product (A) about 1550Kg.
  • the number average molecular weight of the gel permeation chromatography was 920 g/mol, and the sterol prepolymer having a number average molecular weight of 780-920 g/mol accounted for 28.5 mol%, and the sterol prepolymer having a molecular weight of 652-780 g/mol accounted for 15.1 mol%. Above, the sterol prepolymer having a molecular weight of 580 to 652 g/mol or more accounts for 18 mol%.
  • Formaldehyde (concentration 37%): 425; Kg, urea: 200Kg, sterol: 375Kg, PVA: 6Kg ammonia: 6Kg
  • the temperature is further raised to 85 ° C for 1 hour; after the end of the reaction, the temperature is lowered, 200 Kg is dehydrated, 375 Kg of sterol component is added for further reaction for 1 hour; the pH of the material system is adjusted to 3.3-3.5, and the reaction temperature is 95 ° C for 1.5 hours; 20Kg of urea, stir and dissolve, reduce the temperature of the system; dehydrate 28Kg under vacuum conditions, add 9Kg of ammonia water to stir evenly, and release the product (A) about 790Kg.
  • the number average molecular weight of the gel permeation chromatography was 1200 g/mol, and the sterol prepolymer having a number average molecular weight of 980-1200 g/mol accounted for 40.5 mol%, and the sterol prepolymer having a molecular weight of 810-980 g/mol accounted for 11.1 mol%. Above, and the sterol prepolymer having a molecular weight of 560-810 g/mol or more accounts for 16 mol%.
  • test results of the casting binder compositions of Examples 1 to 5 and Comparative Examples 1 to 5 above are shown in Table 1.
  • Analytical method for free sterol content, nitrogen content, free formaldehyde and strength according to JB/T7526-1994 "self-hardening furan resin for casting"; the amount of formaldehyde released according to the acetylacetone spectrophotometric method in GB 13197-91 measuring.
  • Table 1 Test results of the binder compositions for casting of Examples 1-5 and Comparative Examples 1-5
  • a furan resin-based binder composition for casting having a low free sterol content and good mechanical strength, and a kit for preparing the binder composition for casting.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Mold Materials And Core Materials (AREA)
  • Phenolic Resins Or Amino Resins (AREA)

Abstract

本发明提供一种游离糠醇含量低且力学强度好的、基于呋喃树脂的铸造用粘结剂组合物及用于制备它的套组。本发明的铸造用粘结剂组合物包含树脂和糠醇预聚物，所述树脂是选自脲醛呋喃树脂和酚脲醛呋喃树脂中的一种或两种，所述糠醇预聚物的数均分子量在650g/mol以下，所述糠醇预聚物中，分子量在401-650g/mol的糠醇预聚物占20摩尔％以上，分子量在301-400g/mol的糠醇预聚物占10摩尔％以上，且分子量在150-300g/mol的糠醇预聚物占10摩尔％以上。

Description

铸造用粘结剂组合物及用于制备它的套组 技术领域
本发明涉及用于铸造造型制芯用有机粘结剂，具体涉及一种包含聚乙烯醇改性脲醛呋喃树脂的铸造用粘结剂组合物及用于制备它的套组。
背景技术
呋喃树脂是一类结构中含有呋喃环、以糠醇和糠醛作为原料生产的树脂类的总称。铸造用自硬呋喃树脂通常是由糠醇、甲醛、尿素、苯酚以及其他改性物质所制备而成的热固性树脂，通常情况下是淡黄色至深棕色的透明或者半透明均匀液体。自硬呋喃树脂在室温下可以通过酸催化剂使砂型(砂芯)硬化，目前是铸造行业中用量最大的一种有机粘结剂。呋喃树脂优越的性能包括固化快、强度高、发气量低以及溃散性好等优点，其在铸造行业的用量还在逐年增长。
另一方面，铸造是机械制造业中污染最严重的一个行业，其中造型制芯用粘结剂是造成污染的主要根源。目前，市场在售铸造用呋喃树脂中游离糠醇含量高，低糠醇呋喃树脂中游离糠醇含量在45％以上，大多数呋喃树脂中游离糠醇含量在60-80％。呋喃树脂中游离糠醇含量高，铸造时会产生二噁英效应，会对铸造环境产生不良影响。欧洲将游离糠醇含量低于25％的呋喃树脂定为环境友好型树脂，认为这种游离糠醇含量低于25％的呋喃树脂对环境的不良影响小。但是，游离糠醇含量低时会降低呋喃树脂的力学强度，导致制备出的砂芯或者砂型不能满足浇铸要求或者大大提高铸件的生产成本。
因此，迫切需要开发出一种游离糠醇含量低且力学强度好的、铸造用粘结剂组合物。
发明内容
鉴于上述现有技术中存在的技术问题，本发明的目的在于提供一种游离糠醇含量低且力学强度好的、基于呋喃树脂的铸造用粘结剂组合物以及用于制备该铸造用粘结剂组合物以及它的套组(kit)。
本发明人为解决上述技术问题进行了深入研究，结果发现：通过加入特定的糠醇预聚物，能够在铸造用粘结剂组合物中的游离糠醇含量降低的情况下，使该铸造用粘结剂组合物仍保持良好的力学强度，从而完成了本发明。
即，本发明包括：
1.一种铸造用粘结剂组合物，其包含：
树脂和糠醇预聚物；
其中，
所述树脂是选自脲醛呋喃树脂和酚脲醛呋喃树脂中的一种或两种，
所述糠醇预聚物的数均分子量在650g/mol以下，
所述糠醇预聚物中，分子量在401-650g/mol的糠醇预聚物占20摩尔％以上，分子量在301-400g/mol的糠醇预聚物占10摩尔％以上，且分子量在150-300g/mol的糠醇预聚物占10摩尔％以上。
2.根据权利要求1所述的铸造用粘结剂组合物，其中，脲醛呋喃树脂是醇改性脲醛呋喃树脂。
3.根据权利要求2所述的铸造用粘结剂组合物，其中，所述醇选自聚乙烯醇、聚丙烯醇、乙二醇和丙三醇。
4.根据权利要求1～3中任一项所述的铸造用粘结剂组合物，其中，所述铸造用粘结剂组合物中游离糠醇的含量为25重量％以下，以所述铸造用粘结剂组合物的总重量作为100重量％。
5.根据权利要求1～4中任一项所述的铸造用粘结剂组合物，其粘度为80mPa·s以下。
6.根据权利要求1～5中任一项所述的铸造用粘结剂组合物，其中，所述糠醇预聚物的数均分子量在150g/mol以上。
7.根据权利要求1～6中任一项所述的铸造用粘结剂组合物，其中，所述树脂和糠醇预聚物的重量比为1:4～1:2。
8.一种用于制备权利要求1～7中任一项所述的铸造用粘结剂组合物的套组，其包括：
组分A，其为树脂母液，其包含树脂，所述树脂是选自脲醛呋喃树脂和酚脲醛呋喃树脂中的一种或两种；以及
组分B，其为糠醇预聚物液，所述糠醇预聚物液包含糠醇预聚物；
其中，
所述糠醇预聚物的数均分子量在650g/mol以下；
所述糠醇预聚物中，分子量在401-650g/mol的糠醇预聚物占20摩尔％以上，分子量在301-400g/mol的糠醇预聚物占10摩尔％以上，且分子量在150-300g/mol的糠醇预聚物占10摩尔％以上；
所述组分A与组分B独立包装。
9.根据权利要求8所述的套组，其中，所述组分A还包含介质。
10.根据权利要求9所述的套组，其中，所述介质为水。
11.根据权利要求8所述的套组，其中，脲醛呋喃树脂是醇改性脲醛呋喃树脂。
12.根据权利要求11所述的套组，其中，所述醇选自聚乙烯醇、聚丙烯醇、乙二醇和丙三醇。
13.一种制备权利要求1～7中任一项所述的铸造用粘结剂组合物的方法，其包括将下述组分A和组分B混合的步骤；
其中，
所述组分A为树脂母液，其包含树脂，所述树脂是选自脲醛呋喃树脂和酚脲醛呋喃树脂中的一种或两种；以及
所述组分B为糠醇预聚物液，所述糠醇预聚物液包含糠醇预聚物，所述糠醇预聚物的数均分子量在650g/mol以下；
所述糠醇预聚物中，分子量在401-650g/mol的糠醇预聚物占20摩尔％以上，分子量在301-400g/mol的糠醇预聚物占10摩尔％以上，且分子量在150-300g/mol的糠醇预聚物占10摩尔％以上。
14.根据权利要求11所述的方法，其中，所述组分A还包含介质。
15.根据权利要求12所述的方法，其中，所述介质为水。
16.根据权利要求11所述的方法，其中，脲醛呋喃树脂是醇改性脲醛呋喃树脂。
17.根据权利要求16所述的方法，其中，所述醇选自聚乙烯醇、聚丙烯醇、乙二醇和丙三醇。
发明效果
根据本发明，提供一种游离糠醇含量低且力学强度好的、基于呋喃树脂的铸造用粘结剂组合物以及用于制备该铸造用粘结剂组合物的套组。此外，本发明还取得了如下有益效果：
1.制备的低糠醇呋喃树脂环保性能好，降低了浇铸过程中单体包括糠醇、甲醛、苯酚等小分子的释放，对大气不会产生二噁英效应；树脂中没有加入其它价格昂贵的改性剂，生产成本大大降低；
2.在制备树脂过程中控制树脂分子量的分布，最终使低糠醇呋喃树脂的粘度控制在80mPa.s以下(20℃)，大大提高了树脂的使用性能。
3.树脂用醇改性，使树脂砂的抗拉强度衰减减慢，力学性能满足市场使用要求。
发明的具体实施方式
下面结合具体实施方式对本发明进行详细的说明。在无冲突的情况下，本说明书中的科学术语具有本领域技术人员通常理解的含义，如有冲突应以本说明书中的定义为准。
在一个方面中，本发明提供一种铸造用粘结剂组合物(本发明的组合物)，其包含：树脂和糠醇预聚物；其中，所述树脂是选自脲醛呋喃树脂和酚脲醛呋喃树脂中的一种或两种，所述糠醇预聚物的数均分子量在650g/mol以下(分子量下限可以是150g/mol)，所述糠醇预聚物中，分子量在401-650g/mol的糠醇预聚物占20摩尔％以上，分子量在301-400g/mol的糠醇预聚物占10摩尔％以上，且分子量在150-300g/mol的糠醇预聚物占10摩尔％以上。
本发明人发现，本发明的组合物即使在其中的游离糠醇含量降低(意味着对环境产生的不良影响减少)的情况下，仍能保持良好的力学强度。特别是，在本发明的组合物中游离糠醇的含量为25重量％以下(以所述铸造用粘结剂组合物的总重量作为100重量％)时，其力学强度仍未显著降低。
优选地，所述脲醛呋喃树脂是醇改性脲醛呋喃树脂。所述醇可以选自聚乙烯醇、聚丙烯醇、乙二醇和丙三醇。
优选地，本发明的组合物的粘度可以为80mPa·s(20℃)以下，这大大提高了其使用性能。
在本发明的组合物中，所述树脂和糠醇预聚物的重量比可以是1:4～1:2。
本发明的组合物可以通过将树脂母液与糠醇预聚物液进行混合来制备。因此，在另一方面中，本发明提供一种用于制备本发明的组合物的套组(本发明的套组)，其包括：组分A，其为树脂母液，其包含树脂，所述树脂是选自脲醛呋喃树脂和酚脲醛呋喃树脂中的一种或两种；以及组分B，其为糠醇预聚物液，所述糠醇预聚物液包含糠醇预聚物；其中，所述糠醇预聚物的数均分子量在650g/mol以下；所述糠醇预聚物中，分子量在401-650g/mol的糠醇预聚物占20摩尔％以上，分子量在301-400g/mol的糠醇预聚物占10摩尔％以上，且分子量在150-300g/mol的糠醇预聚物占10摩尔％以上；所述组分A与组分B独立包装。
所述组分A中还可以包含介质，所述介质优选为水。
所述组分A例如可以如下地制备：向反应釜中加入甲醛(例如15-25重量份)，调节pH为弱碱性(7.5-8.5)，视需要加入用于改性的醇(例如聚乙烯醇，PVA)(例如0.1-5重量份)，并启动搅拌加热升温一段时间(升温至例如60℃～70℃)，而后加入部分尿素(例如15-30重量份)进行溶解，升温(例如至80℃～90℃)反应一定时间(例如0.5～2小时)；再根据所生产树脂的含氮量的要求加入一部分糠醇(例如35-55重量份)进行反应；加入糠醇后首先在碱性条件下反应一段时间，而后再调整物料体系的pH值为酸性(例如3.0～40)进行反应；随后加入余下部分尿素(例如2-5重量份)，再将整个物料体系在真空条件下脱水至含水率低于20％，然后向脱水后的体系中加入氨水(例如1-3重量份)降醛，搅拌均匀，即得所述树脂母液(组分A)。
这里，所述甲醛可以是液体甲醛，也可以是固体甲醛。调节pH值至碱性所用碱可以是氢氧化钠、氢氧化钾、氨水、碳酸钠、碳酸钾、氢氧化钡等。调节pH值至酸性所用酸可以是甲酸、乙酸、磺酸、盐酸、硫酸等。所述碱或酸最优选为同一种碱或同一种酸。
所述组分B例如可以如下地制备：向反应釜中加入糠醇(例如100重量份)和水(例如1～10重量份)，滴加酸(例如0.1～5重量份)，启动搅拌，升温(升温至例如60℃～70℃)反应0.1～1小时，再升温(升温至例如90℃～99℃)反应0.5～8小时；反应结束后降温，脱水，放料得糠醇预聚物液(组分B)。
将所述组分A和组分B混合，即可得到本发明的组合物。
实施例
下面结合实施例对本发明进行更具体地说明。下面给出的实施例，是为了便于理解本发明，而非对本发明的限定。
实施例1
PVA改性脲醛呋喃树脂的制备
原材料组成:
甲醛(浓度37％):283.7Kg，尿素:120Kg，糠醇:270Kg，PVA:6Kg氨水：8Kg
反应步骤:
向反应釜中加入甲醛(浓度37％)283.7Kg，用NaOH(10％)碱性溶液调节PH值为7.8-8.2，启动搅拌，升温至65℃加入一步尿素100Kg，尿素溶解后，再升温至85℃反应1小时；反应结束后降温，脱水120.7Kg，加入糠醇组分270Kg和PVA 6Kg再反应1小时；调整物料体系PH值为3.5-3.8，反应温度95℃反应1.5小时；加入二步尿素20Kg，搅拌溶解，降低体系温度；在真空条件下脱水15Kg，加入氨水7Kg搅拌均匀，放料得产品(A)550Kg左右。
糠醇预聚物的制备
原材料组成:
糠醇:270Kg，水：13.5Kg,磷酸(50％)：5.67Kg
反应步骤：
向反应釜中加入糠醇270Kg和水13.5Kg，滴加入磷酸(50％)：5.67Kg，启动搅拌，升温至65℃反应半个小时，再升温至95℃反应1小时；反应结束后降温，脱水62.1Kg，放料得产品(B)227Kg。用凝胶渗透色谱测试其数均分子量为520g/mol，且分子量在401-650g/mol的糠醇预聚物占23.5摩尔％，分子量在301-400g/mol的糠醇预聚物占11.1摩尔％以上，且分子量在150-300g/mol以上的糠醇预聚物占14摩尔％。
上述产品(A)和产品(B)以1:3比例混合后即得实施例1的铸造用粘结剂组合物。
实施例2
PVA改性脲醛呋喃树脂的制备
原材料组成:
甲醛(浓度37％):567.4Kg，苯酚：50Kg，尿素:180Kg，糠醇:510Kg，PVA:8Kg，氨水：15Kg
反应步骤:
向反应釜中加入甲醛(浓度37％)567.4Kg，用NaOH(10％)碱性溶液调节PH值为7.5-7.8，启动搅拌，加入PVA 8Kg，加入苯酚50Kg，升温至80℃反应1小时；降温后加入一步尿素160Kg，尿素溶解后，再升温至85℃反应1小时；反应结束后降温，脱水242.4Kg，加入糠醇组分510Kg再反应1小时；调整物料体系PH值为3.0-3.3，反应温度95℃反应1.5小时；加入二步尿素20Kg，搅拌溶解，降低体系温度；在真空条件下脱水20Kg，加入氨水15Kg搅拌均匀，放料得产品(B)1068Kg左右。
糠醇预聚物的制备
原材料组成:
糠醇:500Kg，水：15Kg,甲酸(50％)：10Kg
反应步骤：
向反应釜中加入糠醇500Kg和水15Kg，滴加入甲酸(50％)：10Kg，启动搅拌，升温至65℃反应半个小时，再升温至95℃反应2小时；反应结束后降温，脱水98Kg，放料得产品(B)427Kg。凝胶渗透色谱测试其数均分子量为580g/mol，且数均分子量在401-650g/mol的糠醇预聚物占25.5摩尔％，分子量在301-400g/mol的糠醇预聚物占12.1摩尔％以上，且分子量在150-300g/mol以上的糠醇预聚物占15摩尔％。
将上述产品(A)和产品(B)以1:4比例混合后即得实施例2的铸造用粘结剂组合物。
实施例3
聚丙烯醇改性脲醛呋喃树脂的制备
原材料组成:
甲醛(浓度37％):283.7Kg，尿素:140Kg，糠醇:245Kg，聚丙烯醇:4Kg氨水：6Kg
反应步骤:
向反应釜中加入甲醛(浓度37％)283.7Kg，用NaOH(10％)碱性溶液调节PH值为8.0-8.2，启动搅拌，升温至65℃加入一步尿素120Kg，尿素溶解后，再升温至85℃反应1小时；反应结束后降温，脱水130.7Kg，加入糠醇组分245Kg再反 应1小时；调整物料体系PH值为3.0-3.3，再加入聚丙烯醇4Kg，反应温度95℃反应1.5小时；加入二步尿素20Kg，搅拌溶解，降低体系温度；在真空条件下脱水18Kg，加入氨水6Kg搅拌均匀，放料得产品(A)532Kg左右。
糠醇预聚物的制备
原材料组成:
糠醇:500Kg，水：15Kg,盐酸(10％)：10Kg
反应步骤：
向反应釜中加入糠醇500Kg和水15Kg，滴加入盐酸(10％)：10Kg，启动搅拌，升温至65℃反应半个小时，再升温至95℃反应1.5小时；反应结束后降温，脱水100Kg，放料得产品(B)416Kg。凝胶渗透色谱测试其数均分子量为620g/mol，且数均分子量在401-650g/mol的糠醇预聚物占20.5摩尔％，分子量在301-400g/mol的糠醇预聚物占10.1摩尔％以上，且分子量在150-300g/mol以上的糠醇预聚物占10摩尔％。
将上述产品(A)和产品(B)以1:2比例混合后即得实施例3的铸造用粘结剂组合物。
实施例4
乙二醇改性脲醛呋喃树脂的制备
原材料组成:
甲醛(浓度37％):851Kg，尿素:400Kg，糠醇:750Kg，乙二醇:4Kg氨水：20Kg
反应步骤:
向反应釜中加入甲醛(浓度37％)851Kg，用NaOH(10％)碱性溶液调节PH值为8.2-8.4，启动搅拌，升温至65℃加入一步尿素350Kg，尿素溶解后，再升温至85℃反应1小时；反应结束后降温，脱水420Kg，加入糠醇组分750Kg再反应1小时；调整物料体系PH值为3.2-3.4，再加入乙二醇4Kg，反应温度95℃反应1.5小时；加入二步尿素50Kg，搅拌溶解，降低体系温度；在真空条件下脱水55Kg，加入氨水20Kg搅拌均匀，放料得产品(A)1550Kg左右。
糠醇预聚物的制备
原材料组成:
糠醇:300Kg，水：6Kg,乳酸(30％)：15Kg
反应步骤：
向反应釜中加入糠醇300Kg和水6Kg，滴加入乳酸(30％)：15Kg，启动搅拌，升温至65℃反应半个小时，再升温至95℃反应3小时；反应结束后降温，脱水67.4Kg，放料得产品(B)253.59Kg。凝胶渗透色谱测试其数均分子量为420g/mol，且数均分子量在401-650g/mol的糠醇预聚物占28.5摩尔％，分子量在301-400g/mol的糠醇预聚物占15.1摩尔％以上，且分子量在150-300g/mol以上的糠醇预聚物占18摩尔％。
将上述产品(A)和产品(B)以1:3比例混合后即得实施例3的铸造用粘结剂组合物。
实施例5
PVA改性脲醛呋喃树脂的制备
原材料组成:
甲醛(浓度37％):425；Kg，尿素:200Kg，糠醇:375Kg，PVA:6Kg氨水：6Kg
反应步骤:
向反应釜中加入甲醛(浓度37％)425Kg，用NaOH(10％)碱性溶液调节PH值为8.3-8.5，再加入PVA 9Kg，启动搅拌，升温至65℃加入一步尿素180Kg，尿素溶解后，再升温至85℃反应1小时；反应结束后降温，脱水200Kg，加入糠醇组分375Kg再反应1小时；调整物料体系PH值为3.3-3.5，，反应温度95℃反应1.5小时；加入二步尿素20Kg，搅拌溶解，降低体系温度；在真空条件下脱水28Kg，加入氨水9Kg搅拌均匀，放料得产品(A)790Kg左右。
糠醇预聚物的制备
原材料组成:
糠醇:1000Kg，水：25Kg,醋酸(40％)：75Kg
反应步骤：
向反应釜中加入糠醇1000Kg和水25Kg，滴加入醋酸(40％)：75Kg，启动搅拌，升温至65℃反应半个小时，再升温至95℃反应2.5小时；反应结束后降温，脱水62.1Kg，放料得产品(B)860Kg。凝胶渗透色谱测试其数均分子量为320g/mol，且数均分子量在401-650g/mol的糠醇预聚物占24.5摩尔％，分子量在301-400g/mol的糠醇预聚物占12.1摩尔％以上，且分子量在150-300g/mol以上的 糠醇预聚物占13摩尔％。
将上述产品(A)和产品(B)以1:2.8比例混合后即得实施例3的铸造用粘结剂组合物。
对比例1
脲醛呋喃树脂的制备
原材料组成:
甲醛(浓度37％):283.7Kg，尿素:120Kg，糠醇:270Kg，氨水：8Kg
反应步骤:
向反应釜中加入甲醛(浓度37％)283.7Kg，用NaOH(10％)碱性溶液调节PH值为7.8-8.2，启动搅拌，升温至65℃加入一步尿素100Kg，尿素溶解后，再升温至85℃反应1小时；反应结束后降温，脱水120.7Kg，加入糠醇组分270Kg再反应1小时；调整物料体系PH值为3.5-3.8，反应温度95℃反应1.5小时；加入二步尿素20Kg，搅拌溶解，降低体系温度；在真空条件下脱水14Kg，加入氨水7Kg搅拌均匀，放料得产品(A)546Kg左右。
上述产品(A)用1:3比例的糠醇稀释制备出对比例1的铸造用粘结剂组合物。
对比例2
酚脲醛呋喃树脂的制备
原材料组成:
甲醛(浓度37％):567.4Kg，苯酚：50Kg，尿素:180Kg，糠醇:510Kg，氨水：15Kg
反应步骤:
向反应釜中加入甲醛(浓度37％)567.4Kg，用NaOH(10％)碱性溶液调节PH值为7.5-7.8，启动搅拌，加入苯酚50Kg，升温至80℃反应1小时；降温后加入一步尿素160Kg，尿素溶解后，再升温至85℃反应1小时；反应结束后降温，脱水242.4Kg，加入糠醇组分510Kg再反应1小时；调整物料体系PH值为3.0-3.3，反应温度95℃反应1.5小时；加入二步尿素20Kg，搅拌溶解，降低体系温度；在真空条件下脱水20Kg，加入氨水15Kg搅拌均匀，放料得产品(B)1060Kg左右。
上述产品(A)用1:4比例的糠醇稀释制备出对比例2的铸造用粘结剂组合物。
对比例3
聚丙烯醇改性脲醛呋喃树脂的制备
原材料组成:
甲醛(浓度37％):283.7Kg，尿素:140Kg，糠醇:245Kg，聚丙烯醇:4Kg氨水：6Kg
反应步骤:
向反应釜中加入甲醛(浓度37％)283.7Kg，用NaOH(10％)碱性溶液调节PH值为8.0-8.2，启动搅拌，升温至65℃加入一步尿素120Kg，尿素溶解后，再升温至85℃反应1小时；反应结束后降温，脱水130.7Kg，加入糠醇组分245Kg再反应1小时；调整物料体系PH值为3.0-3.3，再加入聚丙烯醇4Kg，反应温度95℃反应1.5小时；加入二步尿素20Kg，搅拌溶解，降低体系温度；在真空条件下脱水18Kg，加入氨水6Kg搅拌均匀，放料得产品(A)532Kg左右。
糠醇预聚物的制备
原材料组成:
糠醇:500Kg，水：15Kg,盐酸(10％)：10Kg
反应步骤：
向反应釜中加入糠醇500Kg和水15Kg，滴加入盐酸(10％)：10Kg，启动搅拌，升温至65℃反应半个小时，再升温至95℃反应1.5小时；反应结束后降温，脱水100Kg，放料得产品(B)416Kg。凝胶渗透色谱测试其数均分子量为1020g/mol，且数均分子量在900-1020g/mol的糠醇预聚物占30.5摩尔％，分子量在782-900g/mol的糠醇预聚物占10.1摩尔％以上，且分子量在650-782g/mol以上的糠醇预聚物占10摩尔％。
将上述产品(A)和产品(B)以1:2比例混合后即得对比例3的铸造用粘结剂组合物。
对比例4
乙二醇改性脲醛呋喃树脂的制备
原材料组成:
甲醛(浓度37％):851Kg，尿素:400Kg，糠醇:750Kg，乙二醇:4Kg氨水：20Kg
反应步骤:
向反应釜中加入甲醛(浓度37％)851Kg，用NaOH(10％)碱性溶液调节PH值为8.2-8.4，启动搅拌，升温至65℃加入一步尿素350Kg，尿素溶解后，再升温至85℃反应1小时；反应结束后降温，脱水420Kg，加入糠醇组分750Kg再反应1小时；调整物料体系PH值为3.2-3.4，再加入乙二醇4Kg，反应温度95℃反应1.5小时；加入二步尿素50Kg，搅拌溶解，降低体系温度；在真空条件下脱水55Kg，加入氨水20Kg搅拌均匀，放料得产品(A)1550Kg左右。
糠醇预聚物的制备
原材料组成:
糠醇:300Kg，水：6Kg,乳酸(30％)：15Kg
反应步骤：
向反应釜中加入糠醇300Kg和水6Kg，滴加入乳酸(30％)：15Kg，启动搅拌，升温至65℃反应半个小时，再升温至95℃反应3小时；反应结束后降温，脱水67.4Kg，放料得产品(B)253.59Kg。凝胶渗透色谱测试其数均分子量为920g/mol，且数均分子量在780-920g/mol的糠醇预聚物占28.5摩尔％，分子量在652-780g/mol的糠醇预聚物占15.1摩尔％以上，且分子量在580-652g/mol以上的糠醇预聚物占18摩尔％。
将上述产品(A)和产品(B)以一定比例混合后即得对比例4的铸造用粘结剂组合物。
对比例5
PVA改性脲醛呋喃树脂的制备
原材料组成:
甲醛(浓度37％):425；Kg，尿素:200Kg，糠醇:375Kg，PVA:6Kg氨水：6Kg
反应步骤:
向反应釜中加入甲醛(浓度37％)425Kg，用NaOH(10％)碱性溶液调节PH值为8.3-8.5，再加入PVA 9Kg，启动搅拌，升温至65℃加入一步尿素180Kg，尿素溶解后，再升温至85℃反应1小时；反应结束后降温，脱水200Kg，加入糠醇组分375Kg再反应1小时；调整物料体系PH值为3.3-3.5，，反应温度95℃反应1.5小时；加入二步尿素20Kg，搅拌溶解，降低体系温度；在真空条件下脱水28Kg， 加入氨水9Kg搅拌均匀，放料得产品(A)790Kg左右。
糠醇预聚物的制备
原材料组成:
糠醇:1000Kg，水：25Kg,醋酸(40％)：75Kg
反应步骤：
向反应釜中加入糠醇1000Kg和水25Kg，滴加入醋酸(40％)：75Kg，启动搅拌，升温至65℃反应半个小时，再升温至95℃反应2.5小时；反应结束后降温，脱水62.1Kg，放料得产品(B)860Kg。凝胶渗透色谱测试其数均分子量为1200g/mol，且数均分子量在980-1200g/mol的糠醇预聚物占40.5摩尔％，分子量在810-980g/mol的糠醇预聚物占11.1摩尔％以上，且分子量在560-810g/mol以上的糠醇预聚物占16摩尔％.
将上述产品(A)和产品(B)以1:2.8比例混合后即得对比例5的铸造用粘结剂组合物。
以上实施例1～5、对比例1～5的铸造用粘结剂组合物的测试结果见表1。其中游离糠醇含量、含氮量、游离甲醛和强度的分析方法:按JB/T7526-1994《铸造用自硬呋喃树脂》进行；甲醛释放量根据国标GB 13197-91中的乙酰丙酮分光光度法进行测量。
表1：实施例1-5及对比例1-5的铸造用粘结剂组合物的测试结果
Figure PCTCN2018090079-appb-000001
Figure PCTCN2018090079-appb-000002
工业实用性
根据本发明，能够提供一种游离糠醇含量低且力学强度好的、基于呋喃树脂的铸造用粘结剂组合物以及用于制备该铸造用粘结剂组合物的套组。

Claims (10)

  1. 一种铸造用粘结剂组合物，其包含：
    树脂和糠醇预聚物，优选所述树脂和所述糠醇预聚物的重量比为1:4～1:2；
    其中，
    所述树脂是选自脲醛呋喃树脂和酚脲醛呋喃树脂中的一种或两种，
    所述糠醇预聚物的数均分子量在650g/mol以下(优选数均分子量下限为150g/mol以上)，
    所述糠醇预聚物中，分子量在401-650g/mol的糠醇预聚物占20摩尔％以上，分子量在301-400g/mol的糠醇预聚物占10摩尔％以上，且分子量在150-300g/mol的糠醇预聚物占10摩尔％以上。
  2. 根据权利要求1所述的铸造用粘结剂组合物，其中，脲醛呋喃树脂是醇改性脲醛呋喃树脂，优选所述醇选自聚乙烯醇、聚丙烯醇、乙二醇和丙三醇。
  3. 根据权利要求1或2所述的铸造用粘结剂组合物，其中，所述铸造用粘结剂组合物中游离糠醇的含量为25重量％以下，以所述铸造用粘结剂组合物的总重量作为100重量％。
  4. 根据权利要求1～3中任一项所述的铸造用粘结剂组合物，其粘度为80mPa·s以下。
  5. 一种用于制备权利要求1～4中任一项所述的铸造用粘结剂组合物的套组，其包括：
    组分A，其为树脂母液，其包含树脂，所述树脂是选自脲醛呋喃树脂和酚脲醛呋喃树脂中的一种或两种；以及
    组分B，其为糠醇预聚物液，所述糠醇预聚物液包含糠醇预聚物；
    其中，
    所述糠醇预聚物的数均分子量在650g/mol以下；
    所述糠醇预聚物中，分子量在401-650g/mol的糠醇预聚物占20摩尔％以上，分子量在301-400g/mol的糠醇预聚物占10摩尔％以上，且分子量在150-300g/mol的糠醇预聚物占10摩尔％以上；
    所述组分A与组分B独立包装。
  6. 根据权利要求5所述的套组，其中，所述组分A还包含介质，所述介质 优选为水。
  7. 根据权利要求5所述的套组，其中，所述脲醛呋喃树脂是醇改性脲醛呋喃树脂，优选所述醇选自聚乙烯醇、聚丙烯醇、乙二醇和丙三醇。
  8. 一种制备权利要求1～4中任一项所述的铸造用粘结剂组合物的方法，其包括将下述组分A和组分B混合的步骤；
    其中，
    所述组分A为树脂母液，其包含树脂，所述树脂是选自脲醛呋喃树脂和酚脲醛呋喃树脂中的一种或两种；以及
    所述组分B为糠醇预聚物液，所述糠醇预聚物液包含糠醇预聚物，所述糠醇预聚物的数均分子量在650g/mol以下；
    所述糠醇预聚物中，分子量在401-650g/mol的糠醇预聚物占20摩尔％以上，分子量在301-400g/mol的糠醇预聚物占10摩尔％以上，且分子量在150-300g/mol的糠醇预聚物占10摩尔％以上。
  9. 根据权利要求8所述的套组，其中，所述组分A还包含介质，优选所述介质为水。
  10. 根据权利要求8所述的套组，其中，所述脲醛呋喃树脂是醇改性脲醛呋喃树脂，优选所述醇选自聚乙烯醇、聚丙烯醇、乙二醇和丙三醇。
PCT/CN2018/090079 2017-04-06 2018-06-06 铸造用粘结剂组合物及用于制备它的套组 WO2018184601A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201710220239.3 2017-04-06
CN201710220239.3A CN108687301B (zh) 2017-04-06 2017-04-06 铸造用粘结剂组合物及用于制备它的套组

Publications (1)

Publication Number Publication Date
WO2018184601A1 true WO2018184601A1 (zh) 2018-10-11

Family

ID=63712010

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2018/090079 WO2018184601A1 (zh) 2017-04-06 2018-06-06 铸造用粘结剂组合物及用于制备它的套组

Country Status (2)

Country Link
CN (1) CN108687301B (zh)
WO (1) WO2018184601A1 (zh)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116274851B (zh) * 2022-12-15 2023-10-20 江苏华岗材料科技发展有限公司 一种铸造用粘合剂及制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4478962A (en) * 1982-02-25 1984-10-23 Cl Industries, Inc. Binder compositions comprising furfuryl ester and furfuryl ester-furuyl alcohol combinations
CN102665960A (zh) * 2009-12-25 2012-09-12 花王株式会社 自固化性铸型造型用粘结剂组合物
CN103819643A (zh) * 2014-01-17 2014-05-28 山东时风（集团）有限责任公司 一种铸造用呋喃树脂及其制备方法
CN104151515A (zh) * 2014-08-13 2014-11-19 济南圣泉集团股份有限公司 一种石墨烯改性呋喃树脂及其制备方法
CN104497299A (zh) * 2014-11-20 2015-04-08 济南圣泉集团股份有限公司 低游离糠醇粘结剂的制备方法
CN105669927A (zh) * 2016-03-07 2016-06-15 宁夏共享化工有限公司 一种低糠醇含量的高强度呋喃树脂的制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4478962A (en) * 1982-02-25 1984-10-23 Cl Industries, Inc. Binder compositions comprising furfuryl ester and furfuryl ester-furuyl alcohol combinations
CN102665960A (zh) * 2009-12-25 2012-09-12 花王株式会社 自固化性铸型造型用粘结剂组合物
CN103819643A (zh) * 2014-01-17 2014-05-28 山东时风（集团）有限责任公司 一种铸造用呋喃树脂及其制备方法
CN104151515A (zh) * 2014-08-13 2014-11-19 济南圣泉集团股份有限公司 一种石墨烯改性呋喃树脂及其制备方法
CN104497299A (zh) * 2014-11-20 2015-04-08 济南圣泉集团股份有限公司 低游离糠醇粘结剂的制备方法
CN105669927A (zh) * 2016-03-07 2016-06-15 宁夏共享化工有限公司 一种低糠醇含量的高强度呋喃树脂的制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
NIELSEN I. E.: "Effect of Molecular Mass and Structure", POLYMER RHEOLOGY, 31 May 1982 (1982-05-31), pages 65 - 70 *

Also Published As

Publication number Publication date
CN108687301A (zh) 2018-10-23
CN108687301B (zh) 2020-01-10

Similar Documents

Publication Publication Date Title
US5032642A (en) Phenolic resin compositions
CN102127197A (zh) 镁碳砖用酚醛树脂的制备方法
US5288774A (en) Novel low-emission, cold-curing binding agents
JPS6232111A (ja) 鋳物用中子及び鋳型を製造するための、変性フェノールレゾール樹脂を含む自由流動性粒状材料
CN104815943A (zh) 一种铝合金铸造用新型改性磷酸盐无机粘结剂及其制备方法
WO2016090907A1 (zh) 制备木质素改性呋喃树脂的方法
CN102219526A (zh) 镁碳砖用酚醛树脂及其制备方法
CN108609938A (zh) 一种含氧化石墨烯的高强度建筑混凝土及制备方法
CN109093062B (zh) 一种纳米氧化钇改性的磷酸盐粘结剂及其制备方法
CN105750478B (zh) 一种3d砂型打印用高强度耐高温酚醛树脂及其制备方法
WO2018184601A1 (zh) 铸造用粘结剂组合物及用于制备它的套组
CN102276957B (zh) 耐火砖用酚醛树脂及其制备方法
CN113667061A (zh) 一种吸水树脂及其制备方法与应用
CN111299497A (zh) 一种覆膜砂粘结剂的固化剂及其制备方法
CN112142938A (zh) 一种节能环保呋喃树脂铸造粘合剂的制备方法
CN112126029A (zh) 一种覆膜砂用改性酚醛树脂的制备方法
CN109734373B (zh) 一种速干型混凝土及其制备方法
JP2017154157A (ja) 鋳型造型用キットおよび鋳型造型用砂組成物とその製造方法
CN112355232A (zh) 一种基于磷酸盐的无机铸造粘结剂及其应用
CN107721243B (zh) 提高混凝土强度的外加剂及其制备方法
JPS6312700B2 (zh)
JPS5874240A (ja) 鋳型用有機バインダ−
JP2003238227A (ja) 石膏組成物
CN104419361A (zh) 一种糠醇树脂胶粘剂的生产方法
KR102470363B1 (ko) 나노셀룰로스 및 퍼퓨릴 알콜을 포함하는 주물사용 퓨란 점결제 조성물 및 주물사용 점결제 제조방법

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18780581

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18780581

Country of ref document: EP

Kind code of ref document: A1